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^)^us  TH'E  CHEMICAL  NEWS,   AUGUST  3,  1923. 

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I  1  / 
THE 


CHEMICAL  NEWS 

AMD 

JOURNAL  OF  INDUSTRIAL   SCIENCE. 

WITH   WHICH  IS  INCORPOBATID  THE  "  CHEMICAL   GAZETTE." 
IH  THEIR  APPLICATION   TO 

ENGINEERING   AND  MANUFACTURES. 

B»ITBD  BY 

JAMES  H.  GARDINER,  F.ln$i.P.,  F.C.8. 
and 
J    a.  F.  DRUGE,  M.Sc.  (bond.),  R.Nat.Dr.  {Prague). 

VOLUME  CXXVI.      1928. 


LONDON. 
PUBLISHED  AT  THE  OFFICE,  97,  6H0E  LANE,    E.G.  4. 
AND  SOLD  BY  ALL  BOOKSELLERS. 


1923. 


,V<'" 


Feinted  by  Kea,   Walker  &  iNCHsonLO,   I, id 

224,    BLACKFRIARS    ROAD,    SB.l. 
LONDON  : 


JANUARY  5,  1923. 


THE    CHEMICAL    NEWS. 


1 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.     No.  3273. 


A    CONVENIENT    METHOD  FOR   THE 

PREPARATION  OF  AQUEOUS  HYDRO- 

BROMIC  ACID  OF  CONSTANT 

BOILING  POINT. 

By  J.  G.  F.  Druce,  M.Sc,  A.I.C. 

It  is  well  known  that  wh(  n  concentrated 
suplhuric  acid  is  added  to  potassium  bro- 
mide, the  hydrobromic  acid  gas  evolved  is 
not  pure,  since  the  concentrated  sulphuric 
acid  exerts  an  oxidising  action  upon  it, 
liberating  some  free  bromine,  and  being 
partly  reduced  to  sulphur  dioxide. 

Thus  it  is  not  possible  to  prepare  pure 
hydrobromic  acid  by  the  int<'Paction  of  sul- 
phuric acid  and  potassium  bromide  unless 
a  reducing  agent  of  some  kind  is  added  to 
prevent  the  oxidation  of  the  hydrogen  bro- 
mide formed 

Pickles  (The  Chemical  News,  1919, 
CXIX.,  89)  has  described  a  very  simple 
method  for  obtaining  a  strcmg  aqueous 
solution  of  the  acid  free  from  bromine  and 
suliphur  dioxide  by  the  distilktion  of  a  mix- 
ture of  concentrated  sulphuric  acid  (8.4  cc.) 
nnd  potassium  bromide  (15  grams)  dissolved 
in  25  cc.  of  water,  to  which  a  trace  of  stan- 
nous chloride  (0.2  gram)  has  been  added. 

In  repeating  this  work,  it  was  found  that 
a-  distillate  began  to  come  over  at  103"  C, 
and  the  temperature  did  not  ijse  to  120"  C. 
(the  boiling  point  of  the  strongest  solution 
of  constant  B.P.)  until  most  of  the  aqueous 
hydrobromic  acid  had  passed  over.  The 
distillation  was  also  accompanied  by  much 
"  bumping,"  which  was  not  arrested  by 
the  introduction  of  pieces  of  broken  glass  or 
porous  i)ot. 

Much  more  satisfactory  results  were 
obtained  by  increasing  the  quantity  of  sul- 
phuric acia  to  10  cc.,  which  was  added  to 
the  15  grains  of  potassium  bromide  dis- 
solved in  25  cc,  of  water  containing  0.2 
gram  of  stannous  chloride.  The  mixture 
was  allowed  to  stand  overnight,  so  that 
much  potassium  hydrogen  sulphate  crystal- 
lised out. 

The  supernatant  liquid  was  decanted 
from  the  crystals  and  distilled.  Nearly  all 
the  distillate  came  over  at  120-125°.  The 
temperature  rose  ra(pidly  to  120**,  and  then 
very  gradually]  to  125°,    18  cc.  of  distillate 


uere  collected  between  these  two  tempera- 
tures. 

In  order  to  det^ffeine  the  exact  yield  of 
hydrobromic  acid  by  this  method,  ten  cc.  of 
the  distillate  were  made  up  to  250  cc.  with 
distilled  water,  and  quantities  of  10  cc.  were 
withdrawn  and  titrated  with  0.2  norrnal 
potassium  hydrat^e  solution,  using  phenol- 
phthalein  as  indicator. 

It  was  found  that  12.05  cc.  of  the  alkali 
solution  were  required  to  neutralise  10  cc. 
of  the  diluted  hydrobromic  acid  solution. 

Thus  this  diluted  acid  contained  19.48 
grams  of  hydrogen  bromide  per  litre,  and 
this  indicates  that  the  original  distillate 
contained  48.7  per  cent,  of  hydrobromic 
acid  gas. 

Since  stannous  chlwide  was  used  in  the 
preparation  of  the  hydrobromic  acid,  a 
trace  of  hydrochloric  acid  (not  more  than 
0.07  gram)  might  be  present  in  the  product. 

But  disregarding  this  negligible  amount, 
the  yield  of  hydrobromic  acid  was  thus  over 
90  per  cent,  of  that  which  it  is  theoretically 
possible  to  obtain. 


MISSING  ELEMENTS  IN  THE 
PERIODIC  TABLE. 

Part  III. 

By  F.  H.  Loring. 

A  study  of  the  above  subject  (see 
Chemkal  Newn,  Nov.  24,  1922,  vol.  CXXV., 
p.  309;  and  Dec.  29.  vol.  CXXV.,  p.  386) 
leads  to  some  exceedingly  interesting  obser- 
vations in  connection  with  the  relative 
quantitative  production  of  the  chemical 
elements.  It  will  not  be  out  of  place, 
therefore,  to  discuss  the  matter  further. 

The  existence  of  scandium  in  the  sun, 
and  it  may  be  present  there  in  considerable 
relative  quantities,  does  not  necessarily  in- 
validate tho  view  advanced,  namely,  that 
this  element  may  not  exist  in  relatively 
large  quantities  compared  with  that  of  its 
neighbours,  because,  according  to  recent 
speculations,  the  stars  are  manufacturing 
elements  out  of  hydrogen,  and  any  ele- 
ment, for  example  scandium,  appearing  in 
relative  excess  during  the  process  of  manu- 
facture or  element  evolution,  may  not  ulti- 
mately remain  in  the  same  quantities.  The 
following  quotation  from  Aston 's  book, 
"  Isotopes  "  (1922),  p.  103,  bears  upon 
this  subject :  — 


THE   CHEMICAL    NEWS. 


JANUARY  5,  192B. 


"  It  has  long  been  known  that  the 
chemical  atomic  weight  of  hydrogen  was 
greater  than  one  quarter  of  that  of  helium, 
but  so  long  as  fractional  weights  were 
general  there  was  no  particular  need  to  ex- 
plain this  fact,  nor  could  any  definite  con- 
clusions be  drawn  from  it.  The  results 
obtained  by  means  of  the  mass-spectro- 
graph remove  all  doubt  on  this  point,  and 
no  matter  whether  the  explanation  is  to  be 
ascribed  to  packing  or  not,  we  may  con- 
sider it  absolutely  certain  that  if  hydrogen 
is  transformed  into  helium  a  certain  quan- 
tity of  mass  must  be  annihilated  in  the 
process.  The  cosmical  importance  of  this 
conclusion  is  profound,  and  the  po-sibilifcies 
it  opens  for  the  future  very  remarkable, 
greater  in  fact  than  any  suggested  before 
by  science  in  the  whole  history  of  the 
human  race. 

"  We  know  from  Einstein's  Theory  of 
Relativity  that  mass  and  energy  are  inter- 
changeable (Eddington,  '  Time,  Space  and 
Gravitation,'  p.  146),  and  that  in  C.G.S. 
units  a  mass  ni  at  rest  may  be  expressed 
as  a  quantity  of  energy  mc'',  where  c  is  the 
velocity  of  light.  Even  in  the  case  of  the 
smallest  mass  this  energy  is  enormo'US.  The 
loss  of  mass  when  a  single  helium  nucleus 
is  formed  from  free  protons  and  electrons 
amounts  in  energy  to  that  acquired  by  a 
charge  e  falling  through  a  potential  of 
nearly  thirty  million  volts.  A  swift  a  ray 
has  an  energy  of  three  to  four  million  volts, 
so  that  the  change  of  packing  suggested  by 
Brosslera  need  not  be  nearly  so  great  to 
provide  the  energy  needed.  If  instead  of 
considering  single  atoms  we  deal  with  quan- 
tities of  matter  in  ordinary  experience,  the 
figures  for  the  energy  become  prodigious. 

"  Take  the  case  of  one  gramme  atom  of 
hydrogen,  that  is  to  say,  the  quantity  of 
hydrogen  in  9  cc.  of  water.  If  this  is 
entirely  transformed  into  helium  the  energy 
liberated  will  be 

0.0077   X   9  X   10-"  --=  6.93   x   10'«  ergs. 

Expressed  in  terms  of  heat  this  is  1.66  x 
10"  calories,  or  in  terms  of  work,  200,000 
kilowatt  hours.  We  have  here  at  least  a 
soiirce  of  energy  sufficient  to  account  for 
the  heat  of  the  sun  (Eddington,  Brit.  Assoc, 
address,  1920;  Perrin,  Scientia,  Nov., 
1921).  In  this  connection  Eddington  re- 
marks that  if  only  10  per  cent,  of  the  total 
hydrogen  on  the  sun  were  transformed  into 
helium,  enough  energy  would  be  liberated 
to  maintain  its  present  radiation  for  a 
thousand  million  years. 


Should  the  research  worker  of  the 
future  discover  some  means  of  releasing 
this  energy  in  a  form  which  .  could  be  em- 
j)l;/ye(l,  the  human  race  will  have  at  its 
command  powers  beyond  the  dreams  of 
scientific  fiction;  but  the  remote  possibility 
must  always  be  considered  that  the  energy 
once  liberated  will  be  comipletely  uncon- 
trollable, and  by  its  intense  violence  de- 
tonate all  the  neighbouring  substances.  In 
this  event  the  whole  of  the  hydrogen  on 
the  earth  might  be  transformed  at  once, 
and  the  success  of  the  experiment  pub- 
lished at  large  to  the  universe  as  a  new 
star." 

It  is  not  quite  clear  how  this  energy 
cycle  would  work.  When,  for  example, 
small  quantities  of  Hj  and  O^  are  exploded 
to  form  water  (HgO)  great  heat  is  given 
out,  but  to  explr>de  water  and  get  the 
energy  back  is  impossible ;  for  it  is  not 
given  to  us  twice  over.  If  the  formation 
of  the  elements  in  the  sun  is  due  to  the 
combination  cf  protons  and  electrons  taking 
place,  how  can  we  expect  to  get  back  heat 
already  given  away  in  the  form  of  radia- 
tion? This  is  not  probably  the  true  inter- 
pretation of  the  above-quoted  statement. 
It  is  assumed  that  if  the  hydrogen  con- 
tained in  the  waters  of  the  earth  were 
v.nited  by  ponae  temperature  and  pressure 
condition  a-;  ()i)taining  in  the  sun,  the  heat 
evolved  would  reduce  the  earth  to  a  molten 
mass  like  the  sun.  However  this  may  be, 
if  this  idea  can  be  harmonised  with  radio- 
activity, it  would  be  more  acceptable ;  in 
which  case  one  would  have  to  assume  that 
there  are  independent  or  free  protons  in  the 
structure  of  the  radio-element  (very  much 
as  there  are  free  electrons  oscillating  or 
revolving  round  a  nuclear  part),  which 
combine  explosively  to  form  helium,  but 
such  explosions  do  not  seem  to  extend  to 
adjoining  protons,  for  radio-activity  is  only 
concerned  with  a  part  of  the  whole  atom — 
and  therein,   perhaps,  lies  our  safety. 

At  one  time  it  was  roughly  estimated 
that  there  were  50  million  stars  (suns). 
These,  whatever  their  number  may  be,  vary 
in  size  and  temperature,  so  that  the  physi- 
cal condition  favourable  to  the  production 
or  degradation  ct  different  elements  in  vary- 
ing quantities  may  also  vary.  Assuming 
that  these  at  one  time  or  another  become 
most  active  in  the  production  of  elements, 
the  quantitative  production  per  star  might 
vary  considerably;  in  short,  there  would  be 
many  variables. 

Other  views  than  the  above  with  regard 
to  the  origin  of  the  excessive    heat    of    the 


JANUAEY  5,  1923. 


THE    CHEMICAL    NEWS. 


sun  have  been  advanced.  Prof.  Joly 
(Nature,  1922,  vol.  CX.,  p.  112)  has  re- 
cently suggested  that  the  sun's  heat  is  due 
to  temperature  and  pressure  effects  stimu- 
lating radio-activity  in  practically  all  the 
elen.ents  favourably  situated  in  this  respect. 
This  idea  was  discussed  at  considerable 
length  in  my  "Atomic  Theories"  (1921), 
chajpter  XXI. 

Sir  Wm.  CrfX)kes'  theory  of  the  evolution 
of  the  elements  is  of  interest  in  this  con- 
necti(m.  Quoting  again  from  Aston 's  book, 
page  117,  he  says:  "  A  more  attractive 
theory  than  the  one  given  above  [that  all 
the  elements  are  the  result  of  radio-active 
disintegrations,  but  these  radio-changes 
were  continued  beyond  the  ordinary  limit 
observed  at  present]  is  that  the  complex 
atoms  of  matter  have  been  evolved  by  the 
aggregation  of  simpler  atrmis.  This  idea 
has  received  a  gootl  deal  of  attention  in  the 
past.  Crookes  (Brit.  Afmor.  address,  1886) 
remarks  on  it  as  follows: — '  Let  us  picture 
the  very  beginnings  of  time,  before  geologi- 
cal ages,  before  the  earth  was  thrown  off 
from  the  central  nucleus  of  molten  fluid, 
before  even  the  sun  himself  had  con- 
solidated from  the  original  protyle.  Let  us 
still  imagine  that  at  this  primal  stage  nil 
was  in  an  ultra-gaseous  state,  at  a  tem- 
perature inconceivably  hotter  than  any- 
thing now  existing  in  the  visible  universe ; 
so  high  indeed  that  chemical  atoms  could 
not  yet  have  been  formed,  being  still  far 
above  their  dissociation  point.  In  so  far  as 
protyle  is  capable  of  radiating  or  reflecting 
lifjht,  this  vast  sea  of  incandescent  mist,  to 
an  astronomer  in  a  distant  star,  might  have 
appeared  as  a  nebula,  sh.Aving  in  the  spec- 
troscope a  few  isolated  lin(>s,  forecasts  of 
hydrogen,  carbon,  and  nitrogen  spectra. 

"  'But  in  due  c'>urse  of  time  some  [pro- 
cess akin,  to  cooling,  probably  internal, 
reduces  the  temperature  of  the  cosmic 
protyh  to  a  point  at  which  the  first  step  in 
granulation  takes  place ;  matter  as  we  know 
it  comes  into  existence,  and  the  atoms  are 
formed.'  " 

"  This  vivid  picture  [of  Crookes]  may  be 
brought  up  to  date  by  substitution  of  free 
protons  and  electrons  for  the  hypothetical 
protyle.  We  can  imagine  regions  contain- 
ing matter  where  the  temperature  is  so 
high  that  not  only  is  the  dissociation  of 
atoms  from  atoms  and  nuclei  from  planet- 
ary electrons  complete,  but  also  protons 
and  electrons  are  in  a  state  of  agitation  so 
violent  that  even  the  most  stable  nuclei 
cannot  be  formed.       We  should  have  here 


matter  of  the  simplest  form  we  can 
imagine,  or  rather  of  no  form  at  all,  simply 
more  or  less  neutral  electric  gas.  Such  a 
condition  is  by  no  means  impossible  in  our 
universe  and  may  actually  occur  during  one 
of  those  excessively  violent  catastroiphes 
occurring  in  far-distant  space  and  observed 
by  us  as  a  new  star. 

"  By  some  such  cooling  process  as  that 
suggested  by  Crookes  we  easily  imagine  the 
free  charges  combining  to  form  the  nuclei 
of  elements.  Whether  those  of  heavier 
elements  are  formed  direct  by  the  charges 
getting  into  particular  geometrical  relations 
with  each  other,  or  whether  helium  nuclei 
are  formed  first  and  then  subsequently 
coalesce  depends  on  which  theory  of  nu^plear 
structure  is  adopted.  In  any  case  vast 
quantities  of  energy  will  have  to  be 
radiated  off,  and  this  radiation  may  be  of 
such  extremely  high  frequency  that  it  is 
capable  of  disrupting  nuclei  themselves,  so 
that  there  might  be  at  this  stage  rapid  and 
continuous  transformations  from  heavier  to 
lighter  nuclei  and  vice  versa. 

For  the  present  we  are  interest^^d  in 
the  number  of  each  type  of  atom  which 
survives.  It  is  obvious  that  if  the  condi- 
tions of  oo'>ling  are  practically  identical 
throughout  the  wli'^le  mass,  there  is  no 
reason  why  the  composition  of  the  matter 
produced  should  vary.  If  3  atonis  of  CI3r» 
are  formed  to  every  1  of  C'137  at  any  one 
point,  the  same  ratio  must  hold  at  every 
point  so  that  a  complex  [composite]  ele- 
ment of  constant  atomic  weight  will  he 
formed.  But  it  is  much  more  likely  that 
different  iparts  of  this  primordial  mass  will 
undergo  their  transformations  under  dif- 
ferent rates  of  cooling,  etc.,  so  it  is  worth 
while  inquiring  if  variation  in  the  mean 
atomic  weight  of  a  complex  element  is  to 
l>e  expected. 

The  quantity  of  one  particular  atomic 
nucleus  fwmed  will  probably  depend  (a) 
on  the  probability  of  a  certain  configuration 
of  charges  happening  as  a  chance  event; 
(h)  the  stability  of  the  iparticular  nucleus 
formed  as  the  result  of  that  event.  Again, 
to  take  the  case  of  chlorine,  each  isotope 
may  be  regarded  as  completely  stable,  and 
the  relative  quantities  formed  will  simply 
depend  on  condition  (a).  Now  it  is  not  un- 
reasonable to  'juppose  that  this  is  not 
seriously  affected  by  different  rates  of  cool- 
ing, and  in  this  case  the  isotopes  will  be 
evolved  in  constant  proportion.  As  we 
know  of  no  natural  process  by  which  the 
proportion  of  isotopes  can  be  altered  appre- 
ciably, the  complex  elements  will  have  to- 


THE    CHEMICAL    NEWS. 


JANUAEY  5,  1923. 


day  the   same  cheiiiical    atomic  weight     as 
when  they  were  first  farmed. 

...  If  the  matter  forming  the 
earth  went  through  a  iprimordial  stage  su(;h 
as  that  suggested  above,  it  certainly  did  so 
more  than  10^  years  ago.  It  follows  that  of 
the  radio-active  elements  then  formed,  only 
two,  thorium  and  uranium,  will  now  be 
found  on  the  earth,  for  the  other  radio- 
active elements  existing  to-day  are  of  such 
a  short  period  that  they  must  have  been 
formed  since.  Hence  we  may  divide  the 
original  elements  very  simply  and  definitely 
into  two  groups :  (1)  All  the  stable ;  (2) 
Thorium  and  Uranium,  whose  nuclei  are  so" 
complex  that  they  are  only  partially 
stable." 

This  is  all  very  interesting  and  more  or 
less  relevant  to  the  subject  under  con- 
sideration; but,  of  course,  extensive  quota- 
tion widens  the  subject  beyond  the  scope  of 
the  present  argument.  It  is  the  aim,  how- 
ever, to  punctuate  these  papers  with  in- 
teresting matter  apart  frcm  the  particularly 
novel  features  presented. 

Problems  of  the  kind  involved  in  these 
studies  are  very  difficult  of  proper  solution, 
but  converging  lines  of  investigation  often 
focus  different  observations  into  one  com- 
mon one,  and  thereby  establish  quantita- 
tive relations  which  can  be  accepted  as 
being  substantially  true.  It  is  important 
to  keep  in  mind  that  each  lifte  of  study  may 
lead  to  some  definite  scientific  or  technical 
fact  of  permanent  value,  though  at  first  it 
appears  strange  and  contrary  to  common 
experience. 

Summary. 
The  existence  of  scandium  in  the  sun 
does  not  necessarily  invalidate  any  relative 
quantitative  deduction  as  to  the  proportion- 
ate amounts  of  this  element  relative  to  that 
of  those  on  each  side  of  it  in  the  atomic- 
number  series,  for  the  sun  may  be  manu- 
facturing or  degrading  practically  all  the 
eixsting  elements,  and  any  excess  of  one  in 
particular  may  not  appear  in  large,  relative 
quantities  in  the  final  state  when  this  pro- 
cess of  manufacture  and  degradation  is 
finished.  Quotations  from  Aston's  book, 
Isotopes,"  are  given  in  general  support 
of  the  argument.  It  is  incidentally  sug- 
gested that  the  danger  of  the  hydrogen  on 
the  earth  exploding  to  form  helium,  etc.,  is 
not  probable ;  for  if  this  theory  be  true  in 
principle,  then  probably  the  energy  of 
radio-changes,  involving  the  expulsion  of 
an  alpha  particle,  is  derived  from  the  ex- 
plosive combination  of  four  protons  to  form 
helium;    but,    since    other   protons    in    the 


•abom.  are  not  exploded  at  the  same  time, 
the  process  is  of  a  very  prescribed  nature — 
;uid  therein  j)erhaps  lies  our  safety. 

COBRECTIONS. 

In  Part  I.  of  this  series,  p.  309,  the 
bracket  under  Vill.  should  be  extended  to 
embrace  the  numbers  8,  9,  and  10.  In 
Periodic  Table,  same  page,  "  S  "  should 
read  "  Si  ";  and  the  bracket  at  RaF 
should  be  turned  the  other  way.  On  p.  310, 
left-hand  column,  27th  line  from  bottom  of 
page  ,"  Cs  "  should  read  "  E-b."  On  p. 
311,  under  Table  III.,  "  UXj  "  should  read 

UX2  "  for  sake  of  uniformity. 


THE  COLOURING  OF  METAJ.S. 

A  iiieeting  of  the  Birmingham  and  Mid- 
land Section  of  the  Society  of  Chemical  In- 
dustry was  held  at  the  University  of  Bir- 
mingham, on  Tuesday,  Dec.  19,  Dr.  Max- 
ted  in  the  chair.  There  was  a  very  large 
attendance  of  industrial  chemists  and 
metallurgists. 

Mr  .Alex.    E.    Tucker,     F.I.C.,    read    a 
paper  on    "  The  Colouring    of    Metals  " — 
iron,     steel,  copper,  and  brass.     He  stated 
that  with  a  given  action  of  reagents,    with 
or   without   external    currents,     the     colour 
produced    is  a  function  of  the  time  of  the 
action.     In  speaking  about  the  importance 
of  current  in  bringing  about  the  results,  it 
will    be   admitted     that    all     such     actions 
where  reagents  affect    the   surface    of     the 
metal  are  in  the  ultimate  meaning  of  the 
term,  essentially  electrical ;    in  the  process 
described,  there  is  every  indication  of  elec- 
trical cause  and  effect,   though  in  one  pro- 
cess   external  current    is  not    used.        The 
simplest  illustration    is  that  of  the  immer- 
sion of  an  iron    or  zinc  surface    in  copper 
sulphate ;    copper   is    deposited.      Again,    if 
a  piece  of  pickled  zinc    is  immersed    in    a 
weak  solution  of  copper  tartrate  and  caus- 
tic soda,  the  colouring  is  slow,  and  may  be 
arrested  at  any  stage  from  a  violet  to  steel 
blue,   green,   orange,  yellow  to  purple  red. 
Doubtless  the  action  is  entirely  an  electri- 
cal one,   and  the  colour  depends    upon  the 
thickness  of  the  affected  surface,     but  zinc 
eastings  may  be  bronzed  by  treating  them 
with    a    mixture     of  amm.onium     chloride, 
potassium    oxalate,    and    vinegar.       Here, 
there  is  atpparently  no    metal    capable    of 
being  deposited,   and  the  effect    would  ap- 
pear to  be  due  entirely  to  the  altered    sur- 


JANUARY  5,  1923. 


THE  CHEMICAL  NEWS. 


face  of  the  zinc  and  its  consequent  effect  on 
vision.  A  considerable  range  of  effects  can 
also  be  obtained  by  heating  metals  to  cer- 
tain temperatures,  thus  obtaining  a  variety 
of  coloured  oxides,  and  this  range  may  be 
extended  if  they  are  first  coated  with  cer- 
tain reagents,  which  need  not  necessarily 
be  of  metalUc  character.  A  cheap  and  ex- 
tensively used  method  of  blacking  iron  and 
steel  goods  is  to  heat  them  to  a  high  tem- 
perature and  to  plunge  them  in  oil.  A 
superficial  carbonising  of  the  oil  results, 
which  for  many  purposes  is  quite  satisfac- 
tory for  rough  articles;  on  the  other  hand, 
it  is  obvious  that  such  heating  is  not  per- 
missible when  hardness  of  surface  is  re- 
quired. The  process  of  blacking  and  tem- 
pering will  not  often  go  together,  and  the 
process  is  too  crude.  The  well-known  ap- 
pearance of  best  gim  bronzing  is  got  by  the 
rusting  of  the  barrels,  the  ends  being 
plugged;  this  rust  is  converted  into  the 
black  oxide  of  iron  by  boiling  the  barrels  in 
water  through  which  air  is  passing;  they 
are  then  mopped  to  remove  the  loose  oxide, 
and  they  are  again  rusted  and  boiled. 
Thns^  processes  are  repeated  many  times 
in  the  best  work,  after  which  the  work  is 
olel.  The  commoner  bronzing  of  gun  bar- 
rels is  done  with  compounds  of  antimony. 
It  is  easy  to  produce  fine  efTects  by  all 
colouring  proct'ssos,  provided  the  work  is 
originally  polished,  indeed  it  is  hopi'less  to 
treat  any  but  the  best  surfaces — hence  the 
common  use  of  coloured  varnish  or  even 
paint  when  such  ipolishing  is  ab.~ent. 

The  author  explained  and  gave  demon- 
strations of  new  electrolytic  processes — the 
Sentini  Rondelli  processes —in  which  no 
foreign  metal  is  used  for  obtaining  the 
co'oiirs,  those  depending  on  the  alteration 
only  of  the  surfaces  of  metals  of  which  the 
goo<ls  are  made.  There  are  four  processes 
in  practical  operation:  fl)  Dull  black  oxi-. 
dising  process,  by  means  of  which  iron, 
steel,  find  cast  iron  ipaits  may  be  oxidis-'d 
a  dull  black.  (This  process,  electrolytic  in 
nature,  also  includes  the  derusting  of  ir>;n, 
sti'el,  and  cast  iron  parts,  and  their  pre- 
paration for  enanu'llin;^',  painting,  etc.); 
(2)  e;>lour  oxidising  prfvce^s.  by  which  ircn, 
steel,  cast  iron,  and  malleable  iron  parts 
may  be  oxidised  in  various  coloui-s,  from  an 
imitation  of  yellow  brass  to  a  dark  brown 
colour ;  C3)  copper  on  brass  oxidising  pro- 
ecjs.  which  is  similar  to  process  (1).  but 
which  prf)vides  for  the  oxidation  of  copper 
to  a  dull  black,  capable  of  being  polished  to 
a  shiny  black,  and  very  resistant  to  chenii- 


cal  action ;  (4)  the  shiny  blaek  oxidising 
process,  by  which  steel  and  cast  iron  parts 
may  be  oxidised  to  a  brilliant  black.  (No 
current  is  required,  and  the  oxidation  is 
complete  in  a  few  minutes.)  Acetylene 
welded  tanks  are  used,  as  it  is  found  that 
rivetted  tanks  will  not  stand  the  strong 
soda  solutions  and  repeated  heating  and 
cooling.  These  tanks  are  heated  by  gas, 
and  arc  electrically  insulated  in  order  to 
economise  the  heavy  cun-ents  used. 

Regarding  to  process  (1),  the  author 
pointed  out  that  the  first  requirement  is  to 
produce  a  sodium  ferrite  in  the  bath  as  the 
electrolyte.  This  may  be  readily  fonuod 
by  using  a  sheet  of  irtm  a  little  less  in  area 
than  the  long  side  of  the  bath  as  an  anode 
in  a  caustic  soda  solution,  and  using  a  cur- 
rent of  about  45  amps,  for  each  square  foot 
of  the  sheet ;  on  reversing  the  current  every 
few  minutes  for  about  an  hour,  a  ferrite  of 
soda  is  formed,  and  the  bath  is  ready  for 
prodoction  work.  Tht  progressive  dissolu- 
tion of  the  iron  is  shown  by  the  reading  of 
the  voltmeter.  At  the  beginning  the  volt- 
;»gc  stoips  at  a  point  under  1  volt  for  a  very 
short  time  before  reaching  the  stable  value 
cf  about  two  volts.  .This  is  a  direct  read- 
ing of  the  polarisation  phenomenon,  and 
the  intensity  of  this  polarisation  increases 
as  the  formation  of  the  sodium  ferrite  in- 
creases. A  good  bath  requires  at  a  current 
density  of  5  amps,  per  sq.  dm.  2  or  3 
minutes*  depolarisation  period.  The  colour 
and  copper  oxidising  processes  are  simply 
variations  of  the  conditions  of  working  the 
above  solutions.  The  shiny  black  oxidising 
process  is  entirely  different,  in  that  no  cur- 
rent is  used,  the  oxidation  being  effected 
by  using  an  alkaline  bath  containing  an 
oxide  of  a  metal  having  electric  negative 
behaviour  relative  to  the  iron,  so  as  to  pro- 
duce oxidation  of  the  iron  surface  with 
separation  of  the  metal  of  the  oxide  used. 

Mr.  Tucker  j)ointed  out  that  the  ferrites 
and  ferrates  of  the  alkalies  may  be  regarded 
as  compo  mds  of  the  type  Na  Fe  Oj  or 
Na.,  FCj  0^.  in  which  the  ferric  oxide  acts 
as  an  acid  radical.  The  ferrate,  on  the 
ether  hand,  is  a  name  given  to  the  com- 
pounds of  the  type  Na,  FeO,.  and  which 
correspond  to  a  ferric  peroxide  FeO,  and 
the  hypothetical  ferric  acid  T{.,  FeO^.  It 
wo'ild  appear  that  under  the  action  of  the 
powerful  currents  used.  <'ntirely  different 
compounds  must  be  formed ;  it  would  seem 
that  thi'  ferrite  on  which  the  processes  de- 
pend corresponds  to  the  formula  Na^  FeO^, 


THE    CHEMICAL    NEWS. 


JANUARY  5.  1928. 


and  is  a    white-greenish    body    not    easily 
obtained  in  the  solid  state. 

Although  the  surface  produced  on  the 
iron  articles  is  the  magnetic  oxide  Fe^  O^, 
and  therefore  is  not  capable  of  absorbing 
oxide,  it  is  unfortunately  too  true  that  the 
articles  treated  are  not  entirely  rustproof. 
It  would  appear  that  the  surface,  like 
niokel  plating,  is  porous  to  damp  and  car- 
bonic acid,  and  therefore  in  such  atmos- 
pheres they  will  rust  slightly.  On  the  other 
hand,  the  surfaces  are  more  resistant  to 
rusting  than  any  other  process,  with  the 
exception  of  the  old  Bower  Barff  process, 
that  he  knew  of.  But  that  process  de- 
pended on  the  formation  of  a  thick  coating 
of  magnetic  oxide — so  thick  .  that  it  was 
brittle  and  pealed.  At  the  end  of  the  de- 
polarising period,  the  o.d.  at  the  poles- of 
the  cell  rises  considerably,  and  this  point 
coincides  with  the  formation  of  a  stable 
film  of  magnetic  oxide  on  the  electrode,  the 
solution  of  iron  ceasing  on  the  reaching  of 
the  true  surface  of  the  electrode.  There  is, 
therefore,  no  corrosion.  Magnetic  oxide, 
as  resulting  from  the  action  of  the  bath  on 
the  rust,  is  very  easily  reduced  by  cathwlic 
reduction  to  metallic  iron. 

The  time  taken  for  the  oxidising  period 
to  be  completed  depends  upon  the  concen- 
tration of  the  feiTite  in  the  bath  and  the 
length  of  the  negative  period,  but  as  a  rule 
it  is  in  the  vicinity  of  three  minutes.  The 
total  time  for  the  complete  derusting' and 
oxidising  of  an  average  steel  part  is  10  to 
12  minutes.  In  general,  all  cast  iron,  mal- 
leable iron,  steel,  and  wrought  iron  parts 
can  be  successfully  oxidised.  Special 
steels,  such  as  some  chromium  and  tung- 
sten alloys,  show  a  tendency  to  oxidise  to  a 
brO'Wnish-black  tinge,  and  not  to  a  deep 
flat  black.  This  tendency  can  be  overcome 
by  the  prolongation  of  the  reducing  and 
oxidising  periods,  and  by  increasing  the 
current  uowing  through  the  objects  per  sq. 
foot  of  area.  The  hardness  of  the  coloured 
surfaces  obtained  is  remarkable ;  they 
would  stand  any  reasonable  buffing,  but 
not,  of  course,  emery,  etc. ;  the  black  oxide 
of  copper  surface  is  also  remarkably  hard, 
and  is  unaffected  by  sulphur  from  gas  or 
rubber. 

An  interesting  discussion  followed,  Pro- 
fessor T.  Turner  (Birmingham  University), 
Dr.  H.  W.  Brownsdon,  Mr.  Page  (B.S.A. 
works),  Mr.  H.  Silvester,  and  others  taking 
part. 


COLLOIDS    IN    GEOLOGIC 
PROBLEMS.* 

By  George  D.  Hubbard.^ 
{Continued    from    Page    395). 

Colloids  as  Cements. 

It  has  long  been  known  that  nothing 
soluble  occurs  in  the  shales  to  hold  them 
together,  and  yet  they  are  extremely  resis- 
tant to  pulling  strains.  We  say  their  ten- 
sile strength  is  high.  The  ultra  clay  in 
shales  and  clays  has  been  shown  by  cera- 
mists to  consist  largely  of  hydrated  alu- 
minium silicates,  such  as  kaolin  and  halloy- 
site,  also  nontronite,  iron  hydroxides,  silicic 
acid,  orgsnic  naatter,  and  possiblj  alu- 
minium hydroxide.  These  in  their  finely 
divided  state  are  all  colloidal,  and  as 
binders  they  are  stronger  when  dry  than 
Portland  cement.  They  are  the  cement  of 
shales  and  the  strength  of  some  limestones. 
Colloidal  silica  also  serves  as  a  binder  in 
many  sandstones.  It  is  known,  too,  that 
the  silica  cements  now  in  the  crystalline 
state  were  deposited  in  some  cases  in  chal- 
cedonic  or  colloidal  condition. 

In  addition  to  this  colloidal  material  in 
the  shales,  it  is  known  that  opaline  silica, 
when  subjected  to  the  processes  of  meta- 
morphism,  loses  its  HjO  and  becomes  crys- 
talline quartz  in  a  mica  schist.  Clarke''* 
shows  that  colloidal  matter  contained  in 
most  muds  and  clays  is  perfectly  capable  of 
binding  under  the  influence  of  pressure 
alone,  and  believes  that  shales  owe  most  of 
their  coherence  to  unions  of  this  sort.  He 
states  on  page  609  that  it  is  possible  for 
colloidal  silica  and  colloidal  hydroxides  of 
aluminium  and  iron  to  react  and  form  new 
silicates  when  the  shales  are  metamor- 
phosed into  schists.  Thus  these  finely 
divided  materials  play  their  parts  in  the 
make-up  of  metamorphic  products  derived 
from  the  shales. 


*  From  the  American  Journal  of  Science, 
August,  1922,  p.  95. 

'  The  author  is  deeply  indebted  at  many 
points  in  the  paper  to  Dr.  Harry  N. 
Holmes,  of  Oberlin  College,  for  stiggestions 
and  criticism.  His  General  Chemistry  and 
Colloid  Manual  have  been  of  m.uch  help 
also.  This  paper  tvas  presented  to  the  Geo- 
logic Section  of  the  Ohio  Academy  of 
Science,  April  1.5.  1922. 

'^  Clarice,  F.  W.,  Data  of  Geochemistry, 
U.8.G.S.  Bull,  MCXVL,  p.  545. 


JANUARY  5,  1923. 


THE    CHEMICAL    NEWS. 


This  process  must  be  closelj  akin  to  the 
one  going  on  in  the  process  of  binding  the 
materials  of  our  stone  roads.  Grout'*  and 
Cushman'-'  have  been  carrying  on  experi- 
ments on  the  cements  of  roads,  and  they 
think  their  work  shows  rather  conclusively 
that  the  binding  power  of  road-making 
materials  is  due  to  substances  in  the  col- 
loidal state,  developed  by  hydrolyzing  the 
oxides,  probably  of  calcium,  iron,  and  alu- 
minium, thus  making  the  body  more  or  less 
plastic.  Subsequently  by  crystallisation 
and  dehydration  they  become  firm,  making 
a  solid  road. 

Adsorption  and  Mineral  Colours. 

Very  much  can  be  said  on  the  subject  of 
adsorption  and  colloids  which  is  not  geo- 
logic, but  a  number  of  points  certainly 
belong  in  this  paper  at  this  place.  Every 
surface  has  an  attraction  fw  other  sub- 
stances. This  holding-to  a  surface  is  called 
adsorption.  Glue  on  a  board  w  in  a  beaker 
adsorbs  board  or  glass,  that  is,  there  is  a 
strong  attraction  between  the  surface  of  the 
one  and  the  particles  of  the  other. 

Adsorption,  then,  probably  explains  some 
of  the  coloiirs  of  minerals,  inasmuch  as  the 
particle  sof  the  mineral  crystal  correspond 
to  the  surface  of  the  wo<^kI  or  glass,  and  the 
colouring  is  in  such  minute  particles  as  to 
be  in  the  colloidal  state.  Examples  of  such 
intimate  relationships  are  found  in  the  car- 
bon and  iron  oxide  which  give  the  smoky 
tint  to  cairngoi-m,  and  the  carb(Mi  which  is 
believed  to  be  responsible  for  the  colour  of 
amethyst.  Rose  quart/,  owes  its  colour  to 
the  adsorption  of  colloidal  titanium  on  its 
particles  as  they  come  together  to  build  up 
the  crystal,  and  chrysoprase  is  said  to  oe 
coloured  much  in  the  same  way  by  nickel 
oxide.  Feldspars  have  long  been  believed 
to  owe  their  colour  to  traces  of  iron  oxide 
which  seems  to  be  adsorbed  by  the  mole- 
cules of  the  feldspar. 

The  beautiful  blue  colour  of  some  halite 
has  been  shown  to  be  due  to  metallic  col- 
loidal sodium,  and  probably  the  bluish  tint 
of  sylvite  may  be  traced  to  the  same  cause. 
The  oclours  of  harite  are  thought  by  Pat- 
ten to  be  due  to  various  oxides.  He  has 
shown  that  it  adsf^rbs  salts  of  nickel,  cobalt, 
corhmium,   iron   and  manganese.        Calcite 


'*  Oront,  F.  E.,  Joum.  Ant.  Chcvi.  Soc. 
100-).  XXVTI..  1037. 

''  Cushnxm,  A.  S.,  U.S.  Dep.  Agr..  Bur 
Chrm.,  Bull.,  T.XXXV.,  p.  92;  Travs.  Av, 
Ceramic  Soc,  1904,  VI.,  7. 


is  practically  never  a  colloid,  but  it  shows 
rather  high  adsorptive  powers  for  certain 
colloids.  The  amber  calcite  has  been 
shown  to  be  due  to  organic  matter,  and  the 
amber  tiuorite  is  probably  due  to  hydrocar- 
bons. Ruby  spinel  seems  to  owe  its  beau- 
tiful tints  to  adsorbed  chromium  oxide,  and 
cerussite  in  blues  and  greens  to  colloidal 
hydrous  copper  carbonate.  More  than 
likely,  though  this  is  not  demonstrated,  the 
soft  tints  of  the  zinc  salts,  calamine,  and 
smithsonite,  from  Laurium,  Greece,  are 
due  to  the  adsorpfiMi  also  of  copper  car- 
bonates. The  colours  of  many  gems  may 
probably  be  due  to  adsorption  of  some  finely 
divided  substance  which  becomes  so  inti- 
mately mixed  with  the  gem  materials,  yet 
which  occurs  in  such  minute  quantities,  as 
almost  to  defy  detection.  This  problem  has 
only  recently  been  taken  up,  and  we  mav, 
as  the  wcMrk  goes  on,  find  much  more  in  it 
than  has  yet  been  shown. 

Colloids  and  the  Flotation  Process." 
While  the  flotation  process  now  practised 
in  many  of  our  ore  concentration  plants  is 
not  really  a  geologic  problem,  it  is  so  closely 
connected  with  geologic  materials  that  I 
venture  to  call  attention  to  it  here. 

In  the  last  few  years,  many  of  our  large 
concentration  plants  have  installed  elabor- 
ate facilities  for  flotation  of  ores.  By  the 
use  of  this  process,  the  heavy  sulphides  are 
separated  from  the  gangue  minerals  in 
what  might  be  called  a  reverse  gravity 
meth(xl,  because  the  heavy  ores  come  to  the 
top  and  are  from  there  removed,  while  the 
lighter  materials  go  to  the  bottom  of  the 
medium.  But  gravity  has  nothing  to  do 
with  the  process.  If  galena  be  wetted  with 
water,  and  a  drop  of  oil  be  ptit  upon  it.  the 
oil  displaces  the  water.  Galena  adsorbs  oil 
much  more  stronglv  than  it  does  water.  On 
the  other  hand,  if  oil  be  spread  over  a 
quartz  or  calcite  crystal  and  a  drop  of 
water  be  put  upon  it,  the  oil  is  at  once  dis- 
placed by  the  water.  In  other  words,  water 
is  adsorbed  much  better  by  these  common 
gangue  minerals  than  is  ths  oil. 

For  flotation  the  mineral  is  finely  ground, 
usually  in  a  wet  condition,  fine  enough  to 
pass  through  a  48-mesh  sieve.  A  very 
small  amount  of  pine,  or  some  other  oil 
with  air  is  beaten  into  the  water,  which 
already  contains  the  pulp  of  ore  and  gangue. 


'•  Moses,  F.  C,  Colloids  and  Flotation, 
U.S.  Bur.  Mines.  Tech  Paper  CC  furnishes 
many  data  for  this  section. 


8 


THE    CHEMICAL    NEWS. 


JANUARY  5,  1923. 


The  beating  must  not  go  far  enough  to 
make  an  emulsion  or  bring  the  oil  into  a 
colloidal  state.  The  oily  froth  is  made  up 
of  films  of  colloidal  thinness,  but  is  not 
emulsified.  In  this  mixture  the  fine  par- 
ticles of  sulphides  adsorb  the  oil  because  it 
wets  their  sufraces,  float  to  the  top  by 
means  of  their  little  coats,  disperse  them- 
selves in  the  froth,  and  are  scraped  off  the 
flotation  tank.  Then  the  froth  is  beaten 
out  and  the  ore  is  free  from  most  of  the 
gangue  which  has,  because  wet  by  water, 
gone  to  the  bottom  of  the  flotation  tank. 
More  than  60,000,000  tons  of  sulphide  ores 
are  thus  treated  in  the  United  States  every 
year  and  carried  much  more  cheaply  to  a 
higher  concentration  than  was  obtained  by 
the  old  methods. 

In  the  following  ways,  then,  the  subject 
of  colloids  touches  the  flotation  process. 
The  oil  coat  held  by  adsorption  on  the  sul- 
phides is  so  thin  that  the  oil  is  really  in 
colloidal  state;  in  like  manner,  films  of 
water  of  colloidal  thinness  wet  or  are  ad- 
sorbed to  the  gangues.  In  a  few  cases  col- 
loidal kaolins  and  other  clay  substances  are 
present,  which  interfere  with  the  flotation, 
by  adsorbing  the  oil  and  preventing  its  use 
by  the  sulphides.  Here,  too,  the  trouble 
increases  if  the  oil  is  emulsified,  for  the 
finer  the  oil  particles  are,  the  more  readily 
do  the  clay  colloids  adsorb  them.  Usually 
the  ore  is  not  ground  fine  enough  so  that  its 
slime  is  at  all  colloidal.  Electrolytes  are 
sometimes  used  as  an  aid  in  flotation,  for 
they  help  to  prevent  emulsions,  or  coagu- 
late them  if  ormed. 

Plasticity  in  Clays. 

This  subject  has  been  the  theme  for 
many  interesting  papers,  and  of  some 
heated  discussions,  but  the  air  seems  to  be 
clearing,  and  Ashley^^  writes  that  it  is 
pretty_  generally  believed  by  the  students  of 
ceramics  that  the  control  of  plasticity  in 
clays  is  a  matter  of  the  control  of  colloids. 
A  number  of  other  writers  can  also  be 
quoted  in  support  of  this  position.  A 
French  ceramic  chemist,  T.  Schlosing,  in 
1888,  P.  Rohland  in  various  papers  from 
1902-9,  A.  S.  Cushman,  quoted  above,  and 
F.  W.  Clarke  in  the  Data  of  Geochemistry, 
all  agi-ee  that  the  plasticity  of  clays  can  be 
very  directly  traced  to  their  colloid  content. 
Schlosing  shows,  according  to  Ashley,  that 
the  arnount  of  colloidal  material  in  the  best 
clays  is  small,  and  rarely  exceeds    one  and 


''    Ashley,    H.    E..    Bur.    Stand.,    Tech. 
Paper,  1911,  XXIII. 


one-half  per  cent.  As  the  percentage  of 
material  in  the  colloidal  state  decreases,  so 
does  the  plasticity,  and  a  clay  with  one- 
third  of  the  amount  mentioned  is  a  lean 
clay.  Likewise,  if  the  amount  is  greatly 
increased  above  the  one  and  one-half  per 
cent.,  the  clay  becomes  less  plastic,  and 
more  sticky. 

It  is  well  known  that  the  plasticity  of 
clays  is  destroyed  by  ignition,  and  that  the 
colloids  are  also  made  to  change  state  by 
the  same  treatment.  On  the  other  hand, 
many  thoroughly  ignited  clays  absorb 
water  quite  as  well  as  unignited  ones.  This 
makes  it  clear  that  the  colloidal  material  is 
not  the  cause  of  the  absorption  of  water, 
nor  is  the  absorption  of  water  vitally  re- 
lated to  plasticity.  Series  of  experimencs 
have  been  made  with  lean  clays  to  increase 
their  plasticty,  and  it  has  been  found  that 
very  poor  clays  can  be  made  plastic  enough 
to  be  worked  successfully  by  adding  small 
quantities  of  certain  colloids;  agar-agar  0.08 
per  cent,  increases  the  plasticity  of  different 
clays  as  much  as  40  and  in  some  cases  60 
per  cent.,  and  aluminium  cream  produced 
the  same  effects  by  adding  in  much  larger 
quantities,  e.g.,  about  3  per  cent. 

As  was  shown  on  a  previous  page,  col- 
loidal material  increases  the  tensile  strength 
of  shales,  and  it  has  been  shown  to  do  the 
same  for  clays.  Other  colloidal  substances 
have  also  been  used  to  increase  the  plasti- 
city. Humus,  for  example,  an  organic  col- 
loid, produces  beneficial  results  in  lean 
clays.  Clays  in  a  cool,  moist  place  improve 
in  plasticity  even  within  a  few  weeks.  It  is 
believed  that  the  development  of  organic 
matter  in  the  clay  by  the  growth  of  bac- 
teria, or  even  protozoa,  is  responsible  for 
the  improvement,  for  the  protoplasm  of 
these  minute  organisms  is  itself  a  colloid 

If  plasticity  of  clays  should  be  found  to 
be  dependent  upon  the  inorganic  colloids  in 
them,  it  might  be  pertinent  to  ask  if  clays 
an)d  shales  laid  in  the  sea  would  be  more 
plastic  than  those  laid  in  fresh  water, 
where  the  finest  or  colloidal  material  had 
difficulty  in  being  precipitated. 

Ries^*  has  shown  that  the  fineness  of  the 
material,  the  thinness  of  the  plates  in  the 
shale,  and  the  colloids,  are  each  in  them- 
selves inefficient  to  fully  explain  plasticity. 
His  theory  suggests  that  plasticity  may  be 
due  to  cohesion  and  adhesion  factors  which 
depend  on  the  constitution  of  the  molecule. 


^«  Ries,  H.,  Geol.  Survey,  W.  Va..  1905, 
vol.  HI.,  pp.  46-54. 


JANUARY  5,  1923. 


THB   CHEMICAL    NEWS. 


but  not  ou  the  chemical  composition.  It 
might  be  said  that  he  does  not  seem  to  be 
fully  satisfied  with  his  exjpianation,  for  he 
adds  that  "  practical  work  to  improve  the 
plasticity  of  clays  may  follow  lines  already 
stai'ted,  such  as  the  addition  of  colloids, 
and  weathering,  which  may  mean  the  addi- 
tion of  colloidal  material  by  bacterial 
growth." 

One  can  never  understand  the  raw 
materials  and  their  relations  to  the  finished 
products  in  cements,  brick  and  terra-cotta, 
pottei-y,  porcelain,  enamels,  and  glass,  until 
he  has  dipped  rather  seriously  into  the 
study  of  colloids  from  the  geologic  side. 
Weathering  is  a  coUoid-iproducing  process, 
as  well  as  a  maker  of  most  of  the  soils  and 
the  salts  of  the  sea.  Since  macadam, 
brick,  cement,  and  asphalt  roads  all  stai-t 
with  materials  whose  vital  properties  are 
connected  with  the  colloidal  state  of  mat- 
ter and  the  geologic  prrxjesscs  that  produce 
these  materials,  the  road  industry  has  real 
need  of  a  colloid  geologist. 

Colloids  in  Soils. 

Perhaps  this  topic  will  take  us  as  far  into 
questions  of  physiography  as  the  last  has 
into  metallurgical  and  industrial  processes, 
but  in  the  last  analysis,  all  three  go 
straight  back  to  geologic  proceases,  and  in- 
volve geologic  problems.  Soils  result  from 
the  normal  geologic  decay  of  rooks,  primar- 
ily of  silicate  rocks.  In  their  decay,  the 
elements  K,  Na,  C'a,  and  Mg  usually  go 
into  true  solution  in  their  sccondju-y  salts, 
while  silica,  aluminium,  and  iron  go  chieHy 
intrf>  colloidal  solution  and  constituti-  the 
ultra-clay  material  of  clays  and  shales. 

In  solutions,  the  colloidal  material  can 
Ik,'  separated  from  the  crystalline  material 
by  the  use  of  the  Sharpie's  centrifugal 
machine,  capable  of  pnKlucing  a  for'?e 
seventeen  thousand  times  that  of  gravity, 
or  by  the  use  of  the  Pa8teur-Chamt)erland 
filter.  This  separation  can  also  be  brought 
about  by  coagulation  by  the  adflition  of 
salts,  and  by  dialysis. 

In  soils  the  body  is  essentially  sand  and 
clay,  the  sand  being  made  of  fragments  of 
many  kinds  of  minerals,  but  mostly  of 
quartz ;  and  the  clays  mostly  of  hydrous 
aluminium  silicates,  with  smaller  quantities 
of  aluminium  and  iron  hydroxides.  When 
the  salts  mentioned  above  come  to  the  soils 
they  are  carried  on  through,  providing  the 
water  has  free  circulation  and  drainage 
below;  but  if  there  is  insufficient  rainfall  to 
equal  evaporation,  then  these  salts  may  be 


left  in  the  soils  and  be  continually  carried 
to  the  surface  by  evaporation  of  the  water. 
The  colloidal  material,  however,  will  usu- 
ally be  adsorbed  and  will  remain  in  the 
soil.  Too  much  of  the  latter  tends  to  clog  a 
soil  and  prevent  the  free  and  necessary 
movement  of  air  and  water. 

This  last  item  becomes  particularly 
troublesome  in  soils  that  must  be  irrigated, 
for  inigation  waters  differ  from  rain  waters 
in  carrying  both  true  solution  and  colloidal 
solution  materials,  thus  furnishing  more 
material  to  clog  the  soil  than  rain  waters. 
The  difficulty  is  still  further  increased  by 
the  fact  that  most  of  the  water  on  irrigated 
lands  is  removed  by  eva<poration,  so  that 
everything  of  both  kinds  of  solution  is  left 
in  the  soil.  The  colloids  become  a  nuisance 
usually  much  before  the  salts  do  when  ordi- 
nary stream  water  is  used  f<M'  irrigation. 
The  colloids  tend  to  cement  the  soil  to- 
gether some  little  distance  below  the  sur- 
face, usually  not  beyond  the  reach  of  iVie 
plough,  and  produce  there  a  "  hard  pan 
layer.  This  interferes  with  the  movement 
(f>f  the  water,  either  up  or  down,  and  of 
course  prevents  the  roots  striking  deeply. 
It  can  be  broken  up  by  deep  cultivation, 
but  the  soil  ex()erts  are  now  of  the  opinion 
that  treatment  with  an  electrolyte  is  really 
better.  Aluminium  sulphate  has  been 
successfully  used  in  a  number  of  cases,  it 
acts  much  tis  the  salts  do  in  the  sea,  by 
coaguIati(Mi  of  the  colloidal  material  into 
ilttle  pellets,  large  enough  so  that  the  water 
and  the  air  can  get  among  tliem,  and  thus 
prevents  their  operation  as  cements. 

In  western  Unit*  d  States,  where  most  of 
our  irrigation  is  carried  on,  there  have  been 
discovered  in  recent  years  great  quantities 
of  aluminium  sulphate,  and  it  is  beleved 
that  a  large  use  of  this  salt  will  greatly 
extend  the  life  of  our  irrigated  soils. 

The  subject  of  colloids  in  geology  is  just 
ebgiimng  to  attract  the  attention  of  men 
who  should  be  concerned  with  it.  While  the 
chemists  have  tackled  their  colloid  prob- 
le  lis  with  vigour  and  enthusiasm,  the  geo- 
logists have  all  but  neglected  the  whole 
field.  There  should  be  many  geolf>gist8 
turning  their  atU'ution  seriously  to  the  solu- 
tion of  the  great  numbers  of  problems  now 
before  us,  such  as  these  suggested  in  this 
paiper,  and  there  should  be  many  more 
geologists  keeping  up  with  the  literature 
that  (liscus.«ies  these  colloid  problems. 

Drpniimcnt  of  Geology  and  Gcoyiaiiliy, 
Obcrlin  College,  Oberlin,  Ohio. 


10 


THE    CHEMICAL   NEWS. 


JANUARY  5,  1923. 


PROCEEDINGS  OF  SOCIETIES. 


PHYSICAL  SOCIETY  OF  LONDON. 

Proceedings  at  the  Meeting  held  on 

December  8,  1922,  at  the  Imperial 

College  of  Science. 

Alexander  Russell,  M.A.,  D.Sc,  in  the 
Chair. 

1.  A  paper  on  "  The  Relation  between 
Molecular  and  Crystal  Symmetry  as  shown 
by  X-ray  Crystal  Analysis,"  was  read  by 
Mr.  G.  Shearer,  M.A.,  B.Sc. 

Abstract. 

The  methods  of  X-ray  analysis  enable 
the  number  of  molecules  associated  with 
the  unit  cell  to  be  determined.  With  the 
help  of  this  information  an  attempt  is  made 
to  connect  the  symmetry  properties  of  the 
crystal  with  this  number  and  with  the  sym- 
metry properties  of  the  molecules  from 
which  the  crystal  is  formed. 

The  symmetry  number  for  each  of  the  32 
crystal  classes  is  given,  and  is  shown  to 
mean  the  minimum  number  of  asymmetric 
moltcules  necessary  in  the  unit  cell  to  sat- 
isfy the  symmetry  conditions.  The  relative 
orientations  and  positions  of  these  mole- 
cules in  the  cell  are  discussed. 

It  is  suggested  that  this  symmetry  num- 
ber is  the  actual  number  of  molecules  in 
the  cell  when  the  molecule  is  asymmetric ; 
further  that,  if  the  molecule  possesses  sym- 
metry, this  symmetry  appears  also  in  the 
crystal,  and  the  number  of  molecules  in  the 
unit  cell  is  obtained  by  dividing  the  sym- 
metry number  of  the  crystal  by  the  sym- 
metry number  of  the  molecule. 

Evidence  is  produced  in  support  of  these 
hypotheses  and  examples  are  given  of  their 
application  to  inorganic  and  organic  crys- 
tals. 

Discussion. 

The  President,  before  calling  on  Sir  Wil- 
liam Bragg,  congratulated  him  in  the  name 
of  the  Society  on  the  honour  recently  con- 
ferred upon  him  by  the  Paris  Academy  of 
Sciences. 

Sir  William  Bragg,  after  acknowledging 
the  congi-atulations  tenrered  to  him,  said 
that  the  paper  before  the  meeting  was  an 
important  one,  throwing  a  new  light  on  the 
possibilities  of  investigating  crystal  struc- 
ture. The  Author's  intricate  but  lucirl  ar- 
gument affords  a  great  simplification  of  the 


thought  that  the 
Mr.  Shearer  gave 
great  assistance    in 


problem.  Three  unitary  structures  have  to 
be  considered:  (1)  The  chemical  molecule, 
as  it  exists  in  solution;  (2)  the  elementary 
crystal  lattice  or  cell,  consisting  of  groups 
of  (3)  crystal  molecules,  in  which  the  atoms 
and  electron-  arc  not  necessarily  arranged 
in  the  same  manner  as  in  chemical  mole- 
cules. The  author's  method  enables  one  to 
determine  the  symmetry  of  these  groups  at 
once  from  the  geometry  of  the  crystal,  with 
a  very  little  help  from '^X-rays.  A  consider- 
able vista  of  research  is  thus  opened  up, 
which  may  serve  to  settle  such  questions  as 
that  of  the  static  versus  the  dynamic  model 
of  the  atom. 

Dr.  J.  W.  Evans 
methods  employed  by 
promise    of  proving  of 

working  out  the  structure  of  crystals. 
There  were,  however,  some  considerations 
that  must  not  be  neglected : 

(1)  It  is  by  no  means  certain  that  mole- 
cules always  maintain  their  identity  in  the 
crystalline  state. 

(2)  Even  where  they  exist  in  the  crystal, 
thtey  may  not  retain  the  same  form  and 
symmetry  as  in  a  free  state. 

(3)  Although  in  an  ideal  crystal  all  the 
cells  are  identical,  and  have  identical 
orientation,  this  is  by  no  means  always 
actually  true.  We  know  that  cells  of  dif- 
ferent comjposition  may  be  employed  in- 
discriminately if  they  are  approximately 
the  same  in  form  and  -v'olume,  as  in  the 
case  of  the  plagioclase  felspars. 

In  the  same  way,  if  the  outer  forms  of 
cells  of  the  same  substance  approximate  to 
a  higher  symmetry  than  the  cell  itself, 
these  cells  may,  even  when  differently 
orientated,  be  employed  in  building  up  a 
crystal  structure.  The  same  may  be  true 
with  cells  that  are  enantiomorphically  re- 
lated. In  these  cases  the  whole  structure 
may  have  a  higher  symmetry  than  the  in- 
dividual cells  as  the  result  of  either  (a)  a 
symmetrical  arrangement  of  the  cells  in 
the  nature  of  molecular  or  ultramicroscoipio 
twinning — twinning  is  usually  an  attempt 
to  attain  higher  symmetry— thus  forming 
lattice  cells  of  greater  size;  or  (h)  indiscri- 
minate occurrence  of  cells  differing  in  orien- 
tation or  in  onantiomorphic  character.  In 
the  former  case  it  might  be  very  diflRcult  to 
recognise  by  means  of  X-ray  analysis  the 
primary  cells.  In  the  latter  case  it  would, 
I  should  think,  be  impossible. 

The  explanation  of  the  crystalline  struc- 
ture of  potassium  chloride  is  not  convinc- 
ing. The  symmetry  of  the  molecules 
shown     is     that     of     the     quartz     or     tri- 


.J^ANUAEY  5,  1923. 


THE   CSEMiCAL   NEWS. 


11 


gonal  trapezohedral  class  which  is  repre- 
sented by  the  symbol  IllUh  (J.  W.  Evans, 
Min.  Mag.,  Vol.  XV.,  pp.  398-400,  1910;, 
with  three  digonal  axes  at  right  angles  to  a 
trigonal  axis,  and  making  angles  of  120° 
with  each  other;  whereas  that  of  the  crystal 
struoture  is  stated  to  belong  to  the  cuprite 
or  pentagonal  eikositetrahedral,  CUh  class, 
in  which  there  are  four  trigonal  axes  corres- 
ponding to  the  diagonals  of  the  cube  and 
three  digonal  axes  at  right  angles  to  oae 
another  and  parallel  to  the  edges  of  the 
cube.  The  cell  contains  four  molecules, 
and  the  trigonal  axes  of  these  are  supposed 
by  the  author  to  be  at  right  angles  to  the 
diagonals  of  the  cube,  but  it  is  not  ex- 
plained how  the  4x3  digonal  axes  at  right 
angles  to  the  diagonals  are  transformed  into 
three  digcmal  axes  at  right  angles  to  one 
another. 

PVom  the  examination  of  the  material 
iprepared  at  the  Imperial  College  and  n 
comparison  of  the  work  of  other  observers. 
Miss  Knaggs,  of  the  Imperial  and  Birklxck 
Colleges,  has  shown  that  the  symmetry-  of 
the  crystal  structures  of  the  simpler  cMbon 
compounds  frequently  beur  close  relatiwi  to 
that  of  the  molecule.  Substances  of  the 
type  CX^,  where  X  is  an  element,  are 
usually  cubic.  Those  of  the  types  CXjY 
are  trigonal  or  hexagonal,  unless  X  is  hy- 
drogen, when  the  symmetry  is  lower.  Tho«c 
of  the  form  C(CX3)^  are  ns  a  rule  cubic,  and 
those  with  C(CX^Y)^  are  t<stragonal.  In  .ill 
cast's  the  symmetry  is  apt  to  be  that  of  a 
higher  or  different  class  than  would  have 
been  expected,  though  on*-  belonging  to  the 
same  system.  In  the  case  of  the  C(CXjY)« 
compounds  the  symmetry  of  the  molecule 
would  be  that  of  chalcoipyrite  or  tetragonal 
scalenohedral.  IVBk  class,  whereas  that  of 
the  crystal  usually  belongs  to  the  IVBc,  or 
in  one  case  TVBu  class.  It  can  be  shown 
that  symmetry  of  this  character  would  hi- 
obtained  by  appropriate  molecular  twin- 
ning. Soini>  f>f  the  compounds  considered 
are  dimorphic,  rcystals  with  less  symmetry 
forming  at  a  lower  temperature. 

The  Speaker  threw  out  the  suggestion 
that  crystal  structure  might  possibly  be  due 
to  the  repulsion  of  the  electrons  of  different 
atoms  combined  with  an  attraction  of  the 
atoms  as  a  whole.  If  it  be  supposed  thit. 
contrary  to  the  tisual  view,  there  are  nx 
outer  electrons  in  chlorine  having  their 
mean  position  arranged  like  the  points  of 
an  octahedron,  and  that  in  potassium  there 
are  eight  electrons  arranged  like  the  points 
of  a  eul)e,  it  will  be  evident  that  a  position 
of  stability    would    be  obtained    when  the 


points  of  each  chlorine  octahedron  were 
opposite  the  centres  of  faces  of  the  sur- 
rounding potassium  cubes  and  the  points  of 
each  potassium  cube  were  opposite  the 
centre  of  a  face  of  a  chlorine  octahedroa, 
and  that  the  potassiums  and  chlorines 
would  then  be  arranged  alternately  in  a 
cubic  lattice  just  as  we  know  to  be  the 
ca«e. 

The  author's  reply  will  be  communicated 
later. 


2.  A  pa.per  on  a  "  Modification  of  the 
Powder  Method  of  Determining  the  Struc- 
ture of  Metal  Crystals,"  by  E.  A.  Owen, 
M.A  ,  D.Sc,  and  G.  D.  Preston,  B.A., 
was  read  by  Mr.  Preston. 

.\B8TRAcT. 

Piutes  of  ahuninium,  iron,  copper,  lead 
and  magnesium  have  been  examined  oy 
means  of  the  Bragg  X-ray  spectrometer, 
employing  radiation  direct  from  a  molyb- 
denum anti-cath(Kle.  The  maxima  observed 
in  the  spectra  are  sufficiently  intense  to 
measure  with  a<;curacy,  and  the  crystalline 
structure  of  the  materials  examined  are 
readily  determined.  A  few  of  the  resu'ts 
ob'tained  by  the  method  are  included  in  the 
paper  as  typical  exaniiplcs. 

Discussion. 

Sir  William  Bragg  congratulated  the 
authors  on  their  work,  which  indicated  tTiat 
the  techniaue  of  crystal  analysis  is  improv- 
ing, and  that  its  methods  arc  coming  into 
general  use.  A  consideration  to  be  borne  in 
mind  is  that  one  of  the  crystal  planes  may 
become  unduly  acoentuated  by  the  polish- 
ing process.  Further,  in  the  case  of  alu- 
niinitim  and  other  metals,  it  is  possible  for 
individual  crystals  to  be  very  large. 

Dr.  G.  D.  We.st,  after  dwelling  on  the 
mlvantages  of  focussing  the  X-ray  beam  by 
inclining  the  plane  in  which  the  crystals 
lie,  inquired  as  to  the  width  of  the  slits 
emiployed  as  the  conditions  varied,  and  as 
to  the  allowance  to  be  made  for  variations 
in  the  output  of  the  bulb. 

Mr.  Preston,  in  reply,  stated  that  the 
authors  had  been  careful  to  use  crystals  less 
than  1  mm.  in  size.  The  chamber  slit  was 
kept  at  2  mm.,  and  the  bulb  slit  varied 
from  2  mm.  t^  4  mm.  for  different  parts  of 
the  spectrum.  The  output  of  the  bulb 
could  be  kept  constant  by  regulating  l;he 
filam«'nt  current,  but  foi-  moderate  accuracy 
little  regulation  was  required. 


12 


THE   CHEMICAL    NEWS. 


JANUARY  5,  1923. 


3.  A  pa<per  on  "  The  Cathode  Ray  Oscil- 
lograph," by  A.  B.  Wood,  D.Sc,  was  read 
by  Capt.  C.  S.  Wright. 

Abstract 

The  paper  deals  with  a  new  form  ol 
cathode-ray  oscillograph  adapted  for  com- 
mercial production  and  laboratory  use. 
The  instrument  described  is  of  the  low- 
voltage  type,  in  which  a  iTot  cathode  is 
employed  as  a  source  of  the  electron  cur- 
rent. This  low-voltage  type  of  oscillogi*aph 
is  much  more  sensitive  than  the  high- 
voltage  cold-cathode  type  designed  by  M. 
Dufour.  Various  methods  are  described 
for  focussing  the  cathode-ray  stream,  and  a 
proposal  has  been  made  for  an  oscillogi'aph 
with  external  {i.e..  outside  the  vacuum) 
photographic  film.  Experiments  have  been 
made  to  determine  the  most  suitable  photo- 
graphic film  or  plate.  Ordinary  gelatine- 
coated  roll  films  or  plat<^s  are  unsuitab'e, 
owing  to  the  marked  absorption  of  the 
cathwie-rays  by  the  gelatine.  The  best  re- 
sults have  been  obtained  with  Schumann 
plates  containing  a  proportion  of  calcium 
tungstate.  This  material  phosphoresces 
with  a  light  rich  in  ultra-violet,  and  conse- 
quently the  secondary  luminous  effect  on 
the  Schumann  plate  is  very  great. 

Mechanical,  electrostatic  and  electro- 
magnetic methods  are  described  for  generat- 
ing a  time-axis  on  the  ri'cords.  For  certain 
purposes  this  time  axis  is  sinusoidal,  whilst 
for  others  it  is  linear.  Numerous  records 
of  high-frequency  A.C.  wave  forms  and  of 
impulsive  electrical  phenomena  have  been 
obtained,  and  a  few  of  these  are  reproduced 
in  the  paper.  Brief  reference  is  made  in 
conclusion  to  the  applications  of  the  oscil- 
lograph to  research  and  electrical  engineer- 
ing problems,  where  other  well-known 
forms  of  oficiMograph  (Duddell,  Einthov^.n, 
&c.,  types)  cannot  be  employed  on  account 
of  the  inertia  of  the  moving  element. 

Discussion. 
Mr.  Mines  inquired  whether  any  measure- 
ment had  been  made  of  the  poteniial 
gradient  in  the  tube  with  a  view  to  deter- 
mining the  distribution  of  potential  along 
the  path  of  the  rays.  Was  anything  known 
of  the  current  density  of  the  rays,  and  was 
there  (as  in  the  arc  lamp)  a  limiting  value 
to  such  current  density,  involving  a  maxi- 
mum intensity  for  the  spot  of  light  beyond 
which  it  would  be  impossible  to  go?  And 
had  the  author  tried  the  focussing  effect  of 
charging  the  cvlind-'c^l  shield  to  a  poten- 
tial of,  say,  100  volts? 


}.Ir.  R.  A.  Watson  Watt  (partly  com- 
municated) :  I  would  join  in  congratulating 
Dr.  Wood  on  his  very  lucid  account  of  a 
most  important  and  valuable  instrument  of 
research.  Perhaps  the  most  outstanding 
feature  of  his  work  is  the  way  in  which  the 
oscillograph  has  been  converted  into  a 
robust  engincoring  structure,  which  the 
"  glass  shy  "  engineer  can  approach  with 
more  confidence  than  he  feels  towards  the 
older  forms  of  blown  glass  tube,  and  into  an 
instrument  with  a  much  higher  expectation 
of  life  than  those  older  forms  possessed. 

In  considering  cathode  ray  oscillographs 
in  general,  ont^  should  not  lose  sight  of  the 
fact  that  there  is  a  wide  field  of  applica- 
tion for  sensitive  tubes  in  which  it  is  not 
necessary  to  resort  to  photography  with  its 
attendant  difficulties  and  complications. 
Single  axis  working,  in  which  the  tube  is 
valuable  as  a  direct  reading  high-frequency 
voltmeter,  is  in  itself  suflficient  justification 
for  such  tubes.  But  Dufour  has  shown 
that  in  wave  form  work  one  can  obtain 
visual  images  of  radio  frequency  wave 
forms  from  his  high-voltage  tubes,  while 
recently,  l)y  the  courtesy  of  the  Inter- 
national Western  Electric  Co.,  I  have  been 
able  to  satisfy  myself  that  a  reliable  visual 
imago  of  a  ti-ansient  deflection  of  10- ■*  sec. 
duration  can,  be  obtained  with  the  300-volt 
beam  of  their  tube.  The  fluorescent  spot 
had  a  translational  speed  of  about  5x  10-* 
cm.  per  sec.  in  this  experiment.  This, 
whether  due  to  persistence  of  vision  or  to 
persistence  of  fluorescence,  is  much  more 
satisfactory  than  one  had  the  right,  a  priori, 
to  expect. 

On  minor  matters  of  detail  it  might  be 
desirable  in  a  paper  which  will  take  an  im- 
portant place  in  the  chronology  of  cathode 
ray  oscillocfraphs  that  the  author  should 
make  it  cU';u'  that  he  does  not  assign  prior- 
ity for  the  introduction  of  the  hot  cathode, 
of  the  A.C.  time  base,  and  of  the  D.C. 
time  base,  to  the  workers  referred  to  in  this 
paper.  The  author's  own  familiarity  with 
the  history  of  the  subject  might  lead  to  the 
appearance  of  neglecting  the  priority  of 
Wehnelt  (1906)  as  to  the  hot  cathode,  of 
Fleming  (1913)  as  to  the  A.C.  time  base, 
and  of  Dufour  (1914)  as  to  the  D.C.  time 
base,  which  he  superposed  on  the  A  C. 
base,  so  that  the  final  image  is  based  on  the 
plane  projection  of  a  cylindrical  helix. 

I  should  be  grateful  if  Dr.  Wood  could 
say  whether  any  data  are  available  as  to  a 
tube  working  on  the  100  volts,  which  he 
mentions  as  a  lower  limit.  A  tube  of  this 
extreme  sensitivity  would  be  most  valuable, 


I 

I 


JANUARY  5.  1923. 


THE   criEMlCAI.    NEWS. 


13 


but  I  know  of  no  references  to  a  stably 
operating  tube  with  an  accelerating  voltuge 
below  300  volts. 

Finally,  I  should  like  to  ask  the  author 
whether  he  has  any  exipericnce  of  Van  der 
Bijl's  "  positive  ion  "  method  of  focussing, 
as  used  in  the  Western  Electric  tube.  It 
appears  to  be  a  methfKl  of  great  value,  par- 
ticularly in  view  of  the  fact  that  the  com- 
monly used  electro-magnetic  "paralleling" 
method  reduces  the  sensitivity  of  the  tube. 
My  experience  of  low-voltiige  tubes  leads 
me  to  conclude  that  at  the  present  moment 
the  limitation  of  sensitivity  for  visual  ob- 
servation lies,  not  in  the  mechanism  of 
beam  production  or  concentration,  but  in 
the  fluorescent  materials  uaed  for  the 
screen,  and  that  progress  in  that  direction 
can  still  be  made. 

Mr.  R.  S.  Whiipple  said  that  the  beauti- 
ful instrument  described  would  meet  a  real 
demand,  as  oscillographs  using  a  cold  ca- 
thode are  cumbersome  and  costly,  while  the 
one  under  discussion  should  Ije  within  the 
means  of  most  laboratoriis.  The  meth  )d 
of  phosphorescent  sensitisation  opens  up 
great  possibilities.  The  paper  is  written  in 
such  a  wav  as  to  be  unusually  readable. 

The  reply  to  the  discussicHi  will  be  com- 
municated later. 

4.  A  DEMONSTRATION  of  a  Lmo 
Voltage  Cathode  Ray  OHcillograph  was 
given  by  Mr.  R.  Webb,  International  W;s- 
tem  Electric  Company. 

This  instrument,  which  is  designed  to 
work  at  300  volts,  is  intended  for  manuf*)c- 
ture  on  a  commercial  basis.  The  cathode 
consists  of  a  hot  platinum  filament  coated 
wit  hcertain  oxides,  and  formed  into  a  circle 
coaxial  with  the  path  of  the  rays.  It  is 
protected  from  bombardment  by  positive 
arys,  which  would  disintegrate  it,  by  a 
screen  in  which  is  cut  a  circular  hole 
slightly  less  in  diameter  than  the  filament. 
Tt  has  a  life  of  about  200  hours.  The 
anode  is  a  platinum  tube  through  which 
the  rays  pass.  The  deflecting  fields  are 
electrostatis,  and  are  provided  by  two  pairs 
of  platen  at  right  angles.  The  bulb  is  in 
the  fonn  of  a  conical  flask,  the  cathode 
being  at  the  narrow  end  so  that  the  rays 
imping*^  on  the  flat  bottom  which  is  coated 
inside  with  fluorescent  matter.  The  lumi- 
nous triiee  of  the  rays  can  be  seen  from  out- 
side through  the  l>ottom  of  the  flask.  The 
apparatus  was  connected  up*  to  show  the 
oharacteristic  of  an  ()scillation-generating 
valve,  so  that  the  potential    difference  i>e- 


tween  one  pair  of  plates  was  proportional 
to  the  grid  potential,  and  that  between  the 
other  pair  to  the  plate  current.  The  result- 
ing  trace  consisted  of  a  single  curved  line 
terminating  in  a  loop  of  peculiar  form  at 
one  end. 

*  E.  V.  Appleton,  Phil.  Mag.,  August, 
1921. 

The  Annual  Exhibition  of  Ajpparatus  ar- 
ranged by  the  Optical  Society  and  the 
Physical  Societv  of  London,  was  held  on 
January  3rd  and  4th,  1923. 

The  following  leotures  were  given:  — 

"  Reproduction  of  Colour  by  Photo- 
graphic Processes,"  by  Mr.  W.  Gamble  (on 
January  3  at  4  p.m.,  and  January  4  at  8 
p.m.).  ^ 

"  Recent  Photo-Elastic  Researches  on 
Engineering  Prahlems,"  by  .Prof.  E.  G. 
CoKER,  F.R.S.  (on  January  3  at  8  p.m.,  and 
January  4  at  4  p.m.). 


PLAnNUM  DEPOSITS.* 
By  J  antes   M.   Hill. 

The  Salt  Chuck  palladium-copper  mine 
in  Alaska  was  not  operated  in  1921,  though 
one  shipment  of  concentrates  produced  in 
1920  was  sent  to  the  United  States.  The 
output  of  placer  platinum  came  mainly 
from  Dime  Creek,  on  Seward  Peninsula. 

California  dredges  produced  practically 
all  the  crude  platinum  reported  for  1921,  a 
total  of  821  ounces.  Of  this  quantity  480 
ounces  came  from  the  streams  of  the 
mother  lode  region,  and  33.'3  ounces  frnm 
Trinity  County.  A  large  part  of  the  Trin- 
ity County  crude  platinum  is  osmiridium, 
recovered  from  Beegum  and  Hayfork  creeks 
and  by  the  dredg<'s  on  Trinity  River. 

A  large  part  of  the  91  ounces  of  crude 
platinum  reported  by  Oregon  miners  was 
produced  at  the  beach  mines  in  Coos  and 
Curry  counties,  though  some  crude  plati- 
num was  saved  from  the  mines  near  Kerby 
and  Waldo,  in  Josephine  Coimty,  and  near 
Sumptt^r,  in  Baker  County. 

The  Electrolytic  ^formerly  Rambler) 
mine,  near  Holmes,  Albany  County,  Wyo., 
was  under  development  during  the  year, 
and  a  car  of  ore  was  shipped  principally  for 
its  copper  value. 


14 


THE  CHEMICAL  NEWS. 


JANUARY  5,  1923, 


A  number  of  platinum  booms  were 
launched  in  1921,  notably  one  based  on  re- 
ports of  rich  platinum  ore  11  miles  from 
Winnemucoa,  Nev.,  and  another  on  a  re- 
ported deposit  of  platinum  near  Batesville, 
Ark. 

Canada. 

The  largest  production  of  platinum 
metals  in  Canada  comes  from  the  refiners 
of  the  Sudbury  nickel-copper  ores.  The 
Interaational  Nickel  Co.  closed  its  mines 
and  refinery  September  1,  1921.  The  Moud 
Co.  is  the  only  one  now  operating. 
Colombia. 

Two  dredges  of  the  South  American  Gold 
and  Platinum  Co.  were  in  operation  in 
Colombia  throughout  the  year,  and  a  third 
dredge  was  expected  to  be  in  operation 
early  in  1922.  The  boat  of  the  British 
Platinum  and  Gold  Corporation  is  reported 
to  have  made  satisfactory  recovery,^  the 
output  from  December  21,  1920,  to  May 
21,  1921.  being  966  ounces.  A  dredge  has 
been  ordered  by  the  newly  organised 
Colombia  Proprietary  Gold  Mines  (Ltd.),  a 
British  concern,  to  operate  on  Llantin 
River,  70  miles  south  of  Buenaventura.  It 
is  stated  on  good  authority  that  the  native 
production  of  platinum  decreased  consider- 
ably during  1921,"  owing  to  the  lower  price 
paid  for  the  metal  by  local  buyers,  which 
naturally  was  reduced  in  conformity  with 
the  New  York  market.  It  is  believed  that 
the  production  may  decline  somewhat  from 
that  maintained  during  the  war  period  for 
a  few  years,  until  sufficient  dredges  are  in- 
stalled to  handle  adequately  the  large  re- 
serves of  gravel. 

Papua. 

The  first  recorded  shipment  of  osmiridium 
from  Papua  was  made  in  1921  and 
amounted  to  88  ounces.  Australians  evi- 
dently believe  that  the  east  end  of  New 
Guinea  may  yet  prove  a  mining  field  for 
this  valuable  iridium-osmium  alloy. 
Russia. 

Very  little  real  news  concerning  the 
situation  in  the  Russian  platinum  fields  has 
been  forthcoming.  Apparently  a  little 
hand  mining  is  going  on.  Late  in  1921  it 
was  reported  that  a  State-controlled  plati- 
num trust  had  been  organised  by  the 
Soviet  Government,  and  in  May,  1922,  it 
was  rtported  that  Louis  Duparc^  is  going  to 
Russia  to  reorganise  the  platinum-mining 
industry  at  the  invitation  of  the  Soviet 
Government. 

It  is  reported-"*  that  the  production  of 
.platinum  during  the  first  half  of  1921  was 
about  2,700  ounces. 


Tasmania. 
The  production  of  osmiridium  in  Tas- 
mania in  1921  was  1,750  ounces,  as  com- 
pared with  2,009  ounces  in  1920,  1,670 
ounces  in  1919,  and  1,607  ounces  in  1918. 
This  is  rather  surprising  in  view  of  the 
fact  that  the  prices  paid  for  the  alloy  have 
been  continually  lowered  until  it  was  re- 
ported that  many  miners  had  abandoned 
operations.  An  excellent  desCjription  of 
the  various  fields  in  Tasmania  in  which  os- 
miricruim  is  mined  is  that  by  Reid,*  pub- 
lished in  1921. 


*  By  James  M.  Hill.  Mineral  Resources 
of  the  United  States,  1921—  Part  I.  Gov- 
ernment Printing  Office,  Washington,  1922. 

1  Min.  Jour.  (London),  1921,  vol.  XXV., 
p.  50. 

^  Eng.  and  Min.  Jour. -Press,  1922,  vol. 
CXIII.,  No.  18,  p.  786. 

"  Note  by  Dept.  Commerce  of  a  transla- 
tion from   Economic  Life. 

*  Reid,  M.  A.,  Osmiridium  in  Tasmania: 
Tasmania  Gcol.  Survey  Bull  32,  1921. 


A  PRELIMINARY  STUDY  OF  ZIRKITE 
ORE. 

By  J.  G.  Thompson. 

(Frotn  the  Journal  of  Physical  Chemistry, 
New   York,   December,   1922.) 

This  investigation  consists  of  a  study  of 
zirkite  ore  (crude  zirconium  oxide),  with 
attempts  to  improve  the  refractory  proper- 
ties by  the  elimination  of  certain  of  the  im- 
purities present  in  the  raw  material. 

Pure  zirconium  oxide,  if  available  in 
sufficient  (juantity,  would  aid  materially  in 
solving  thi'  problems  of  the  users  of  high- 
temperature  refractories,  particularly  those 
problems  connected  with  the  extreme  tem- 
peratures encountered  in  the  use  of  the 
electric  furnace.  As  a  refractory  for  high 
temperatures  zirconium  oxide  is  far 
superior  to  any  of  the  materials  commonly 
employed  for  this  purpose,  and  in  some  re- 
spects it  apiproaches  the  ideal  refractory. 
It  possess^  a  melting  point  higher  than  that 


^  Meyer:  Met.  Chem.  Eng.,  1914,  XII., 
791;  1915,  XIII.,  268;  Hedvall:  Zeit. 
<inorg.  Chem.,  1915,  XCIII.,  818;  Brad- 
ford: Chevi.  Trade  Jour.,  1918,  LXIL, 
284;  Arnold:  Jour.  Soc.  Chem.  Ind.,  1918, 
XXXVII. ,  724;  Granger:  Chem.  News, 
1919,  CXVIIL,  115,  121. 


J 


JANUARY  5,  1923. 


THE  CHEMICAL  NEWS. 


15 


of  any  other  known  metallic  oxide;  it  is 
roll-volatile  below  its  nielting-point;  it  is 
neutral  in  character  and  inert  to  the  action 
of  practically  all  of  the  civnimon  reagents ; 
it  possesses  low  coefficients  of  thermal  and 
electrical  conductivity.  These  properties 
ensure  the  successful  use  of  pure  zirconium 
oxide  as  a  refractory,  even  for  the  most  ex- 
treme service  conditions,  at  any  time  when 
it  becomes  available  in  quantity. 

{To  be  Continued.) 


GENERAL    NOTES. 


INTERVIEWS   WITH  HIS  MAJESTY'S 

COMMERCIAL  SECRETARY  IN 

ARGENTINA. 

Mr.  H.  O.  Chalkley,  His  Majesty's  Com- 
mercial Secretary  at  Buenos  Aires,  will  be 
in  attendance  at  the  Department  of  Over- 
seas/ Trade  for  a  few  days,  from  January 
18,  1923.  and  will  be  pleased  to  interview 
manufacturers  and  merchants  interested  in 
trade  with  Argentina. 

Applications  for  interviews  should  bo 
made  as  soon  as  possible,  and  in  any  case 
not  later  than  January  17,  to-^he  Comp- 
troller-General, Department  of  Overseas 
Trade,  85,  Old  Queen  Street,  London. 
S.W.I,  the  reference  ,  T.G. 4880.  being 
quoti'd  in  all  cases. 

Department  of  Overseas  Trade. 


BOARD  OF  T1;aDE  ANNOUNCEMENT. 
Safkouakdino  ok  Industriks  Act — Part  I. 
Arbitrations  under  Skction  1  (5). 
Oxalic  Acid. 
Judfi;ment  has  l>een  given  by  the  Referee 
in    the    matter    of  a  complaint    under    the 
above  sub-section,     that    Oxalic    Acid    has 
been   improperly   included    in    the  lists    of 
articles  chargeable  with  duty  under  Fart  I. 
of  the  Act.     The  Referee  has  awarded  that 
the  complaint  fails,  and  the  lists  therefore 
remain  unaltered. 
Board  of  Trade, 

20th  December,  1922. 


NOTICES  OF  BOOKS. 

Smith's   Intermediate     Chemistry,     re- 
vised and  rewritten  by    James    Kendall 


and  Edwin  E.  Slosson.     Pp.  XV.  +  666 

+  16  plates.     For  Great  Britain :  G.  Bell 

&  Sons,  Ltd.,     Portugal  St.,     Kingsway, 

W.C.     1922.     Price  8s.  6d. 

Alexander  Smith's  Chemistry  bears  the 
stamp  of  much  originality,  and  was  written 
by  one  possessed  of  great  teaching  quali- 
ties. Although  in  some  resipects  the  book 
was  not  perfect,  it  undoubtedly  was  a  very 
good  textbook. 

The  present  edition  has  been  extensively 
revised  and  brought  well  up  to  date  by 
Profs.  Kendall  and  Slosson.  It  is  eminently 
suitable  for  students  in  colleges  and  tech- 
nical institutes,  and  also  for  those  who  do 
not  regard  chemistry  as  their  principal  sub- 
ject. 

Besides  the  usual  textbook  features  there 
is  much  interesting  and  apposite  informa- 
tion upon  matters  usually  ignored  in  such 
works  as  this,  which  are  intended  to  main- 
tain and  retain  the  students'  live  interest  in 
the  subject. 

Extensive  additions  to  the  earlier  edition 
have  been  made  to  incQriporate  the  latest 
information  concerning  Atomic  Energy  and 
Structure  The  subject  matter  is  fre- 
quently treated  from  the  viewpoint  of 
physical  chemistry.  The  importance  of  this 
in  the  study  of  general  chemistry  is  justly 
emphasised. 

The  Introduction,  *'  Why  Study  Chemis- 
try.'" makes  very  refreshing  reading.  It 
is  i>ointed  out  that  chemistry  began  as  a 
secret  scionco.  The  early  chemists  con- 
cea'ed  their  knf.wledge  (and  their  ignorance) 
under  mystic  symbols.  The  modern  chem- 
ist, on  the  other  hand,  is  more  anxious  to 
explain  what  he  knows  than  people  are  to 
listen  to  him. 

Chemistry  is  well  fitted  to  give  training 
in  the  scientific  nuthod,  since  it  is  experi- 
mental. Properly  taught  —  or  properly 
learned  —  it  inculcates  self-reliance  and 
independence  of  thought.  Further,  the 
qualified  chemist  has  two  strings  to  his 
bow.  If  he  does  not  like  teaching,  he.  may 
enter  the  industrial  field.  He  may  be 
engaged  in  routine  analysis  of  raw  and 
finished  products,  or  be  in  control  of  pro- 
cesst^s,  f>r  engaged  in  research  to  utilise 
waste  products,  or  to  invent  new  com- 
pounds or  new  uses. 

In  s'>me  fields  of  Chemistry,  women  ha\re 
almost  an  equal  chance  with  men. 

Chemistry  should  have  an  interest  and 
utility  for  everyone.  J.G.F.D. 


The  Mysteries  of  Hypnosis    {Les  My»- 


16 


THE  CHEMICAL  NEWS. 


JANUARY  5,  1923. 


teres    de    VHypnosc),      by    Georges    de 

DuBOR,  translated  by  G.  M.  Hort.     Pp. 

IX.    +   235.     Ijondon :    William  Rider    & 

Son,   Ltd.,    8,   Paternoster  Row,    E  C.4. 

1922.     Price  5s.  net. 

It  is  regrettable  that  psychical  pheno- 
mena have  been  exploited,  in  the  past,  by 
charlatans,  and  consequently  their  study 
has     been     discredited.  Happily,     this 

stage  is  rapidly  passing,  particularly 
in  view  of  the  number  of  eminent 
scientists  who  have  witnessed  and  investi- 
gated these  phenomena,  and  who  vouch  for 
their  authenticity. 

This  interesting  scientific  and  authorita- 
tive treatise  upon  Hypnosis  can  be  safeiy 
recommended  to  those  desirous  of  ascer- 
taining the  facts  and  jjhcnomena  concerning 
this  subject. 

The  author  has  been  careful  to  select 
fully  authenticated  cases,  and  has  included 
those  instances  which  are  most  striking  and 
illustrate  his  cont<?ntions.  J.G.F.D, 


BOOKS  RECEIVED. 

Smith's  Intermediate  Chemistry,  revised 
and  rewritten  by  James  Kendall  and  Edwin 
E.  Slosson.  Pp.  XV.  +  566.  1922.  New 
York:  The  Century  Co.  Sold  in  Great 
Britain  by  Messrs.  G.  Bell  &  Sons,  Ltd., 
Portugal  Street,  Kingswa-y,  W.C.2.  8s.  6d. 
net. 

The  Theory  of  Emnlsions  and  Emulsifi- 
cation,  by  William  Clayton,  D.Sc.  (Liver- 
pool), F.I.C.,  Foreword  by  Professor  F. 
G.  DoNNAN,  C.B.E..  M.A.,  &c.  Pp.  VL  + 
160.  1923.  Messrs.  J.  &  A.  Churchill,  7, 
Great  Marlborough  Street,  W.l.  9s.  6d.  net. 

Bleaching  Poivder  and  its  Action  in 
Bleaching,  Original  Memoirs  bv  R.  L.  Tay- 
lor, F.I.C.  Pp.  78.  1922.  Messrs.  John 
Heywood.  Ltd.,  121,  Deansgate,  Manches- 
ter.    4s.  6d. 


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Acrents,  of  5,  Chancery  Lane.  London,  from  whom 
all  information  relating  to  Patents.  Trado 
Marks,  and  Desiprns.  can  bo  obtained  gratuitously. 

Latest   Patent   Applications. 
331'09— Harris,   H. — Separation   of   arsenic   and  tin 
in  presence  or  absence  of  antimony.  Dec.  4. 
3307&— Hi  robber  sr,    L.    M.— Extraction     of    sulphur 

and    sulphur    compounds.     Dec.   4. 
33605— Williams.  J.  G.— Manufacture   of  low   rela- 
tive  density  oxide   and   carbonates  of  mvf}^- 
nesium.    Dec.  8. 

Srycifications   Published   this    Week. 
163047— Nitrogen  Corporation.— Process  of  prepar- 


ing  mixtures     of  nitropfen     and   hydrogen 
such  as  are  suitable  for  the  production  of 
ainmonia. 
167156 — Man,     W. — Manufacture     of    concentrated 

hydrogen  peroxide  solution 
188772— Wolverkamp,     M.      E.- Salts     of   oxidised 

protalhinic  and   h-salbiuic  acids. 
188811— Deutsclio        Gold  '  &     Silber-Scheideanstalt 
vorm  Roesseler     an  Schaidliauf,     Dr.   A. — 
Process  of  bleaching  textile  fibres. 
188815— General   Electric  Co.,  Ltd.— Apparatus  for 
transforming     the     crystal      structure     of 
wires,  filaments,   and   the   like 
177972— L'Air  Liquide  Soc.  Anon.  Pour  L'Etude  et 
TExploitation   des   Procedes,   G.,   Claude.  - 
Synthesis  of  ammonia. 
188933— British   Dyestiiffs    Corporation,   Ltd.      and 
Wyler,   M. — Manufacture     of   phenyl     gly- 
cine compounds. 
172944 — Aktieselskal>et  Labrador.— Precipitation   of 

iron  in  mineral  acid  alumina  solutions. 
189160-Gitsham,  J.,  and  Evershed,  H.  R.— Process 

for  the  raanufacturo  of  sulphate  of  lead. 
189193 — Wake,  .1.  F.— Rotary  apparatus  for  drying, 
calcining,  or   roasting  ores,     low  temi>era- 
ture  distillation  of  fuel,  and  apparatus  for 
similar   purposes. 
181375— Akticsclskabet     de     Norske     Saltverker.— - 
Process     of  producing  anhydrous     magne- 
sium chloride. 
1854(03^-rarbwoike  vorm.   Meister  T,ucius  &  Brun- 
ing. — Manufacture  of  thiohydrins. 
Abstract  Published  this   Week. 
Manures;  Aynmonium   Salts;   Ammonia. — Patent 
No.   187251. — Some  improvements   in  processes   for 
obtaining  artificial  manures  have  been  devised  by 
Mr.  E.  L.  Pease,  of  Hurworth  Moor,  Darlington, 
County  Durham. 

Manures  containing  an  ammonium  compound 
or  componndft  and  a  secondary  fertilising  agent 
or  agents,  sntjh  as  a  salt  of  potassium  or  a  phos- 
phate, are  obtained  by  reaction  between  gases 
containing  amniouia  and  the  semi-dry  product 
obtained  by  troaHng  with  acid  a  naturally-occiir- 
ring  material  that  contains  the  secondary  ferti- 
lising agent  or  agents,  biit  which  is  free,  or  al- 
most free,  from  lime,  and  is  not  generally  re- 
garded as  a  manure  in  itself.  Thus  clay  contain- 
ing a  compound  of  potassium  may  be  treated 
with  sulpliuiic  acid,  if  desired,  after  drying  and 
pulverising  in  sufiicient  amount  to  constitute  a 
serai-dry  mass,  which  is  brought  into  contact 
with  gases  containing  ammonia.  The  product 
contains  the  oxides  of  iron  and  aluminium,  and 
ammonium  sulphate,  together  with  a  soluble 
compound  of  potassium,  the  content  of  which  may 
be  increased  by  direct  addit'on  of  potassium 
salts.  Other  examples  of  nnturally-occurring 
materials,  suitable  for  use  in  the  process,  are 
alunite  and  shales  containing  iron  aluminium, 
sulphur  and  potash,  with  or  with'nut  phosphorus. 
Alunite  may  be  calcined  and  used  without  any 
addition  of  acid.  Instead  of  sulphuric  acid  there 
m;iy  be  used  sulphur  dioxide  or  trioxide,  hydro- 
chloric or  phosphoric  acid,  snent  pickling-liquor, 
or  acid  salts,  or  mixtures  of  any  of  these.  Where 
phosphoric  acid  is  used,  gases  containin.;?  n^^- 
monia  ri7ay  be  treated  in  a  heated  condition:  if, 
however,  fhe  absorption  is  allowed  to  proceed  for 
a  lona:  time  at  atmospheric  temperature,  material 
containing  tri-ammonium  phosphate  is  obtained. 
The  products  may  be  lixiviated  to  remove  tlie 
soluble  saltP.  or  they  may  be  heated  to  about  400° 
C,  when  a' "out  50  per  cent,  of  the  ammonia  pre- 
sent is  evnl  ved,  leaving  a  residue  still  suitable  for 
use  as  .a  fertiliser  or  for  re-use  in  the  process. 
Alternatively  "^he  asrimonia  may  be  expelled  by 
means  of  lime. 

Messrs.  T?avner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications-  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


JANUARY  12.  1923. 


THE   CHEMICAL   NEWS. 


17 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.     No.  3274. 


THE  BRITISH  EMPIRE  EXHIBITION 
(1924). 

The  Chemicals  Section. 

Arrangements  have  now  been  completed 
for  organising  on  a  very  large  scale  the 
Chemicals  Section  of  the  British  Empire 
E.xhibition.  The  wganisation  of  the  Sec- 
tion has  been  entrusted  to  the  Association 
of  British  Chemical  Manufacturers,  whose 
CommitttK'  will  be  reinforced  by  represen- 
tatives of  the  Society  of  Chemical  Indus- 
tries and  kindred  bfxlies  coimected  with  the 
Chemical  Industry  and  Scii-nce.  The  work 
of  letting  space  is  now  proceeding,  25,000 
sq.  ft.  having  been  allotted  to  the  Chemical 
Section. 

Mr.  W.  J.  Wooloock,  of  116,  Piccadilly, 
is  acting  as  Secretary,  and  there  is  every 
indication  that  the  exhibit  will  be  one  fully 
worthy  of  the  great  Chemical  Industry.  In 
fact,  it  may  'be  said  that  this  section 
stands  next  to  the  engineering,  electrical, 
and  transport  sections  of  thc^  Exhibition  in 
the  satisfactory  demand  for  space.  A  large 
numbi-r  of  the  big  manufucturing  firms  of 
the  kingdom  have  already  applied.  It  is 
probable  that  a  portion  of  the  section  will 
l)e  devoted  to  perfumery.  Suggestions 
have  also  been  received  from  firms  desiring 
to  show  the  whole  process  of  toilet  soap 
making  by  modem  machinery,  with  shav- 
ing and  toilet  soaps  of  all  descriptions,  den- 
t'fric(\   and  other  toilet  pix-parations. 


TTTE    ESTBf.ATION    OF    MAGNESIUM 
IN    ALUMINIUM    ALLOYS. 

By  W.  H.  Withey,  B.A.  (Cantab.),  of  the 
National  Physical  Laboratory. 

The  increasing  use  of  magnesium  in  alu- 
minium alloys  containing  several  metals 
has  cornplicated  the  analysis  of  such  alloys, 
and  any  method  by  which  it  can  be 
shortened  without  loss  of  accuracy  is  very 
miich  to  be  desirerl. 

In  a  paper  read  before  the  Institute  of 
Metals  in  1016,  the  author  published  de- 
tails of  a  methfxl  in  which  use  was  made  of 
the  fact  that  tartaric  acid  prevents  the  prf- 
cipitation  of  iron  and  aluminium  by  am- 
monia,    but  at  the    same    time    does    not 


prevent  the  estimation  of  magnesium  as 
phosphate  even  in  the  presence  of  a  large 
quantity  of  aluminium. 

In  the  process  as  originally  devised, 
metals  such  as  zinc,  copper,  nickel,  iron, 
and  any  others  which  could  be  separated 
by  sulphuretted  hydrogen,  were  removed 
prior  to  determining  the  magnesium  as 
phosiphate.  This  necessarily  lengthened 
the  process,  since  it  prevented  the  estima- 
tion of  the  magnesium  in  a  separate  por- 
tion. 

As  a  result  of  experiments  it  has  now 
be^n  shown  that  it  is  not  necessary  to  re- 
move metals  such  as  zinc,  copper,  nickel 
and  iron  (if  present  in  only  small  amounts), 
and  that  the  accuracy  in  the  subsequent 
determination  of  the  magnesium  is  quite 
as  high  as  when  the  metals  are  absent.  The 
method  has  been  tested,  as  regards  accur- 
acy, by  adding  a  definite  amount  of  mag- 
nesium to  solutions  of  aluminium  contain- 
ing coipper,  zinc,  ancl  nickel,  in  proportions 
which  are  not  likely  to  be  exceeded  in 
practice,  and  then  estimating  the  amount 
«>f  magnesium  present.  The  figures  thus 
obtained  agree  very  closely  indeed  with 
those  found  in  the  same  amount  of  the 
pure  magnesium  solution.  The  details  as 
given  below  for  the  test  experiments  are 
applicable  to  th(^  analysis  of  aluminium 
alloys  not  containing  more  than  1  per  cent. 
(>{  magnesium,  the  amount  of  alloy  used 
for  the  analysis  being  2  gms.  To  obtain 
successful  results  the  conditions  must  be 
careully  observed,  particular  care  being 
taken  to  «ee  that  the  solution  is  very 
distinctly  alkaline  before  the  addition  of 
the  sodium  phosphate,  otherwise  there  is  a 
risk  of  contaminating  the  magnesia  pre- 
cipitate with  some  of  the  heavy  metallic 
phosphate.  If,  on  addition  of  the  sodium 
phosphate,  a  precipitate  is  produced  im- 
mediately, more  ammonia  should  be  added, 
when  it  will  be  found  that  the  precipitate 
redissolves,  and  that  only  after  some  time 
does  the  magnesia  commence  to  come 
down. 

For  the  purpose  of  the  tests,  a  very  im- 
pure aluminium  (Si  0.36,  Fe  1.50,  Cu  0.65) 
was  chosen,  and  several  portions  of  2  gms. 
dissolved  in  a  mixture  of  30  cc.  hydro- 
chloric acid,  10  cc.  nitric  acid.  This  was 
follr  wed  by  evaporation  to  dryness  after  the 
addition  of  15  cc  sulphuric  acid.  The 
dried  mass  was  dissolved  in  water,  and  the 
silica  removed  by  filtration.  To  each  of 
these  solutions  was  added  15  gms.  of  tar- 
taric aoid  dissolved  in  75  cc.  water,  6  gms. 
ammonium  chloride,  and  5  cc.  of  a  stand- 


18 


THE    CHEMICAL    NEWS. 


JANUARY  12,   1923: 


ard  solution  of  magnesium  sulphate.  The 
metal  whose  action  was  to  he  investigated 
was  added  in  the  form  of  a  standard  solu- 
tion, and  one  metal  only  was  used  for  each 
separate  t«st. 

The  solutions  as  thus  prepared  were 
next  treated  with  strong  ammonia  (s.g. 
0.830)  until  they  were  very  distinctly  alka- 
line, 40  cc.  was  found  to  be  sufficient  lor 
the  purpose.  Twenty-five  cubic  centi- 
metres of  a  saturated  solution  of  sodium 
phosphate  were  then  added  and  the  liquids 
vigorously  stirred,  and  more  ammonia 
added  until  it  formed  at  least  one-third  of 
the  total  volume,  which  should  be  about 
400  cc.  After  allowing  to  stand  overnight, 
the  solutions  were  filtered,  washed  with 
dilute  ammonia,  and  then  dissolved  in  hy- 
drochloric acid,  and  precipitated  again  in 
the  presence  of  1  cc.  of  a,  saturated  solu- 
tion of  sodium  phosphate,  as  in  the  case 
of  pure  magnesium  in  solutions. 

When  the  precipitates  had  settled  for 
several    hours,    they     were   again    filtered. 


washed  as  before,  and  ignited.  In  the  case 
of  alloys  containing  manganese  it  will 
usually  be  found  that  the  magnesium  (pre- 
cipitate contains  a  portion  of  the  man- 
ganese. The  ignited  precipitate  should, 
therefore,  be  dissolved  in  nitric  acid  s.g. 
1.2,  cooled,  treated  with  sodium  bismuth- 
ate,  filtered  and  titrated  with  ferrous 
ammonium  sulphate,  and  any  manganese 
thus  found  calculated  as  Mn2P207  and  de- 
ducted from  the  weig^ht  of  the  imnpure 
phosphate. 

Any  traces  of  calcium  present  in  the 
alloy  would  also  iprobably  be  precipitated, 
but  as  a  rule  calcium  is  only  likely  to  be 
introduced  by  means  of  the  magnesium 
used  ill  making  the  alloys,  the  actual 
amount  of  calcium  is  likely  to  be  very 
small  indeed,  and  for  any  but  the  most 
accurat '  analyses  could  be  ignored.  In 
ctu'tiin  eases  where  calcium  is  added  inten- 
tionally, although  in  small  amounts,  a 
modification  of  the  process  may  be  neoes- 
sarv. 


Experimental  Results" 


Weights  of  metals  present. 


Al 

Fe 

Cu 

Zn 

Ni 

Mg.I^O,  found 

Mg  Calculated 

nil 

nil 

nil 

nil 

nil 

0.0568 

0.0124 

2.0000 

0.0300 

nil 

nil 

0.0r)62 

0.0125 

2.0000 

0.0300 

0.1000 

nil 

nil 

0.0566 

0.0124 

2.0000 

0.0300 

0.5000 

nil 

nil 

0.0570 

0.0125 

2.0000 

0.0300 

0.2278 

nil 

0.0580 

0.0127 

2.0000 

0.0300 

nil 

0.4556 

nil 

0.0604 

0.0129 

2.0000 

0.0300 

nil 

nil 

0.2000* 

0.0562+ 

0.0123 

2.0000 

0.0300 

nil 

nil 

0.4000* 

0.0552  + 

0.0121 

+  In  these  cases  pure  metallic  nickel  was  used,  dissolved  in  aqua-regia. 

*  In  the  first  experiments  made  with  nickel  a  sample  of  nickel  ammonium  sulphate 
was  used,  which  proved  to  be  contaminated  with  magnesium.  1  gm.  of  the  salt  was 
added  to  one  solution  and  2  gms.  to  the  other.  The  weights  of  precipitates  obtained 
were  0.0714,  0.0838;  on  treating  some  of  the  nickel  salt  alone  in  the  presence  of  tar- 
taric acid  and  phosphate  2  gms.  gave  0.302,  which  amount  of  Mg^V^Oj  was  also  ob- 
tained after  separating  all  other  metals  previous  to  precipitating  the  phosphate. 
Making  the  corrections  for  the  magnesium  in  the  nickel  salt,  the  amounts  corrected 
shoull  have  been  0.0563  and  0.0536,  corresponding  with  0.0123  and  0.0118  Mg. 


The  method  has  also  been  tried  on  two 
alloys  of  a  fairly  complex  type,  which  on 
analysis  by  decomposing  with  caustic  soda 
and  subsequent  determination  of  the 
metals  seriatim,  gave 

1  2 

Si      0.22  0.22 

Cu      2.29  3.91 

Mn       0.58  nil 

Mg        0.61  1.56 

Zn        19.10  nil 

Ni      nil  1.93 


After  removal  of  the  silica  and  applying  the 
tartaric  method  as  above,  the  magnesium 
found  was  respectively  0.59  per  cent,  and 
1.54  per  cent.,  as  against  0.61  and  1.56. 

The  precipitates  obtained  in  the  first 
series  of  experiments  were  also  examined 
for  possible  contamination,  by  dissolving 
them  in  dilute  hydrochloric  acid  followed 
by  careful  neutralisation,  addition  of 
sodium  acetate  and  dilute  acetic  acid.  The 
slight  precipitate  was  redissolved,  and  re- 
precipitated,  and  on  ignition  was  proved  to 


JANUARY  12,  1923. 


be  a  minute  quantity  of  ferric  phosphate 
which  was  without  significance  in  the  re- 
sult. It  should  also  be  ipointed  out  that 
with  the  exception  of  the  filtrate  from  the 
magnesium  phosphate  .'solution  obtained 
from  the  copper  solution,  only  a  faint  dar- 
kening, but  no  precipitate,  with  sulphur- 
etted hydrogen  could  be  obtained.  The 
method  may,  therefore,  be  regarded  as  re- 
liable, and  is  more  expeditious  than  the 
older  methods,  as  it  enables  the  magnesium 
to  be  estimated  on  a  separate  portion  of  the 
alloy. 


THE   CHEMICAL    NEWS. 


19 


LEGAL  INTELLIGENCE. 


RICHMOND  POLICE  COURT. 

Arsenic  in  Cocoa.* 

Summvna  Under  Sale  of  Foods  and  Drugs 
Act,  1875. 

At  the  instance  of  the  Surrey  County 
Council,  on  December  18,  1922,  the  Home 
and  Colonial  Stores,  Ltd.,  were  summoned 
fo  r"  selling  at  their  George  Street  shop, 
Richmond,  to  the  iprcjudice  of  Robert  Al- 
fred Houghton  (county  inspector),  the 
purchaser,  coooa  which  was  not  of  the 
nature,  substance,  and  quality  of  the 
article  demanded  by  such  purchaser,  but 
was  adulterated  with  arsenic  (arsenious 
oxide)  to  the  extent  of  one-fortieth  of  a 
grain  per  pound  of  cocoa,  contrary  to  Sec- 
tion ()  of  the  Sale  of  Foods  and  Dnigs  Act, 
1875."  Messrs.  Rowntree  and  Co.,  Ltd., 
Cocoa  Works,  Haxby  Road,  York,  were 
summoned  for  aiding  and  abettinff  in  the 
commission  of  the  alleged  offence  by  the 
Home  and  Colonial  Stores,  Ltd. 

The  Mayor  (Alderman  P.  E.  Metzner) 
presided  over  the  Bench.  Mr.  R.  O.  B. 
Lane  (instructed  by  the  Surrey  County 
Council)  prosecuted;  Mrs.  Travere  Hum- 
phreys appeared  for  Messrs.  Rowntree ; 
and  Mr.  W.  Ricketts  appeared  for  the 
Home  and  Colonial  Stores,  Ltd. 

Both  defendants  put  in  a  formal  plea  of 
"  Guilty." 

Mr.  Lane,  for  the  prosecution,  said  the 
summonses  were  taken  out  by  Mr.  Houj;h- 
ton,  an  inspector  of  the  Surrey  County 
Council.  On  October  2  Mr.  Emery,  an 
assistant  to  Mr.  Houghton,  went  to  the 
Home  and  Colonial  Stores,  Richmond,  and 
asked  for  a  quarter  of  a  pound  of  cocoa. 
lr{v  was  served  with  a  ipacket  from  und<^r 
the  counter,  for  which  ho  paid  4^.     It  was 


marked,  *'  Home  and  Colonial  piu-e  cocoa 
essence,  highest-grade  quality,  guaranteed 
absolutely  pure  coooa."  He  was  informed 
that  the  cocoa  in  question  was  not  the 
actual  manufacture  of  the  Home  and 
Colonial  Stores,  but  a  blend  of  seven  dif- 
ferent cocoas,  one  of  which  was  manufac- 
tured by  Messrs.  Rowntree.  Samples  of 
the  seven  different  cocoas  were  given  to 
Mr.  Emery,  and  when  Messrs.  Rowntree 's 
sample  was  analysed,  it  was  found  to  con- 
tain arsenic  to  the  extent  of  one-tenth  of  a 
grain  per  pound.  He  wanted  to  say  at 
once,  and  acting  on  his  instructions,  that 
he  did  not  suggest  that  the  Home  and 
Colonial  Stores  were  really  to  be  blamed  in 
the  matter.  Thene  had  been  a  breach  of 
the  law,  but  he  did  not  think  it  could  be 
said  that  there  was  any  moral  culpability 
attaching  to  them ;  but  the  law  had  to  be 
carried  out. 

Mr.  Edward  Hinks,  analyst  to  the  Sur- 
rey County  Council,  said  that  he  analysed 
a  sample  of  cocoa  in  which  he  discovered 
arsenic  to  the  extent  of  one-fortieth  of  a 
grain  per  pound.  The  quantity  was  exces- 
sive. On  November  14  he  received  furtiier 
samples  of  cocoa,  and  with  regard  to  one 
marked  "  Rowntree  "  he  found  it  to  con- 
tain arsenic  to  the  extent  of  one-tenth  of  a 
rgain  to  a  pound  of  cocoa.  The  other 
samples  he  found  to  be  genuine.  In  reply 
to  Mr.  Travers  Humphreys,  who  asked  him 
if  he  suggested  that  anyone  was  in  the  least 
likely  to  be  injured  in  health  by  the  use  of 
the  cocoa  C(mtaining  one-tenth  of  a  grain 
per  pound,  w'tnoss  said  he  thought  it  was 
on  the  line  where  it  might  be  harmful.  He 
had  not  heard  of  anyone  being  harmed  by 
it. 

Mr.  Travers  Humphreys  said  Messrs. 
Rowntree  took  absolute  responsibility  for 
the  position  in  which  the  Home  and  Colo- 
nial Stores  had  been  placed.  They  bought 
from  Messrs.  Rowntree  what  they  believed 
to  be  pure  cocoa.  Messrs.  Rowntree  were 
most  anxious  that  two  matters  should  be 
put  clearly  before  the  Bench.  They  desired 
first  to  put  before  the  public  through  f.he 
Bench  that  in  the  opinion  of  the  most  com- 
petent scientific  men  there  was  not  the 
smallest  cause  for  anxiety  as  to  illness  or 
danger  to  the  public  from  drinking  the 
cocoa  which  was  the  subject  of  the  prose- 
cution. The  other  matter  was  that  this 
was  an  accident  which  might  have  hap- 
pened to  any  manufacturer  of  any  article  of 
ff>od.  in  spite  of  the  greatest  possible  care 
being  taken  to  prevent  impurities  being 
present.       In  July  last  there  was  brought 


20 


THE    CHEMICAL    NEWS. 


JANUAEY  12,  1923. 


to  the  notice  of  Messrs.  Eowntree  by  some 
chemist  that  some  of  the  loose    cocoa  sup- 
plied contained  some  faint  traces  of  arsenic. 
The  news  came    like  a  thunderbolt  to  the 
firm.       Their  chemists  were  put  on  double 
shifts,  working  day  and  night.     Everythhig 
in  the  plaee  was  analysed,     and  for    some 
time    there    was    not  the    faintest    notion 
where  the  arsenic  could  have    come  from. 
It  was  found  that  the  impurity  was  in  the 
alkali  carbonate  of  potash,  which  had  been 
used  by   Messrs.   Rowntree  for  years.       It 
was  used  in  small  quantities    to  make  the 
cocoa  soluble   and  more  digestible.       They 
got  it  from  the  best  people    in  the    trade. 
They     found    it    contained    a    substantial 
quantity  of  arsenic,  and  they  wrote  to  the 
manufacturers  about  it,  but  so  far  had  not 
received   any  explanation.      There  was  one 
thing  they  could  do,  and    they  did    it    in- 
stantly— they   sacrificed  the    whole   of  the 
cocoa,    350  tons,    representing  many   thou- 
sands of  pounds,  sacrificed  it  absolutely  m 
order  that  nothing   more  might    go  out  of 
their  works.     They  then  instituted   a  new 
test,   and  they  were  able  to  say  with  abso- 
lute certainty  that  as  from  August  1  every 
ounce  of  cocoa  from  their  works  was  made 
from  ingredients  absolutely  free  from    this 
Impurity.     There  was  on  the  market  some- 
where the  amount  of  cocoa    they  had  sent 
out   containing    this   impure    carbonate     of 
ipotash.     They  first  ascertained  if  it  could 
do  any  harm.     The    view  of  the  chemists 
was  that    the   amount    of  arsenic    preseat 
could  not  possibly  injure  anyone  in  health 
who     consumed     it.         They       considered 
whether  it  was  .possible    to  get  back    the 
cocoa  they  had  sent  out  to  the  trade,  but 
decided  it  was  absolutely  useless  to  try  to 
get  it  back,    because  they  had  65,000  ciis- 
tomers    many  of  them  wholesalers.        Ihe 
period  during  which  the  impure  cocoa  was 
sent     out  was     only  two     months  m     a!.. 
Messrs.   Eowi;tree  came  to  the   conclusion 
honestly  that  it  was  in  the  interests  of  the 
public  not  to  create   a  quite    unjustifiab  e 
scare   in   connection  with   such   a   valuable 
article   of  food   as   cocoa.       He   wished   to 
emphasise   that     chocolates   did  not     come 
into  the  matter  in  the  least.       Chocolates 
were  made  from  cocoa  which  contamed  no 
addition  of  the  carbonate  of  P^^ash. 

Mr  Arnold  Rowntree  said  his  firm  had 
never  spared  any  expense  in  regard  to 
analysin,c,  articles  of  food  With  regard  to 
the  incident,  witness  said  the  whole  of  the 
stock  was  sacrificed,  amountmg  ^^  aboat 
300  tons,  varying  m  value  from  £100  to 
£520  a  ton. 


Mr.  Ricketts,  on  behalf  of  the  Home  and 
Colonial  Stores,  said  they  purchased  the 
cocoa  with  a  warranty  froui  Messrs.  Rown- 
tree. Directly  they  heard  that  the  cocoa 
contained  impurity  they  withdrew  sixty- 
five  tons  from  their  shops  and  twenty  tons 
from  their  warehouses,  involving  them  in  a 
loss  of  £12,000.  .     X    .u 

A  fine  of  40s.  was  imposed  against  the 
Home  and  Colonial  Stores,  and  £20 
against  Messrs.  Rowntree,  with  60  guineas 
costs. 

*  From  the  "  Pharmaceutical  Journal 
and  Pharmacist,"  December  23rd,   1922. 


THE     TEMPERATURE     COEFFICIENT 

OF  THE  REFRACTIVE  INDEX  OF 
AMERICAN  TURPENTINE. 

By  Gartha  Thompson  (B.Sc,  F.I.C). 

It  is  a  remarkable  fact  that  while  it  is 
generally  recognised  that  it  is  impossible  to 
comipare  refractive  indices  unless  these  re- 
fer to  the  same  temperature,  few  attempts 
have  been  made  to  measure  and  record  the 
variation  of  the  refractive  index  with  tem- 
perature. This  is  specially  true  of  com- 
mercial liquids.  Hence,  there  have  been 
demands  by  analvsts  that  all  workers 
should  adhere  to  a  standard  temperature 
when  measuring  refractive  indices.  The 
better  way,  however,  is  to  ascertain  both 
the  refractive  index  and  its  temperature 
coefficient  {i.e.,  the  decrease  in  refractive 
index  per  degree  Centigrade),  for  then  a 
small  calculation  is  all  that  is  necessary  to 
reduce  refractive  indices  to  any  desired 
temperature.  The  advantage  of  being  able 
to  calculate  the  refractive  index  for  any 
temperature  when  its  yalue  is  known  at 
one  temperature  is  obvious. 

It  is  a  fortunate  fact,  from  this  stand- 
point, that  while  liquids  of  analogous 
chemical  constitution  vary  in  their_  refrac- 
tive indices,  the  temperature  coefficients  of 
these  refractive  indices  remain  fairly  con- 
stant ;  and  it  is  an  equally  fortunate  fact, 
from  another  standpoint  (viz.,  that  of 
differentiating  between  substances  of  dis- 
similar chemical  constitution),  that  while 
the  refractive  indices  are  often  the  same  at 
one  temperature,  yet  the  temperature  co- 
efficients of  the  refractive  indices  vary 
widely.  In  fact,  where  dissimilar  liquids 
are  concerned,  it  is  frequently  found  that 
there  are  far  wider  differences  in  the  tem- 
perature coefficients  of  the  refractive  in- 
dices than  in  those  constants  themselves. 


JANUAKY  12,  1923. 


THE   CHEMICAL   NEWS. 


21 


As  is  the  case  with  many  other  liquids, 
the  temperature  coefficient  of  the  refrac- 
tive index  of  turpentine  appears  to  have 
been  neglected  The  only  information 
which  could  be  found  on  this  subject  is 
given  in  Kanthack's  "  Refractive  Indices 
of  Essential  Oils  "  (Adam  Hilger,  Ltd.). 
Here  the  temperature  coefficient  of  the  re- 
fractive index  of  American  turpentine  is 
given  as  0.00037,  and  it  may  be  remarked 
that  this  figure  is  so  low  as  to  be  quite 
outside  the  usual  range  of  essential  oils.  It 
was  therefore  decided  to  carry  out  a  series 
of  tests,  using  the  best  commercial 
varieties  of  American  turpentine. 

The  samples  of  tuipentine  numbered  1, 
3,  and  4  were  described  as  "  Genuine  Com- 
mercially refined  Spirits  of  American  Tur- 
pentine ";     sample    2    was    described     as 

best  American  Turpentine." 

A  Pulfrich  refractometi'r  constructed 
and  recently  calibrated  by  Messrs.  Adam 
Hilger,  Ltd.,  was  used  for  the  work,  and 
temperature  control  was  maintained  by 
allowing  a  stream  of  wat^r  at  the  desired 
temperature  to  flow  throiifjh  the  jackt-ts 
enclosing  the  prism  and  a>ll  and  through 
the  heater  which  was  inserted  in  the  tur- 
pentine in  the  cell.  A  so<liura  flame  was 
used  as  illuminant  throughout  the  experi- 
ments. 

From  the  third  columns  in  the  tables  it 
will  be  seen  that  there  is  little,  if  any,  ten- 
dency for  the  temperature  coeflBcient  to 
alter  with  temperature. 

All  four  samples  of  turpentine  were  ex- 
amined chemically;  for  the  fifjures  in  table 
4  (with  the  exception  of  those  for  the 
second  sa'nple)  I  am  indebted  to  the 
Routine  Section  of  the  Laboratories. 


In  conclusion,  I  desire  to  express  my 
thanks  to  the  Directors  and  Chief  Chemist 
(Mr.  W.  B.  Parker,  F.I.C.),  of  the  British 
Thomson-Houston  Company,  Ltd.,  for  per- 
mission to  use  the  research  laboratories  for 
this  work. 


Table  1.     Sample  1, 


Refractive 

Temperature 

Temperature 

Index. 

Coef^eient. 

14.2"  C. 

1.47-1428 

0.0004672 

20.5 

1.47M86 

0.0004603 

32.1 

1.46r,076 

0.0004723 

39.2 

1.40-J722 

0.0004633 

48.0 

1.4r)S(',-M 

0.0004732 

57.4  1.454197      Mean  0.0004684 


Table  2.     Sample  2. 


Refractive 

Temperature 

Temperature 

Index. 

Coefficient. 

20.0"  C. 

1.460002 

0.0004675 

80.0 

1.46r)227 

0.0004710 

45.0 

1.458163 

0.0004705 

60.0 


1.451110      Mean  0.0004696 


Table  3.     Sample  3. 


Temperature 
15.5"  C. 
80.0 
50.0 


Refractive 

Index, 
1.472804 

1.400022 


Temperature 
Coefficient. 
0.0004677 
0.0004735 


1.45()552      Mean  0.0004706 


Table  4.     Sample  4. 


Temperature 
15.5"  C. 
30.0 
50.0 


Ri^fr  active 

Index. 
1.472858 
1.466022 
1.450652 


Temperature 
Coefficient. 
0.0004711 
0.0004685 
Mean  0.0004698 


Sample 
No. 

Specific 

Gravity 

15.5"  C 

Iodine 
Value.* 
24  hour.-; 
Hupl 

1st  drop 

Table 

Beiow 
155"  C 

5. 

Di.stillc 
165" C  to 
165"  C 

ition. 
Below 
175"  C 

Below 
185"  C 

Above 
1850C 

1 

0.8670 

423.1 

152"  C 

0.05% 

95.0% 

96.5% 

97.0% 

3.0% 

2 

0.8724 

407.3 

153°  C 

2.05% 

flO.0% 

93.0% 

96.0% 

4.0% 

3 

0.8705 

399.2 

155"  C 

— 

93.0% 

95.5% 

96.0% 

4.0% 

1 

0.8707 

306.0 

154°  C 

0.05% 

92.0% 

94.0% 

95.0% 

5.0% 

*  150%  excess  iodine  was  used. 


22 


THE   CH^MICAJL   NEWs. 


JANUARY  12,  1923. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


ROYAL  SOCIETY  OF  ARTS, 

John  Street,  Adelphi,  London,  W.C.2. 

169th   Session,   1922-23. 

Arrangements  for  Meetings  during 
January,  1923. 

Wednesday,  Jan.  17th,  8  p.m.  (Ordinary 
Meeting) :  C.  A.  Klein,  Hygienic  Methods 
in  Painting — the  Damp  Rubbing  Down 
Process.  T.  M  .Legge,  C.B.E.,  M.D.,  will 
preside. 

Friday,  Jan.  19th,  4.30  p.m.  (Indian  Sec- 
tion):  The  Earl  of  Ronaldshay,  G.C.I.E. 
(late  Governor  of  Bengal),  A  Clash  of 
Ideals  as  a  Cause  of  Indian  Unrest.  The 
Right  Hon.  Viscount  Peel,  G.B.E.,  Secre- 
tary of  State  for  India,  will  preside. 

Wednesday,  Jan.  24th,  8  p.m.  :  Sir  Wil- 
liam Henry  Bragg,  K.B.E.,  D.Sc, 
F.R.S.  (Quain  Professor  of  Physics,  Uni- 
versity of  London),  The  New  Method  of 
Crystal  Analy.sis,  and  their  Bearing  on 
Pure  and  Applied  Science.  "Truemnn 
Wood"  Lecture.  Alan  A.  Campbell  Swin- 
ton,  F.R.S. ,  late  Chairman  of  the  Council, 
will  preside. 

Wednesday,  Jan.  31st,  8  p.m.  (Ordinary 
Meeting):  Thomas  H.  Fairbrotiikr,  M.Sc, 
F.I.C.,  and  Arnold  Renshaw,  M.D., 
D.P.H.,  The  relation  between  Chemical 
and  Antiseptic  Action  in  the  Coal  Tar  Dyes. 


THE  FARADAY  SOCIETY. 

Ordinary  Meeting,   Monday,   January   15, 

1923,  AT  8  P.M. 

At  the   Chemical  Society,    Burlington 

House,  Piccadilly,   W.l. 
Papers  to  be  read:  — 

E.  W.  J.  Mardles  :  The  Scattering  of 
Light  by  Organosols  and  Gels  of  Cellulose 
Acetate. 

Study  of  the  Reversible  Sol  to  Gel  Tran- 
sition in  Non-Aqueous  Systems. 

I.  The  Change  of  Viscosity  tvith  Time 
during  Gelation. 

II.  Viscosity   Changes   associated  tvitJi 
the  Gel  to  Sol  Transition. 

Changes  of  VoluDte  and  Refractive  Index, 
associated  icith  (a)  The  Formation  of  Or- 
ganosols an  dGcls.  (b)  The  Reversible  sol 
to  gel  Transition. 

Prof.  J.  R.  Partington  and  W.  G.  Shil- 
ling :  The  Variatiori  of  the  Specific  Heat 
of  Air  with  Tem^perature. 


Prof.  A.  W.  Porter  and  J.  J.  Hedges  : 
The  Law  of  Distribution  of  Particles  in 
Colloidal  Suspensions,  with  Special  Refer- 
ence to  Perrin's  Investigations.     Part  II. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

1st  January,  1923. 

Meeting  at  Nottingham. 

A  Joint  Meeting  of  the  Society,  with  the 
Nottingham  Section  of  the  Society  of 
Chemical  Industry,  will  be  held  at  the  Uni- 
versity College,  Nottingham,  on  Wednes- 
day, January  17th,  at  7.15  p.m. 

The  chair  will  be  taken  by  the  Chairman 
of  the  Nottingham  Section  of  the  Society 
of  Chemical  Industry,  Mr.  S.  F.  Burfoid, 
F.I.C. 

A  general  discussion  on :  The  Detection 
and  Determination  of  Small  Quantities  of 
Arsenic,  will  be  opened  by  Mr.  A.  Chaston 
Chapman,  F.R.S.,  President  of  the  Insti- 
tute of  Chemistry. 

Mr.  J.  M.  Wilkie  will  read  a  paper  on 
the  subject,  and  among  those  taking  part 
in  the  discussion  will  be  :  Mr.  S.  R.  Trot- 
man,  Mr.  H.  Droop  Richmond,  and  Dr.  G. 
W.  Monier- Williams.  The  Chairman  will 
call  upon  further  speakers  by  name,  and 
those  desiring  to  contribute  to  the  discus- 
sion should  communicate  with  the  Honor- 
ary Secretary. 

Apparatus  for  the  electrolytic  determina- 
tion of  arsenic  will  be  exhibited  by  Dr.  G. 
W.  Monier-WilHams  and  Mr.  J.  M.  Wilkie. 

In  order  to  promote  a  free  discussion,  tne 
meeting  will  be  iprivate,  and  closed  to  the 
Press,  but  an  official  summary  will  be 
issued  subsequently. 


MINERALOGICAL    SOCIETY. 
Tuesday,  January  9,  at  5.30. 

A.  Brammall  and  H.  F.  Harwood  : 
Dartmoor  Granite,  (a)  Rutile,  Brookite  and 
Anatase  :  Genesis ;  (b)  Varieties  of  Zircon  : 
their  significance. 

Dr.  a.  Hutchinson  :  A  graphical 
method  of  correcting  specific  gravity  deter- 
minations. 

Dr.  L.  J.  Spencer  (with  microscopical 
determinations  by  W.  Campbell  Smith, 
and  chemical  analyses  by  E.  D.  Moun- 
tain) :  A  davyne-like  m,inera  land  its 
pseudomorphs  from  St.  John's  Island, 
Egypt. 


JANUARY  12,  1923. 


THE  cnEMlCAL  NEWS. 


23 


We  have  been  asked  to  make  known  that 
the  membership  of  the  American  Chemical 
Society  Is  open  to  members  of  any  of  the 
recognised  EngHsh  chemical  societies. 

Fcwms  for  membership  and  full  particu- 
lars will  be  sent  on  application  to  the  Sec- 
retary, American  Chemical  Society,  1,709. 
a.  Street,  N.W.  Washington  D.C.,  U.S.A. 


BOOKS  RECEIVED. 

Formulary  of  the  Parisian  Perfumier,  by 
R.  M,  Gattefosse.  Pp.  82.  1st  English 
Edition.  1923.  La  Parfumerie  Moderne, 
19,  Rue  Camille,  Lyon. 

Cements  and  Artificial  Sfone  (a  descrip- 
tive Catalogue  of  the  specimens  in  thv^ 
Sedgwick  Museum,  Canipridge),  by  JoiiX 
Watson  (late)  Hon.  M.A..  F.G.S.  Pp.  XIL 
+  131.  1922.  W.  HeflEer  A  Sons.  Ltd., 
Cambridge.     68.  net. 


.\   1  III'J.IMINARY  STUJ)Y  OF  ZIRKITK 
ORE. 

By  J.  G.  Thompson. 

(From  the  Journal  of  Physical  Chemistry, 
New  York,   December,   1922.) 

(Continued  from  Page  16.) 

Zirconium  was  discovered  by  Klaproth 
in  1789;  but,  for  many  years  after  it^s  dis- 
covery, it  was  considered  one  of  the  rare 
earths,  and  occasional  samples  of  zircon, 
the  orthosilicate  of  zirconium,  were  <he 
only  sources  of  supply.  At  present  de- 
posits of  zircon  sands,  usually  associated 
with  monazite  sands,  are  known  to  exist  ''n 
many  localities,  but  the  deposits  usui'ly 
are  of  limited  extent  and  the  zircon  con- 
tent is  small.  Zirconium  also  occurs  in 
small  amounts  in  a  nimiber  of  rare  ores, 
but  these  are  important  only  for  the  traces 
of  radio-active  elements  which  they  con- 
tiin.  Present  interest  centres  solely  upon 
the  oxide  ores  of  zirconium  generally 
known  as  "  Baddeleyite  "  ores.  This 
group  includes  a  number  of  ores  of  indefi- 
nite and  variable  composition  in  which  the 
zirconium  oxide  content  varies  up  to  99  per 
cent.  The  name  "Zirkite"  has  been  re- 
stricted to  the  baddeleyite  ore  from  the 
huge  Brazilian  deposits  which  now  supply 
practically  all  of  the  demand  for  zirconium. 
Zirkiti'  ore  is  varigble  in  composition,  but 
careful  sorting  at  the  mine  furnishes  a  pro- 


duct which  is  fairly  uniform  in  composition 
averaging  about  80  per  cent.  zirconiu:n 
oxide.  It  is  stated^  that  an  unlimited  sup- 
ply of  this  ore  is  available,  as  the  deposits 
are  of  vast  extent.  The  only  factors  limit- 
ing the  output  are  the  difficulties  due  to 
primitive  methods  of  mining  and  transpor- 
tation. 

The  use  of  zirconium  oxide  always  has 
depended  upon  its  refractory  properties; 
but  this  use,  luitil  recently,  was  confined 
to  the  small  amounts  of  very  pure  material 
required  for  the  incandescent  element  in 
the  Nemst,  Druinmcnd,  and  Bleriot  lamps; 
as  an  additional  element  mixed  with  »he 
thoria  and  ceria  in  Wolsbach  mantles ;  etc. 
The  discovery  of  the  huge  Brazilian  de- 
posits of  high-grade  ore  has  awakened 
much  interest  in  the  possibility  of  using 
this  ore  on  a  large  scale  as  a  refractory. 

Many  of  the  properties  of  the  raw  ore' 
are  comparable  with  those  of  the  pure 
oxide,  but  the  melting  point  (2, 950"- 3, 000° 
C.  for  Pure  ZK),)  drops  to  l,200°-2,000°  C. 
for  the  raw  ore,  depending  upon  the  com- 
position. Zirkite  is  an  excellent  refractory 
within  the  limits  set  by  its  softening  and 
melting  points,  but  the  low  melting  point 
obviously  detra<'ts  greatly  from  the  refrac- 
tory value  of  the  ore.  It  has  been  used 
successfully  as  raw  material  in  the  manu- 
facture of  combustion  boats,  tubes,  etc., 
for  high  temperature  work  in  the  labora- 
tory ;  but  the  successful  use  of  the  material 
on  a  large  scale  awaits  the  development  of 
metuis  of  reusing  the  melting  point. 

The  problem  obviously  is  the  elimination 
of  the  element  or  elements  which  exert  so 
detrimental  an  effect  upon  the  melting 
point  of  the  ore.  No  definite  information 
is  available  regardmg  the  specific  effect  of 
the  various  impurities  upon  the  melting 
point  of  pure  zirconium  oxide,  but  silicon 
and  iron,  which  together  constitute  the 
bulk  of  the  impurities,  naturally  are  le- 
garded  as  the  chief  sources  of  trouble. 

Methods  of  purification,  as  recorded  in 
the  literature,  may  be  divided  into  two 
classes : 


'  Meyer:  Foote  Mineral  Company  publi- 
cation for  November,  1916. 

•  Meyer:  Met.  Chem.  Eng.,  1914,  XII., 
791;  Audley:  Trans.  Eng.  Ceram.  Soc, 
1917,  XVT..  121;  Rosenhain:  Trans.  Fara- 
day Soc,  1017.  XIT.,  178;  Dcvcrcun:  Met. 
Ind.,  1920,  XVI.,  414. 


M 


THE   CHEMICAL   NEWS. 


JANUAKY  12,  1921 


_  (1)  Methods  for  the  preparation  of  pure 
zirconium  compounds.* 

(2)  Methods  for  partial  purification  of 
the  ore  by  elimination  of  imipurities,  either 
by  leaching^  or  by  volatilization.^ 

Those  methods  in  the  first  class  which 
are  successful  are  adaptable  only  for  the 
production  in  the  laboratory  of  small 
amounts  of  pure  zirconium  compounds. 
The  methods  in  class  two  have  been  con- 
fined almost  entirely  to  the  removal  of  iron. 
The  refractory  silicates  of  zirconium  were 
not  affected  at  the  relatively  low  tempera- 
tures used  in  Phillips'  chlorination  experi- 
ments and  are  not  susceptible  to  leaching 
unless  they  have  been  recomposed  by  a  ipre- 
liminary  fusion. '^  The  methods  in  this  class 
are  better  adapted  for  large  scale  operation 
but  are  successful  only  to  a  limited  extent 
in  producing  satisfactory  refractory 
material  from  the  raw  ore. 

The  remarkable  stability  at  high  tem- 
peratures of  certain  compounds  of  zir- 
conium, particularly  the  oxide  and  carbide, 
together  with  the  fact  that  these  com- 
pounds are  not  apprecifibly  volatile  below 
their  decomposition  points,  suggested  the 
use  of  electric  heating  as  a  means  of  purify- 
ing zirkite  ore  by  the  elimination  of 
impurities  whose  oxides  and  carbides  pre- 
sumably are  less  refractory  than  the  corres- 
ponding zirconium  compounds.        Hitherto 

*  Berlin:  Jour,  prakt.  Cheni.,  1853, 
LVIIT.,  147;  Hermann:  Ibid.,  1866, 
XCVII.,  330,  340;  Bailerj:  Chem.  Neivs, 
1886,  LIII.,  55,  260,  287;  Dorevius  :  Jour. 
Am.  Chem.  Soc,  1886,  VIII.,  91;  Bayer: 
Zeit.  angew.  Chem.,  1910,  XXIIl.,  485; 
Anonymous:  Ceramique,  1911,  XIV.,  204; 
Loveman:  U.S.  Patent  No.  1,261,984, 
1918;  Imray:  British  Patent  No.  16,555. 
1913;  Leuchs  :  German  Patent  No.  285,344. 
1914;  Meyer:  loc.  cit.,  and  Granger:  loc. 
cit. 

^  Wedekind:  Zeit.  angew  Cheyn.,  1908, 
XXI.,  2270;  Weiss  and  Lehmann:  Zeit. 
anorg.  Chem.,  1909,  LXV.,  178;  Wede- 
kind: Ber.  deutsch.  chem.  Ges.,  1910, 
XLIII.,  290;  Ramsden:  Met.  Ind.,  1920, 
XVT.,  3;  Audley ;  Granger;  Rosen:  loc. 
cit. 

"  Phillips:  Jour.  Am.  Ceramic  Soc, 
1918,  I,,  791. 

^  Weiss  and  Lehmann :  loc.  cit.,  Jost 
and  Plocker :  German  Patent  No.  285,981, 
1914. 


the  electric  furnace  has  been  employed* 
only  as  a  preliminary  step  in  the  purifica- 
tion of  zirkite,  apparently  for  the  sole  pur- 
pose of  decomposing  refractory  silicates. 
This  investigation,  therefore,  was  under- 
taken for  the  sake  of  ascertaining  to  what 
extent  zirkite  might  be  freed  from  impuri- 
ties iby  direct  heating  in  an  electric  furnace. 

Before  the  experimental  portion  of  this 
investigation  could  be  undertaken,  a 
scheme  of  analysis  had  to  be  outlined.  A 
search  of  the  literature  revealed  many  con- 
flicting statements,  and  considerable  time 
was  devoted  to  the  investigation  of  the 
various  methods  before  a  satisfactory 
scheme  was  obtained.  A  brief,  critical  re- 
view of  some  of  the  methods  proposed, 
together  with  a  description  of  the  scheme 
adopted,  is  therefore  included  in  this  re- 
port. 
The  Analysis  of  Zirconium  Compounds. 

The  characteristic  properties  of  zir- 
conium ores  which  make  them  valuable, 
i.e.,  the  refractory  properties  and  chemical 
inertness,  formed  the  first  obstacles  to  be 
overcome  in  the  decomposition  of  the  ore. 

Four  general  methods  of  attack  have 
been  proposed : 

(1)  Fusion  with  hydrofluoric  acid  or  with 
fluorides.® 

(2)  Conversion  to  carbides  in  the  electric 
furnace.'" 

(3)  Fusion  with  sulphuric  acid  or  its  de- 
rivatives.^^ 


*  Moissan:  Comptes  rendus,  1893, 
CXVI..  1222;  Troost:  Ibid.,  1893,  CXVI., 
1428;  Podszus:  Jour.  Soc-  Chem..  Ind., 
1917,  XXXVI.,  217;  Barton:  U.S.  Patent 
No.  1,342,084,  1920;  Weiss  and  Le^iviann: 
loc.  cit. 

^  Marignac:  Ann.  Chim.  Phys.,  1860  (3), 
LX.,  260;  Weiss  and  Neumann:  Zeit. 
anorg.  Chem..  1909,  LXV.,  248;  Anony- 
mous: The  Brass  World,  1911,  VII.,  46; 
Meyer:  Foote  Mineral  Compajiy  Pitblica- 
tion  for  November,  1916;  Weiss  and  Leh- 
m,ann  :   loc  cit. 

^^  Granger:  Moissan;  Podszus;  Troost; 
Weiss  and  Lehmann :  loc.  cit. 

"  Baskerville:  Jour.  Am.  Chem.  Soc, 
1894,  XVI.,  475;  Ditfrich  and  Frcvnd: 
Chem.,  1907,  LVL,  337; 
,  1910,  LXVIL,  456;  Wede- 
deutsch.  chem.  Ges.,  1910, 
Johnstone:  "The  Rare  Earth 
Industry,"  1915;  Powell  and,  Schoeller : 
Analyst,  1919,  XLIV.,  397;  Weiss  and 
Lehm^ann;  Bayer:  loc  Sit. 


Zeit.     anorg. 
Weiss  :    Ibid, 
kind :      Ber. 
XLIII..  290; 


JANUARY  12,  1923. 


ims   CHEMICAL   NEWS. 


(4)  Fusion  with  alkalies.'^ 

Fusion  with  sodium  tetraborate  (borax) 
was  found  to  furnish  the  best  means  for 
the  decomposition  of  the  materials  encoun- 
tered in  this  investigation.  Borax  fusions 
usually  produce  complete  decomposition  in 
one  operation,  but  the  boric  acid  must  De 
eliminated  thereafter  if  a  complete  analy- 
sis is  desired.  Fusion  with  alkalies  pro- 
duces decomposition  of  the  silicates  and 
phosiphates,  but  is  not  apj)licable  to  oxide 
ores.  Fusion  with  pyrosulphates  decom- 
pr>ses  oxide  ores,  bu  tis  not  applicable  to 
silicates.  Methods  invf)lving  fusion  with 
fluorides  or  conversion  to  carbides  in  the 
electric  furnaces  are  objectionable  on  ac- 
count of  loss  through  volatilisation.  A 
combination  of  alkali  fusions,  followed  or 
preceded  by  pyrosulphato  fusions,  eventu- 
ally produces  complete  decompoeition  and 
total  solution  of  any  zirconium  compound, 
but  the  procedure  is  tedious  and  involved. 
In  all  cases  the  method  oniployed  for  de- 
comfKjsition  is  determined  by  the  nature 
and  characteristics  of  the  material. 

After  the  ore  has  been  decomposed  by 
fusion  methods  and  brought  into  complete 
solution,  the  problem  of  the  separation  of 
the  various  elements  arises. 

Analytical  Separations. 

Silicon  is  removed  frf>ni  the  solution 
without  diflficulty  owing  to  the  insolubility 
in  acids  of  its  dehydrated  oxide. 

Iron  interferes  with  almost  all  of  the 
methods  for  the  precipitation  of  zirconium 
from  solution,  and  should  be  removed  be- 
fore such  precipitation  is  attempted. 
Leaching  of  freshly  precipitated  or  ignited 
oxides  by  acid  solutions,  including  oxalic 
and  sulphurous  acids"  is  not  successful.'* 
Smith"  claims  to  have  effected  complett^ 
separation  of  iron  and  zirconium  by  electro- 
lytic methods,     using  a  mercury    cathode. 


"  Jewett :  "Bibliography  of  Zirconium." 
1893;  Dennis  and  Spencer:  Jour.  Am. 
Chcm.  Soc.  1896,  XVI 11..  674;  Ahcgg : 
Handbuch,  1913,  IV.,  490;  Schiotz  :  Chem. 
Abstracts,  1918,  XII..  661;  Travers  :  Chim. 
Ind.,  1919,  II.,  385;  LundeJJ  and  Knowles : 
Jour.  Am.  Chcm.  Soc,  1920,  XLII..  1439; 
Bayer;  Berlin;  John$1ovc :  Powell  and 
Schoeller :   loc.  cit. 

'•''  Dubois  and  Silvcirn  :  Ann.  Chim. 
Phifs.,  1820(1)  XIV..  110;  Bcrthier:  Ibid., 
1832,  (2)L.,  302;  Wundcr  and  Jeannerei: 
Zfit.  analyt.  Chem.,  1911,  L.,  738. 

'*  Berlin;  Hermann:   lor.  rit. 

"  Smith:   "  Electro-Anahjsia,"  1911. 


and  Price"  records  the  foruiatiou  of  soluble 
pcrzirkonates  by  methods  which  would 
leave  the  iron  insoluble.  Neither  of  these 
results  could  be  duplicated  during  this  in- 
vestigation. 

Only  two  really  successful  methods  have 
been  devised  for  the  separation  of  iron  from 
solutions  containing  zirconium.  These  are 
based,  respectively,  upon  selective  solubil- 
ity of  ferric  chloride  in  ether,"  and  the 
fact  that  iron  is  and  zirconium  is  not  pre- 
cipitated by  hydrogen  sulphide  from  am- 
moniacal  solutions  containing  tartaric 
acid."  The  ether  separation  method  is  the 
better  of  the  two  for  the  removal  of  large 
amounts  of  iron  such  as  are  encountered  m 
the  analysis  of  zirconium  steels  or  ferro- 
zirconium.  The  preciipitation  method  is 
not  as  satisfactory  for  the  removal  of  large 
amounts  of  iron,  owing  to  the  difficulties 
encountered  in  handling  largo  volumes  of 
precipitated  ferrous  sulphide.  It  is  indis- 
pensable, however,  for  the  removal  of  the 
traces  of  iron  which  almost  invariably  sur- 
vive the  ether  separation,  and  is  adaptable 
for  the  analysis  of  zircMiium  ores  in  which 
the  iron  oxide  content  does  not  greatly  ex- 
ceed five  per  cent. 

A  few  attempts  to  precipitate  zirconium 
and  titanium  separately  are  recorded  in  the 
literature,"  but  the  success  of  some  of 
these  attempts  has  been  questioned.'"  For 
analytical  puri)oses  the  separation  of  zir- 
conium from  titanium  is  unnecessary,  as 
titanium  is  readily  determined  by  Weller's" 
colorimetric  method  using  hydrogen  per- 
oxide. The  pres4'nce  of  zirconium  does  not 
interfere  with  this  determination. 

A  variety  of  methods  have  been  proposed 
for  the  simultaneous  precipitation  of  zir- 
conium    and     titanium.         Dittrich       and 


"  Price:  "  Per- Acids  and  Their  Salts," 
1912. 

"  Noycs,  Bray  and  Spear:  Jour.  Am. 
Chem.  Soc,  1908,  XXX.,  481. 

"  Wedekind :  loc.  cit. 

"  Bailey:  Jour.  Chem.  Soc,  1886, 
XLIX..  149;  Crookes:  "  Select  Methods  in 
Chemical  Analysis,"  1894;  Dittrich  and 
Freund  :  loc.  cit. ;  Brotvning,  Simpson  and 
Porter:  Am.  Jour.  Science,  1916,  XLII., 
106;  Hcadden:  Chem.  Abstracts,  1917, 
XL,  2311. 

'"M'ltthcws:  Jour.  Am.  Chem.  Soc, 
180M,  XX..  815;  Weiss  and  Lehmann:  loc 
cit. 

="  Weller:  Ber.  deutsch-  chcm.  Ocs., 
1882,  XV.,  2599. 


^6 


THE    CHEMICAL    NEWS. 


JANUARY  12,  1923. 


Freund^^  claim  that  sodium  acetate  will 
produce  complete  precipitation  of  zir- 
conium and  titanium.  The  use  of  sulphur- 
ous acid  or  its  derivatives  has  been  pro- 
posed,^^  but  Johnstone^"*  says  that  this  re- 
agent also  precipitates  some  of  the  rare 
earths  as  well  as  traces  of  iron  and  alu- 
minum, and  Hermann-^  reports  that  the 
separation  resulting  from  the  use  of  sulphur 
dioxide  is  not  satisfactory.  A  number  of 
these  separations  were  attempted  during 
the  present  investigation  with  complete 
lack  of  success.  The  manipulation  is 
tedious,  precipitation  seldom  is  complete, 
and  the  precipitate  usually  is  badly  con- 
taminated. Precipitation  of  zirconium  and 
titanium  by  weak  organic  bases  has  been 
reopmmended,^^  and  a  number  of  these  pre- 
cipitations were  attempted,  using  phenyl- 
hydrazine  as  the  most  promising  member 
of  this  class.  The  experiments  uniformly 
were  unsuccessful,  the  precipitation  was 
slow  and  incomplete,  and  the  precipitate 
usually  was  contaminated.  Variations  of 
Hillebrand's  method  for  the  precipitation 
of  zirconium  phosphate-^  have  been  recom- 
mended. Lundell  and  Knowles^*  discuss 
the  method  in  detail,  and  point  out  that 
the  variations  in  composition  of  the  preci- 
pitate prevent  the  use  of  the  method  ex- 
cept for  very  small  amounts  of  zirconium. 


22  Dittrich  and  Freund :  loc.  cit. 

23  Berthier:  Ann.  Chim.  Phys.,  1832, 
(2)  L.,  362;  1843,  (3)  VII.,  84;  Chancel: 
Jour.  praU.  Chem.,  1858,  LXXIV.,  471; 
Imray:  Jour.  Soc.  Cheiyi.  lud.,  1890,  IX., 
941;  Trautmann:  Zeit.  angew.  Chem., 
1911,  XXIV.,  62;  BaskerviUc;  Dittrich  and 
Freund;  Weiss  and  Lehmann;  Trayers; 
Granger;  Powell  and  Schoeller  :   loc.  cit. 

24  Johnstone  :  loc.  cit. 
2^  Hermann  :  Ihid. 

2«  Hess  and  Campbell:  Jour.  Am.  Chem. 
Soc,  1899,  XXI.,  776;  Jefferson:  Ihid., 
1902,  XXIV.,  540;  Allen:  Ibid.,  1903, 
XXV.,  421;  Hartivell:  Ihid.,  1903,  XXV., 
1128. 

27  HiUehrand:  U.S.  Geol.  Survey,  Bull. 
No  CXLVIII.;  Biltz  and  Mecklenburg: 
Zeit.  angew.  Chem.,  1912,  XXV.,  2110; 
Ferguson:  Eng.  Min.  Jour.,  1918,  CVl., 
356",  793;  Steiger:  Jour.  Wash.  Acad.  Sci., 
1918  VIII.,  637;  Nicolardot  and  Reglade  : 
Comptes  rendus,  1919,  CLXVIII.,  348; 
Browning,  Simpson  and  Porter :  loc  cit.; 
Schiotz  :  loc  cit. 

28  Lundell  and  Knoivles:  Jour.  Am. 
Chem.  Soc,  1919,  XLI.,  1801. 


The  most  satisfactory  method  for  the  ana- 
lytical detex-mination  of  zirconium  and  ti- 
tanium was  foiuid  to  be  precipitation  by 
cupferron,  the  ammonium  salt  of  nitroso- 
phenylhydroxylamine.  The  use  of  this  re- 
agent has  been  proposed  by  several 
authors, 2^  and  has  been  recommended  re- 
cently by  Lundell  and  Knowles,^**  who  dis- 
cuss the  method  in  detail,  including  a  list 
of  the  elements  which  interfere  with  the 
precipitation  and  a  discussion  of  the  pre- 
cautions which  must  be  observed. 

The  filtrate  from  the  cupferron  precipi- 
tation contains  the  aluminum,  rare  earths, 
and  traces  of  other  elements.  The  scheme 
of  separation  for  the  elements  in  this  fil- 
trate depends  upon  the  nature  and  number 
of  elements  present,  as  determined  in  the 
preliminary  qualitative  examination. 

From  the  foregoing  data  a  complete 
scheme  of  analysis,  adaptable  to  low-phos- 
phorus baddeleyite  ore,  was  evolved.  In 
view  of  the  time  and  labour  required  for  a 
comiplete  analysis,  a  modified  scheme  was 
adopted  for  the  numerous  analyses  which 
attended  the  progress  of  this  investigation. 
This  modified  scheme  allows  only  the  de- 
termination of  silicon,  iron,  titanium,  and 
zirconium,  as  follows: 
Modified  Scheme  for  Routine  Analysis. 

The  sample  is  ground  to  80-100  mesh. 
0.5  gram  of  the  sample  si  weighed  out  and 
fused^^  in  platinum  with  5  grams  of  borax 
until  a  clear,  fused  mass  results.  When 
fusion  is  complete  (usually  requiring  about 
one-half  hour  at  the  full  heat  of  a  Meker 
burner)  the  crucible  is  removed  from  the 
flame.  While  solidification  of  the  melt  is 
taking  place,  the  crucible  is  kept  in  motion 
so  that  when  cold  the  fusion  is  distributed 
around  the  sides  of  the  crucible.  The 
cooled  melt  is  dissolved  in  5  per  cent,  hy- 
drochloric acid  in  a  porcelain  casserole, 
solution  being  hastened  by  gentle  warming. 
When  solution  is  complete,  the  crucible  is 
removed  and  rinsed  out,  10-15  cc.  concen- 


2»  Ferrari:  Chem.  Abstracts,  1915,  IX., 
1019;  Thornton  and  Hayden:  Am.  Jour. 
Sci.,  1914,  XXXVIIL,  137;  Thornton: 
Ibid.,  1916,  XLIL,  151;  Broicn:  Jour.  Am.. 
Chem..  Soc,  1917,  XXXIX.,  2358. 

^°  Lundell  and  Knowles :  Jour.  Ind. 
Eng.  Chem.,  1920,  XII.,  344. 

^^  The  usual  practice  is  to  dehydrate  the 
borax  in  the  crucible,  add  the  weighed 
sample,  and  proceed  xvith  the  fusion.  Car- 
bide samples  should  be  ignited  to  the 
oxides  before  attempting  the  fusion. 


JANUAKY  12,  1923. 


THE   CHEMICAL   NEWS. 


27 


trated  sulphuric  acid  are  added,  and  the 
solution  is  evaporated  on  a  hot  plate  until 
fumes  of  sulphur  trioxide  appear.  The 
final  fuming  is  done  over  a  free  flame, 
agitating  the  solution  to  prevent  spattering. 
The  residue  is  cooled,  dissolved  by  diluting 
with  water,  and  filtered.  The  precipitate 
on  the  filter  is  washed  with  hot  water, 
ignited,  weighed,  treated  with  hydrofluoric 
and  sulphuric  acids,  again  ignited  and 
weighed,  and  the  loss  of  silica  determined. 
A  slight  residue,  mainly  iron,  is  recovered 
by  fusion  with  pyrosulphate  and  added  to 
the  original  filtrate. 

The  filtrate  from  the  removal  of  silica  is 
diluted  to  about  500  cc,  precipitated  with 
ammonia,  and  boiled  to  coagulate  the  ipre- 
cipitate.  After  settling,  the  supernatant 
liquid  is  decanted  as  completely  as  possible 
to  remove  the  bulk  of  the  alkalis  and 
boron.  The  ammcmia  precipitate  is  redis- 
solved  by  adding  6-10  cc.  of  concentrated 
sulphuric  acid.  One  gram  of  tartaric  acid 
is  added,  and  the  solution  is  made  dis- 
tinctly ammoniacal.  The  volume  of  the 
solution  at  this  point  should  be  150-200  cc. 
The  solution  is  treated  with  hvdrogen  sul- 
phide for  twenty  minutes,  boiled  for  8-4 
minutes,  allowed  to  cool,  and  filtered.  The 
precipitate  is  covered  and  allowed  to  drain 
thoroughly,  but  is  not  washed,  owing  to 
the  decided  tendency  of  the  ferrous  sul- 
phide to  pass  through  the  filter  when  any 
washing  solution  is  used.  The  filtrnt«'  is 
subjected  to  a  second  precipitation  with 
hydrogen  sulphide,  and  is  again  boiled  and 
filtered.  The  two  precipitates  of  ferrous 
sulphide  are  ri'dissolved  in  dilute  aqua  regia 
and  the  iron  is  determined  gravimetrically. 
The  presence  of  hydrochloric  acid  and 
small  amounts  of  organic  matter  (fiom  'he 
tartaric  acid)  precludes  the  determinati«Mi 
of  iron  by  volumetric  methods. 

The  filtrati'  from  the  removal  of  ferrous 
sulphide,  boiled  to  remove  most  of  the  hy- 
drogen sulphide,  is  made  acid  with  a 
known  excess  of  sulphuric  acid,  boiled 
again,  and  the  precipitnU'd  sulphur  filtered 
off  and  discarded.  Th(>  filtrate  is  cooled, 
diluted  to  600  cc.  containing  7.5-10  per 
cent,  free  sulphuric  acid,  chilled  in  ice 
water,  and  precipitated  by  the  addition  of 
a  cold  6  per  cent,  aqueous  sohition  of  cup- 
ferron.  During  this  precipitation  the  tem- 
perature must  not  exceed  15°  C.  The  pre- 
cipitate is  allowed  to  stand  one-half  hour, 
and  is  then  filt<^red,  usiufj  pentle  suction 
and  washing  with  cold  5  per  cent,  hydro- 
chloric acid.  The  filtrate  and  washings  are 
discarded.     The  precipitate    is  ignited   and 


weighed  as  ZrO^  +  TiO^.'^^  The  weighed 
precijpitate  is  fused  with  pyrosulphate,  dis- 
solved in  5  per  cent,  sulphuric  acid,  and 
the  titanium  determined  colorimetrically. 

On  account  of  the  variable  amounts  cf 
carbon  in  the  different  samples,  the  analy- 
tical results  were  computed  to  a  metallic 
basis,  and  the  ratio  of  the  elements  deter- 
mined on  the  basis  of  100  parts  §f  metallic 
zirconium.  For  the  comparison  of  the 
various  electric  furnace  products  a  study  of 
this  ratio  is  more  easily  understood  than  a 
study  of  the  percentage  comiposition  of  the 
samples. 

Experimental. 

The  zirconium  ore  employed  in  this  in- 
vestigation was  a  finely  ground  zirkite,  65 
per  cent,  of  which  passed  through  a  100- 
racsh  sieve.  Duplicate  analyses  of  ignited 
samples  of  the  ore  gave  the  following  com- 
position ;  Per  Per 

cent.        cent. 

ZrO,        72.55      72.78 

SiO,        17.34      17.26 

Fe,0,        4.11         4.14 

TiO,        0.80        0.81 

A1,0,        5.28        5.91 

Rare       Earths       (cerium 

group)        1.04         1.13 

P,0,        0.49        0.45 

MnO,        0.25        0.27 

MgO       trace      trace 

Total       101.86     102.75" 

Loss  on   ignition   ...         2.88        2.88 
Ratio,     on  a  metallic  basis,     of  the  ele- 
ments present  in  the  ore : 

100  Zr :  15.1  Si :  5.37  Fe :  0.89  Ti 

"  .Any  iron  tvHich  escapes  the  precipita- 
tion icith  hydrogen  sulphide  will  appear  in 
this  precipitate.  Experience  has  shown, 
however,  that  the  amount  of  iron  which 
survives  a  double  precipitation  uAth  hydro- 
gen sulphide  ix  so  small  that  it  may  be  dis- 
regarded for  all  except  the  most  exact  de- 
terminationn.  The  coUiur  of  this  ignited 
precipitate  in  a  reliable  indicator  of  the 
composition.  .4  pure  white  colour  indicates 
that  zirconium  alone  is  present.  Titanium 
produces  a  yellow  colour,  and  a  reddish  or 
brownish  tinge  indicates  the  presence  of 
iron. 

"  The  error  in  the  analyses  probably  is 
due  to  adsorption  of  alhalis  by  the  cup- 
ferron  precipitate;  but  may  be  due  in  part 
to  the  existence  in  the  ore  of  elements,  e.g., 
iron  and  manganese,  in  different  states  of 
oxidation  than  the  ones  represented  in  the 
above  table.  The  composition  of  the  sili- 
cates of  zircotiiuni,  which  occur  in  zirkite 
ore.  has  not  been  determined  definitely. 


28 


THE   CHEMICAL   NEWS. 


JANUAia'  12.   1928 


Owing  to  the  time  and  labour  consumed 
by  the  ° necessary  analytical  work,  it  was 
decided  to  limit  this  investigation  to_  the 
three  impurities,  siHcon,  iron  and  titanium. 
Since  silicon  is  present  in  far  larger 
amounts  than  any  other  impurity,  this  m- 
vestigation  was  directed  primarily  towards 
the  elimination  of  silicon.  The  removal  ot 
iron  is  a  secondary  object  of  the  investiga- 

Two  possibiUties  were  considered  for  the 
removal  of  silicon  and  iron  in  the  electric 
furnace:  , 

(1)  Eeduction  of  the  oxides  to  the  metals 
in  the  presence  of  an  excess  of  iron,  form- 
ing ferro-silicon  which  could  be  removed 
subsequently  by  mechanical  means. 

(2)  Reduction  of  the  oxides  to  the  metals 
or  carbides  with  subsequent  volatilisation 
resulting  from  the  application  of  higher 
temperatures. 

The  first  method  was  tried  out  in  a  small 
crucible   furnace   heated   by     a  direct     arc. 
Iron  oxide  was  added  to  the  charge  m  an 
amount    sufficient  to  unite  with  all  of  the 
silicon  to  form  ferro-silicon   containing    oU 
ner  cent    iron.       Several  runs  were  made, 
but  no  evidence  of  the  formation  of  ferro- 
"i^icon  was   obtamed.  .    ^f /.^f  ^y  „^^f  ^*„'f 
iron   and   silicon   remained   distributed  un 
formly  throughout  the  charge,  probably  on 
Sc^unt  of  the    high  viscosity  of  the  melt 
whTh  prevented  the  desired  formation  and 
coalescence     of     ferro-sihcon.        I^J^^^Jf^- 
the  ten^perature   would  increase   the   fluid 
ifcy  of  the  melt,     and    a    point    might    be 
reached   at  which    the   ferro-sihcon    wou.d 
coalesce   and  settle  out.        The  indications 
are    however,   that  the   desired    degree     of 
fluidity   would    not  be  reached  below    the 
tempe^rature     at     which     -^-^     become 
volatile.     If  it  is  necessary  to  employ  tern 
npratures  high    enough   to   cause    at   least 
Sar^iri   volatilisation   of   the   impurities,    it 
^tid  seem  advisable  to  rely  wholly^;? on 
volatilisation    to    remove     the     i^^Fi^^^^^^- 
The  latter  method  also    would  avoid    con- 
toinating  the  ore  by  tlje  a^ditioW  iron^ 
which     is     necessary     if     the     terrosiiicon 
rcheme   is  followed.      Accordingly,,  the   at- 
tempt to  eliminate  silicon     a^d   iron      a 
ferro-silicon,   were   abandoned  m  tavour   oi 
Ittopts     to     volatilise       the     impurities 

"^'preifminary  experiments  conducted  in  a 
J^Z  furnace  indicated  that  -rconium 
Side  is  stable  at  temperatures  above  the 
drcompoeition  point  of  silicon  carbide  (car- 


borundum).^*  This  led  to  the  belief  that 
conversion  of  the  entire  ore  to  carbides, 
followed  by  the  exposure  of  the  mixed  car- 
bides to  temperatures  above  2,220°  C,  at 
which  temperature  silicon  carbide  deconi' 
poses,  would  eliminate  silicon  and  perhaps 
some  or  all  of  the  iron  and  other  impuri- 
ties. If  this  elimination  of  impurities  were 
successful,  it  would  then  be  possible  to 
inite  the  zirconium  carbide  to  the  oxide, 
thus  producing  pure  and  highly  refractory 
zirconia. 

The  first  experiments  were  carried  out  in 
a  fumac^  of  the  silicon  carbide  type,  sufH- 
cient   carbon   being   added     to   ensure    the 
transformation     of   all   the    oxides     present 
into  carbides.        Later    experiments     were 
performed   in   an   arc  furnace,    the   amo'int 
of  carbon  being  varied  rom  run  to  run. 
Experiments  with  a  Resistance  Furnace. 
The  resistance  furnace  was  built    in  the 
form  of  a  rectangular  trough  7  inches  wide 
at  the  bottom,  8  inches  wide  at  the  top,  9 
inches  deep,  and  29  inches  long.     The  floor 
was   built  of  zirkite   brick   supported   by   a 
double  layer  of  fire  brick.     The  sides  were 
ibuilt   of  fist-size  lumps   of  zirkite,     backed 
with  the  fire  brick  and  faced  smooth  with 
ground  zirkite  bonded    with  a  little  water- 
glass.     The  sides  and  floor  were  permanent. 
The    end    walls    were    faced    with    zirkite 
brick,     which    were    backed    up    with  fire 
brick,  and  were  torn  out  after  each  run    to 
facilitate  removal  of  the  charge.     The  elec- 
trodes were  pieces  of  4-inch  square  carbon 
electrodes,      which     entered      through     the 
centre  of  the  end  walls  and  protruded  four 
inches  into  the  furnace.     The  outer  ends  of 
the  electrodes  were  water-cooled   and   con- 
nected to  bus  bars  by  flexible  leads.  Power 
was     supplied    by    a     75    kilowatt     motor- 
generator  set.     Two  thousand  amperes  was 
the  largest  current  available,     representing 
the      maximum    output      of      the      motor- 
generator  set. 

The  complete  conversion  of  100  parts  of 
ore  to  the  various  carbides  and  carbon  mon- 
oixde  requires  aip proximately  33  parts  of 
carbon.  To  ensure  the  presence  of  an  ex- 
cess of  carbon,  a  ratio  of  45  parts  of  carbon 
to  100  parts  of  ore  was  used.  Petroleum 
coke,  10-20  mesh  in  fineness,  supplied  the 
carbon  for  most  of  the  runs,  although  in 
one  or  two  cases  granular  electrode  carbon 
was  tried. 

Four  runs  were  made    in  the  resistance 


3'   Gillett:     Jour.     Phys.     C^iern.,     1911, 
XV.,  213. 


JANUARY  12,  1923. 


THE   CHEMICAL   NEWS. 


29 


furnace.  Since  the  runs  were  all  more  or 
less  alike,  the  first  one  only  will  be  de- 
scribcfl  in  detail, 'as  f(;llows: 

liUN    1. 

Ratio  of  ore  to  carbon  in 

charge        100  :  45 

Total  weight  of  charge   ...       86.5  pounds 

Core       A   double     line 

of  graphite  eIectro<Je  pieces ,  one  inch  in 
diameter  ,the  junclionfi  packed  in  petro- 
leum coke  to  ensure  contact 

Duration  of  run   1  hour,  52  min. 

Power    consumption    60K.W.H. 

The  charge  was  -  packed  loosely  in  the 
furnace  up  to  the  levtl  of  the  electrodes. 
The  core  was  inserted  and  the  remaining 
charge  added,  filhng  the  furnace.  At  first 
it  required  a  potential  of  46  volts  to  pro- 
duce a  ourrent  of  400  amperes  through  the 
furnace.  Small  gas  volcanoes  appeared 
almost  at  once,  followed  by  flames,  bright 
yellow  at  the  base,  with  reddish  yellow 
tips.  The  power  input  wa«  maintained  as 
high  as  possible,  being  limited  by  the  vio- 
lence of  the  gas  evolution  which  resulted  in 
loss  of  charge  when  the  power  input  be- 
came too  high.  After  the  first  violent  evo- 
lution of  gas  subsided,  the  charge  pre- 
sented the  appearand'  of  gentle  boiling. 
After  half  an  hour,  when  the  total  power 
input  had  reached  15  K.W.H.,  one  end  of 
the  charge  ceased  boiling  and  settled  to 
form  a  crust.  This  efi«ct  spread  gradually 
until  the  entire  charge  was  crusted  over 
and  quiet.  Heating  w  as  continued  about 
half    an  hour    more.      The    entire    charge 


finally  became  bright  red  in  colour,  but 
the  temperature  could  not  be  raised  fur- 
ther. At  first  the  cun-cnt  was  carried  al- 
most entirely  by  the  core;  but  the  charge 
itsel  soon  began  to  conduct  with  the  re- 
sult that  the  current  rose  and  the  voltage 
fel  loff  rapidly,  until  at  the  end  of  the  run 
the  current  reached  1,750  tunperes  and  the 
voltage  dropped  to  5.  These  results  made 
it  evident  that  the  conductivity  of  the  core 
and  heated  charge  was  too  great  to  allow 
the  input  of  power  at  a  rate  sufficient  to 
prtKluoe  the  very  high  temperature  desired. 

When  the  cooled  charge  was  examined,  a 
greyish  black  granular  core  about  4  inches 
in  diameter  was  found  in  the  centre,  ex- 
tending thi'  length  of  the  charge  between 
the  electrodes.  Small  deposits  of  spongy 
material,  metallic  in  appearance  and  rather 
bluish  in  colour,  which  subsequent  exami- 
nation proved  to  be  zirconium  carbide, 
were  found  in  close  proximity  to  the  origi- 
nal core.  The  total  weight  of  "sponge" 
was  about  six  pounds.  The  remaining  con- 
tents of  the  furnace  consisted  of  unchanged 
charge.  The  original  graphite  core  was  not 
attiicked,  indicating  the  presence  of  an 
adequate  supply  of  carbon  in  the  charge. 
Some  slight  indications  of  the  volatilisa- 
tion of  silica  were  found  on  the  furnace 
walls,  but  thi-  power  input  evidently  was 
too  low. 

The  three  subsequent  runs  were  made  in 
an  attempt  to  increase  the  power  input, 
but  without  marked  success.  The  results 
of  the    four  runs    may  be  summarised    as 


Table  I 

louows: 

Carbide 

Metal  in 

S,p( 

jnge  when  Zr  =   100 

K.W.H. 

Av.  Kw. 

"sponge"    pounds 

Si 

Fe                         Ti 

60 

32 

6.0 

3.7 

4.48                    0.79 

75 

34 

6.5 

11.0 

5.50                    0.78 

100 

38 

10.0 

12.2 

7.60                    0.79 

80 

40 

7.5 

5.5 

2.60                    0.87 

Original  Ore 

15.1 

5.87                    0.89 

The  iK^haviour  of  the  carbide  "sponge" 
on  analysis  showed  tliiit  most  of  the  silicon 
was  present  as  the  carbide,  thus  indicating 
that  in  general  the  temperature  of  the  mass 
was  not  high  enough  to  ensure  the  removal 
of  the  silicon  by  volatilisation.  As  the 
data  indicate,  the  removal  of  silicon  varied 
in  a  very  irregular  manner,  being  fairly 
complete  in  some  cases  but  very  incom- 
plete in  others.  Other  samples  from  por- 
tions of  the  charge    farther  removed    from 


the  core  showed  higher  ratios  of  silicon  to 
zirconium.  This  follows  naturally,  since 
volatilisation  of  silicon  would  occur  first  in 
the  hottest  portion  of  the  charge  »  e 
around  the  core,  and  would  be  less  evident 
m  regions  at  a  greater  distance  from  the 
source  of  heat. 

The  data  indicate  little  or  no  elimination 
of  titanium  or  of  iron,  except  in  the  fourth 
run     where    eonsidernble     iron    was   annar 
ently   removed.       In     this    run.     however, 


30 


THE  CHEMICAL  NEWS. 


JANUARY  12,  1923. 


about  9  pounds  of  common  salt  was  added 
to  the  charge  resulting  in  the  elimmation 
of  approximately  half  the  iron,  presumab  y 
through  the  formation  of  the  x'^latile 
chloride.  All  things  considered,  the  re- 
sults obtained  with  the  resistance  turnace 
were  unsatisfactory,  and  this  type  of  fur- 
nace was  abandoned  in  favour  of  one  ot 
the  arc  type. 

Experiments  with  an  Arc  I^urnace. 
The  furnace  shell  of  the  arc  furnace  con- 
sisted of  an  iron  pot,  lined  with  fist-sized 
pieces  of  zirkite  ore.     The  lining  was  faced 
smooth  with  ground  zirkite  bonded  with    a 
little  water  glass,   and  contained  the  same 
ratio  of  carbon  to  zirkite  as  the  charge  pro- 
per       The    resulting    hearth     was     cone- 
shaped,  8  inches  in  diameter  at  the  top     4 
inches  in  diameter  at  the  bottom,  and  8-10 
inches  deep.       This    lining  was    torn   out 
after  each  run  to  facilitate  removal  of  the 
charge        The   lower,    horizontal   electrode, 
composed  of  two    2-inch    square     gfaphite 
electrodes,  formed  the  floor  of  the  hearth 
entering  through  a  rectangular  opening  m 
tSe  side  of  thi  cast  iron  pot.       The  upper 
electrode  was  a  4-inch  square  carbon  elec^ 
trode,  suspended  in  a  vertical  Vo^}^^^^^^^ 
counter-weighted      to     allow      adjustment. 
Both  electrodes    were    clamped    m    water- 
cooled  electrode  holders  and  connected    to 
huB  bars  by  means  of  flexible  cables 

The  first  run  performed  in  this  furnace 
will  be  described  in  detail,  as  bemg  typical 
of  all  the  runs  carried  out  subsequently^ 


m 


EuN  5. 
Ratio    of     ore    to    carbon 

charge        ]^  ^  ^5 

Total  weight   of  charge    11  pounds 

Time   of  run   ....; !LTwH 

Power   consumption    ci^.o  iv.  w  .xi. 

The  run  was  started  by  striking  an  arc 
between  the  bare  electrodes.  The  walls  ot 
the  cone  immediately  began  to  slag  down 
so  that  the  first  addition  of  charge  was 
made  as  soon  as  possible  after  starting  the 
arc  The  charge  was  fed  in  slowly  and 
was  observed  to  solidify  when  it  reached 
the  zone  of  the  arc.  Durmg  the  early 
staoes  of  the  run  the  arc  was  smothered  by 
the°  charge,  but  after  all  the  charge  had 
been  added  the  arc  was  run  open,  and  re- 
mained fairly  quiet.  The  current  was 
maintained  at  about  1,000  amperes  until 
the  evolution  of  fumes  had  almc^t  ceased, 
when  the  arc  became  noisy  and  hard  to 
maintain.  The  run  was  stopped  when  this 
point  was  reached.  . 

The  top  of  the  charge  oxidised  during 
cooling,  forming  a  layer  of  fine  white 
oxides  below  which  lay  a  brittle,  black 
mass  weighing  approximately  3.5  pounds 
A  sample  for  analysis  was  taken  from  the 
centre  of  this  cake,  and  gave  the  following 

'^%OZr:  4.85  Si:  6.38  Fe  :  0.70  Ti 

A  series  of  runs  was  made  m  which  the 
ratio  of  carbon  (petroleum  coke)  to  zirkite 
ore  was  varied  systematically.  -Liie  re- 
sults are  assemhled  in  the  following  tables. 


Table  II. 

Effect  of  Varying  Ratio  of  Ore  to  Carbon. 
Carbon 


Run 
5 

10 
'11 
19 
19 


Charge  Pounds     per  100  ore 

11.0  45 

121.5  25 

12.0  20 

15.4  15 

15.4  10 

16.8  5 


K.W.H. 
32.5 
18.25 
17.5 
21.5 
19.3 
27.0 


Yield  purified 
product  pounds 
3.5 
3.0 
3.1 
5.0 
7.0 
9.9 


Metal  Ratio  in  Product. 


Run 

Zr 

5 

100 

9 

100 

10 

100 

11 

100 

18 

100 

19 

100 

Ore 

100 

Si 

Fe 

Ti 

4.85 

6.38 

0.70 

3.03 

6.50 

0.64 

2.21 

5.00 

0.55 

0.88 

5.92 

0.70 

1.31 

8.73 

0.69 

1.86 

6.67 

0.73 

15.70 

5.37 

0.89 

Table  III. 
Elimination    of   Impurities. 

Percentage  en- 


Run     Carbon  per  100  ore 

5  45 

9  25 

10  20 

11  15 

18  10 

19  5 


mination 

of 

Si         Fe 

Ti 

68      —19 

21 

80      —21 

28 

85            7 

38 

94      —10 

21 

91      —62 

22 

88      —24 

IS 

JANUAKY  12,  1923. 


THE  CHEMICAL  NEWS. 


81 


The  data  obtained  with  the  arc  furnace 
sh  >w  a  maximum  in  the  removal  of  siHcon 
when  the  ratio  of  zirkit^  to  carbon  is 
103  :  15.  Calculations  based  on  the  silica 
content  of  the  ore  show  that  a  little  more 
than  10  parts  of  carbon  to  100  parts  of  ore 
is  just  enough  to  transform  all  of  the  silica 
into  carbide  (carborundum)  and  carbon 
monoxide.  We  have,  therefore,  come  to 
conclusion  that  the  best  high-temperature 
elimination  of  silicon  is  obtained  when 
little  more  than  enough  carbon  is  used  to 
form  carbide  with  the  silicon  oniy,  leaving 
the  zirconium  oxide  undecomposed. 

When  more  than  15  parts  of  carbon  are 
used  the  elimination  of  silicon  becomes 
steadily  less  complete.  Under  these  cir- 
cumstances it  is  known  that  zirc(  nium  car- 
bide is  actually  produced  in  the  arc.  The 
zirconium  carbide  theref<^>re  appears  to  re- 
tain some  of  the  silicon  and  the  suggestion 
is  offered  that  stable  double  carbides  of 
silicon  and  zirconium  may  be  pr(Kiuced  or 
that  the  two  carbides  form  solid  solutions 
or  mixed  crystals.  Runs  in  which  granu- 
lar electrode  carbon  wa«  substituted  for 
petroleum  coke  showed  that  better  results 
may  be  obtained  aa  a  small  scale  with  the 
more  finely  divided  coke. 

An  interesting  fact  brought  out  by  these 
experiments  is  the  high  melting  point  and 
stability,  in  a  reducing  atmosphere,  of  the 
carbide  of  zirconium.  As  long  as  there  was 
an  excess  of  carbon  present,  over  and 
above  the  amount  required  for  the  com- 
plete crmversion  of  the  oxides  to  carbides, 
it  was  imipossible  to  melt  the  product  even 
under  the  direct  action  of  a  40-50  kilowatt 
arc. 

(To  be  Cotifinued.) 


BACTERICIDAL  PROPERTIES  OF  THE 
PRODUCTS  OF  RADIUM  EMANATION. 

By  John  Albert  Marshall,  Collkoe  of 
Dentistry,  University  of  California. 

Communicated,   October  7,  1922.* 

The  following  abstract  deals  with  a  de- 
scription of  the  use  of  radium  .therapy  in 
periapical  infections,*  and  supplements  a 
preliminary  note*  in  which  it  was  pointed 
out  that  solutions  of  the  products  of  radium 
emanation  possess  distinct  bactericidal  pro- 
perties. Additional  data  have  been  com- 
piled, but  the  analysis  of  them  clearly  indi- 
cates that  with  the  present-day  knowledge 
it  is  impossible  to  state  definitely  and  con- 
clusively why  the  products  of    the  emana- 


tion produce  such  characteristic  effects. 

Although  it  was  reiported  in  1909'  that 
radium  exerts  an  inhibitory  influence  on 
pathogenic  and  non-pathogenic  organisms, 
no  further  work  was  done  in  this  field  until 
ten  years  later,  when  the  former  observa- 
tions were  confirmed.*  Bacteria  of  various 
types  were  exposed  to  radium  emanation 
with  the  result  that  a  distinct  inhibitory 
effect  upon  the  cultures  was  observed. 

In  this  present  experiment  a  solution  of 
the  products  of  radium  emanation  is  em- 
ployed. The  emanation  tubes  are  usually 
discarded  by  the  laboratories  after  they 
have  undergone  disintegration  in  respect  to 
their  content  of  gamma  ray.  However, 
they  still  contain  in  varying  proportions 
radium  A.  B,  C,  and  D.  The  effects  which 
have  been  obtained  are  presumably  not  due 
to  the  hard  gamma  ray,  but  result  in  all 
probability  from  the  action  of  the  softer 
beta  ray. 

The  ra<lioactive  solution  is  prepared  as 
follows:  a  "  de-emanated  "  emanation 
tube  is  placed  in  a  sterilised  mortar  of 
about  20  cc.  capacity,  covered  with  Ringer's 
solution  hand  then  crushed  with  a  pestle. 
On  account  of  the  ra,pidity  with  which  the 
radic«ctivity  of  this  solution  diminishes,  it 
is  advisable  to  crush  the  tubes  immediately 
l)efore  use.  This  solution  is  carried  directly 
to  the  infected  area  by  means  of  sterile 
dressings.  In  the  ca.se  of  chronic  or  acute 
apical  abscessis,  found  about  the  roots  of 
teeth,  the  radioactive  liquid  is  forced  into 
the  infected  an-a  through  the  pulp  canal  of 
the  tooth  and  allowed  to  remain  for  24 
hours.  Subse(juently  the  dressings  are  re- 
moved, the  canals  tested  for  sterility  and 
finally  filled.  With  two  possible  exceptions 
there  has  been  no  evidence,  after  three 
years  of  time,  of  succeeding  soreness  or 
pain.  The  individual  dosage  in  terms  of 
millicuries  of  gamma  radiation  has  varied 
from  0.046  to  0.138. 

Failures  in  this  method  of  treatment  have 
'been  recorded,  but  the  fact  remains  that 
sterile  tests  have  been  obtained  more  often 
by  using  the  radioactive  solution  than  in 
similar  experiments  with  other  antiseptic 
agents. 

Summaries  of  experimental  and  clinical 
data  are  present<^d  which  indicate  the  varia- 
tions in  the  pathology,  age  of  patient,  eti- 
ology, treatment,  clinical  n>sult  and  labora- 
tory findings. 

In  many  instances  tubes  have  been  used 
in  which  de-emanation  had  (proceeded  to 
such  a  degree  that  it  was  not  possible  to 
oibtain  a  reading  by  the  electroscope.  These 


32 


THE  CHEMICAL  NEWS. 


■TANUAIJY  12,  1923. 


have  given  similar  results  insofar  as  bac- 
tericidal action  is  concerned,  but  they  have 
not  caused  the  soreness  which  sometimes 
accompanies  the  use  of  solutions  containing 
a  recorded  amount  of  gamma  rays. 

In  general  the  cases  selected  have  been 
those  in  which  previous  treatments  were 
without  satisfactory  result.  Dichloramin  T, 
Tormocresol  beechwood  cresote,  phenol,  and 
other  antiseptics  of  a  similar  nature  had 
been  used  without  producing  a  noticeable 
change  in  condition.  In  fact,  the  greater 
majority  of  the  cases  carried  a  history  of 
unsuocess'ful  treatment.  Most  of  them 
yielded  to  the  action  -of  the  radioactive 
solution. 

The  precautionary  measures  which  are  to 
be  observed  are  naturally  those  referring  to 
dosage  and  technique  of  apiplication.  Severe 
radium  bums  resulted  in  monkeys  when 
emanation  tubes  containing  eighteen  milli- 
curies  were  sealed  into  pulp  canals  of  cen- 
tral incisors.  These  burns  were  so  extreme 
that  the  hard  palate  and  orbit  were  in- 
volved. It  is  believed  to  be  impracticable 
to  use  the  radium  except  as  a  solution  of 
the  solids.  The  tubes  should  'be  thoroughly 
crushed  under  Ringer's  solution  exactly  at 
the  moment  of  use,  and  it  has  been  custom- 
ary to  have  three  or  four  patients  prepared 
and  ready  at  one  time  in  order  to  secure 
the  greatest  economy  of  material.  The 
limited  availability  of  de-emanated  tubes 
exceipt  at  emanation  laboratories  is  a 
serious  drawback  to  an  extensive  applica- 
tion of  this  therapy.  However,  it  is 
planned,  if  funds  become  availahle,  to  fur- 
ther extend  these  researches  to  include  not 
only  additional  data  upon  dosage,  but  also 
to  report  upon  the  application  of  other 
radioactive  preparations  which  may  be 
found  to  be  more  plentifully  distributed. 


*  Proceedings  of  the  National  Academy 
of  Scknees  of  the  United  States  of  America, 
November  15,  1922. 

^  Marshall,  John  A.,  "  Badimn  in  Peria- 
pical Infections  "  (in  press). 

2  Marshall,  John  A.,  "  Bactericidal 
Action  of  Solutions  of  Radium  Em^anation," 
Calif.  State  Med.  J.,  Jan.,  1922. 

^  Iridell  and  Minett,  "Notes  of  the 
Effect  of  Radium  in  Relation  to  Some 
Pathogenic  and  Non-Pathogenic  Organ- 
isms," Lancet,  1909,  I.,  p.  1445. 

■*  Lequeux  and  Chrome,  "  Action  of 
Radium  on  Bacteria,"  Arch,  Memo.  Ohst. 
gynec,  Dec,  1919,  III.,  p.  698. 


This  list  is  specially  compiled  for  the  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade 
Marks,  and  Designs,  can  bo  obtained  gratuitously. 

Latest   Patent   Applications. 
34397 — Chemical    and    Metallurgical      Corporation, 
Ltd. — Continuoiis  process  for  conversion  of 
lead  chloride   into  sulphate,     and   recovery 
of  hydrochloric  acid.     Dec.   16. 
Abstract  Published  this   Week. 
Chromium    Compounds.— P&ient     No.  187636. — A 
Patent  has  l>een  granted  to  Messrs.  C.  K.  Potter, 
of  1.   St.   Georgo^s  Square,   St.   Annes-on-Sea,   and 
F.  Eobinson.  of  225,  Green  Lane,  Bolton,  both  in 
Lancashire,   for  a   process  for  the  preparation   of 
chromium    compounds,    such    as   chromium    oxide, 
chromium      sulphate,      acetate,      carbonate,      and 
chloride,     chrome   alum,     sodium   and   potassium 
chromates,  iron  sulphate. 

Chroraite  is  decomposed  by  treatment  with  sul- 
phuric acid  and  an  oxidizing  agent,  such  as 
chromic  acid,  at  a  teini)erature  above  150°  C, 
the  oxidizing  agent,  whether  added  directly  to, 
the  reaction-mixture  or  generated  in  situ  by 
electrolysis,  being  present  in  amount  insufficient 
to  oxidize  the  iron  completely.  The  chromite 
may  first  be  treated  with  carbonaceous  matter  or 
a  gaseous  reducing  agent  at  a  red  heat  and  part 
of  the  iron  then  extracted  with  dilute  acid. 
Under  the  conditions  sot  out  above,  the  chro- 
mium and  part  of  the  iron  are  converted  into  in- 
soluble sulphates,  from  which  the  chromium  is 
separated  by  adding  a  reducing  agent  to  the 
diluted  reaction-mixture  when  the  ferric  sulphate 
is  reduced,  leaving  a  residue  of  Insoluble  chro- 
mium sulphate.  This  compound  may  be  decom- 
posed by  boiling  in  aqueous  suspension  with 
caustic  alkalis  or  alkaline-earths,  alkali  sulphides 
or  carbonates,  alkaline-earth  carbonates  or  arn- 
monia  to  yield  chromium  hydroxide  and /or  basic 
carbonate;  it  may  be  heated  with  caustic  soda  or 
potash  in  prosonce  of  air  and  with  the  optional 
addition  of  otlier  oxidizing  agents  to  yield  sodium 
or  potassium  chromate;  or  it  may  be  boiled  with 
strong  barium-chloride  or  -acetate  solution  to 
yield  the  corresponding  chromium  salt  and 
barium  sulphate.  Alternatively  it  may  be  dis- 
solved in  dilute  sulphuric  acid  in  presence  _  of 
ferric  oxide,  and  a  small  amount  of  oxidizing 
agent,  and  the  solution,  after  reduction  _  of 
any  ferric  salt  formed,  treated  with  potassium 
sulnhate  for  the  production  of  chrome  alum.  In- 
stead of  first  separating  the  insoluble  chromium 
sulphate,  the  mixture  of  insoluble  chromium  and 
iron  sulphates  obtained  in  the  initial  decom- 
position may  >>e  treated  directly  for  the  produc- 
tion of  chromium  oxide.  In  one  process  the 
mixed  sulphates  are  washed  and  heated  with  ex- 
cess of  coal  in  a  reducing  atmosphere,  a  mixture 
of  iron  sulphide  and  chromium  oxide  being 
obtained.  In  another  process,  the  mixed  sul- 
phates are  boiled  with  a  slight  excess  of  alkali- 
siilphide  solution,  and  the  black  precipitate 
obtained  ignited  in  a  reducing  atmosphere  at  red 
heat.  In  a  third  process  the  mixed  sulphates  are 
calcined,  and  the  resulting  oxides  mixed  with 
coal  and  heated  in  a  reducing  atmosphere.  In 
each  case  the  product  is  treated  with  acids  to 
dissolve  the  iron,  and  the  residual  chromium 
oxide  may  be  dissolved  in  sulphuric  acid  in  pre- 
sence of  a  small  amount  of  oxidizing  agent  and 
used   for     the   preparation     of   other     chromium 

compounds.  .,,,,.  .   l   ■, 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  tiie  published  Specifications,  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


JANUABY  19,  1923. 


THE   CHEMICAL   NEWS. 


33 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3275. 


A   NEW    SYSTEM   FOR    THE   LINEAR 

REPRESENTATION  OF  THE 

STRUCTURE  OF  ALL  ORGANIC 

COMPOUNDS. 

By  T.  Sherlock  Wheelkr,  B.Sc, 
A.R.C.Sc.L,  A. I.e. 

The  system  given  below  was  iprimarily 
designed  to  enable  the  structure  of  all  ring 
compounds  to  be  rcpresontcd  linearly  by  a 
simple  arrangement  of  lettirs  and  figures, 
from  which,  with  the  aid  of  a  few  rules,  the 
graphical  formula  could  Ix^  easily  deduced. 
This  is  at  present  possible  with  the  less 
complicated  aliphatic  cf)Hipounds,  e.g., 
adiipic  acid  can  be  written  (COOH). 
CH3.CH2.CH,.CH,.(COOH);  the  ordinary 
line  of  type  need  not  be  disturbed  to  show 
its  structure.  But  it  is  far  otherwise  with 
ring  compounds,  and  it  was  a  linear  system 
for  these  compounds  which  might  save  the 
great  amount  of  space  that  is  now  perforce 
devoted  in  chemical  journals,  ond  dic- 
tionaries, to  printing  their  extended  graphi- 
cal formula,  that  the  author  first  sought. 
In  that  search  he  was  successful;  as  the 
system  developed,  however,  it  appeared  it 
could  be  used  equally  W{>11  to  represent  all 
organic  compounds,  and  from  the  represen- 
tations thus  obtained  for  any  type  of  com- 
pound, names  clearly  showing  the  consti- 
tution could  be  deduced. 

The  principle  of  the  systena  is  best  out- 
lined by  beginning  with  ring-compounds.  I 
is  the  graphic    formula  of    a  possible    aro- 


matic hydrocarbon.  To  represent  it,  the 
centres  of  the  rings  are  joined  as  shown, 
and  one  supposes  oneself  to  pass  along  the 
dotted  line  from  "  a."  All  rings  are  num- 
bered independently  and  clockwise,  the  first 
ring  is  numbered  from  any  carbon,  in  others 
the  numbering  begins  on  the  left  hand  of 
one  entering  the  ring  along  the  "  structure 
line."  Then  L  is  Ar.  VI.  2.  3  IV.  2,  3  VI,  4, 
5  VL  2,  3  IV.  Ar.  shows  the  system  to  be 
aromatic,  the  Roman  numerals  give  the 
number  of  elements  in  each  ring,  and  the 
carbons  common  to  any  ring  and  the  next 
are  shown,  left  hand  carbon  first,  aft^r  the 
former's  Roman  numeral,  by  their  numbers 
in  the  former.  Since  the  "structure  line" 
always  crosses  the  join  of  the  common  car- 
bons, the  compound  may  be  said  to  be  re- 
presented by  describing  the  course,  as  it 
were,  of  its  structure  line. 

AH  information  about  any  ring  is  given 
in  brackets  immediately  nftt^r  the  numeial 
representing  it.  Substituents  are  indica':ed 
by  the  number  of  the  substitute<l  carbon 
followed  by  the  chemical  symbol  of  the 
substituent;  should  any  of  the  carbons  be 
replaced  by  another  element,  the  symbol  of 
that  element  comes  before  the  number    of 


W 


its  position.  In  some  aromatic  compounds 
it  may  be  necessary  in  the  case  of  five  and 
other  odd-membered  rings  to  show  which  of 
the  carbons  is  saturated,  i.e.,  lack  the  cen- 
tric bond.  Thi.s  is  done  by  indicating  thnt 
this  particular  carbon  has  two  hydrog.^n 
atoms  attached  to  it.  IL  is  Ar.  VL  (1-NO,, 
4-NH,)  2,  3  V.  (4  =  H,)  2,  3  V.  (2  =  H,)  3, 
4  IV.  (N-2). 

When  branches  occur  in  the  structure 
line,  the  main  structure  line  is  given  first, 
and  then,  separated  by  semi-colons,  the 
various  branches  fshown  — •  — • — • — •), 
the  rings  from  which  these  latter  start  being 


34 


THE   CHEMICAL    NEWS. 


JANUAEY  19,   1923. 


f 

2' 

1 

'z 

^ 

M 

1 

v^ 

I  / 

L'' / 

\ 

rA 

fA 

/ 

/ 

->{ 

) 

vi 

['d 

\ 

/  /V/   VA  \ 

/  ii^ 

r 

X    2^ 

1 

\ 

i. 

a 

i 

; 

identified  by  indices.  III.  is  Ar.  VI.  3, 
4  VI.'  2,  3  VI."  2,  3  VI. ;  4',  5'  VI. ;  4",  5" 
VI.  In  the  main  structure  line  it  is  un- 
necessary to  attach  indices  to  those  num- 
bers which  refer  in  the  ordinary  way  to  the 
indexed  rings. 

Alicyclic  compounds  are  prefixed  by  the 
symbol  Al.  In  representing  compounds 
containing  both  types  of  rings  one  symbol 
holds  until  cancelled  by  the  other.  Double 
bonds  are  shown  in  the  usual  way — a  A 
followed  by  the  number  of  the  carbon  from 
which  the  bond  begins.  Doubly  linked 
substituents  are  joined  by  two  hyphens  to 
the  number  of  the  carbon  to  which  they  ere 
attached. 

Other  than  ortho-fused  ring  systems  must 
now  be  considered.  IV.  is  a  simple  ».x- 
ample  of  a  spiro  compound.    It  is  Al.  VI.  3 


CHi 


V.  The  structure  line  is  drawn  through  the 
spiro  carbon  and  the  numbering  of  the 
second  ring  is  clockwise  from  that  carbon. 
When    rings    are    linked    by    chains,     the 


structure  line  passes  along  the  chain.  The 
chain  is  indicated  by  the  number  of  ele- 
ments in  it,  but  the  Roman  numeral  for  a 
chain  has  a  bar  placed  over  it.  The  chain 
is  numbered  from  where  the  structure  line 
enters  it,  and  in  the  direction  in  which  that 
line  passes  along  it.  The  carbon  at  which 
the  hne  leaves  the  chain  is  indicated  as 
with  rings :  the  ring  to  which  the  chain 
leads  is  numbered  ckxjkwise  from  where  it 
is  entered.  Substituents  and  non-carbon 
elements  are  shown  as  above ;  the  carb  >ns 
common  to  chain  and  ring  are  numbered 
twice  as  before.  The  effect  of  the  symbols 
Ar.  and  Al.  is  taken  to  persist  on  the  far 
iside  of  a  chain.  Branches  in  the  chaia 
which  do  not  lead  to  rings  are  numbered 
and  shown  on  the  same  plan ;  the  structure 
line  system  is  used  for  then)  as  for  those 
that  are  attached  to  rings.  V.  is  Al.  III.  2 
IV.'  4  IV. ;  2'  III.  3  V. ;  3'  III.  (3 -Br.) 

The  system  can  now  be  applied  to  any 
open  chain  compound.  VI.  is  IX.'  5  IV. ; 
4'  III.  (3-Cl.J  The  main  structure  line 
passes  along  the  principle  chain,  then  alo.ig 


3  |iC  Hj^  6a> 


3z: 

the  longest  branch,  and  so  on,  being 
drawn    to  be  as  long    as    possible, 
branches  are  given  in 


alwavs 
Other 


JANUARY  19,  1923. 


THE   CHEMICAL   NEWS. 


35 


8 


9 


CH,.GH,.GHj.     CH  .        CH  .  CH,.CH,.CH,.CH, 
(4^)2      CH,  CH,      2  '  (5») 

(4^)3        CH;C1        CH..    3     (5^) 
CH,    4     (6») 


Main  Structure  line 
Branch     — . — . — , — 


VI. 

tho  order  of  their  iniiportance.  Neglect  of 
this  rule,  however,  does  not  cause  am- 
biguity. The  Genevan  synt^im  of  "  index 
numbering  "  for  fc«-anches  could  be  applied 
here.  Its  numbering  of -the  chains  is  shown 
in  brackets  in  VI.  Using  it,  VI.  would  be 
TT.  (4-Et.  6-  Pr,  4»-Cl).  But  it  is  not 
applicable  to  ring  compounds,  and  so  for 
the  sake  of  uniformity  the  structure  line 
system  is  best  applied  right  through.  Also 
the  Genevan  system  leads  to  confusion  with 
complicated  aliphatic  coi^pounds.  (See 
Richtcr,  B.,  XXIX.  (1896).  rm). 

The  following  further  examples  will  make 
the  new    system    clear    ff>r  aliphatic   com- 
pounds.      VII.    is    TY.  (0-3,  N-7,  6 -CI 
9  =  0,  9-OH,  A') 

12        3    4        5        6 
CH,.GH,.0.CH,.CHC1.CH, 
VII. 


7      8        9 
N:  CH.COOH. 


VIII.  \rY.  (S 


8.3  =  0) 
O 


CH,.CH,  .S.CH,.CH,. 
VIII. 

TX.  jc;  T^.  (    A  ».  ')  5  (VT) 


IX. 

It  is  to  be  noted  that  the  carbon  at  which 
a  double  bond  terminates  need  never  be 
shown,  owing  to  the  exact  indication  of  the 
chain  or  ring  to  which  it  belongs. 


CH,  aCH 


HjC      *CH 


CHj.CHj.CHj.CHj 


2       8        4 
CH|.CH..CM.. 
C  =  CH.CH,.CH  =  CH, 


12        8      4  5 

(To  be  Continued.) 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


ROYAL  SOCIETY  OF  ARTS. 

Monday,  Fcbniarj-  5,  8  p.m.  (Canton 
Lectiu-e)  r  Henry  P.  Stkvens,  M.A., 
Ph.D.,  F.I.C,  The  Vulcanisation  of  Euh- 
her.     (Ijccture  1.) 

Tuesday,  February  6,  4.80  p.m.  (Do- 
minions and  Colonies  and  Indian  Sections) : 
Sir  Richard  A.  S.  Rkdmayne,  K.C.B.. 
M.Sr..  M.Inrt.C.E.,  M.I.M.E.,  F.G.S.. 
The  Base  Metal  Resourcen  of  the  British 
Empire. 


Wednesday.  February  7,  8  p.m.  (Ordin- 
arv  Meeting) :  Charles  R.  Darling, 
F.Inst.P.,  A.R.C.So.I.,  Electrical  Resist- 
ance Furnaces  and  their  Uses. 

Monday,  Febni.iry  12,  8  p.m.  (Canton 
Lecture):  Henry  P.  Stevens,  M.A., 
Ph.D.,  F.I.C.  The  Vulcanisation  of  Rub- 
ber.    (Lecture  2.) 

Wednesday,  FebruAry  14,  8  p.m.  (Ordin- 
ary Meeting) :  W.  J,  Rees,  Lecturer  on  Re- 
frnctcries  in  the  University  of  Sheffield, 
Progress  in  the  Manufacture  of  Refractories. 

Friday,  February  16,  4.30  p.m.  (Indian 
Section):    J.   T.     Marten,    I.C.S.,     M.A.. 


36 


THE    CHEMICAL    NEWS. 


JANUARY  19,  1923. 


Imperial  Census  Commissioner  in  India, 
The  Indian  Census,  1921.  Sir  Edward  A. 
Gait,  K.C.S.I.,  C.I.E.,  Member  of  the 
India  Coimoil,  will  preside. 

Monday,  February  19,  8  p.m.  (Canton 
Lecture):  Henry  P.  Stevens,  M.A., 
Ph.D.,  F.I.C,  The  Vulcanisation  of  Rub- 
ber.    (Lecture  3.) 

Wediiesday,  February  21,  8  p.m.  (Ordin- 
ary Meeting) :  C.  Ainsworth  Mitchell, 
M.A.,  F.I.C.,  Handwriiing  and  its  Value 
as  Evidenec.  Sir  Richard  D.  Muir  will 
preside. 

Wednesday,  February  28,  8  p.m.  (Ordin- 
ary Meeting) :  Professor  W.  E.  S.  Turner, 
D.Sc,  Head  of  Department  of  Glass  Tech- 
nology, The  University,  Sheffield,  Heat  Re- 
sisting Glasses. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

Annual  General  Meeting. 

The  Annual  General  Meeting  of  the 
Society  will  be  held  on  Wednesday,  Feb.  7, 
at  the  Chemical  Society's  Rooms,  Burling- 
ton House,  Piccadilly,  W.,  at  8  p.m. 

The  accounts  for  the  year  will  be  pre- 
sented, the  President  will  deliver  his  an- 
nual address,  and  the  election  of  officers 
and  council  for  the  ensuing  term  will  take 
place.  The  appointment  of  auditor  will 
also  take  place. 

The  o:"dinary  monthly  meeting  of  the 
Society  will  be  held  immediately  following 
the  Annual  General  Meeting,  when  the  fol- 
lowing papers  will  be  read:  — 

Notes  on  the  Examination  of  Preserved 
Meats,  etc.,  by  Osman  Jones,  F.I.C. 

Titanium  in  Nile  Silt,  by  E.  Griffiths- 
Jones. 


PATENTS  IN  1922. 

We  think  it  will  interest  everyone  to 
know  that  in  spite  of  poor  trade  and  unem- 
ployment in  1922,  Messrs.  Rayner  &  Co., 
patent  agents,  of  Chancery  Lane,  London, 
inform  us  that  there  is  an  increase  of  more 
than  300  patent  applications  over  1921  the 
figures  being  about  35,500,  standing  next  to 
the  highest  in  record. 

The  subject  of  "  Wireless  Telegraphy  " 
shows  considerable  increase  in  the  number 
of  inventions,  and  after  this  comes  rein- 
forced concrete  building  construction, 
which  is    greatly  practised    in  these    days, 


and  probably  the  matter  of  most  general  in- 
terest is  that  numerous  patents  have  been 
taken  in  labour-saving  devices  for  the 
household,  and  many  lady  inventors  have 
come  successfully  into  this  important 
branch,  but  aviation  patents  have  gone 
entii'ely  put  ol  favour  and  show  a  consider- 
able decrease. 

Recent  mouths  show  a  distinct  inclina- 
tion to  increasing  business  in  H.M.  Patent 
Office,  which  should  be  an  indication  of 
better  industrial  times,  as  inventions  nearly 
always  precede  improvements  in  commerce. 


NOTICES  OF  BOOKS. 

Formulary  of  the  Parisian  Perfumer, 
by  R.  M.  Gattefosse.  4th  Edition.  Pp. 
85.  Edition  Parfumerie  Moderne,  No. 
112,  Ro'uto  de  Crenieu,  Villeur  Banne- 
lez-Lyon  (France). 

The  fourth  edition  of  this  excellent  little 
handbook  has  just  been  published  by  the 
Societe  Fraii^aise  de  Produits  Aromatiques, 
and  M.  Gattcfo&se,  whose  association  with 
the  Societe  proves  him  an  authority  upon 
perfumes,  has  maintained  his  high  stand- 
ard. As  the  author  exiplained  in  his  pre- 
face, the  work  is  one  calculated  to  be  in- 
valuable to  extensive  manufacturers  and 
lesser  specialists  alike.  Part  I.  embodies 
the  classification,  extraction,  and  testing  of 
essential  oils  and  the  concentration  of 
flower  juices;  the  principles  of  perfume 
composition ;  and  exhaustive  formulse  and 
lists  O'f  fixators  and  resindors.  Part  II.  is 
more  practical,  and  contains  two  recipes  for 
eau  de  Cologne,  three  for  dentifrices,  and 
three  for  toilet  lotions;  as  well  as  the  com- 
ponents of  cold  cream,  brilliantines,  and 
cosmetics.  Considering  that  the  volume 
only  comprises  82  pp.,  it  is  extraordinarily 
comprehensive.  Not  only  does  it  cover  a 
wide  field,  but  the  matter  contained  has 
been  carefully  selected  and  intelligently 
listed.  If  M.  Gattefosse  has  erred  at  all  in 
its  compilation,  it  is  by  being  a  trifle  too 
brief  at  the  expense  of  coherency;  although, 
perhaps,  for  purposes  of  rapid  reference, 
this  is  an  advantage.  J.M. 


Second  Year    College    Chemistry    and 
Second     Year    Laboratory    Manual,      by 
William  H.  Chapin.     Chapman  &  Hall.  jHj 
15s.  and  7s.  6d.  ^i 

The  author's  familiarity  with  the  modem 
requirements  of  chemical  students  and  the 


JANUARY  19,  1923. 


THE   CHEMICAL   NEWS. 


37 


more  up-to-date  methods  of  tuition  is 
clearly  evidenced  by  these  two  books, 
which  have  just  been  published  for  the  first 
time.  The  former  constitutes  the  theory — 
and  (beliefs,  but  upon,  rudimentary  fact — of 
not  built  upon  a  meaningless  mass  of  rules 
the  course;  the  latter,  the  practice.  Valu- 
able suggestions  as  to  procedure  through 
the  course  have  also  been  incorporated. 
But  what  appear  with  prominence  are  '.he 
chapters  upon  ionisation,  osmotic  pressure, 
radioactivity,  and  the  periodic  system.  The 
last-mentioned  is  especially  enlightening, 
but  the  other  three  could,  perhaps,  be  ex- 
tended with  advantage,  as  could  the  sec- 
tion U)pon  the  deter'minatimi  of  atomic 
weights,  although  the  author  has  quoted 
several  works  dealing  exclusively  with  these 
sections.  The  Laboratory  Manual  follows 
closely  the  theoretical  treatise,  and  the  pre- 


scribed experiments  are  well  chosen  and 
lucidly  explained.  One  important  omission, 
however,  is  the  application  and  modifica- 
tion of  Avogadro's  Law,  dealing  with  gases 
at  or  near  the  point  of  liquefaction;  and 
greater  attention  could  have  been  given  to 
ion  migration  under  the  influence  of  elec- 
tric currents.  The  two  books,  used  con- 
jointly, would,  without  doubt,  not  only 
teach  the  student,  but  also  compel  him  to 
feel  that  he  has  a  grip  uipon  his  subject, 
inspiring  him  with  confidence,  and  thus 
facilitating  the  learning-processes.  This, 
to  say  the  least,  is  a  novel  feature,  as  the 
majority  of  textbooks  seem  to  be  written 
diatribes  of  uninteresting  facts  and 
fonnulflB.  The  "tone"  of  the  work  is  some- 
thing unusual,  and  that  alone  should  induce 
demonstrators  to  adopt  it  as  a  standard 
course.  J.M. 


LIESEGANG     RINGS.       I.       SILVER 

CHROMATE  IN  GEr..\TIN  AND 

COLLOIDAL  GOLD  IN 

SILICIC  ACID  GEL.* 

l!v  Earl  C.  H.  Davies. 

[Coyitrilmtion  from  the  Chemical    Labora- 
tory, West  Virginia  University.] 

Introductk  V 

It  is  generally  agreed  tint  whili-  the  pre- 
sent theories  regarding  Liesegang  rings  may 
cover  the  broa<l  features  of  this  phenomenon 
they  are  quite  inadequate  to  explain  its 
many  details,  complexities  and  variations. 
To  study  this  phenomenon  further,    I  have 

Table  I. 
Rate  of  Diffusion 


in  the  first  iplaco  investigE^d  the  effect  of 
gravity  on  the  formation  of  bands  of  silver 
chromate  in  gelatin.  In  the  second  place, 
I  have  studied  the  formation  of  rhythmic 
bands  of  colloidal  gold  in  silicic  acid  gel, 
since  this  presents  an  ideal  opportunity  for 
ofllowing  changes  in  the  sizes  of  the 
particles. 

Silver  Chromate  Bands  in  Gelatin. 
Effect  of  Gravity . — An  aqueous  solution 
of  silver  nitrate  was  ma<ie  containing  8.5  g. 
in  100  cc.  The  gel  contained  4  g.  of 
powdered  gelatin,  0.12  g.  of  potassium  di- 
chromate,  and  120  g.  of  water.  The  gelatin 
was  boiled  with  the  water  and  the  aichro- 


at  0" 


Time  in  days. 


Tube 
A  right 
A  left 
A'  right 
A'  left 
B 
B' 

C  upper 
C  upper 
C  lower 
C  lower 

D 

D' 


20 
Cm. 


25 
Cm. 


27 
Cm. 


32 
Cm. 


34 

Cm. 


39 


46 


Cm.   Cm. 


The  two  ends  had  met 


10.60 
10.60 


11.29     12.62     13.10     14.35 
11.27     gelatin  frozen 


14.80     16.25     16.5 


The    two   ends  had    met 

9.80  10.80         13.17 

Gelatin  frozen 


14.65 


*  Prom    "  The  Journal  of  the  American     Chemical  Society,"  December,  1922. 


^ 


THE   CHEMICAL   NEWS. 


JANUAK^  19,  1923. 


mate  for  a  few  minutes  on  a  water-bath 
until  solution  had  taken  place,  and  the 
solution  was  then  filtered  into  tubes.  After 
it  had  solidified  (standing  over-night)  and 
had  been  left  in  the  ice-room  at  0°  for  about 
2  hours,  the  tubes  were  arranged  as  fol- 
lows :  A  and  A'  were  horizontal  with  silver 
nitrate  contact  at  both  ends;  B  and  B' 
were  horizontal  with  silver  nitrate  contact 
at  one  end;  C  and  C  were  vertical  with  sil- 
ver nitrate  contact  at  both  ends ;  D  and  D' 
were  vertical  with  silver  nitrate  at  the  lower 
ends ;  E  and  E'  were  vertical  with  silver  ni- 
trate contact  at  upper  ends.^ 

The  results  given  in  Table  I.  show  that 
diffusion  is  slowest  when  it  operates  against 
gravity  (Tube  D),  and  that  hydrostatic 
pressure  may  partially  counterbalance 
gravity  (Tube  C,  lower). 

After  the  18th  day  the  tubes  were  re- 
moved from  the  ice-room  while  observations 
were  made  at  room  temperatures  and  with 
varying  light,  either  artificial  or  sunlight. 
Hence  the  results  previous  to  the  18th  day 
are  most  satisfactory.  After  that  elapsed 
time  all  tubes  were  removed  for  the  same 
length  of  time  and  subjected  to  practically 
the  same  light  and  heat  conditions. 

Preliminary  Bands- — It  seems  frrm  ob- 
servations so  far  recorded  that  in  the  case 
of  silver  chromate  in  gelatin  the  method  of 
ring  formation  is:  first,  the  silver  nitrate 
diffuses  into  the  gelatin  and  gives,  what 
seems  to  be  an  opaque  region  which  in 
reahty  consists  of  small  opaque  bands. 
These  preliminary  bands  have  not  beon 
observed  in  the  earlier  stages  of  diffusion. 
Tube  B'  at  13.5  to  15  cm.  from  the  surface 
of  entrance  of  the  silver  nitrate  had  28 
bands.  Tube  D  had  16  bands  at  12.8  to 
13.8  cm.  from  the  point  of  the  beginning  of 
the  silver  nitrate  penetration.  Tube  E'  had 
26  opaque  bands  at  10.5  to  11.5  cm.  from 
the  surface.  From  this  point  it  a<ppears 
that  there  is  a  tendency  for  the  opaque 
bands  to  be  closer  together  in  the  earlier 
stages  of  diffusion  and  to  be  farther  apart 
as  the  distance  from  the  surface  of  initial 
diffusion  increases.  It  is,  therefore,  not 
unlikely  that  this  formation  of  preliminary 
bands  extends  to  all  portions  of  the  tube, 
but  that  the  bands  are  at  first  so  close  that 
they  iseem  to  merge. 


^  Data  for  E  and  E'  were  not  given  in 
Table  I.  because  the  silver  nitrate  had  not 
the  same  strength  as  that  used  in  the  other 
tubes. 


In  the  case  of  silver  chromate  in  gelatin 
the  reaction  as  carried  out  in  a  test-tube 
would  be,  KjCraO,  +  H^O  +  4AgN03  = 
2  KNO3  +  2  Ag^UrO^  +  2  HNO3.  We  are 
not  dealmg  simply  with  silver  chromate. 
and  it  is  a  well-known  fact  that  electrolytes 
have  a  profound  effect  on  gels.  They  not 
only  inlluence  the  rate  of  imbibition  of 
water,  but  also  tend  to  produce  peiptization. 
As  tne  gelatm  gel  ordinarily  used  is  not  as 
dilute  as  possible  we  know  that  it  is  capable 
of  abi&orbaig  more  water.  The  presence  of 
nitric  acid  would  disturb  the  layer  of  gelatin 
where  it  is  produced.  There  is  a  isimilar 
change  in  rate  of  imbibition  when  a  base  is 
one  ot  the  products.  The  potassium  nitrate 
and  nitric  acid  have  the  greatest  concentra- 
tion at  the  layer  of  reaction  between  the 
potassium  dichromate  and  silver  nitrate. 
From  microscotpic  observations  it  appears 
that  at  least  at  0°"  some  of  the  potassium 
nitrate  is  crystallised  simultaneously  with 
the  small  particles  of  silver  chromate.  The 
nitric  acid  is  moi-e  soluble,  and  hence, 
iiccord'ing  to  Fick's  law,  iditiu&es  faster  than 
the  potassium  nitrate  because  it  is  poten- 
tially more  concentrated. 

It  is  to  this  unequal  rate  of  diffusion  that 
we  attribute  the  preliminary  bands.  The 
groups  of  silver  ohromate-potassium  nitrate 
■'crystals"  are  gradually  broken  up  as  the 
potasisium  nitrate  diffuses  away  and  the  sil- 
ver chromate  particles  become  larger  be- 
cause of  the  oncoming  silver  nitrate.  Hence 
the  small  bands  lose  their  identity  and  the 
larger  band  is  formed.  Below  the  small 
band  the  silver  nitrate  and  nitric  acid  and 
some  potassium  nitrate  are  diffusing  into 
the  potassium  dichromate.  Of  course,  the 
potassium  dichromate  is  diffusing  "up"  but 
because  of  its  low  concentration  the  rate  of 
diffusion  is  low. 

Colloidal  Gold  in  {Silicic  Acid  Gel. 

Light  a  Factor  in  Formation  of  Rythmic 
Bands. — To  ascertaui  the  effect  of  periodic 
illumination  in  the  production  of  bands,  I 
have  carried  out  the  following  experiments, 
using  colloidal  gold  in  silicic  acid  at  the  con- 
centrations suggested  by  H.  N.  Holmes, ^ 
who  apparently  carried  out  his  exiperiments 
in  changing  light. 

Tubes  gave  no  bands  either  at  0°  or  at 
room    temperatures    when    covered,    Hght- 


^  Holmes,  Jour.  Amer.  Chem.  Soc,  1918 
XL.,  187. 


JANUAKY  19,  1923. 


THE  CHEMICAL  NEWS. 


39 


tight,  with  black  paper  and  placed  in  a  dark 
room  even  after  9  days.  Instead,  the  gold 
precipitated  in  sparkling  yellow  iparticles.  A 
band  of  about  1.5  cm.  width  was  formed  in 
these  tubes  by  removing  the  black  paper 
and  exposing  them  to  the  light  from  a  pro- 
jection lantern  for  an  hour.  The  band  did 
not  start  as  a  fine  line  and  then  graflually 
grow ;  rather,  it  began  as  a  faint  colour 
thorughout  the  entire  region,  becoming 
gradually  more  intense  by  longer  exposure 
to  the  light  until  it  reached  a  maximum  at 
which  all  the  gold  adsorbed  by  the  fibrils  in 
this  region  had  been  precipitated.  Thi- 
colour  was  lighter  at  the  top  of  the  band 
and  most  intense  near  the  bottom.  Below 
the  coloured  7x>ne,  yellow  crystals  of  gold 
could  be  seen  for  a  distance  of  8  to  9  mm. 

Second,  slits  were  cut  in  the  black  paper 
in  such  a  way  as  to  expose  2  mm.  cover  8 
mm.,  expose  2  mm.,  etc..  throughout  the 
length  of  a  tube.  This  tube  was  placed  in 
the  dark  room  at  a  distance  of  14  cm.  from 
an  80- watt.  110- volt  Mazda  light.  Slightly 
green  colloidal  bands  developed  at  the 
fypcniiigs  after  9  days,  and  at  each  qpening 
there  were  distinct  yellow  bands  of  gold 
crystals. 

Third,  a  similar  tube  which  had  been  in 
the  <lark  at  0°  for  6  days  showed  no  bands 
at  the  openings.  When  this  tube  was  ex- 
posed to  the  strong  light  of  the  projection 
lantern  for  a  few  minutes,  bands  developed 
at  2  of  the  openings  in  th(>  same  region  as 
in  the  cswe  of  a  tube  which  had  been 
handled  exactly  similarly,  except  that  it 
had  no  protection  from  the  light  of  the  lan- 
tt^rn.  Between  these  openings  the  bands 
did  not  form,  although  the  tube  was  in  the 
strong  light  for  1  hour.  This  tube  was  then 
put  in  the  dark  for  7  more  days  at  0**.  The 
black  slit  paper  was  then  entirely  removed 
and  the  tube  put  in  front  of  the  lantern  for 
3  hours.  There  was  a  slight  blue  colour 
developed  in  the  8  mm.  zone  between  these 
2  bands.  From  the  faint  coloiu:  of  this  blue 
it  was  apparent  that  the  light  is  not  the 
only  factor  in  promoting  the  band  forma- 
tion of  the  gold.  There  must  also  be  proper 
concentrations  of  the  oxalic  aoid  and  the 
gold  chloride.  The  sodium  sulphate  is  not 
included  because  it  is  presumably  uniformly 
distributed. 

Hence  it  seems  that  the  molecular  gold 
adsorbed  bv  the  walls  is  in  some  way  at 
first  protected  from  immediate  precipitation 


by  the  oxalic  acid.  It  is  probably  oriented.' 
After  a  time  such  gold  is  gradually  precipi- 
tated in  the  dark,  but  not  in  bands.  At 
some  other  concentrations  bands  may  be 
obtained  in  the  dark;  but  so  far  I  have  ob- 
served no  tendency  for  the  gold  to  form  in 
bands  in  silicic  acid  except  under  more  or 
less  periodic  light  changes.  For  examiple, . 
E.  Kiister*  found  under  certain  conditions, 
in  the  case  of  bands  of  silver  chromate  in 
gelatin,  that  when  the  silver  nitrate  had 
diffused  into  the  gelatin  in  the  dark  there 
wjvs  an  evenly  distributed  precipitate,  but 
when  the  diffusion  area  was  exposed  to  light 
rhythmically,  that  is,  alternate  exposure 
(25  minutes)  and  darkness  (45  minutes)  the 
precipitate  took  the  characteristic  ring  for- 
maticm.  I  have  obtained  just  as  good  bauds 
of  silver  chromate  in  the  dark  as  in  the 
light,  both  at  0°  and  at  room  temperature 
of  about  20". 

Two-phiue  Character  of  Silicic  Acid  Qei. 
— It  seems  that  the  'protected"  gold 
chloride,  which  we  have  assumed  to  be  ad- 
sorbed by  the  more  solid  pwtion  of  the  gel 
cells,  gradually  diffuses  away  and  is  pre- 
cipitated if  the  band  is  not  started  by  the 
light,  or  the  peptizing  and  imbibition  action 
of  the  products  of  reaction.  It  is  because 
of  this  migration  and  precipitation  that  the 
null  spaces  are  formed. 

When  in  the  dark  w  in  mild  light  there  is 
a  rather  broad  band  which  fwms  at  the  tqp 
of  the  silicic  acid  layer.  This  band  was  in 
Home  cases  reddish-purple  in  transmitted 
light  end  yellow  in  reflected  light.  Below 
this  there  were  sparkling,  yellow  crystals  of 
gold.  These  latter  precede  the  usual  bands. 
Observed  with  a  powerful  Tyndall  cone  it  is 
seen  that  the  particles  of  gold  are  mo.^t 
numerous  just  btneath  the  band.  They  be- 
come relatively  fewer  until  they  cease  to 
appear  at  a  distance  of  about  8  to  9  mm. 
Then  a  band  begins  to  foi-m  in  the  region 
already  best  filled  with  *Jie  larger  particles 
of  go\(i.  The  band  owes  its  formation  to  the 
condensation  of  the  molecular  gold  to  the 
size  of  colloidal  particles.  Much  of  the  gold 
has  already  been  precipitated  as  micro- 
scopic particles.  Hence  in  the  formation  of 
these  bands  there  comes  a  time  when  there 


'  For  discussion  of  the  suhjeet  of  molecu- 
lar orientation-  see  Harkins,  Davies  and 
Clark,  Jour.  Amer.  Chem.  Soc,  1917, 
XXXIX.,  541. 

*  Kiister,  Kolloid-Z.,  1913,  XIII..  192. 


40 


THE   CHEMICAL    NEWS. 


JANUAEY  19,  192i 


is  a  considerable  accumulation  of  the  pro- 
ducts of  reaction,  hydrochloric  and  carbonic 
acids.  Also  the  concentration  of  the  gold 
chloride  becomes  quite  small,  due  to  the 
previous  precipitation  of  the  microscopic 
particles.  The  whole  experiment  behaves 
as  would  be  expected  if  the  gold  chloride 
were  held  in  the  gel  in  two  ways.  First, 
some  of  it  is  most  free  to  move  and  forms 
the  larger  particles.  Second,  the  accumu- 
lation of  the  products  of  reaction  affects 
the  "protective"  coating  on  the  other  gold 
chloride  molecules  so  that  they  are  attacked 
by  the  oxalic  acid.  It  would  seem  that 
these  colloidal  particles  which  form  the 
bajids  must  likewise  be  protected  by  the 
gel,  as  they  remain  unaffected  by  further 
diffusion  of  the  electrolytes.  This  is  what 
might  be  expected  if  we  had  films  of  the 
solid  gel  and  pockets  of  the  amorphous  geJ. 
W.  Moeller^  has  observed  such  a  formation 
in  the  case  of  gelatin,  where  he  finds  fibrils 
of  a-gelatin  imbedded  in  amoriphous  (:i- 
gelatin. 

However,  the  structure  of  the  gel  is  not 
the  only  factor.  Many  experiments  on  band 
formation  have  been  performed  where  gel 
was  replaced  by  solids,  as  sand,  sulphur, 
etc.  There  is  also  in  these  cases  a  p::?;sibil- 
ity  that  an  oriented  adsorption  of  one  of  the 
reacting  substances  by  the  solid  plays  an 
important  part.  Some  oi  the  precipitate  is, 
in  nearly  all  cases,  of  a  preliminary  nature. 
It  may  be  scattered,  as  in  the  case  of  gold, 
o_  rin  preliminary  bands,  as  in  the  case  of 
silver  chromate  in  gelatin.  These  prelimi- 
nary particles  may  sometimes  be  later  par- 
tially converted  into  colloids  by  the  excess 
of  electrolytes  but  in  the  case  of  gold  there 
seems  to  be  no  such  tendency.  The  gold 
originally  precipitated  as  blue  remains  blue, 
the  red  remains  red.  This  shows  that  it  is 
formed  in  protective  coats  of  the  gel.  Other- 
wise we  might  expect  the  red  particles  to 
enlarge  gradually  and  become  blue  as  more 
of  the  diffusion  takes  place.  The  molecu- 
lar gold  in  the  fibrils  forms  the  bands.  The 
gold  chloride  in  the  amorphous  portion  of 
the  gels  forms  the  granules. 

In  all  the  bands  of  gold  ohserved,  the  red 
has  formed  first  where  it  has  formed  at  all. 
In  the  region  in  which  it  is  formed  we  have 
relatively  large  concentrations  of  oxalic 
acid  as  compared  with  the  small  amount  of 
adsorbed  gold.     After  a  red  band,  the  blue 


213 


Moeller,  Kolloid-Z.,    1916,    XIX.,    205- 


forms.  Under  this  same  red  band  relatively 
large  amounts  of  the  yellow  gold  have  been 
observed  for  a  distance  of  8  to  9  nana, 
beyond  it.  Hence,  where  the  blue  bands 
form  there  are  relatively  large  amounts  of 
the  products  of  reaction,  hydrochloric  and 
carbonic  acids,  with  relatibely  high  concen- 
tration of  adsorbed  molecular  gold.  Under 
the  latter  conditions  we  should  have  greater 
tendency  for  adsoription  of  the  oxalic  acid 
with  miore  of  the  "protected"  molecular 
gold  collecting  in  each  "protected"  colloid- 
al particle. 

Effect  of  Temperature. — Upon  a  study  of 
the  literature  on  Liesegang  ring  formation 
one  is  impressed  .by  the  small  attention  paid 
to  the  effect  of  temperature.  Experiments 
have  nearly  always  been  caiTied  out  at 
room  temperatures.  Yet  it  is  recognised 
that  the  elasticity  of.  gels^  is  du-ectly  re- 
lated to  the  formation  of  Liesegang  rings. 
In  the  present  experiments  with  silver 
chromate  in  gelatin,  the  bands  were  closer 
when  made  at  0°  than  when  formed  at  room 
temperatures.  Particularly  in  the  case  of 
gelatin  should  studies  be  made  at  different 
and  regulated  temperatures.  Thus  the  ordi- 
nary gelatin  gels  melt  between  25°  and  29", 
depending  upon  the  concentration.  When 
working  at  room  temperatures  .with  a  4  jper 
cent,  gelatin  gel  (m.p.  about  26°),  we  are 
very  close  to  the  limit  of  non-elasticity. 
When  we  lower  the  temperature  to  0°  we 
have  lowered  the  distance  from  the  melting 
point  by  several  hundred  per  cent.  There- 
fore, we  have  greatly  affected  the  elasticity 
and  may  expect  marked  influence  on  ring 
formation.  At  lower  temperatures,  the 
rate  of  diffusion  is  also  lessened.  It  is 
doubtful  whether  as  low  a  temperature  as 
0°  is  desirable,  but  it  is  certainly  advisable 
to  work  at  a  uniform  temperature  not  too 
close  to  the  melting  point  of  the  gel.  With 
the  silicic  acid  there  is  not  the  difficulty  of 
melting  at  higher  temperatures.  In  fact  it 
seems  best  many  times  to  work  at  higher 
temperatures ;  hut  here  also  conditions  of 
light  and  heat  should  be  carefully  regulated 
if  the  observations  are  to  be  more  than 
qualitative. 

Conclusion. — The  oriented  adsorption  in 
the  gel  or  porous  solid  of  the  reacting  sub- 
stances asi  well  as  the  products  of  reaction 
have  not  received  the  attention  which  they 
deserve.  On  lookuig  through  the  literature 
we  find  that    the  concepts,    which    exisk^d 


^  See  Hatschek,  ibid.,  1914,  XIV.,  115-22. 


JANUARY  19,  1923^ 


TMS  CHEMICAL   NEWS. 


41 


prior  to  our  knowledge  of  colloids,  are  car- 
ried over  to  explain,  facts  which  are  clearly 
related  to  the  phenomena  of  colloidality. 
Thus  we  read  statements  to  the  effect  that 
the  ions  diffuse  toward,  each  other  until 
the  solubihty  product  is  exceeded."  It  is 
not  clear  how  this  applies  to  the  formation 
of  bands  which  consist  altc^ether  of  col- 
'  loidal  particles.  The  colloidal  conception 
would  be  that  a  number  of  molecules,  in 
some  cases  about  100  as  for  the  usual  col- 
loidal silver,  are  congregated  into  a  particle 
of  rather  definite  size.  If  too  many  of  the 
molecules  collect  on  one  "crystal"  we  have 
the  usual  precipitate  (in  our  case  the  yellow 
crystals  of  gold).  Hence  it  is  necessary  to 
regulate  the  number  of  these  gold  moli- 
cuies  which  are  reduced  in  a  "protective" 
coating  or  pocket  of  the  gel.  Thus  we  are 
not  surprised  that  light,  heat,  peptizing 
electrolytes  and  the  rate  of  diffusicm  all 
iplay  important  roles  in  regulating  the  for- 
mation of  bands  and  the  ahe  of  particles  in 
those  bands,  and  in  case  of  colloidal  gold 
the  colour  which  The  Svedl)erg'  has  shown 
is  directly  related  to  the  size  of  particles. 

Forecast. — It  seems  possible  to  predict 
that  subsequent  experiments  will  show 
that  in  many  cases  of  Liesegang  rings 
which  occur  in  nature  light  will  be  found  to 
be  an  important  factor.  This  is  because  of 
the  natural  periodicity  of  sunlight.  Diff'i- 
sion  takes  place  at  night  with  iperh:ip8 
chemical  reactions.  Then  in  the  davtime 
the  combined  action  of  the  light  and  the 
products  of  the  reactions  is  to  cause  a  band 
to  form  iwhcre  the  concentrations  and  the 
nature  of  the  diffusion  medium  are  suit- 
able. Further  experiments  will  be  made, 
especially  with  silicic  acid  gel  to  determine 
the  effect  of  light  as  a  factor. 

"  Preliminary  "  bandn  of  silver  chromate 
were  observed  after  the  diffusiwi  in  gelatin 
had  extended  10  to  12  cm.  at  0**.  The  pre- 
sence of  these  is  attributed  to  the  unequal 
rate  of  diffusion  of  the  iproduots  of  reaction. 
About  3  of  these  preliminary  bands  gradu- 
ally form  the  nucleus  of  the  final  band;  26 
such  bands  were  ob8<:'rved  in  a  space  of  1 
cm.  These  "preliminary"  bands  gradually 
lose  their  identity  as  the  silver  chromate  is 
carried  to  the  final  band  by  the  excess  of 
silver  nitrate. 


^     Ostwald,     "  Theoretical    and    Applied 
Colloid  Chemiairy,"  1st  ed.,  1917,  p.  60. 


Light  is  one  of  the  most  important  vari- 
ables in  maping  rhythmic  bands  of  gold  in 
silicic  acid.  At  the  concentrations  used  no 
bands  were  formed  in  the  dark  at  either  0° 
or  room  temperatures.  Periodic  variations 
of  strong  light  and  darkness  produce  bands 
in  those  regions  in  which  there  is  still  ad- 
sorbed molecular  gold,  excess  of  acid  and 
suitable  amounts  of  the  by-products  of  the 
reaction.  These  by-iproducts  make  precipi- 
tation in  bands  possible  because  they  in- 
fluence the  tendency  toward  imbibition  and 
peptization  so  that  the  gold  is  precipitated 
in  "pockets"  just  large  enough  to  give  a 
colloidal  dispersion.  There  is  no  fundamen- 
tal difference  between  the  bands  of  blue 
gold  and  those  of.red.  Any  combination  of 
conditions  which  tend  to  precipitate  the 
gold  from  the  "fibrils"  in  relatively  large 
"pockets"  will  produce  blue  bands.  The 
red  bands  are  made  when  the  pockets  are 
not  eo  large.  Rhythmic  bands  of  silver 
chromate  form  in  gelatin  in  the  dark  at  0° 
and  at  room  temperatures. 

Silicic  acid  gel  ia  at  2-phase  ayBiem ;  the 
gold  chloride  is  held  in  the  gel  in  two  ways. 
Some  of  it  is  most  free  to  move  and  forms 
the  larger  yellow  crystals  before  the  bands 
begin  to  appear.  The  remainder  of  the 
gold  chloride  see  ma  to  be  more  "protected" 
by  the  gel.  Oriented  adsorption  takes  place 
at  the  mterface  between  "fibrils"  of  a-gel 
and  the  amorphous  /8-gel.  This  oriented 
adsorption  may  set  up  a  temporarily  "paiS- 
eive"  state,  even  where  the  adsorbed  sub- 
stance is  not  actually  coated  by  a  film  of 
the  gel.  Such  orientation  can  occur  when 
solids  such  as  alundum  and  sulphur  are  the 
mediums  in  which  Liesegang  rings  are 
made. 

At  room  temperatures  gelatin  gel  is  near 
its  point  of  minimum  elasticity.  More  ex- 
periments should  be  carried  out  with  it  at 
lower  and  uniform  temperatures. 

Summary. 

Gravity  decreases  the  rate  of  diffusion 
upward  during  the  formation  of  Liesegang 
rings  of  silver  chromate  in  gelatin  dicnro- 
mate. 

In  conclusion  the  author  wishes  to  ex- 
press appreciation  for  the  co-operation  of 
W.  B  .Shirey  and  Professor  Friend  fi.  Clark 
of  this  Laboratory. 

Morgantown,   West  Virginia. 


42 


THE   CHEMICAL   NEWS. 


JANUARY  19,  1923. 


MALBIC   AND 


TITR    USE    OF   MALIC, 
™MARIC  ACIDS  IN  VOLUMETRIC 

ANALYSIS.* 

By  N.  a.  Lange  and  Harry  Kline. 

Wontrihution  from  the  Chemical    Lahora- 
tory,  Case  School  of  Applied  Science.} 

Malio.  maleic  and  fumaric  acids^  are  now 
available  in  large  quantities  ^^dj:^  com- 
paratively low  prices,  and  an  i™stigation 
IL,  therefore,  made  to  determine  whether 
the^  might  replace  the  more  costly  suc<Mnic 
acid=^  for  standardising  basic  sohi^i^^^-  ,^- 
Astruc^  has  shown  that  when  phenolphtha- 
lein  is  used  as  the  indicator  many  of  the  di- 
carboxyl  acids,  including  the  jcids  men- 
tSiedlbove,  behave  as  though  fey  have  2 
replaceable  hydrogen  atoms  whereas  with 
methyl  orangi  the  end-pomt  ^^  uncertain 
No  methods  of  purification  nor  data  of  ti- 
trations were  given  for  these  acids 

In  the  experiments   below,    the    sodium 
hydroxide    solutions  free    from  carbon    di- 
oxide were  prepared  in  the  usual  manner  ^y 
the  addition  of  barium  chloride    and  then 
standardised  against  hydrochloric  acid    the 
normality  of  which  was  determined  by  pre 
c^^ation  of  silver  chloride;  the  norm  ah  ty 
of  the    sodium  hydroxide    wa^  ^^^./^l^i' 
mined  by  titration  with  pure  succinic  acid. 
Maleic    Acid.-Commercial    maleic    acid 
was  found  to  be  too  impure  to  use  directly 
The  acid  was,  therefore,  purified  by  crysta  - 
lisati^  in  four  different  ways:    (1)  a  single 
c'ystllisation  from  water;  (2)  two  crystal- 
Usations  from  water;  (3)  ^ne  crystallisakon 
from  200  cc.  of  water    to  which  had  l^en 
added  4  drops  of  cone,  nitric  acid,  (.4)  cry 
stali^ation  as  in    (3)  and  then  once  more 
from    pure    water.       After   ,air-drying     the 
crystals  were  dried  to  constant  weight  over 
sulphuric    acid  or  in  an  oven  at    f  J^^    ^ 
hours.     Definite  amounts    of  the  acid  were 
dSVed  in  distilled  water,  which  was.  ,pre- 
V  ouslv  boiled  to  expel  carbon    dioxide  and 
InS  to  cool  to  a£out  50°  before  add.t,on 
of  the  acid.      In    each    case    the    standard 
sodium  hydroxide  solution    was  then  added 


*  From  "  The  Journal  of  the  American 
Chemical  Societyr  December,  1922. 

1  U.S.  pat.  1,818,631-2,  -3.  . 

^  Phelps  and  Weed,  .im.  J-  Scu^  ^^^ 
XXVI.,  138;  Z.  anorg.  Chem.,  19^^,  -L«iA., 

^^^-Astruc,  Z.  anal.  Chen.,    mi^^l^.,^1^- 
Compt.  rend.,  1900,  CXXX.,  253. 


until  the    end-pomt  with    pheno  phthalein 
was  obtained.       The  normality  ot  the  base 
against    standard     hydrochloric    acid    was 
0  1087  N-  4  titrations    with    succinic    acia 
gave  a^  .aiverage  value  of  0.1087  N  with  an 
Ltreme  variation  of  =  0.0001  N;  the  nor- 
mality   determined    with     16    samples    of 
maleic  acid  dried  over  sulphuric    acid  and 
varying  in  weight  from  0.1696  to  0.2642  g. 
averaged  0.1088  N  with  an    extreme  varia^ 
tionof  +0.0001  to  -0.0003  N;  titration  with 
4  .samples  of  maleic  acid  d^'jed    at^    and 
varvinS  in  weight  from  0.1987  to  0.2339  g. 
ga7e  an  averale  value  of  0.1087  N  wi  h  an 
extreme  variation  of  =  0.0001  N.      It  was 
found  that  maleic  acid,  after  one  crystallr- 
sation  from  water  or  from  water  with  a  lew 
drops  of  nitric  acid,  will  give  results  as  ac- 
orn-ate as    obtainable  with  succmic  or    hy- 
dChloirc  acids.       Several    determinations 
with  samples  of  maleic  acid  dried    at  105 
and  120°  showed  that  a    small  amount  of 
maleic  anhydride  is  f-^med ;  such  samples 
after  standing  in  the  open  air  for  24  hours 
are  hydrolysed,  giving  accurate  results  alter 
drying  ag/in  in  a  desiccator  oyer  sulphuric 
acid  ov  in  an  oven    at  90°  and    reweighmg 
before  titration.  .        .  , 

Fumaric  Acid. -Commercial  fumaric  acul 
was  found  to  be  too  impure  to  use  directly 
any  one    of  the  four   methods  given    above 
maVbe  used  to  purify  it.    The  normality  of 
Ihe  base    determined  with    16  samples    of 
fumarto  acid  ckied  to  constant  weight  ov^ 
sulphuric  acid  and  varymg  m  weight  from 
0.1280  to  0.4249  g.,    gave  an  average  value 
of  0.1082  N  with    an  extreme  variation    ot 
+0  0003  to  -0.0001  N;  the  normality  of  the 
base  determined  with  4  samples  o±  s^ccimc 
acid    averaged  0.1081  N  and    with    hydro^ 
chloric   acid  0.1082  N.       The  results  with 
fumaric  acid  dried  for  2  hours  m  an  oven  at 
temperatures  from  90-120°  gave  an  average 
vahie  of  0.1082  N  with  an    extreme  var  a- 
Ifon  of  Vo.0002  to  -0.0001  N.     The  results 
show  that    fumaric    acid    may  serve    as    a 
standard  in  alkalimetry  after  one  crystalli- 
sato  from  water,  although  a  higher  tem- 
perature of  the  solution,  must  be  maintained 
during  the    titration  because    of  the    lower 
solubility.  . 

Malic  ^cuJ. -Malic  acid  is  very  soluble  m 
water  and  was  therefore  recrystalhsed  by 
r^so  ving  in  hot  acetone,  filtering,  and  then 
•addinl  carbon  tetrachloride  to  the  hot  solu- 
tion and  allowing  the  acid  to  crys  alhse,  on 
cooling.  The  crystals  were  dried  m  air  lor 
about1^4  hours  and  then  dried  m  a  deBicca- 
;?or  over  sulphuric  acid  for  an  equal  length 


JANUARY  19,  1928. 


THE   CHEMICAL   NEWS. 


43 


of  time,  or  for  2  hours  in  an  oven  at  tem- 
peratures from  90°  to  120°.  The  normality 
of  the  base  determined  with  4  samples  of 
malic  acid  dried  over  sulphuric  acid  and 
varying  in  weight  from  0.2071  to  0.2742  g., 
gave  an  average  value  of  0.1081  N  with  an 
extreme  variation  of  +0.0001  N ;  the  nor- 
mality of  the  base  determined  with  hydro- 
chloric acid  and  with  sviccinio  acid  was 
0.1081  N ;  the  determination  with  samples 
of  malic  acid  dried  at  90  120°  gave  an  aver- 
age valu(!  of  0.1082  N  with  an  extreme 
variation  of  +0j0002  to  0.0001.  It  is  evi- 
dent that  malic  acid  can  i;i»ily  be  obtained 
pure,  and  because  of  its  greater  solubility 
would  be  more  valuable  a.s  a  standard  than 
either  maleic  or  fumaric  acids. 

Maleic  and  fumaric  acids  are  oxidised  by 
potassium  permanganate  according  to  the 
following  equation:*  C^H/)^  +  60  SCOj 
+  HjO  +  HCOOH.  Conflicting  statements 
are  made  by  previous  investigators  concern- 
ing the  quantitative  oours«'  of  this  reaction. 
TWs  work  was  repeated,  and  it  was  found 
that  although  these  acids  may  be  used  as 
standards  for  permanganate  solutions,  they 
are  not  as  accurate  nor  as  convenient  as 
sodium  oxalate.  This  is  due  to  the  low 
hydrogen  equivalent  of  the  acids  which 
necessitates  using  very  small  samples  with 
the  consequent  greater  cffoct  of  any  small 
errors  in  weighing  and  the  difl&culty  of  ti- 
trating boiling  solutions.  Titrations  of 
malic  acid  were  conducttd  in  the  same 
manner  but  the  results  were  too  variable 
and  inaccurate  to  be  of  any  value.  Experi- 
ments with  maleic  or  fumaric  acid  as  titrat- 
ing agent  with  0.1  N  iodine  solution  using 
starch  as  indicator  did  not  give  accurate 
results. 

Attempts  to  standardise  a  0.1  N  ammo- 
nium hydroxide  solution  by  titrating 
against  known  weights  of  malic,  maleic, 
fumaric  and  succinic  acids  using  either 
cochineal  or  methyl  red  as  indicator  were 
not  successful.  Although  it  is  evident  for 
theoretical  reasons  that  a  sharp  end-point 
cannot  be  obtained  in  titrating  a  weak  acid 
with  a  weak  base,  nevertilicless  conflictuig 
statements  have  been  made  by  previous  in- 
vestigators   on  the  use    of  succinic  acid   in 


*  Perdrix,  Bull.  toe.  chim.  Paris,  1900, 
[3]  XXIII.,  645.  Clarke,  Am.  Chem.  J., 
1881,  III.,  201.  Micko,  Z.  anal  Chem., 
1802  XXXI..  4fi5.  Z.  allgem.  ogterr. 
Apotheker  Ver..  1891.,  XXX..  197. 


the  standardisation  of  anunonium    hydrox- 
ide solution  with  cochineal  as  isua.  indicator.* 

Summary. 

It  is  evident  that  malic,  maleic,  and 
fumaric  acids  may  be  used  with  great  accu- 
racy as  standards  for  sodium  hydroxide  so- 
lutions; it  is  further  obvious  that  all  3 
acids  may  be  obtained  in  a  pure  form  very 
readily,  and  all  may  be  dried  over  sulphuric 
acid;  malic  and  fumaric  acids  may  be  dried 
for  2  hours  at  temperatures  from  90°  to 
120°;  iHHjause  of  the  formation  of  the  anhy- 
dride, samples  of  maleic  acid  should  not  be 
dried  above  100°.  As  standards  in  alkali- 
metry and  acidimetry  these  acids,  in  the 
pure  state,  are  as  (accurate  as  hydrochloric 
acid  determined  gravimetrically  as  silver 
chloride.  The  most  serviceable  of  these 
organic  acids  are  those  most  soluble  in 
water — malic  and  maleic  acids — although 
thev  are  no  more  accurate  than  fumaric 
acid.  Although  maleic  and  fumaric  acids 
may  be  used  as  standards  for  potassium 
pennangaoate  solutions,  they  are  neither 
as  aocinate  nor  as  convenient  as  sodium  ox- 
alate fcMT  this  purpose.  Succinic,  malic, 
maleic,  and  fumaric  acids  caimot  be  used 
as  standards  for  ammonium  hydroxide  ^so- 
lutioQs ;  the  Last  2  acids  cannot  be  used  for 
iodine  titrations. 

Cleveland,  Ohio. 


*  Phelps  and  Hubbard,  Z.  anorg.  Chem., 
1907,  LIIL,  361;  Am.  J.  Sci.,  1907, 
XXIU.,  211.  Peters  and  Sauchelli,  Am.  J. 
Set.,  1916,  XLI.,  244. 


A  PRELIMINARY  STUDY  OF 
ZIRKITE  ORE. 

By  J.  G.  Thompson. 

{From   "  The  Journal  of  Physical 
Chemistry,"   New  York,    December,   1922.) 

(Continued  from  Page  31.) 

The  partially  purified  carbide  apparently 
had  a  higher  melting  point  than  the  oxide 
product  with  the  same  relative  composi- 
tion. This  was  shown  in  the  runs  in  which 
the  ore  melted  and  formed  a  pool  under  the 
arc,  the  pool  solidifying  as  soon  as  more 
carixm  was  added.        In  order  to  use  the 


44 


THE   CHEMICAL   NEWS. 


JANUARY  19,  1923. 


carbide  as  a  refractory,  however,  it  would 
be  necessary  to  protect  it  from  oxidation. 
The  black  carbides  all  burned  readily  in 
the  air  to  forai  light,  fluffy  oxides.  Heat- 
ing the  powdered  carbides  to  dull  redness 
is  sufficient  to  start  the  oxidation,  which 
then  proceeds  slowly  but  persistently. 

The  data  show  that  some  titanium  was 
also  eliminated  but  no  iron,  there  being  an 
apparent  increase  in  the  amount  of  the 
last  impurity.  This  apparent  increase  in 
the  iron  content,  especially  in  the  case  of 
Bun  18,  is  due  to  the  difficulties  encoun- 
tered in  analysis.  The  samples  of  furnace 
products  must  be  pulverised  for  analysis, 
and,  since  the  amount  of  silicon  present  is 
of  primary  importance,  grinding  such 
abrasive  material  in  an  agate  mortar  is  out 
of  the  question.  The  only  other  method 
available  was  the  use  of  a  cast-steel  buck- 
ing board,  which  resulted,  naturally,  in 
contamination  of  the  samples.  In  view  of 
the  time  required  for  analysis  it  was  not 
considered  advisable  to  grind  additional 
samiples  in  an  agate  mortar  for  the  deter- 
mination of  iron.  From  a  consideration  of 
the  data  in  Table  III.,  therefore,  one  may 
safely  conclude  only  that  little  if  any  iron 
was  eliminated  under  the  conditions  of  ex- 
periment. 

Other  runs  were  made  in  which  sodium 
chloride  was  added  to  the  charge  of  ore 
and  coke  to  aid  in  the  removal  of  iron,  but 
curiously  enough  no  iron  was  eliminated  in 
this  way.  It  is  possible  that  the  rapid  at- 
tainment of  the  high  temperature  under 
the  arc  decomposed  the  chloride  before  it 
could  be  volatilised  away. 

Since  the  treatment  in.  the  electric  fur- 
nace was  not  successful  in  eliminating  the 
iron,  other  means  of  accomplishing  this 
end  were  sought. 

EXPERIMEKTS    ON    THE    REMOVAL    OF    IrON. 

Different  samples  o  fthe  various  electric 
furnace  products  all  showed  magnetic  pro- 
perties, due  presumably  to  the  presence  of 
iron  either  as  carbide  or  alloy.  Accord- 
ingly attempts  were  made  to  use  these 
magnetic  properties  as  a  basis  of  separa- 
tion of  the  iron,  but  the  attempts  were  not 
successful.  The  magnetic  portions  con- 
tained approximately  half  of  the  ziiroonium 
and  the  non-magnetic  portions  contained 
aippreciable  amounts  of  iron. 

Attempts  were  next  made  to  remove  the 
iron  by  leaching  with  5  per  cent,  sulphuric 


acid.^^  Both  the  carbide  and  the  corres- 
ponding oxidised  products  of  the  electric 
furnace  runs  were  leached  with  hot  and 
with  cold  5  per  cent,  sulphuric  acid.  The 
iron  in  the  carbide  appears  to  be  more 
susceptible  to  leaching  than  is  the  iron  in 
the  oxidised  material;  but,  even  in  the 
case  of  the  carbide,  less  than  half  of  the 
iron  could  be  removed  in  this  way. 

A  series  of  experiments  was  next  carried 
out  on  the  removal  of  iron  by  treatment  of 
the  carbides  or  mixed  oxides  with  chlorine^® 
at  both  low  and  high  t-emperatures.  The 
experiments  were  carried  out  in  a  small, 
horizontal,  tube  furnace,  and  the  frequent 
clogging  of  the  apparatus  by  the  volatile 
products  of  the  reactions,  especially  at 
Kigh  temperatures,  showed  plainly  that  a 
furnace  of  special  design  is  essential  for 
investigiation  of  this  possibility.  Never- 
theless, results  were  obtained  which  indi- 
cated that  iron  may  be  removed  in  this 
way  from  zirconium  carbide  at  low  tem- 
peratures, and,  at  high  temperatures,  from 
zirconium  oxide  from  which  silicon  had 
been  largely  eliminated  in  the  arc  furnace. 
It  would  seem,  therefore,  that  a  fairly  pure 
zirconia  for  refractory  purposes  might  be 
made  from  crude  zirkite  ore  by  eliminating 
in  an  electric  furnace  as  much  as  possible 
of  the  silicon  and  by  following  this  by 
treatment  with  chlorine  or  phosgene^ ^  to 
remove  the  iron. 

This  investigation  is  admittedly  incom- 
plete in  many  ways.  The  limited  time  at 
our  disiposal  and  the  difficulty  of,  and  the 
time  consumed  by,  the  analytical  work  in- 
volved, may  be  offered  as  an  excuse.  It  is 
hoped,  however,  that  attention  will  be 
called  to  the  problem  of  large-scale  purifi- 
cation of  zirconium  oxide,  so  that  the  lat- 
ter may  become  more  generally  available 
as  a  refractory  material  for  very  high  tem- 
peratures. A  summary  of  the  results 
obtained  follows : 

Summary. 

(1)  Ninety  to  ninety-five  per  cent,  of  the 
silicon  may  be  removed  from  siliceous  zir- 
kite ore  by  heating  a  mixture  of  ore  carbon 
to  a  temperature  greater  than  2,220°  C.  in 
an  electric  furnace. 

(2)  The  best  results    appear    to  be    ob- 


■'''''  Barton :  loc.  cit. 
■^•^  PhiUips  :  loc  cit. 
'^  BashervUle :   Science,  1919, 


L.,  443. 


JANUARY  19,  1923. 


THE    CHEMICAL    NEWS. 


45 


tained  by  feeding  into  an  arc  furnace  a 
mixture  of  ore  aud  coke,  the  amount  of 
carbon  being  aipproximatoly  that  required 
to  transfonn  only  the  silicon  to  the  car- 
bide. 

(3)  The  eixstence  of  stable  double  car- 
bides of  silicon  and  zirconium,  or  of  solu- 
tions of  silicon  carbide  in  Bolid  zirconium 
carbide,  has  been  suggested  ae  an  explana- 
tion of  the  incomplete  removal  of  silicon 
when  carbon  in  excess  of  that  required  to 
form  only  silicon  carbide  is  used. 

(4)  It  is  suggested  that  zirconia  sufli- 
ciently  pure  for  refractory  purposes  might 
be  obtained  from  zirkite  ore  by  removing 
the  silicon  in  an  electric  furnace  and  fol- 
lowing this  treatment  with  chlcwine  or 
phosgene  to  remove  the  iron. 

(5)  Attention  has  been  called  to  the  re- 
frnctory  properties  of  zirconium  carbide 
and  the  factors  which  limit  its  use. 

(0)  Methods  of  analysis  of  zirconium 
compounds  have  been  reviewed  briefly  and 
a  modified  scheme  of  analysis  has  been 
outlined  for  the  determination  of  zir- 
conium and  the  three  major  imipuritics, 
silicon,  iron,  and  titanium. 

Cornell  UnivergiUj,  1920. 


THE  ODOUROUS    CONSTITUENTS  OF 

APPLES.     II.     EVIDENCE  OF  THE 

PRESENCE  OF  GERANIOL.* 

By  Frederick  B.  Power  and  Victor  K. 
Chesnut. 

[Contribution    from      the     Phytochemical 

Lahoratonj    of  the    Bureau    of   Chemistry, 

United  States  Department  of 

AgricuUiire .] 

In  a  previous  commimioation*  it  was 
shown  from  the  results  of  a  somewhat  ex- 
tended investigation  that  the  odourous  con- 
stituents of  the  apple  consist  chiefly  of  the 
amyl  esters  of  formic,  acetic  and  caproic 
aoids,  with  a  very  small  amount  of  the 
caprylic  ester  and  a  considerable  proportion 
of  acetaldehyde.  It  has,  however,  been 
noticed  by  us  and  remarked  by  others  that, 
in  addition  to    the  odour  imparted    by  the 


♦  From  "  The  Jmimial  of  the  American 
Chemical  Society,   December,  1922. 

'  Power  and  Chesnut,  Jour.  Am.  Chem. 
Soc,  1920,  XLIT..  1509. 


above-mentioned  esters,  some  particularly 
choice  varieties  of  the  apple  have  a  dis- 
tinctly rose-like  odour.  We  had  further- 
more observed  in  the  j)revious  investiga- 
tions that  when  the  esters  contained  in  a 
concentrated  distillate  from  apple  parings 
were  hydrolysed,  the  alcoholic  product  so 
obtainwl  possessed  an  odour  which  was 
more  pleasant  than  that  of  pure  amyl  alco- 
hol, although  the  presence  of  the  latter  in 
predominating  amount  was  completely 
established.  It  was  thus  evident  that  the 
amyl  alcohol  was  aooompanied  by  a  rela- 
tively small  proportion  of  another  sub- 
stance of  alcoholic  naturc,  but  the  amount 
of  matt^rial  available  did  not  permit  of  its 
identification.  The  odour  of  the  above- 
mentioned  hydrolytic  product  had  sug- 
gested the  possibility  of  the  presence  of  the 
aliphatic  terpcnc  alcohol  geraniol,  C,nH,gO,^ 
which  is  known  to  (possess  a  rose-like  fra- 
grance, and  the  correctness  of  this  supposi- 
tion has  been  confirmed  by  the  results  of 
the  present  investigation. 

Experimental. 

In  order  to  accomplish  the  particular 
pxirpoee  in  view  it  was  desirable  to  employ 
one  of  the  most  fragrant  varieties  of  the 
apple,  and  the  well-known  Mcintosh  apple 
was  oonsequently  selected.  The  fniit  was 
obtjiined  from  the  Boston  market  and,  as 
in  the  previous  investigations,  only  the  par- 
ings were  used.  The  separation  of  the  thin 
rind  was  accomplished  by  means  of  a 
machine,  which  wae  so  adjusted  as  to  re- 
move only  a  very  small  portion  of  the  white 
substance  of  the  apple.  By  some  prelimin- 
ary weighings  it  was  frnmd  th.at  the  (propor- 
tion of  the  fresh  parings  to  the  entire  fruit 
was  approximately  12.5  per  cent. 

Extraction  of  the  Essential  Oil 
From  Apple  Parings. — A  quantity  (31.75 
kg.)  of  the  apple  parings,  without  any  fur- 
ther addition  of  water,  was  subjected  to 
distillation  with  steam  and  76  litres  of  dis- 
tillate collected.  The  entire  distillate  was 
"then  cohobated  in  a  current  of  stefljn  until 
the  odourous  consitituents  were  finally  con- 
tained in  a  volume  of  0.5  litre.  This  con- 
centrated liquid  was  extracted  five  times 
successively  with  ether,  the  ethereal  liquids 
being  then  dri(^d  with  anhydrous  sodium 
suliphate,  and  the  greater  part  of  the  sol- 
vent removed  by  distillation.  The  remain- 
ing liquid  was  allowed  to  evaporate  spon- 
taneously in  a  small,  tared  flask,  until  the 
residue  was  of  practically  constant  weight. 


46 


THE  CHEMICAL  NEWS. 


JANUARY  19,  1923. 


A  pale  yellow,  somewhat  viscjid  oil  was 
thus  obtained,  which  had  a  fra^mnt  and 
characteristic  apple-like  odour.  The 
•amount  of  this  product  was  0.6977  g., 
■which  corresponds  to  0.0022  per  cent,  of 
the  atpple  parings,  or  about  0.00027  per 
toent.  of  the  entire  fruit.  This  essential  oil 
gave  very  slight  reactions  for  acetaldehyde 
and  for  furfural,  and  was  similar  in  its 
general  characters  to  the  analogous  pro- 
ducts from  other  varieties  of  the  apple 
which  the  present  authors  have  previously 
described.^ 

From  Apple  Pulp. — In  order  to  ascertain 
whether  any  appreciable    amount  of  essen- 
tial oil  is  contained    in  the  fruit  -after  the 
removal  of  the  rind,     an  experiment    was 
conducted  with  a  ismall    quantity    of    the 
same  Lot  of  •Molntoish  apples  as  that  used 
for  the  main  investigation.    The  fruit,  alter 
being  pared  by  means  of  a  machine,    was 
cut  into  quarter  sections,  and  the  core  and 
seeds  completely  removed.     This  material, 
amounting  to  5  kg.,  was  then  distilled  in  a 
current  of  steam,  and  about  3  litres  of  dis- 
tillate collected.       The  slightly  opalescent, 
neutral  Hquid  was  less    fragrant  than  the 
'distillate  from  the  parings,  the  odour  some- 
•what  resembling  that  of  a  baked  apple,  and 
!t  gave  la  strong  reaction  for  acetaldehyde. 
The  entire  distillate    was  cohobated    in    a 
current    of  steam  until  the   odourous  con- 
fetituents    were    contained  in  a    volume  of 
0.5  litre.       This  concentrated    liquid    was 
completely      extracted     with     ether,      the 
ethereal  liquid  dried  with  anhydrous  sodium 
sulpha.te,   and  the  solvent  removed  as  pre- 
viously described.       A    pale  yellowish    oil 
was  thus    obtauied,     which    amounted    to 
0.0614  g.     or  0.000123    per    cent,     of    the 
weight  of  material  employed.     It  was  evi- 
dent from  this  result  that  the  odourous  con- 
stituents of  the    fruit  are  contained    most 
largely  in  the  outer  portion  or  rind.      This 
essential    oil    had     a    pleasant,     apple-like 
odour  and  gave  no  reaction  for  furfural. 

Hydrolysis  of  the  Esters  Contained  in 
THE  Apple  Distillate. 
For  the  purpose  of  obtaining  furtlier  in- 
formation respecting  ,the  esters  contained  m 
the  apple,  and  especially  to  ascertain 
•whether  geraniol  could  be  detected  in  them, 
a  considerable  quantity  (36.85  kg.)  of  apple 
parings  wafi  employed.  The  fresh  material 
was  hrought  into  a  still  and,  without  any 
further  addition  of  water,  subjected  to  dis- 
tillation in  a  current  of  steam.  About  76 
litres  of  distillate  was  collected,    and    this 


was   subsequently     cohobated   with     steam 
until  the   odourous  constituents  were   con- 
tained in  a  volume  of  1  litre.     To  this  con- 
centrated liquid,  which  was  contained  in    a 
flask  provided  with  a  reflux  condenser,  20  g. 
of  pure  sodium  hydroxide  was  -added,   and 
%he  whole  kept  in  a  state    of  active  ebulli- 
tion for  2  hours.       It  had  then  acquired  a 
'deep    yellow    colour     and    become    turbid, 
owing  to  the  separation  of  aldehyde  resin. 
After  cooling,  the  lalkaline  mixture  was  dis- 
tilled,   and  0.5  litre  of  distillate    collected. 
'This  liquid,    which  had  a    pleasant    odour 
and    contained    so-me  oily  drops,  was    ex- 
tracted 5  times  successively  with  pure,   al- 
*dehyde-free     ether,     the     imited     ethereal 
liquids  were   dried  with   anhydrous  so-di\im 
sulphate,  and  the  greater  part  of  the  ether 
was  removed  by  distillation.     The  residual 
liquid  was  then  brought  into  a  small  pres- 
sure   fliask,     in  which    it    was    allowed    to 
'evaporate  spontaneously  until  all  the  ether 
"had  been  removed.       A  yellowish  oil    was 
thus  obtained,    which  amounted  to  0.3641 
g.  and,  therefore,    represented  0.00098  per 
fcent.  of  the    weight  of    the  apple    parings 
employed.    This  oily  liquid  possessed  a  dis- 
tinct lodour  of  lamyl  alcohol,    biit  the  pre- 
sence of  a  more  fragrant  substance  was  >aiso 
■indicated. 

'Oxidation  op  the  Alcohols   Obtained   by 

Hydrolysis.      Formation  of  Valeric  Acid 

and    Citral  together  with    Acetone  and 

Levulinic  Acid. 

To  the  small  a-mount  -of  the  above-men- 
tioned hydrolytio  product  icontained  in  a 
pressure  flask  there  was  -added,  while  being 
kept  cool,  10  cc.  of  a  chromic  acid  mixture'^ 
hnd,  after  cln-sing  the  fl.ask,  the  whole  was 
heated  on  a  wa-ter-bath  at  a  temperature  of 
about  90°  for  15  minutes,  with  occasional 
agitation.  After  being  allo-wed  to  cool,  the 
toixture  was  diluted  with  water  and  ex- 
"bracte-d  5  times  sxiccessively  with  freshly 
distilled,  aldehyde-free  ether.  The  united 
ethereal  liquids  were  washed  thrice  with 
water,  dried  with  anhydrous  sodium  sul- 
•phate,  and  the  greater  part  of  the  ether  was 
removefl  by  -distillation.  The  liquid  was 
then  transferred  to  a  small  distilling  flask 
*in  which  the  remaining  ether  was  allowed 
to  evaporate  spontaneously,  the  last  portion 
of  the  solvent  being  removed  -by  aspiration. 
A  small  a.mount  of  an  oily  liquid  was  thus 


J.  praht.  Chem.,  1892,  XLV.,  599. 


JANUARY  19,  1923. 


THE  CHEMICAL  NEWS. 


47 


obtained,  to  which  some  water  was  added, 
and  the  product  then  distilled  in  a  current 
of  steani.  Two  fractions  of  distillate, 
amounting  to  5  oc.  and  25  oc.  respectively, 
wert'  collected.  The  first  portion  was 
strongly  acid,  contained  on  the  surface  a 
small  globule  of  yellowish  oil,  and  possessed 
a  distinctly  lemon-like  odour  together  with 
the  odour  of  valeric  acid. 

Occurrence  of  Geraniol  in  the  MdnioHh 
Apple. — A  very  small  portion  of  the  above- 
mentionerl  acid  distillate  gave  with  SchifT's 
reagent  a  deep  ipurplish  colouration,  similar 
to  that  yieFded  by  oitral  and  quite  different 
from  the  colour  produwd  bv  the  ordimirv 
aliphatic  aldehydes,  it  is  also  rapirily  re- 
duced an  ammoniatMil  solution  of  silver 
oxifk*.  These  rci^ults,  together  with  the 
odour  of  the  original  h.\(lralji;ic  product, 
olearly  indicated  the  prow-noe  in  the  latter 
of  aismall  amount  of  geraniol.  Inasmuch 
as  th<'  further  oxidation  products  of  geraniol 
orcitral  are  acetone  .and  Icvulinic  «cid.  the 
probable  formatirm  of  small  amounts  of 
these  suUtanees  was  also  c^msidered.  About 
0.5  oe.  of  the  above-mentioned  5  oo.  of  dis- 
til laU*  was  oonsequenrtly  ti^stod  for  acetone 
by  imeans  of  the  iodoform  n\'Mjtion ;  distinct 
oryistals  of  the  latter  subetence  were 
obtained. 

In  order  to  obtain  evidence  of  the  pre- 
sence of  levulinio  acid,  \kw  amount  of  which 
would  be  extremely  snail,  consideration 
was  taken  of  its  kotonic  character  and  ca<pa- 
bllitv  of  yielding  iodofomi.  The  following 
method  was  therefore  employed  for  its  de- 
tection. After  the  complt  tv  distillation  of 
the  oxidation  produot  with  steam,  as  above 
described,  the  liquid  remaining  in  the  dis- 
tillation flask-  was  extracted  thrice  with 
ether,  the  united  ethereal  liquids  were  dried 
with  anhydrous  sodium  sulphate,  and  the 
greater  portion  of  the  ether  was  removed 
by  distillation,  the  residual  liquid  being 
allowe-<l  to  evaporate  ispontaneously.  A  very 
slight  amorf)hous  rt^sidue  wa.s  thus  obtained 
which  was  heated  for  a  <?hort  time  on  a 
stmm-hath  in  order  to  expel  any  trace  of 
volatile  substance.  When  cold  it  was 
tn'at^'d  with  a  little  water,  the  filtered 
liquid  made  slightly  alkaline  with  sodium 
hydroxide  and  a  few  droips  of  iodine  solu- 
tion added,  when  a  separation  of  iodoform 
soon  ensued. 

The  results  of  the  above  tests  will  be 
seen  to  have  given  quite  definite  indications 
of  the  formation  of  smiall  amounts  of  both 
acetone  and  levulinio  acid,  together  with 
citral,     by    the   oxidation    of   the     above- 


described  product  of  hydrolysivs,  and  they 
are  therefore  believed  to  afford  satisfactory 
evidence^  of  the  presence  in  the  latter  of 
geraniol, 

Occiirrence  of  Amyl  Esters  in  the  Mc- 
intosh Apple. — Although  a  previous  inves 
tigation  by  the  present  authors'  had  estab- 
ilshed  the  fivct  that  the  odourous  constitu- 
ents of  certain  varieties  of  the  apple  consist 
chiefly  of  various  amyl  estei-s,  their  pre- 
sence in  the  Mcintosh  apple  has  now  also 
been  determined.  As  already  noted,  the 
product  obtained  by  the  hydrolysis  of  the 
concentrated  aqueous  distillate  possessed  a 
dist'nct  odour  of  amyl  alcohol,  and  when 
subjected  to  oxidation  by  chromic  acid, 
with  subsequent  extraction  by  ether  and 
distillation  of  the  ethereal  extract  in  a  cur- 
rent of  steam,  it  yielded  a  strongly  acid 
liquid  containing  some  oily  drops.  It  was 
al.so  observed  that  the  odour  of  this  liquid 
indicated  the  presence  of  both  citral  and 
valeric  acid. 

In  order  tf>  ♦stablish  the  identity  of  the 
last-montif>ned  substance,  the  first  portion 
of  the  aqueous  <liBti]1ate,  which  had  re- 
sponded to  tiu'  tests  for  both  citral  and 
acetone,  \vns  made  alkaline  with  baryta, 
when  the  oilv  drops  almost  comipletely  dis- 
appeared and  the  lemon-like  odour  of  the 
liquid  became  much  more  pronounced.  The 
Wo  portions  of  distillate  were  then  imited, 
and  the  alkaline  liquid  was  extracted  thrice 
with  pure  ether.  The  ethereal  liquids, 
after  being  washed  with  a  little  water  and 
dried  with  anhydrous  sodium  sulphate, 
were  allowed  to  evaporate  spontaneously, 
when  a  slight  residue  was  obtained  which 
(possessed  a  distinct  lemon-like  odour. 
When  this  residue  was  shaken  with  sensi- 
tized Schiff'e  reagent  it  soon  developed  the 
characteristic  purple  colour  produced  by 
citral. 

After  extraction  with  ether,  as  above  de- 
scribed, the  alkaline  liquid  was  concen- 
trated, filtered,  the  excess  of  baryta  re- 
moved by  carbon  dioxide,  and  the  liquid, 
which  was  now  perfectly  neutral,  again  fil- 
tered and  concentrated.  On  the  addition 
of  silver  nitrate  it  yielded  a  small  amount 
of  a  white,  curdy  precipitate,  which  was 
collected,  dried,  and  analysed. 

.Analysis.  Subs.,  0.0685:  Ag,  0.0848. 
GjiIc.  for  Ag,  CjH.O,:  Ag,  51.7.  Found: 
50.8. 

A  trace  ol  the  silver  «alt,  when  moistened 
with  dil.  sulphuric  acid,    developed   a  dis- 
tinct odour  oif  valeric  acid.     These  results 


THE  CHEMICAL  NEWS. 


JANUAEY  19.  1923. 


may,  therefore,  be  considered  to  confirm 
the  presence  of  amyl  esters  in  the  particular 
variety  of  apple  now  examined. 

Although  the  present  investigiation^  of 
Mcintosh  apples  was  conducted  primarily 
for  the  purpose  of  deteraiining  the  presence 
of  geraniol,  consideration  was  also  given  to 
all  the  constituents  that  had  previously 
been  found  in  other  varietiesi  of  the  fruit. 
The  methods  adopted  for  the  separation 
and  identification  of  these  constituents, 
with  the  exception  of  the  oxidation  products 
of  the  alcohols,  were  practically  the  same 
as  those  previously  employed,  and  therefore 
require  no  further  description.  The  results, 
with  the  following  slight  exception,  were  in 
com)plete  a-ocordiance  with  those  previously 
obtained.  A  very  small  amount  (0.06  g.)  of 
a  paraffin  hydrocarbon,  which  separated 
from  the  original  distillate  of  the  a,pple  par- 
ing®, was  obtained  in  the  form  of  minute, 
acicular  crystals,  melting  quite  sharply  at 
54°.  It  differed  in  appearance  from  the 
analogous  substance  previously  obtained 
from  the  Ben  Davis  apple,  which  melted  at 
63°. 

Conclusions. 

An  examination  of  Mcintosh  apples, 
which  represent  a  pni'ticularly  fragrant 
Variety  of  the  fruit,  has  confirmed  the  re- 
sults of  a  previous  investigation  thatthe 
odourous  oorLstituents  of  the  apple  consist 
chiefly  of  amyl  esters,  and  it  has  also 
afforded  further  information  respecting  the 
substance  which  imparts  to  some  ajpples  a 
distinctly  rose-like  odour.  Although  the 
propqirtion  of  this  substance,  even  in  the 
Mcintosh  apple,  is'  extremely  small,  it  has 
nevertheless  been  possible  to  determine 
with  a  considerable  degree  of  certainty  that 
it  consists  of  the  aliphatic  terpene  alcohol 
geraniol  G^^H^fi.  The  evidence  for  this 
conclusion  imay  be  adduced  from  the  fact 
that  by  the  hydrolysis  of  the  esters  of  the 
apple  a  product  was  obtained  which 
possessed,  in  addition  to  the  odour  of  amyl 
alcohol,  a  rose-like  fragrance,  and  that  by 
the  oxidation  of  this  product  it  yielded,  be- 
sides valeric  acid,  a  substance  which  had 
the  characteristic  odour  and  other  proper- 
ties of  the  laldehyde  citral.  At  the  same 
time  the  formation  in  very  smiall  amounts 
of  the  further  oxidation  products  of  geraniol 
or  citral,  which  are  acetone  and  levulinic 
acid,  was  decisively  indicated.  It  is  prob- 
able that  geraniol,  either  iri  the  free  state 
or  in  the  form  of  esters,  is  contained  in 
varying    amounts    in     all     the     numerous 


vaireties  of  the  apple,  although  to  the 
gi-'eatest  extent  in  those  which  possess  its 
disitiinotttve  odour. 

Washingto7i,  D.C. 


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Latest  Patent  Applications. 

348&1 — Etablissements  Pouleno  Freres. — Manufac- 
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acids.    Dec.  21. 

34846 — Made],  G. — Roasting  or  calcining  ores. 
Deo.  21. 

34479 — Parrish,  P. — Distillation  of  ammoniacal 
liquors.    Dec.  18. 

Specifications  Published  this    Week. 

18947.5 — Helps,  G. — Manufacture  of  gas. 

189542— Ironside,  T.  G.— Process  of  distilling  oil 
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Abstract  Published  this  Week. 
Synthetic  Drugs. — Patent  No.  188127.— Messrs. 
Cassella  &  Co.,  Ges.  L..  of  Frankfurt-on-Main, 
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fatty  acids.  The  product  is  prepared  by  treating 
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methylacridinium  stearate,  2  :7-dimethyl-3  :6-di- 
amino-10-methylacridinium  stearate,  and  3 :6- 
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I 


JANUAEY  26,  1923. 


THE   CHEMICAL    NEWS. 


49 


THE   CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3276. 


A   NEW    SYSTEM   FOR   THE   LINEAR 

REPRESENTATION  OF  THE 

STRUCTURE  OF  ALL  ORGANIC 

COMPOUNDS. 

By  T.  Sherlock  Wheeler,  B.Sc, 
A.R.C.Sc.L,  A. I.e. 

(Contiwaed  from  I'age  35.) 
Bridges  are  shown  as  cliain-s  linked  to  a 
ring  in  two  positions,  just  as  two  positions 
at  which  rings  are  fused  an-  shown.  X.  is 
AI.  VI.  2,  3  VI.  2,  5  III.  (N-2,  2 -Me).  It 
is  to  be  noted  that  the  niunbering  of  the 
bridge  is  from  the  oomnion  camon  first 
given,  in  this  case  from  "  2."  Bridged 
rings  can  also  be  considered  as  two  ring 
systems  fused  in  ortho,  ineta,  para  rnd 
other  positions.  The  rules  given  for  the 
ortho-hold  for  the  meta-  and  para-  fused 
rings,  except  that  it  is  the  extreme  (t'}r- 
tiary)  common  carbons  that  are  given  in 
passing  from  one  ring  to  another;  the  num- 
bering of  the  second  ring  begins  at  the  ex- 
treme left-hand    common    carbon.       Some 


CH^ 


ZL 


meta- fused  rings  are  known;  with  the  ex- 
ception of  bridged  rings  para-fused  rings  sre 
unknown  to  the  present.  Compounds  of 
the  type  of  XL  do  not  seem  impossible 
especially  if  the  six  membered  ring  shown 
be  aromatic,  as  then  the  valencies  "ab" 
«uid  "cd"  are  fixed  dn  a  plane.  XI.  is 
Al.  VI.  1,  4  XIV.  The  second  ring  in  para- 
fused  compounds  can  usually  lie  equally 
well  on  either  side  of  the  first.  Adherence 
to  the  rule  that  the  left-hand  common  car- 
bon is  given  first  is  sufficient  to  show  on 
which  side  of  the  first  ring  the  second  one 
lies.  Al.  VI.  4,  1  XIV.  would  be  XI.  with 
the  second  ring  on  the  other  side  of  the 
first.  In  the  example  given,  these  tvvo 
compounds  would  be  identical,  but  cases 
oould  occur  where  that  would  not  be  to. 
The  same  holds  for  rings  fused  in  any  posi- 
tion, but  the  (lucstaon  is  not  likely  often  to 
arise. 

The  same  syn^bols  preceded  by  Ar.  and 
Al.  always  reprt^sint  similar  systems  except 
in  one  case.  That  is  when  .jv  ring  has  two 
adjacent  sides  common  t-o  two  other  rings. 
XII.  is  Ar.  VL  2,  3  VL  T),  6  VI.,  and  val- 
ency considerations  show  that  the  first  and 
the  thin!  rings  must  be  fused  as  shown. 
But  the  consistent  interpretatic«i  of  Al.  VI. 
2,  8  VI.  6,  6  VI.    is  XIII.,    and  not    XII. 


31 


fully  reduced.  To  describe  the  latter,  the 
third  ring  is  considered  as  a  chain  joining 
the  second  and  the  first,  and  it  becomes 
Al.  VI.'  2,  3  VL  6,  4'  T.  Any  alioyolio 
conipound  can  be  dealt  with  in  this  way.  It 


50 


M 


THE   CHEMICAL    NEWS. 


JANUARY  26,  1923. 


will  be  noted  how    the  index  identifies  the 
ring  to  which  we  return. 

Since  aromatic  rings  are  seldom  written 
with  the  fourth  bond,  there  is  no  need  to 
indicate  which  method  of  disposing  of  it  is 
being  used.  Should  it  be  necessary  to  do 
this  ,a  prefix  "On"  for  the  centric,  or  "K" 


^H^ 


for  Kekul^'s  method,  tan  be  employed.  If 
it  be  desired  to  have  :iny  conjugated  bonds 
represented  on  Thiele's  system,   the  prefix 


"Th"  is  placed  before  the  ordinary  symbol 
for  them.  "  Cis, "  "  trans,"  and  such  like 
stereo-chemical  terms  are  to  be  used  with 


H.C 


o^n; 


X 

c 

II 

c 

3 


fio. 


U       S 


Yv 


their  present  meanings.  They  are  put  in 
between  the  symbols  of  the  groups  or  the 
elements  to  which  they  refer.  XIV.  is 
TV.  (1:4=  (OH).,  1:4^(0.)2,  A  ",  1  trans 
4).  XV.  is  "v.  (2-Br  trans  3- NO,,  A  ^). 
Fischer's  "  +  "  and  "-"    system  is    used 

I  OttvON 

1.    W  ceH 

3.   H  coH 
(^   Ho6  H 

6.    CHrOK 


for  the  sugars    and  such    Uke    asymmetric 

+ 

comjpounds.     XVI.  is"VI.   (2  : 3  : 5  S  (011)3 

+  +  -  + 

4£(T)H),  l:6  =  (OH)2),  or  VI.  (1:2:3:4:5:6 
=  (OH)g).      Cis  and  trans  compounds  can 

"also  be  shown  by  the  use  of  the  same  nota- 

+ 

tion;  XVII.,  e.g.,  is  W(2-G1,  3-Br,  A  ')• 
Of  course  "  + "  and  "  -  "  then  have  not 
quite  the  same  meaning  in  lasymmetric  and 
in  stereo-chcmioal  compounds,  but  the  no- 
tation is  convenient  and  no  ambiguity  is 
likely  to  arise.  In  compounds  like  the 
sugars,   etc.,    the    conventions    as    to    the 


1 

-C-OL 

II 

ISt.  - 

-'^-^ 

graphical  formula  being  written  with  the 
aldehyde  group  on  top  before  the  plus  and 
minus  rule  is  applied,  etc.,  are  adoipted. 

J 
{To  be  Continued.) 


JANUARY  26,  1923. 


THE  RAKE  EARTHS  AND  THEIR 
METALS. 


THE   CHEMICAL    NEWS. 


51 


By  John  Missenden. 


I. — The  Composition  of  the  Rake  Earths. 

(a)  In  view  of  the  fact  that  so  little  has 
been  known  of  the  properties  and  reactions 
of  many  of  the  rare  earth  metals  (and, 
accepting  the  periodic  system  for  the  classi- 
fication of  the  elements  as  mathematically 
authentic,  there  is  littk'  doubt  that  others 
have  yet  to  be  discoverer!),  and  that  the  re- 
sults of  the  majority  of  cliemists  differ  to  a 
more  or  less  marked  degree,  it  is  small 
wonder  that  consideralile  differences  of 
opinion  prevail.  The  difficulties  have  not 
lain  so  much  in  the  metals  themselves  as 
in  their  sources.  The  complexity  of  the  so- 
called  rare  earths — their  very  composition, 
in  the  majority  of  instances,  comprising 
moi'e  separate  elements  in  l)oth  mechanical 
and  chemical  association  than  any  other 
class  of  earth — demands  so  much  care  and 
precision  in  analysis,  that  only  the  most 
up-to-date  methods  of  investigation  can  be 
cal'ed  into  use  for  the  production  of  satisfy- 
ing and  exhaustive  data. 

But  the  diflBculties  confronting  modem 
researchers  are  not  nearly  so  formidable  as 
those  faced  by  Klaproth.  Berzelius,  and 
Hisinger,  Gadolin,  Moeander,  and  a  host  of 
otluTs.  These  chemists — whose  investiga- 
tions ran  over  a  perio<l  from  1793  (or 
1794)  to  the  end  of  the  nineteenth  century 
— examining  m)t  only  the  actual  earths 
thoms^-Ives,  but  also  (as,  specifically,  in  the 
case  of  Mcndel(5eff,  who  will  be  dealt  with 
later)  daring  to  predict  the  presence  of  im- 
discovered  elements,  stark^d  u^pon  a  tram 
of  research  which  was,  perhaps,  one  of  the 
most  difficult  branches  of  chemistry.  Cer- 
tainly, it  was  (and  still  is)  the  meet  interest- 
ing of  all  the  metal  groups. 

(h)  Because  the  first  of  these  mineral 
earths  was  discovered,  according  to  the  re- 
cf>rd«  dealing  with  that  period,  in  S'weden, 
much  of  the  credit  for  finding  them  is  due 
to  the  professors  and  others  studying  in 
thaf  country.  Some  idea  of  the  arduity  of 
thoir  task  can  be  gained  by  noting  the  dat.cs 
which  mark  the  intervals  of  bringing  to 
light  even  the  actual  earthe  themselves, 
disregarding  for  a  moment  the    separation 


of  the  metals.  For  instance,  six  years 
elapsed — six  years  of  strenuous  work — be- 
tween the  discovery  of  gadoUniie  (1788), 
and  yttria  (1794),  which  formed  part  of  its 
composition.  Geria  (1803)  was  not  siplit  up 
until  'thirty-six  years  had  elapsed;  while 
didymia  (1841)  resisted  analytical  efforts 
for  thirty-eight  years. 

(c)  GadoUniie,  then,  discovered  by  Pro- 
fessor Gadolin,  who  came  from  Abo,  the 
one-time  capital  of  Finland,  formed  the 
basis  of  subsequent  experiments.  Referring 
to  the  works  of  Petersson,  which  are  dated 
more  than  a  century  later,  it  is  found  that 
this  mineral  earth  consists  of,  among  other 
compounds:  yttrium  oxide,  YjO,,  45.3  per 
cent. ;  cerium  t^es^ui  oxide,  CcjO^,  3.84  per 
cent.  (?);  didyraium  trioxide,  DijO,,  and 
lanthanum  oxide,  LajO,,  jointly  2.57  per 
cent. ;  and  a  profusion  of  the  simple  oxides 
of  the  commoner  elements,  such  as  iron, 
manganese,  and  silicon.  So  gadolinite  has 
come  to  be  regarded  as  one  of  the  main 
sources  of  yttria,  which,  in  its  turn,  yields 
the  corresponding  metal. 

Following  Gadolin 's  separation  of  yttria 
from  gadolinite  in  1788,  Mosander  further 
separated  the  earth  into  three  parts,  pro- 
ducing the  yttria  (as  it  is  generally  accepted 
to-day),  erhia,  and  terbia.  This  was  in 
1843.  Here,  it  seems,  he  abandoned  his 
investigation,  for  in  1860,  Berlin  re-named 
terbia  as  erbia.  In  1878,  Delafontaine  re- 
named the  former  erbia  as  terbia,  and  de- 
clared it  to  be  incapable  of  further  separa- 
tion. Soret,  in  the  same  year,  more  closely 
investigated  the  newly  aippellated  erbia, 
with  the  result  that  he  separated  an  un- 
known earth  (Soret'«  X). 

Even  now,  these  earths  were  not  in  their 
more  elementary  form.  Erbia  was  further 
examined  by  Cleve  (1879),  and  another 
earth,  thulia,  discovered;  but  this  discovery 
settled  finally  the  complete  separation  of 
this  particular  compound, 

Soret 's  X  was  also  studied  bv  Cleve  in 
the  same  year,  and  he  re-nameci  it  holniia, 
although  it  was  left  to  Lecoq  de  Boisbou- 
dran  to  ipr<jduce  jet  another  base,  which 
he  called  dyaprosta.  In  order  to  show  the 
extreme  complexity  of  the  original  yttria, 
the  following  table  is  appended:  — 


52 


THE   CHEMICAL    NEWS. 


JANUARY  26,  1923. 


Yttria 


Yttria 


Erbia 

I 
Terbia 


Terbia 

.     I 

Erbia 


Soret's  X 
(Holmia) 


Erbia 


Holmia  Dysprosia     Thulia 


Erbia 


ogy  is  found  a  detail<-'<l  tabulated  analysis 
of  cerite  compiled  from  the  results  of  Ldnd- 
strom  (1873).  The  figures  tally,  to  a  cer- 
tain extent,  with  those  obtained  from  the 
recently  mined  (specimen ;  but  Lind&trdm 
felT  .short  of  his  100  parts  by  0.48  per  cent. 
As,  however,  he  only  shows  3.44  per  cent, 
of  wiater,  the  probability  is  that  he  lost  the 
remaining  negligible  peroenitage  by  evapora- 
tion. The  recent  sipecimen  showis  a  con- 
aiderable  i:ncrea.se  in  water;  that  is  to  say, 
5.63  per  cent. 

In  the  reduction  of  this  earth,  insoluble 
oxalates  of  >the  metals  are  precipitated  from 
the  (salits  in  solution.  Betoauise  all  the 
earths  differ  from  each  other  to  such  a 
small  extent,  discrimination  between  them, 
save  by  processes  of  separation  and  chemi- 
cal peculiarities,  is  impossible.  This 
branch  of  the  subject  will  be  dealt  with 
later. 

(d)  The  next  of  these  mineral  earths  to 
be  discovered  was  ceriite.  This  was  due  to 
Klaproth  (1803),  who  found  it  at  Riddar- 
"hyttan.  Subsequent  examination  by  two 
other  cihemists  was  responsible  for  the 
opinion — astonishingly  erroneous — ^that  this 
oerite  was  the  oxide  of  the  new  elementary 
anetal  which  they  christened  cerium. 
Mosander,  however,  in  1839,  proved  that 
such  was  not'  the  case,  and  produced  an- 
other mineral  which  he  called  lantJiana. 
As  in  the  ciase  of  yttria,  so  in  the  case  of 
oeria.  This  new  lanthana  comprised  didy- 
mia,  from  which  samaria  (Boisbaudran), 
neodymia  and  praseodymia  (Aver  von 
Welsbach)  were  obtained.  Thus  a  second 
table  may  be  evolved,  as  follows:  — 


Ceria 


Ceria 


Lanthana 

(Aav^ttvw) 


Lanthana 


Samaria 


Didymia 

(SlSv/lhol) 


Didymia 


Neodymia 


Praseodymia 


A  specimen  of  oerite,  mined  at  Lovon, 
bore  isome  similarity  to  I'etersison's  gadoH- 
nite,  wliich  was  mined  at  Ytterby.  It  con- 
tained , among  other  compounds,  26.87  per 
cent,  of  cerium  sesquioxidc,  GgOg ;  18.22 
per  icent.  of  lUdymium  trioxide;  and  15.95 
per  cent,  of  lanthanum  oxide,  La^Og ;  the 
bulk  of  the  remaining  100  parts  being  com- 
iposed  mostly  of  silicia.     In  Dana's  Minfirai- 

(e)  Feryudonite,  described  as  a  niobate  of 
erbium,  cerium  and  yttrium,  wias  examined 
by  Rammelsberg.  He  selected  a  specimen 
from  the  Godtbaab  region  in  Greenland, 
and  found  that  it  contained  24.87  iper  cent, 
of  yttrium  oxide,  9.81  per  cent,  of  erbium 
oxide,  2  per  cent,  of  cerium  sesquioxide, 
44.55  per  cent  .of  niobium  jxintoxide,  5.63 
pe  roent.  of  lanthanum  oxide,  and  6.3  per 
cent,  of  tantalum  pentoxide.  In  his  ex- 
amination, however,  he  fell  short  of  the  100 
parts  by  0.9.  There  is  no  ©vidence  to  hand 
to  show  the  cause  of  this  deficiency,  but  the 
belief  is  justified  that  he  also  liost  a  con- 
siderable amount  of  water  by  evaiporation. 

A  specimen  obtained  from  Chattanooga, 
in  Tennessee,  differs  widely  from  Rammels- 
berg'e  specimen.  Here,  only  20.08  per 
cent,  of  yttrium  oxide  was  present,  with  a 
corresponding  decrease  in  the  quantities  of 
the  other  oxides,  and  an  increase  in  iron 
monoxide.  Tables  embodying  the  later 
analyses  will  be  reproduced  at  the  conclu- 
sion of  this  section. 

(/)  Saniarskite.  This  earth,  perhaps, 
contains  a  more  varied  assortment  of  the 
rare  earth  metals  than  any  other.  It  is  re- 
garded as  the  main  souixie  of  didymia,  from 
which  the  pure  didymium  is  obtained.  In 
1877,  Allen  succeeded  in  analysing  it  with 
a  remarkable    degree    of    accuracy;    whiie 


JANUARY  26,  1923. 


THE   CHEMICAL   NEWS. 


53 


Welabach  (1884-5),  studying  it  even  more 
cIoBcly,  pnxluced  the  two  metals,  neody- 
miuiii  and  prast'(Klymiiini.  This  has  been 
already  dealt  with  in  brief,  the  original 
ceria.  being  quoted  as  the  prinjaiy  source. 
Samarsldte,  also,  contains  eonsiderablo 
puantities  of  uranium  and  (tantalum;  so 
much,   indeed,    that  Roscoe  refers  to  it  as 

Urano-tantalate."  At  the  same  time,  it 
is  by  no  means  the  chief  source  of  uranium, 
pitcheblende  containing  the  impure  urano- 
uranic  oxirle,  UjOg,  to  tht  extent  of  75  per 
cent.  approxim«tely. 

Aoconiing  to  Allen,  who  obtained  his 
specinit-ns  from  the  mountainous  west  of  N. 
Carolina,  cerium  8es<juir)xide,  didymium 
trioxide  and  Innthanum  oxide  are  jointly 
present  to  the  extent  of  4.17  p«^r  cent. ; 
while  of  uranium  trioxide  there  is  12.45  per 
cent.,  and  of  tantalum  p<'ntioxide  there  is 
18.2  per  cent.  A  later  specimen  from  the 
same  district  more  or  lesB  confirms  his 
figures.  The  earth  is  described  as  a  tanta- 
]Rte  and  niobate  of  yttrium,  erbium, 
cerium,  uranium  and  iron. 

(g)  Euxcnitc  hws  In^en  investigated  by 
Nilfton  in  1879  (Bcr.  Dcuf.  Chew.  Qes., 
1879,  XII.,  554),  froffn  which  he  obtained 
the  oxirle  of  soanduim.  Ri'ferrinp;  Again  to 
the  analyses  of  lljimmelsl)erg,  it  is  com- 
posed mainly  of  yttrium  oxide,  erbium  ox- 
ide, wrium  sesquiox-ido,  and  the  higher 
ox.ides  of  niobium  and  tin.  Uranium  is 
also  present.  Although  RamimeJsberg 
made  a  very  careful  s«'paraiion,  extending 
his,  study  with  great  oarc  he  failed  to  ob- 
tain accurate  results,  finally  obtaining 
101.50  parts.  This  considerable  error  is 
prolwibly  due  to  his  estimation  of  niobiimi, 
the  figure  for  which  is  35.83  per  cent.  Pro- 
portions which  will  Iw  far  more  acceptable 
are:  yttrium  oxide,  18.02;  erbium  oxide, 
9.85;  CA'rium  si'squiexide.  2.38;  niobium 
pentf>xide,  32.21  ;  stannic  oxide,  25.97. 

(h)  Thorite,  fvwo  for  its  .')8.91  per  cent,  of 
thorium  oxide,  tand  its  iscanty  complement 
of  uranium  trioxide  (1.72  per  cent.)  is 
barely  worth  mention.  Yttrocerite,  which 
is  the  main  source  of  cerium  fluoride  and 
yttriimi  flucrite,  is  found  in  numerous 
places,  but  a  detailed  analysis  is  not  yet  to 
hand ;  it  will  bi'  dealt  with  more  fully  flt  a 
alter  date.  Mmia-zite,  which  was  discovered 
by  Karsten  while  he  was  investigiating  the 
properties  and  source  of  thorium,  is  de- 
scribed fus  a  phosphate  of  lanthanum  and 
cerium.  Kai-sten  gives  the  figures  :  lantha- 
num oxide,  23.4  per  cent. ;  and  cerium  ses- 
quioxide,    26  per  cent.        Yttrotantalite    is 


composed  of  27.69  per  cent,  of  yttrium 
oxide,  12.44  per  cent,  of  erbium  oxide.  1.9 
per  ceut.  of  cerium  (sesquioxide,  42.12  f»er 
cent,  of  niobium  ipemtoxide,  and  0.22  per 
cent  .of  tungsten  trioxide  (Rammelsberg). 
Orafujeite,  investigated  by  Bergman,  con- 
tains 74.26  per  cent,  of  thorium  dioxide. 
Cohnnhite,  investigated  bv  Blomstrand  in 
1865  (Journ.  Prakt.  Chev,\,  1866,  XCVII., 
87),  varies  greatly  according  to  ilfcs  locality. 
Whereas  n  Matvsachu setts  it  contains  28.55 
per  cent,  of  t-antalum  pentoxide  and  no 
traces  of  leml.  the  specimen  obt4vined  from 
Godthaab  contained  no  tantalum  whatso- 
ever, the  oxide  being  replaced  by  a  con- 
siderable increase  in  the  amount  oif  niobium 
pentoxide,  while  the  amount  of  lead  mon- 
oxide extant  is  0.12  per  cent.  Tantalite  Is 
composed,  in  the  main,  of  76.34  per  cent, 
of  ttfvntalum  ptmtoxide.  13.9  per  cent,  of 
iron  monoxide,  and  7.54  ,per  cent,  of  nio- 
Wuni  pentoxid*'.  Pyrochhr  contains  10.98 
per  cent,  of  tiitanium  dioxide,  7  per  cent, 
frf  cerium  sesquioxide,  7.56  per  cent,  of 
thorium  dioxide,  and  50.11  per  cent,  of  nio- 
bium  pentoxide.  Both  of  these  last  earths 
were  investigattvl  ,by  Rammelsiberg. 

There  is  also  an  extensive  list  of  other 
earths,  as,  for  instance,  orthite,  acanthite, 
and  daUminzitc.  These  do  not,  however, 
yield  sufficient  quantities  of  the  metals  to 
be  regarded  as  important.  In  every  case, 
they  come  within  the  aiphere  of  othw 
meitatlR,  such  as  silver,  aluminium,  etc. 

A  few  little-known  rare  earths  are  le- 
lieved  to  exisft  as  separate  from  thoee  al- 
ready mentioned.  Lanthanite  contains 
cerous  carbonate ;  decipite  is  a  component 
of  some  forms  of  samarskite ;  and  lanthano- 
fantalitc  is  a  complex  earth  undiscovered 
until  the  end  of  1921.  These  are  typical 
examples. 

(0  The  accompanying  table,  comipilcd 
from  accepted  authorities,  has  had  per- 
sonal results  added.  The  uppermost  quo- 
faitions  are  the  results  obtained  by  the 
chemist  whose  name  appears  at  the  head  of 
the  column.  It  would  perhaps  be  as  well 
to  mention  that  the  table  is  by  no  means 
comiplete,  numerous  unimportant  oxides 
being  omiHtd.  It  does,  however,  embody 
everything  having  significant  bearing  upon 
the  subject  in  hand. 

(/)  Two  earths  have  been  described  by 
various  chemists  as  moifnndrio-  and  philip- 
pia,  but  both  of  these  have  been  resolved 
into  other  earths,  being  mechanical  mix- 
tures of  the  same.  (Boncoe  and  Schorleni' 
mer;  IT.,  622). 


54 


THE    CHEMICAL    NEWS. 


■TANUABY  26.  1023. 

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.Kri<><ji,<o^ 


JANUAKY  26,  1923. 


THE  CHEMICAL  NEWS. 


A  considerable  number  f>f  the  more  ele- 
menbary  earths  have  been  formulated. 
Keilhauite,  for  instance,  has  been  symbol- 
ised thus:  Ca  Y  (Ti  Al  Fe)  SiO^.  A  vana- 
dium-bearing earth,  vanaclinite  (also  de- 
>;oribed  as  lead  vandate,  in  sipite  of  the  pre- 
sence of  a  chloride)  has  the  formula : 
3Pb3  (VO,),  +  PbCI,.  also  Pb,  (VOJ,  + 
rb,  (VO4)  CI.  For  m(..  t  practical  purpK)ses 
f  f  exipres«ion,  the  method  is  sound  enough, 
as  it  denotes  the  main  components  of  the 
earths.  It  does  not  admit  the  embodiment 
of  their  natural  composition,  however,  con- 
sequently is  far  from  accurate.  It  is  also 
cumbersome.  liCt  the  composition  of 
8«(marBikite  be  considered  as  a  case  in  point. 
This  is  determined  to  be  a  aioba-tan.talnte 
of  thirteen  rare  earth  metals,  calcium,  ura- 
nium and  iron.  To  express  this  as  a  form- 
ula would  be  absurd,  and  its  very  complex- 
ity, by  virtue  of  the  number  of  symbols, 
would  tend  to  confound. 


APPARATUS  FOR  THE  RECOVERY  OF 

BROMINE  FROM   SODIUM 

HYPOBROMITE. 

By  C.  H.  C0LLINO8. 
I. — ^The  Apparatus. 
In  The  Chemical  News  ff>r  December  1, 
1916.  I  (U'soribed  a  simpK-  apparatus  to 
recover  bromine  from  sodiiun  hypobromitc, 
whether  new  or  stale,  u«d  or  not.  and  to  at 
cmcv  rooombine  it  with  NnHO  as  fresh  hy- 
pobromitc. The  method  was  simple:  to 
mix  slowly  the  waste  hypobronnte  with  ft 
minernl  «cid.  thus  gradually  disengaging 
the  Br,  simultaneously  aspirating  the  lat- 
ter as  a  vapour  into  fresh  NaHO.  In  its 
first  form,  the  apparatus  suffered  from  one 
marked  defect,  however,  and  that  was  the 
considerable  residuum  of  Br  left  in  tlio 
mixed  acid  and  waste.  A  fa«r  amount  of 
(.xperimenting  was  needed  to  .overcome 
this;  but  the  im,proved  form  now  illustrated 
has  l>eon  in  use  for  a  oonsiderab  e  tune 
with  consistently  satisfactory  results,  and 
T  would  call  the  attention  of  all  consider- 
able users  of  sodium  hypobromite  to  it  a!j 
ft  simplo.  compact,  effective  and  rapid 
mi'ans  of  recovering  Br  from  was  e  tliat 
otherwise  goes  down  the  sink,  to  the  dis- 
tinct disadvantage  of  ^}'^''\V,^^^l^-,  .™ 
new  form  does  not  require  skilled  attention 
and  prnetically  speaking,  runs  }tf  ^^  •  /"[; 
ther  no  Br  vapour  can  escape  into  the  air 
c.f  th.  rr>om.  By  its  use^one  can  evc«  avoid 
altogether  the  need  to  handle  and  store  Br 


as  such,  as  by  obtaining  the  hypobromite 
ready-made  one  can  readily  recover  fi^om  it 
needed  Br  (to  recombrne  asi  NaBrO)  as 
convenient.  This  creates  a  great  advan- 
tage, by  eliminating  the  cost,  delay  and 
trouble  attending  the  transit  of  a  dangerous 
chemical  like  Br;  further,  where  admission 
of  Br  into  one's  geographical  area  happens 
to  be  inhibited,  the  hypobromite  may  be 
imported  and  regarded,  from  the  point  of 
\'iew  of  the  apparatus,  as  a  convenient 
storehouse  of  Br. 

On  reference  to  the  illustration  (kindly 
lent  by  Messrs.  Baird  and  Tatlock,  who  are 
putting  the  apparatus  on  the  market),  it 
will  be  seen  that  the  operations  needed  are 
few  and  simple.  The  whole  thing  is  con- 
nected up  first  with  an  aspirator  or  pump 
nt  (P).  Caustde  soda  sf>luti(>n  of  the  usual 
hypobromite  fo-mula  is  introduced  into 
(HJ)  via  the  c.ilibrated  cup  (H).  Acid 
(HXO,)  is  poured  into  (A)  up  to  the  mark, 
then  run  into  the  mixing-chamber  (MC), 
and  the  acid  tap  turned  off.  Waste  hypo- 
brocnite  from  which  the  Br  is  to  be  ex- 
tracted is  poure<l  into  (W)  up  to  the  mark, 
the  aspirator  st.i-ted,  the  t^p  of  (W)  timed 
to  allow  a  drip  1  f  60  of  feu-er  drops  to  the 
minute — and  the  aflfair  may  be  left  to  run 
Itself  with,  perhafM,  one  subsequent  re- 
adjustment, if  neoeaeery,  of  the  dripping 
tap.  The  stream  of  aspired  air  passing 
through  the  reacting  substances  from  bot- 
tom to  top,  canies  practically  the  whole  of 
the  Br.  by  degr.  •-?.  into  the  waiting  NaHO 
and  so  forms  n<  w  hypobromite.  The  valve 
(V)  is  nearly  fillr.l  with  NaHO  solution  (not 
water),  and  both  physically  and  chemically 
inhibits  any  back  pressure  of  Br  into  the 
air  of  the  room.  The  whole  process  takes 
about  20  minute  s.  The  mixed  acid  and 
•  xhausted  waste  are  then  emptied  (by  turn- 
ing tjhe  tap  at  hott'^n  '>-f  t..ivWi.'-pli.imber) 
into  (RJ)  below. 

IT._On  Certain  Expkrimexts  with  the 

Apparatus. 
Having  established  the  successful  work- 
ing of  the  '«.  n«f^  observed  that  (as 
mgnht  be  .  i)  a  slight  residuum  of 
unrecoverable  hi  remainerl  behind,  in  solu- 
tion, in  the  mixing-chamber,  the  next  step 
was  to  ascertain  the  allowance  to  be  made 
for  this  in  fixing  ttie  quantity  of  waste 
sodium  hypobromite  from  which  2.2  ce.  of 
Br  could  be  actually  recovered  to  rcconi- 
bine  with  fresh  NaHO  solution  in  the  hypo- 
bromite jar.  The  simplest  way  was  to  ex- 
haust the  urea-deoomprsing  power  of 
ordinary  hypobromite,     made   according  to 


56 


THE    CHEMICAI.    NEV7S. 


JANUARY  26,   1923. 


the  usual  formula  (25  cc.  NaHO  +  2.2  cc. 
Br),  reco'ver  the  Br  from  this,  sdmilarly  ex- 
haust the  recovered  Br  hypobromite,  and 
compare  the  total  N  percentages  in  each 
case  (expressed  as  urea) :  thus  obtaining 
ithe  ratio  by  which  the  extra  quantity  of 
waste  siodium  hypobromite  to  anticiipate  Br 
loss  in  the  mixing-chamber  could  be 
directly  calculated.  This  necessary  ex- 
periment led  to  a  quite  unexpected  result. 

The  total  urea  percentage  obtained  by 
exhausting  ordinary  hypobromite  was 
found  to  range  around  9.5.  Such  ex- 
hausted hypobromite  then  yielded  up  its 
Br  via  the  apparatus  into  a  new  lot  of 
NaHO,  and  the  corresiponding  figure  of 
this,  so  far  fromn  being  less  than  9.5,  was 
found  (in  each  of  several  experiments)  to 
range  round  11.3  per  cent. !  Again,  such 
an  exhausted  hypobromite  was  instead  kept 
for  a  week,  its  Br  recovered,  reoombined  as 
hypobrcffnite,  and  duly  exhausted.  It  gave 
a  total  of  11.8  per  .cent,  of  urea. 

It  is  la  famiUar  fact  that  sodium  hypo- 
bromite has  to  be  newly  made  for  urea 
estimation,  as  it  soon  deteriorates  as  re- 
gards this  function.  I  have  found  the  rate 
of  deterioration  to  be  about  10  per  cent, 
per  day,  the  percentage  not  being  calcu- 
lated on  the  initial  value,  after  the  first 
day,  but  on  the  residual  value  of  each  day. 
Now  the  singvilar  thing  is  that,  as  far  as  my 
experimenting  has.  gone,  hypobromite  that 
has  been  kept  a  week  in  its  original  unused 
condition  (and  whose  urea  value  in  the  first 
instance  would  be  about  9.5)  on  being 
passed  througTi  the  apparatus  yielded  Br 
thatfc,  combined  with  the  usual  25  cc. 
NaHO,  pro.'lucjed  a  hypobromite  oi  total 
urea  va^kie  of  13.3  per  cent.  Further,  hyy)o- 
bromite  made  in  the  usual  way,  and  simi- 
larly treated  without  waiting  a  week,  pro- 
duced hypobromite  of  total  urea  value  of 
13.0  per  oerat. 

The  practical  consequence  of  these 
fignree  is  that  an  amount  of  waste  equal  to 
the  contents  of  the  original  hypobromite 
bottle  is  qiiite  adequate  to  yielding  a  suffi- 
ciency of  Br,  which,  reoombined  under  the 
conditions  ruling  in  the  apparatus,  more 
fhan  balances  the  trifling  loss  of  Br  in  the 
mixing-chamber.  This  holds  good  whether 
the  original  hypobromite  be  newly  made 
and  used  or  not,  or  has  stood  a  week  un- 
used, or  has  been  used  new  and  is  now 
stale,  or  used  when  stale,  and  is  either  par- 
tially or  wholly  exhansted. 

The  above  facts  and  figures  suggest 
more  than  one  iproblem  of  varying  interest. 


Two  of  them  might  be  briefly  considered  : 

(1)  The  total  urea- decomposition  capa- 
city of  recovered  Br,  when  reoombined 
with  NaHO,  is,  in  the  first  recovery, 
greater  than  that  of  the  hypobromite  from 
which  it  has  been  recovered. 

(2)  Such  increase  is  groa-test  in  the  case 
of  unused  hypobromite,  new  or  even  ten 
days  old. 

llegarding  (1) — 

When  urea  is  "lacted  upon"  by  sodium 
hypobromite,  the  following  ensues:  — 

6o(NH2),+3NaBrO    =   N,+CO,+2H,0+3 
NaBr. 

This  reaction  naay  be  the  outcome  of 
simple  chemical  affinity  (as  is  implied  by 
the  expression  "acted  uipon")  between  the 
urea  and  the  NaBrO :  althoug'h  as  no  com- 
bination of  any  kind  between  the  urea  or 
any  of  its  constituents  is  formed  with 
NaBrO  or  NaBr,  chemical  affinity  would 
seem  hardly  a  happy  term.  Further,  as 
NaBrO  spontaneously  breaks  down  into 
NaBr  and  0,  it  can  hardly  be  called  reduc- 
tion. Alternatively,  in  view  of  the  fact 
that  from  its  first  formation  NaBrO  stead- 
ily breaks  do'wn  into  NaBr  and  0,  it  may 
be  that  urea  exerts  a  catalytic  .action  on  it, 
accelerating  its  transformation  from  NaBrO 
to  NaBr.  The  rapid  disengagement  of  O 
atoms  at  once  ensuing  would  react  upon 
the  urea,  to  each  molecule  of  which  three 
atoms  of  0,  as  per  the  equation,  would  be 
attracted,  leading  to  its  breaking  down  into 
free  N,  COj  and  HjO.  This  explanation 
seems,  on  the  face'  of  it,  to  be  as  good  as 
the  other,  and  for  this  reason  the  ca.talytic 
hypothesis,  if  not  already  entertained, 
miglit  be  considered. 

We  are  now,  however,  concerned  with 
the  comiposiition  of  the  mixture  usua.Uy,  in 
urine  analysis,  referred  toi  as  sodium  hypo- 
bromite. The  nature  of  ithis  demands 
close  scrutiny  if  we  are  to  cope  with  the 
two  points  just  raised,  and  explain  in  a 
rational  manner  the  associated  percentage 
figures.  The  usual  equation  is:  — 
Br^  +  2NaH0  =  Na,Br  +  NaBrO  +  H^O. 
Here  the  ratio  of  Br-0  to  total  Br  is  as  2 
to  4. 

It  will  be  borne  in  mind,  of  course,  that 
the  NaBrO  at  once,  slowly  and  steadily 
spontaneously  parts  with  its  oxygen  and 
becomes  the  stable  but  useless  form,  NaBr. 
Hence  sodium  hypobromite  does  not 
"  keep." 

Now,  to  exiplain  the  increased  power  of 
the  hypobromite  solution,   as  furnished  by 


JANUAEY  26,  1923. 


THB    CHEMICAL    NEWS. 


57 


the  .apparatus,  we  must  keep  in  mind  at 
least  three  points :  that  the  urea  breaks 
down  in  response  to  the  action  of  oxygen 
atoms  qualified  by  their  intimate  assocda- 
tion  with  Br  atoms  up  to  the  last  moment ; 
that,  consequently,  oxygen  linked  with  Br 
musit  be  present  to  the  maximum  extent; 
that  sources  of  oxygen  other  than  those 
available  under  ordinary  circumstances,  be 
demonstrated.  The  Br  is.  for  practical 
purposes,  a  constant  factor. 

In  the  case  of  sodium  "hypobromite" 
made  in  the  usual  way  for  urine  analysis, 
there  is  practically  ahvavs  &  slight  white 
precipitate.  This  is  evidently  NaBrO,, 
formed  as  a  consequence  of  the  heat 
evolved,  and  represents  sf>  much  unavai'- 
able  oxygen  (+  Br,  in  solid  form)  for  the 
purposes  of  urea  decomposition.  The 
usual  solution,  then,  starts  handicapper. 
In  hypobromite  made  in  the  apparatus 
there  is  no  such  precipitate.  d')ubtle9s  owing 
to  the  cooling  effect  of  the  rapidly  passing 
air  bubbles  through  the  foinjing  hypobro- 
mtie — which  latter,  afain,  forms  relatively 
slowly,  thus  ke<'ping  down  the  temperature 
and  avoiding  the  precipitation  of  NaBrO, : 
hence,  in  the  apparatus -formed  hypobro- 
mite, a  trifle  extra  NaBrO  is  derived  from 
this  circunmstaince. 

During  the  mixin;,-  process  between  the 
neid  and  the  waste  sfxlijuii  hypobromite, 
with  the  <'volution  of  free  Br,  passes  froni 
the  bf-ittom  of  th<'  chamber  up  through  the 
mixed  iicid  and  waste,  tht  purpose  of  which 
is  to  disengage  from  the  mixture  the  Br 
freefl  by  the  acid,  and  tf>  ean-y  it,  togipther 
with  that  in  the  air  of  the  mixing-chamber, 
in  vapour  form  to  the  boittle  in  which 
NaHO  awaits  it  to  form  therewith  fresh 
hypfvbromite.  It  seems  possible  that  be- 
sides doing  this,  the  air  may  contribute  a 
little  of  its  oxygen  to  the  general  atomic 
rearrangement  gfxing  on,  which,  with  easily 
available  hydrogen  would  combine  with  a 
modicum  of  the  Br  into  hypobiomous  acid. 
The  latter,  in  aqueous  solution,  passes  over 
ill  vapour  form,  to  be  decomposed  in  the 
NaHO  bottle,  and  so  forcibly  oontribute  an 
extra  atom  of  oxygen  along  witti  its  atom 
of  Br:  the  first  stage  of  this  process  being 
perhaps  reduction  to  hydrobromlc  aoid 
(HBr)  with  free  oxygen.     Shortly — 

Br„  +  HBrO+8NaHO  ^   NaBr+2NaBrO 

+2HjO 

(Ratio  of  BrO  to  total  Br,  2  to  3). 

White  fumes  of  what  almost  certainly 
would  be  hydrohromic  acid  have  been  ob- 
served on  different    occasions  at  the  top  of 


the  mixing-chamber  and  simultaneously  in 
ihe  deivery-tube,  NaHO  bottle  and  even, 
rarely,  as  far  as  the  aspirator  itself. 

So  far  the  above  two  equations  corres- 
pond roughly  to  the  figures  obtained  with 
hypobromite  made  in  the  usual  way  (9.5 
oiixsa)  and  those  from  recovered  exhausted 
hypobromite  (11.5  circa)  with  nittios  of  0  to 
Br  as  2  to  4  and  2  to  3  respectively,  i.e.,  an 
increase  of  urea-detonating  oxygen  in  the 
latter  case  over  the  former.  There  still  re- 
main the  figuras  (13.0  circa)  obtained  from 
hypobromite  made  from  Br  recovered  from 
hypobromite,  new  or  stale,  that  has  re- 
mained unustvl.  Now.  as  the  NaBrO 
steadily  breaks  down  to  NaBr  and  free  O  it 
seems  reasonable  to  assume  that  such  un- 
used hypobromite  contains  spare  oxygen 
either  still  in  t<nii)porary  combination  with 
NaBr  or  but  latelv  parted  therefrom.  This 
would  go  to  enrich  the  oxygen  content  of 
the  air  stream,  and  would  thus  bring  into 
contact  with  the  nascent  Br  vapour  an 
atmnnphere  especially  full  of  oxygen  :  cir- 
cumstances peculiarly  favourable  to  the 
formation  of  fully  oxidised  Br  compounds. 
Hert',  then.  I  would  suggest  an  hypothesis, 
not  (I  think)  altogether  r.nreasonable,  and 
one  moreover  that  assists  to  meet  and  ex- 
plain the  observed  facts,  viz.,  thait  a  com- 
pound usually  assumed  not  to  exist  may 
be  formed  und<'r  these  unusual  carcum- 
stanoes,  to  wit,  sodium  bromite  (NaBrOj) ; 
a  oomipound  which  at  the  cost  of  merely 
the  usual  one.  neceflsarj',  Br  atom,  would 
furnish  double  the  reaction  energy  (0,)  in 
relation  to  its  dissociating  action  upon  the 
urea  molecule. 

Assimiing  this  for  the  moment,  and  ex- 
cluding pro  temp,  the  hypothesis  of  HBrO 
being  formed  and  carried  over,  let  us  write 
an  equation  conesponding  to  the  possible 
facts:  no  more  than  one  free  oxygen  mole- 
cule being  adde<l  to  represent  tlie  contribu- 
tion of  the  rich  atmosphere  previously 
described:  — 

2Brj+Oj+4  NaHO  =   NaBr+2  NaBrO 
+XaBrOj+2HjO 
With  a  ratio  of  Bi-0  to  Br  as  2  to  2. 

I  do  not  know  if  this  view  will  be 
jiocetpited ;  but  this  can  at  least  be  said  for 
it,  that  it  furnishes  the  necessary  mechan- 
ism to  aoocunt  for  the  observed  result,  for 
the  sitartling  ineniase  (approaching  40  per 
cent.)  in  the  total  urea  decomposable  by 
hypobromite  made  in  this  manner  (in  the 
apparatus)  over  that  made  in  the  usual 
way,  Br  and  NaHO  bein^  as  near  as  may 
be  identical  quantities    in  each    case — ^the 


58 


THE    CHEMICAL    NEWS. 


JANUARY  26,  1923. 


Br,  if  anything,  being  a  trifle  less  in  tlie 
recovered  quantity.  Equally,  has  sodium 
hypobromite  been  put  together  in  this 
manner  by  other  exiperimenters,  the  Bv 
largely  as  vapour  with  a  copious  admixture 
of,  at  least  atmo'spheric  oxygen?  If  not,  it 
might  be  worth  someone's  while  to  do  it, 
and  see  what  may  happen  under  these 
conditions. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAT.  SOCIETY. 

List  of  Probable  Papers  for  Reading, 

January  25,  1923. 

Prof.  A.  V.  Hill,  F.R.S.,  The  Potential 
Difjerenoe  occurring  in  ci  Donnan  Equili- 
brium and  the  Theory  of  CoUoidal  Be- 
haviour. 

E.  F.  Armstrong,  F.R.S. ,  and  T.  P. 
HiLDiTCH,  A  Study:  of  Catalytic  Actions  at 
Solid  Surfaces.  X.—The  Interaction  of 
Carbon  Monoxide  and  Hydrogen  as  con- 
ditioned by  nickel  at  relatively  low  Tem- 
peratures. A  Practical  Synthesis  of 
Methane. 

J.  HoLKER,  D.Sc,  The  Periodic  Opacity 
of  Certain  Colloids  in  progressively  increas- 
ing Concentrations  of  Electrolytes.  Com- 
munioated  by  Prof.  A.  V.  Hill,  F.R.S. 

E.  K.  RiDEAL  and  R.  G.  W.  Norrish, 
The  Photochemistry  of  Potassium  Permari- 
ganate.  Part  I.— The  Application  of  the 
Potentiometer  to  the  Study  of  Photochemi- 
cal Change.  Part  II.— On  the  Energetics 
of  the  Photo-decomposition  of  Potassium 
Permanganate.  Oommunioated  by  Sir 
WiHiam  Pope,  F.R.S. 

E.  A.  Fisher,  Some  Moisture  Relations 
of  Colloids.  I. — A  Comparative  Study  of 
the  Rates  of  Evaporation  of  Water  from 
Wool,  Sand  and  Clay.  Communicated  by 
Prof.  A.  Smithells,  F.R.S. 

R.  Whytlaw-Ctray,  J.  B.  Speakman,  and 
J.  H.  P.  Campbell,  Smokes,  A  Study  of 
their  Behaviour  and  a  Method  of  Determin- 
ing the  Number  of  Particles  they  contain. 
Com-municated    by      Prof.     A.     Smithells, 

F.R.S.  ^    ^ 

R.  Whytlaw-Gray  and  J.  B.  Speakman, 
A  Method  of  determining  the  Size  of  the 
Particles  in'Smokes.  Part  II.  Communi- 
cated by  Prof.  A.  Smithells,  F.R.S. 

R  C  Day,  The  Effect  of  long  Grinding 
on  QuaHz  (Silver  Sand).  Communicated 
by  Dr.  M.  W.  Travers,  F.R.S. 


Thursday,  January  18,  1923,  at  4.30  p.m. 

Papers  read :  — 

J.  Barcuoft,  F.R.S.,  Observations  on 
the  Effect  of  High  Altitude  on  the  Physio- 
logical Processes  of  the  Human  Body. 

Prof.  E.  W.  MacBride,  F.R.S.,  Re- 
marks on  the  Inheritance  of  Acquired 
Characters.     (Verbal  commumoation  only). 

C.  F.  Cooper,  Baluchitherium  osborni. 
(?  syn.  Indriootherium  turgaicum.  Bor- 
rissyak).  Communicated  by  Dr.  A.  S. 
Woodward,  F.R.S. 

J.  A.  GuNN  and  K.  J.  Franklin,  The 
Sympathetic  Innervation  of  the  Vagina. 
Communicated  by  Sir  Charles  Sherring- 
ton, P.R.S. 

H.  G.  Cannon,  On  the  Metabolic  Gradi- 
ent of  the  Frog's  Egg.  Commvmicated  by 
Prof.  E.  W.  MacBride,  F.R.S. 

Basiswar  Sen..  Otu  the  Relation  between 
Permeability  Variation  and  Plant  Move- 
ments. Communicated  by  Sir  William 
Bayliss,  F.R.S. 

H.  L.  Duke,  M.D.,  An  Enquiry  into  an 
Outbreak  of  Human  Trypanosomiasis  in  a 
"  Glossina  morsitans  "  Belt  to  the  East  of 
Mwanza,  Tanganyika  Territory.  Communi- 
cated by  Mr.  C.  Dobell,  F.R.S. 

Louis  Dollo,  ScD.,  Le  Centenaire  des 
Iguanodons  (1822-1922).  Communicatiid 
by  Prof.  A.  C.  Seward,  F.R.S.    • 


MINERALOGICAL  SOCIETY. 
January  9. 

Dr.  A.  E.  H.  Tutton,  Past-President,  in 
the  chair. 

A.  Brammall  and  H.  F.  Harwood,  Dart- 
moor occurrences  of  (1)  rutile,  brooyite  and 
anatase,  (2)  zircon. 

(1)  AnatasG,  with  less  abundant  brook- 
ite  and  scanty  rutile,  is  common  in  Dart- 
moor stream -sands,  etc.  Anatase  and 
brookite,  absent  from  the  unaltered  grey 
granite,  have  been  found  in  pneumatolysed 
rocks,  especially  "  red  "  granites,  and  the 
mode  of  genesis  of  these  two  minerals  is 
discussed.  Data  provided  'by  chemical 
work  on  "baueritised"  Dartmoor  biotite 
(containing  about  1.8  per  cent.  TiOj)  and 
by  the  occurrence  of  anatase  granules  en- 
crusting detritial  grains  of  ilmenite  are  ex- 
amined in  their  bearing  on  the  possibility 
that  some  anatase  may  have  developed  (or 
existing  crystals  may  have  continued  to 
grow)  in  detrital  material  after  sedimenta- 
tion. 


JANUAKY  26,  1923. 


THE   CHEMICAL    NEWS. 


59 


(2)  Two  strongly  contrasted  kinds  of  zir- 
con crystals  are  described :  differences  in 
crystal  habit,  nature  of  inclusions,  and 
mode  of  occurrence  in  the  granite  suggesit 
that  the  dominant  kind,  which  is  tawny, 
zoned,  and  rich  in  inclusions,  crystallised 
out  from  (the  magma  early,  and  that  the 
subordinate  kind,  water-clear  and  contain- 
ing few  inclusions  , separated  out  at  a  much 
later  stage. 

Dr.  L.  J.  Spercer,  with  chemical  analy- 
ses by  E.  D.  Mountain,  and  microscopical 
determinations  of  the  pseud omorphs  by  W. 
Campbell  Smith,  A  davyne-lihe  mineral 
and  its  pseudoTnorpha  frow  St.  John' 8 
Island,  Egypt. 

Two  snriall  crystals  found  with  perid  >t, 
gamierite,  etc.,  showed  the  physical  char- 
acters of  davyno,  but  consist  of  a  complex 
silicate  (with  sulphate  and  carbonate)  of 
aluminium,  calcium,  magnesium,  and 
sodium,  together  with  a  considerable 
amount  of  water.  Pseudomorphs  after 
(this  miaterial  are  more  abundant:  they 
consist  of  a  oomiplex  of  hydrated  crilicatee  of 
aluminium  and  magnesium,  together  with 
small  amounts  of  corundu  and  spinel. 


UNIVERSITY    OF     LONDON,     KING'S 

COLLEGE.     AND     KINGS     COLLEGE 

FOR    WOMEN. 

Public  Lectures  and  Arranobments  in 
THE  Lent  Term.  1023. 

AduiisRion  to  public  loctures  is  free  and 
without  ticket  unless  othorwise  stated. 
When  cards  of  iuhni«aion  are  required,  they 
can  b<'  obtained  on  application  to  the  Regis- 
tan*,  to  whom  all  enquiries  with  regard  to 
public  lectures  should  be  made  in  the  first 
instance.  A  stamped  addressed  envelope 
should  bo  enclosed. 

Faci'lty  of  Natural  Science. 

A  Course  of  Eight  Public  Lectures,  on 
Wednesdays,  at  ry.SO  p.m. 

"  Some  Aspects  of  Naturai,  Philosophy." 

January  24:  "  The  Quest  of  Scienoo  To- 
day, and  as  exemplified  in  its  History, "  by 
Professor  A.  N.  W^hitehead,  F.R.S.,  M.A., 
Sc.D.  (Camb.),  LL.D.  (St.  Andrews), 
D.Sc.  (Manchesrfcer). 

January  31 :  "  The  Measurement  of  Stcl- 
ler  Di«tanc<>s,'    by  The  Astronomer  Royal. 

February  7:  "  The  Fundaniontal  Conceip- 
tions  of  Biology,"    by    Dr.  J.  S.  Haldane, 


F.R.S.,  M.A.,  M.D.,  LL.D.  (Edin.),  M.A. 
(Oxford),  LL.D.   (Birmingham). 

February  14 :  "  The  Succession  of  Floras 
in  the  Past,"  by  Dr.  Dukinfield  Scott, 
F.R.S.,  M.A.,  LL.D.,  D.Sc. 
February  21:  "A  Physico-Chemical  The- 
on-  of  the  Instability  of  Western  Civilisa- 
tion," by  Professor  F.  Soddy,  F.R.S., 
M.A. 

February  28:  "The  Limitations  of 
Natural  Science,"  by  Principal  L,  P.  Jacks, 
C.A.  (Lond.),  Hon.  M.A.  (Oxford),  Hon. 
LL.D.  (Glasgow),  Hon.  D.Litt.  (Liver- 
pool), Hon.  D.D.  (Harvard). 

March  7:  "  Some  Thoughts  on  the  Re- 
lations of  Science  and  Industry,"  by  Sir 
Herbert  Jackson,  K.B.E.,  F.R.S., 
A.R.C.M.,  F.I.C.,  F.C.S.,  Director  of 
liesearch,  British  Soientifio  Instruments 
Research  Association;  Emeritus  Professor 
of  Chemiatry,  University  of  Ix>ndon. 

Maroh  14:  "The  Influence  of  Science," 
by  Sir  Richard  A.  Gregcny,  D.Sc.  (Leeds), 
F.R.A.S.,  F.InHt.P.,  F.J.I. 

Department  of  Classics  and  History. 

An  inaugural  Uxsture  will  be  delivered  on 
Friday,  January  19,  at  5.30  p.m., 
"  Prolboomena    to  the  Study  of  Ancient 

Grebgb," 

by  Edwyn  Bevan,  M..\..   LL.D.,  Lecturer 

in  Hcllenistio  Language  and  Literature. 

Faculty  of  Theology- 

A  Coune  of  Three  Pubic  Lectures 

{arranged  by  the  I'niversity),  at  5  p.m.,  on 

March  8,  .March  18,  and  March  15. 

"  Ethics  and  tub  Philosophy  of 

HiSTOBY," 

by  ProfessOT  Ernst  Troeltsch,    of  the  Uni- 
versity of  Berlin. 

A  Course  of  Ten  Public  Lectures,  on  Tues- 
days, at  5.3{)  p.m.,    illustrated  by  Lantern 
Slides. 
"  Sixteenth-Century    Art." 

Commoncing  January  23. 

Tickets  for  these  lectures  can  be  ob- 
tained before  each  lecture  outside  the  Great 
Hall,  ryr  between  10  and  4  at  the  College 
Office.  Fee:  Is.  for  one  lecture,  78.  6d.  for 
the  coiu*8e  of  ten.  By  the  Rev.  Percy 
Deanner,  D.D.,  Professor  of  Ecclesiastical 
Art. 

A  Course  of  Six  Public  Lectures  and  Prac- 
tioes,  on  Mondays,  at  5.30  p.m. 
"  Ecclesiastical  Music." 
Commencing  February  5. 
This  course  is  arranged  by  the  Rev.  C,  F 
Rogers,   M.A.,     Professor  of  Pastoral  The 
ology. 


00 


THE    CHEMICAL    NEWS. 


JANUARY  26,  1923. 


Department  of  History. 

A  Course  of  Six  Public  Lrciures   [arruiujed 

by  the  Ihiiccrsity),  ou-  Thursdays,  at  5.30 

p.m.,   beginning  January  18. 

"  The  Nomads  of  Central  Asia." 

By  Professor  V.   Bart  hold,    Professor  of 

the  University  of  Petrograd. 

Department  of  Philosophy. 
A  Course  of  Six  Public  Lectures,    on  Tues- 
days,  at  5.30  p.vi..  commencing  February 
20. 
"  Physical  Casuality  and  Modern 
Science." 
By  H.  Wildon  Can-,  D.Litt.,     Professor 
of  Philosophy. 

A  Course  of  Four  Public  Lectures  on  Tues- 
days, at  5.30  p.m.,  comm,encing  January 
23. 
"  The  Enigma  of  Socrates." 
By     Miss     Hilda     D.     QaJseley,     M.A., 
Reiader  in  Philosophy. 

A  Course  of  Three  Pubic  Lectures  on 

Fridays,  at  5.30  p.m.,  commencing 

March  2. 

"  The  Case  for  Pluralism." 

By  C.  E.  M.  Joad,  M.A. 

Department  of  Psychology. 

A  Course  of  Three  Public  Lectures  on 
Mondays,  at  5.30  p.7n.,  commencing 

February  19. 
"  Psychology  and  Psychotherapy." 
By  William  Brown,  M.A.,  M.D.,  D.Sc, 
M.R.C.P.,  Wilde  Reader  in  Mental  Philo- 
sophy in  the  University  of  Oxford,  and 
Honorary  Consulting  Psychologist,  Beth- 
lem  Royal  Hospital,  eitc. 

School  of  Slavonic  Studies. 
The  following  lectures    will  be  deliver<!d 
in  Room  14D,  unless  otherwise  stated  : 
A  Course  of  Eight  Public  Lectures  on 
"  Poland," 

On  Mondays,  at  5.30  p.m.,  commencing 
January  22. 
By  Professor  Roman  Dyboski  (Professor 
of  English  Literature  in  the  University  of 
Cracow). 

A  Public  Lecture,  on  Monday,  February  5, 
at  5.30  p.m. 
"  The  Original  Home  of  the  Slavs." 
By  N.  B.  Jopson,  M.A.,  Reader  in  Com- 
parative Slavonic  Philology. 

A  Course  of  Nine  Public  Lectures,  on 
Tuesdays,  at  5.30  p.m.,  commencing 

January  23. 
"  Contemporary  Russia  From   1861." 
By  Sir  Bernard  Pares,  K.B.E.,  Professor 
of  Russian. 


A  Course  of  Three  Public  Lectures,  on 
Thursdays,  at  5.30  p.m.,  beginning 
January  25. 
"  Modern  Czech  Novelists." 
By  Otakar  Vocadlo,    Doctor  of  the  Uni- 
versity    of   Prague;    Lecturer    in     Czecho- 
slovak. 

Tivo  Public  Lectures,  on  Thursdays,  at 

5.30  p.m^. 
February  15:     "Slowacki   and  the    King 
Spirit." 

February  22 :   "  Some  Poetry  of  Mickie- 
wiez." 

By  Leonard  Wharton,  M.A.,  Lecturer  in 
Polish  Literature. 

A  Public  Lecture,   on  Thursday,   March  1, 
at  5.30  p.m. 
"  Post- War  Poetry  in  Poland." 
By  F.  Sobienowski. 

Three  Public  Lectures,   on  Thursdays, 

March  8,  15,  and  22,  at  5.30  p.?w. 

"Three  Russian  Poets,  Pushkin,  Leskov, 

AND  Blok." 

By    Prince    D.    S.    Mirsky,    Lecturer  in 

Tlus&ian  Literature. 

A  Course  of  Ten  Public  Ijcctures,  on 
Fridays,  at  5.30  p.m.,   commencing 
January   19. 
Serbia  and  the  Jugo-Slav  Movement." 
By  R.  W.  Seton- Watson,   D.Litt.,     Pro- 
fessor Off  East  Euro'pean  History. 

School  of   Spanish   Studies. 
A  Course  of  Three  Public  Lectures,  on 
Thursdays,  February  22,  March  1,  and 

March  8,  at  5.30  p.m. 
"  The  Present   Conditions,    Historic 
Origins  and  Recent  Reforms  of 
Spanish  Education." 
By  Senor  Don  Jos^  Castillejo,  Professor 
in  the  University  of  Madrid  and  Secretary 
to  the  Junta  para  Ampliacion  de  Estudios. 
H.E.  The  Spanish  Ambassador  will  take 
the  chair  at  the  first  lecture. 

Those  particularly  interested  in  this 
course  should  enquire  from  the  Registrar 
(enclosing  a  stamped  addressed  envelope). 
T«'o  Public  Jjectures,  on  Thursday,  March 
15,  and  Thursday,  March  22,  at  5.30  p.m. 
"  The  Tendencies  of  the  Spanish  Drama 
Since  1868." 
By  Walter  Fitzwilliam  Starkie,  M.A., 
Trinity  College,  Dublin. 

Department  of  Modern  Greer 

A  Course  of  Six  Public  Lectures,  on 

Tuesdays,  at  5.30  p.m.,  comm,encing 

February  20. 

"The  Expansion  of  Europe  Overland: 

The  Route  of  the  Steppes." 


JANUARY  26,  1923. 


f^Ji   CHEMICAL   NEWS. 


61 


The  first  of  these  lectures  will  be  illus- 
trated by  lantern  slides. 

By  A.  J.  Toynbee,  M.A.,  Professor  of 
Modem  Greek. 

Department  of  Zoology. 

A  Course  of  Three  Public  Lectures 

{arranged  by  the   University),  on   February 

20,  22,  and  23,  at  5.15  p.m. 

The  Bionomics  of  Marine  Animals." 
\iy/  J.  H.  Orton,  D.Sc. 

Faculty  of  Laws. 

A  Public  Lecture  {arranged  by  the  Univer- 

city),  on  Friday,  February  \J,  at  5.30  /;.m. 
Chief  Justice  Sir  William  Bereford." 
By     W.     G.     Bolluod,     M.A.,     Sanders 

lieadier  in  Bibliogra^phy    at  the  University 

of  Cambridige. 

Department  of  Enginebbino. 

Three  Courses  of  AdvaucH;d  Lectures  for 

Post-Graduate  and  other  Advanced 

Students. 

1.  "  Recent  Developinents  in  Electrical 
Ti'actioii."  Thnee  lectures  l)y  F.  Lydall, 
B.A.,  B.Sc.,  M.LIi^^E.,  on  Tuead&y^,  it 
5.30  p.m.,  beginning  January  28. 

2.  "  Recent  Developments  in  Central 
Station  Design."  Three  lectures  b^  W.  B. 
Woodhouse,  M.Inst.C.E.,  M.Inst.E.E.,  on 
Mondays,  at  5.30  p.m.,  beginning  February 
12. 

3.  "  The  Erection  of  Sbeilwork."  Tluve 
lecture®  by  J.  Stuart  Lewis,  on  Tuesdays, 
ut  5.30  p.m.,  beginning  Miu-ch  6. 

These  lectures  are  free  only  to  engineer- 
ing students  of  the  College. 

Shakespeare  Association. 

Friday,  January  26,  5.30  p.m. :  Profes- 
sor Parrott,  of  Princeton  University, 
"  Tmon  of  Athens." 

Friday.  February  16,  5. .30  p.m. :  Dr. 
Scripture,  "  Shakespeaiv's  Verse  in  the 
Light  of  Exiperimental  Phonetics."  (With 
lantern  illustrations.) 

Friday,  March  16,  5.30  p.m. :  Biblio- 
giapliical  Meeting. 

Gtiier    Arrangements. 

Wednesrlay,  January  17:  College  Term 
begins.  10  a.m.  Service  in  the  College 
Chapel. 

Thursday,  January  18 :  University  Term 
begins. 

Monday,  January  22,  6  p.m. :  Gilbart 
liectures  on  Banking,  fii-st  of  a  course  >f 
four  lectures  by  Mr.  Heber  Hart,  K.C. 


Thursday,  March  15,  6  p.m. :  Gilbart 
Examination. 

Wednesday,  Mai-ch  28 :  College  and  Uni- 
versity Terms  end. 

Ernest  Barker,  M.A.,  D.Litt.,LL.D., 

Principal. 

W.  R.  Matthews,  M.A.,  D.D.,       Dean. 

S.  T.  Shovelton,  M.A.,  Secretary. 


UNIVERSITY  OF  BIRMINGHAM. 

Principal  Grant  Robertson,  of  the  Uni- 
versity of  Birmingham,  states,  in  his  an- 
nual report,  that  the  Standing  Joint  Com- 
mittee of  Council  and  Senate  "to  organise 
a  policy  of  research"  has  been  in  full  work- 
ing for  the  whole  session.  The  ajppoint- 
ment  of  the  Committee  was  a  wise  st»^p, 
excellent  work  having  already  been  done. 
It  is  clear  that  the  existence  of  such  a 
Committee  has  stimulated  the  impetus  to- 
wards research,  and  that  the  number  of 
appHoaitdons  from  the  staff  will  increase.  It 
is,  abow  all,  important  that  research  (he 
bays)  should  not  be  identified  solely  with 
work  oarried  on  by  the  Faculty  of  Science, 
essential  as  that  i.s,  but  that  every  Faculty 
should  realise  that  original  contributions  to 
knowledge  are  a  duty,  which  is  closely  con- 
nected with  efficiency  in  teaching,  and  that 
the  influence  then'by  exercised  on  the  stu- 
dents is  incalculable  alike  in  its  value  and 
in  the  attitude  of  mind  ut  can  create. 


CUPROUS  SULPHITES. 

It  was  suggested  in  a  previous  conmiuni- 
oation,  published  in  The  Chemical  News  of 
March  4,  1921,  thait  the  yellow  cuprous 
oxide,  obtained  by  an  alkaline  solution  of 
oupric  sulphate  with  glucose,  might  con- 
tain an  appreciable  amount  of  cuprous 
hydroxide.  Att<'niptiB  were  made  to  pre- 
pare cuprous  salts  of  some  oxygen  acids 
with  this  yellow  oxide.  In  the  course  of 
these  trials  a  re<l  \ariety  of  basic  cuprous 
sulphite  wafi  det<3c'.ted.  Its  method  of  pre- 
paration and  properties  are  detailed  below. 

Known  Sulphites. 
Besides  the  white  cuprous  aulphito, 
obtained  by  passing  sulphur  dioxide 
through  a  solution  of  cuprous  acetate  in 
acetio  iioid,  a  garnet-red  cupro-cupric  salt 
(Sp.  Gr.  3.57)— CujSOj.  OuSO,,  2H2O— is 


62 


THE  CHEMICAL  NEWS. 


JANUAEY  26,  1923. 


known  to  exist.  It  is  prepared  by  heating 
the  double  salt,  cuprous  ammoniiun  sul- 
phite. Another  cupro-cuprio  salt — ^CUgSOg, 
CuSOg,  5H2O — greenish  yellow  in  colour, 
is  also  mentioned. 

Preparation. 
Basic  cuprous'  sulphite  can  be  prepared 
by  saturating,  with  sulphur  dioxide,  a  weak 
solution  <xf  isodium  or  potassium  hydroxide 
in  which  yellow  cuprous  oxide  is  suspended. 
A  bright  red,  heavy  (Sp.  Gr.  3.26)  granular 
precipitate  settles  down  in  a  few  minutes. 
The  substance  so  prepared  was  washed  free 
from  sulphites  and  »ther  impurities,  dried 
at  105°  C.,  and  used  in  the  following  ex- 
periments. 

Properties. 

1.  When  heated  in  a  test  tube,  the  sub- 
stance loses  SO2  and  HjO,  the  residue  be- 
coming yellow,  then  red,  and  finally  black. 
When  gradually  heated  in  the  air-oven,  it 
undergoes  no  change  up  to  145°  C,  when  it 
begins  to  lose  w-ater.  The  residue — grejash 
yellow  in  colour- — contains  oupric  sulphate 
and  bright  yellow  cuprous  oxide. 

2.  When  boiled  with  water,  a  small  poi*- 
tion  of  the  salt  is  readily  hydrolysed,  and 
a  bright  lemon  yellow  substance  sticks  fast 
to  the  bottom  of  the  ves-sel  as  a  thin  layer. 
It  readily  dissolves  in  caustic  alkalies, 
forming  a  pale  blue  solution.  The  rest  of 
the  substance  slowly  hydrolysos  with  the 
formation  of  cupric  sulphate  and  yellow 
cuprousi  oxide. 

3.  With  dilute  hydrochloric  acid  cuprous 
chloride  is  formed  with  the  evolution  of 
sulphur  dioxide. 

4.  With  dilute  alkalies  a  pale  blue  solu- 
tion containing  alkali  sulphite  is  formed 
and  yellow  cuprous  oxide  is  deposited  with 
no  fe-ace  of  cupric  hydroxide.  When  the 
blue  solution  is  warmed,  yellow  cuprous 
oxide  is  thrown  out,  and  pure  alkali  sul- 
phite remains  in  solution. 

5.  The  substance  is  not  laffected  by  sul- 
phurous aciid. 

Composition. 
To  ascertain  the  composition  of  the  sub- 
stance   several    determinations    were    made 
which  gave  consistent  results  with  the  fol- 
1  owing  percentages  :  —  % 

(a)  Cu — estimated  as  CuO  50.46 

(b)  SO3 — estimated  as  SO2  by 
treating  the  salt  with  dilute 
HCl  and  absorbing  the  SO^  in 
NaOH '.....     21.15 

(c)  H2O — calculated  from  loss  of 
weight  on  heating  the  salt  in  air 

oven  up  to  160°  C 4.65 


(d)  The  substance,  after  heating  in 
the  air  oven  up  to  160°  C.  was 
treated  with  water;  the  result- 
ing yellow  cuprous  oxide  was 
washed  free  from  CuSO^,  dried 
and  reduced  to  metallic  copper 
in  a  current  of  hydrogen.  The 
percentage  of  copper  was  found 
to  be  59.12,  giving  the  formula 
Cu20,4H20  to  the  j^ellow  oxide. 
Hence  the  H,0  and  O2  which 
are  in  combination  with  copper 
as  this  hydra  ted  yellow  oxide 
must  account  for  the  remaining 
28.74  per  cent,  lof  the  salt  re- 
quired to  complete  the  percent- 
age composition  of  the  sub- 
stance  (100-76.26)   23.74 

These  percentages  do  not  accord  with 
the  composition  of  either  of  the  oupro- 
cupric  salts  mentioned  above.  The  general 
behaviour  land  percentage  composition,  as 
given  above,  point  to  the  conclusion  that 
the  red  substance  under  investigation  is  a 
basic  cuprous  sulphite  and  cannot  be 
identified  with  either  of  the  cupro-cupric 
sulphites  which  are  known  to  exist.  Its 
formula — which  accords  with  its  percent- 
age composition  —  may  probably  be 
Cu  (Cu20,4H20)S03,  H2O,  in  which  a 
molecule  of  hydrated  yellow  cuprous  oxide 
takes  the  place  of  one  hydrogen  atom  in 
sulphurous  acid  while  the  other  hydrogen 
atom  is  displaced  by  monovalent  copper. 

V.  V.  Sarma. 

Govt.   College  Laboratory, 
Kumhakonain,  S-  India. 
20th  December,  1922. 


GENERAL  NOTES. 


PREPARATION  OF  A  TRIOXYMETHY- 
LENE. 

By  D.  L.  Hammick  and  A.  R.  Boerce. 

a  Trioxymethylene  is  a  polymeride  of 
formaldehyde,  and  can  be  prepared  by  a 
modified  form  of  Pratesi's  method,  which 
consists  in  heating  10  pents  of  paraformal- 
dehyde and  one  part  of  1:1  sulphuric  acid 
in  a  vacuum  tube  to  115°  C.  in  an  oil  bath. 
The  crystalline  trioxymethylene  forms  as 
slender  needles  on  the  cool  part  of  the  tube. 
The  yield  of  purified  substance  is  10  per 
cent.     Better  results  were  obtained  on  the 


JANUARY  26,  1923. 


THE  CHteMlCAL  NEWS. 


63 


lines  of  Anerbach  and  Barschall's  process 
under  definite  conditions.  By  reipeated 
sublimation  of  a  trioxyiriethylene,  a  new- 
poly  meride,  e  polyoxymethvlene,  is  foitned. 
—{Trans.  Ghem.  Soc.,  1922,  p.  2738.) 

ABSORIT^ION     OF     CARBON 

DISULPHIDE    VAPOUR. 

By  a.  J.  CuRRiKR  AND  A.  W.  Browne. 

For  the  absorption  of  carbon  diKuIphide 
vapour  frc'.m  gases,  the  authors  proipose  to 
use  a  !+olution  of  sodium  triuitride, 
NaN,  +  CSj  =  NaSCSN,, 
in  which  the  trinitride  and  carbon  disyj- 
phide  combine  to  give  sfxlium  azido-dithif>- 
carbonate.  The  strength  of  the  sodium 
trinitride  solution  should  Ix'  at  least  5  per 
cent.,  and  although  aqueous  solutions  of 
sodium  azido-dithi<x5arlx>nat<'  decompose  to 
give  free  nitrogen  gas,  this  deoomposition 
is  t<x)  slow  to  affect  the  results  in  gas 
analysis. — (J.  Am.  Chem.  Soc,  1022,  p. 
2849''.) 


BOARD  OF  TRADE  ANNOUNCEMENT. 

Dykstuffs  AnvisoRY  Licknsino  Committke. 

The  Board  of  Trade  announce  that  on 
the  nomination  of  the  Association  of  Brit- 
ish Chemical  ManiifaMun-rs,  they  ha^rc 
appointetl  Mr.  W.  H.  Dawson,  the  Mana- 
ger of  the  British  Alizarine  Company, 
Limited,  TraflFord  Park,  Manchestir.  to  be 
a  member  of  the  Dyesluffs  Advisory 
Licensing  Committee,  set  up  under  Sec- 
tion 2  (3)  of  the  Dyestuffs  (Import  Regula- 
tion) Act,  1920,  in  the  place  of  Mr.  E.  V. 
Evans,  O.B.E.,  F.I.C.,  resigned;  and  that 
they  have  appointed  Mr.  liionel  BiundeJl, 
of  the  North  British  Chemical  Co.,  Ltd., 
Droylesden,  Manchester,  to  be  a  member 
of  the  Dyestuflfe  Industry  Development 
Conmiittee,  seit  up  under  Sub-Seobion  2  t6) 
fvf  the  Dyestuffs  (Import  Regulation)  Act, 
1920,  in  the  plaoe  of  Mr.  E.  V.  Evans, 
O.B.E.,  F.I.C.,  resigned. 

Board  of  Trade,  lOth  January,  1923. 


PERU. 

A  Land  of  Mystery. 
Peru,  in  which  once  flourishtxl  the 
ancient  civilisation  and  culture  of  the 
Inoas.  is  still  a  land  of  mystory.  Though 
not  large  as  South  American  Republics  are 
measured,  it  is  three    countries  with  three 


distinot  climates.  The  tropical  lowlands  of 
the  steaming  Amazon  valley  are  cut  ofi 
from  the  temperate  coast  region  of  the 
Piicific  by  mountain  ranges  within  which 
dwell  Indians  in  a  low  state  of  civilisation 
and  in  a  chronic  condition  of  unrest.  The 
dry  coast  9tri,p,  cooled  by  the  Humboldt 
current,  contains  the  principal  cities  and 
most  of  the  white  population  of  some 
700,000  people.  There  is  here  little  or  no 
rainiall,  the  land  is  cultivated  by  irriga- 
ton,  and  the  prcxlucts  are  cotton  and  sugar, 
wool,  hides  and  skins,  and  petroleum.  This 
coastal  strip,  though  limited  in  area,  is  the 
chief  district  in  which  agi'iculture  and 
pasture  flourish.  The  rain,  which  is  denied 
to  the  cxiastal  region  by  the  barrier  of  the 
Andes,  falls  abundantly  all  the  year  round 
n  the  mountain  districts.  But  though  the 
soil  of  the  eastern  slope  is  rich,  the  lack  of 
transport  makes  it  unproductive.  It  is 
this  unexploited  and  almost  impenetrable 
mountain  region  which  so  effectively  cuts 
off  the  Amazon  valley  from  the  Pacific 
ooast  that  it  needs  to  be  approached  from 
the  Atlantio  side.  We  see  in  this  great 
valley  illimitable  forests,  yet  all  the  tim- 
ber used  on  the  Pacifio  coast  has  to  be 
imported  from  overseas.  The  collection  of 
wild  rubber  has  declined  with  the  fall  in 
the  price  of  the  mat^t  commodity.  About 
Iquitoe  in  the  upper  waters  of  the  Amazon 
lie  an  indefinite  number  oS  rich  agricultural 
acres  which,  umler  bappier  geographic! I 
oircunMtaivoes,  could  support  a  large  popu- 
lation, yet  there  Ls  at  present  no  more  than 
one  human  being  to  every  two  and  a  half 
square  miles.  I(]uitos  is  over  a  month's 
journey  by  land  from  Lima,  the  capital  of 
Peru,  on  the  Pacific  ooast,  and  a  voyage  by 
sea,  the  Pamuna  Canal  and  the  Amazon 
from  Callao  to  Iquitos,  recently  occuipied  a 
steamer  no  less  than  80  days.  The  moun- 
tain barrier,  which  has  remor.selc^sly  cut 
off  the  oompjiratively  civilised  coast  from 
its  hinterland  by  the  Amazon,  has  set  the 
white  Peruvians  an  economic  problem 
which  is  «s  yet  far  fnom  solution. — Board 
of  Trade  Journal. 

ON  A  RECENTLY  FOUND  METEORIC 

IRON  FROM  CUASGOW,   BARREN 

COUNTY.  KENTUCKY. 

By  Georoe  P.  Merrill.' 

(Front  "The  American  Journal  of  Science," 

January,  1923,) 

Tilt      iron     metoorite     briefly     described 

below  was  first  brought  to  my  attention  in 


64 


THE  CHEMICAL  NEWS. 


JANUARY  26,  1923. 


June,  1922,  by  Prof.  Arthur  M.  Miller,  of 
Lexingtoa,  Kentucky,  by  whom  it  has 
since  been  given  a  brief  notice  in  Science 
for  September  1,  page  249. 

Aoeording  to'  Professor  Miller,  two  pieces 
of  the  iron  were  found  during  the  work  of 
ploughing  a  field  for  three  miles  south- 
west of  GJasyow,  in  Barren  County.  The 
pieces  are  stated  to  have  weighed  about  25 
and  20  pounds  respectively,  and  while  very 
badly  oxidised,  ex'hibited  on  bToken  sur- 
faces, even  without  etching,  coarse  Wid- 
nianstatten  figures.  The  smaller  of  the  two 
pieces  was  sent  yy  Professor  Miller  to  the 
National  Museum,  and  it  is  upon  this  piece 
that  the  description  here  given  is  vased.  As 
received,  the  mass  weighed  but  about  7 
kilogr.ams  (15|-  lbs.). 

The  iron  is  of  the  ordinary  octahedral 
type,  with  kamaoite  lamina  from  1  to  2 
mm.  in  thickness,  and  is  therefore  classed 
as  a  coarse  ootahedrite.  No  troilite  nodules 
are  visible  on  the  cut  surface  and  neither 
taenite  nor  schreibersite  are  conspicuous. 
Plessite  areas  are  small.  The  iron  Is  in  an 
advanced  condition  of  oxidation  that  is 
difficult  to  arrest,  suggestive  of  a  high  con- 
tent of  lawrencite.  An  analysis  by  Dr.  J. 
E.   Whitfield  yielded: 

Per  cent. 

Iron 70.632 

Nickel        7.270 

Cobalt       0.620 

Suliphur        0.110 

Phosphorus      0.121 

Carbon        0.062 

Chlorine      0.863 

Nickel  iron  oxides    19.220 

Silica      Trace 

Ignition       1.650 

Total        100.048 

Satisfactory  chlorine  determinations  in 
meteoric  irons  are  none  too  abundant. 
Cohen  gives  figures  running  from  0.003  to 
1.48  Oper  cent.  There  are  reasons  for  sup- 
posing that  the  Kigher  are  not  .absolutely 
correct.  Be  this  as  it  may,  Whitfield  s 
find  of  0.363  per  cent.  CI,  equivalent  to 
0.623  per  cent.  FeCi,  is  Wgh,  and  doubt- 
less accounts  for  the'  too  rea4y  disintegra- 
tion mentione  dabove. 

U.S.  National  Museum, 
Washington,  B.C. 


1  Puhlisked  with  the  iiermission    of    the 
Sedretary  of  the  Smithsonian.  Institution. 


This  list  is  specially  compiled  for  the  Chemical 
News,  by  Messrs.  Eayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade 
Marks,  and  Designs,  can  he  obtained  gratuitously. 


Latest  Patent  Applications. 

35356— Ashai  Glaes  Co. — Forcing  agent  of  manure. 

Dec.  29. 
3522— Edwards,     G.   W.— Treatment     of     oxidised 
oopi>er  ores.    Dec.  27. 

35502 — Thernia;  Industria  &  Chemica  Research 
Co. — ^Apparatus  for  heat-treatment  by  mol- 
ten metal.    Dec.  20. 


Specifications  Published   this    Week. 

190212 — Mond,  A.  L. — Process  for  the  continuous 
leaching  of  ores,  metallurgical  products, 
and  other  materials  on  the  counter-cur- 
rent principle. 

190246— Perkins,  W.  G.— Treatment  of  copper 
ores. 

190269 — British  Cellulose  and  Chemical  Manufac- 
turing Co. — ^Treatment  of  cellulose  ace- 
tates. 

174041 — L'Air  Liquide  Soc.  Anon  Pour  L^etude  et 
L'Exploitation  Des  Products. — ^Apparatus 
for  the  synthesis  of  ammonia. 

190390— Bichowsky,  F.— Processes  for  the  synthe- 
tic production  of  alkali  metal  cyanides. 


Abstract  Published  this  Week. 

Titanium-N  itregen  Compounds.  — Patent  No. 
188558.— Messrs.  Bichowsky,  F.  von,  and  Har- 
tham,  J.,  of  1412,  San  Fernando  Building,  Glen- 
dale,  California,  TT.S.A.,  have  developed  a  process 
for  the  production  of  the  above  compounds.  They 
are  produced  by  heating  a  mixture  of  ilmenite, 
carbon,  and  an  alkali-metal  compound  containing 
oxygen  but  not  containing  sulphur,  in  presence 
of  nitrogen  or  gaseous  mixtures  containing  the 
same,  the  temperature  being  slightly  below  the 
melting  jwint  of  the  mass.  The  carbon  ma,y_"be 
supplied  as  soot,  coke,  or  a  comi>ound  containing 
carbon,  such  as  crude  oil,  and  these  materials 
may  be  supplemented,  or  even  supplanted,  by 
gaseous  mixtures  containing  hydrocarbons,  such 
as  natural  gas.  In  one  example,  100  parts  of 
finely  ground  ilmenite,  5  parts  of  anhydrous  soda 
ash,  and  10  parts  of  pitch  are  briquetted  and 
heated  under  slight  pressure  for  six  hours  in  pre- 
sence of  natural  gas  containing  20  per  cent,  by 
volume  of  nitrogen.  The  temperature  may  -be  at 
first  between  1,100-1,200°  C,  but  is  finally  main- 
tained at  1,000-1,100°  C.  to  avoid  melting  the  iron. 
The  product  is  allowed  to  cool  in  an  atmosphere 
of  neutral  gas,  and  the  iron  dissolved  out  with 
warm  dilute  sulphurio  acid.  Another  example 
illustrates  the  use  of  crude  oil  tar  as  the  reduc- 
ing agent,  and  sodium  silicate  and  soda  ash  as 
the  alkali-metal  compounds  The  titanium  ni- 
tride or  cyanonitride  obtained  may  be  used  for 
the  preparation  of  ammonia,  or  directly  as  a 
fertiliser. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


d 


FEBRUARY  2,  1923. 


THE   CHEKOCAL    NEWS. 


65 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.     No.  3277. 


BRITISH   INDUSTRIES   FAIR,     1923 
VIII. — Stationery  and  Printing  Sections. 

The  Paper,  Printing,  Stationery,  and 
Office  Appliance  Sections  of  the  Fair  form 
one  of  the  largest  groups  exhibiting,  and 
all  the  various  trades  coniiocted  with  these 
important  industries  will  be  well  repre- 
sented. 

A  well-known  firm  of  paper  makers  will 
he  exhibiting  their  noted  tinted  papers, 
which  are  guaranteed  fast  to  Ught.  This 
firm  also  make  a  speciality  of  coiled  papers 
in  all  widths.  Others  will  be  showing  a 
large  range  of  pa,per8  and  lK)ards,  together 
with  manufactured  stationery,  and  office 
furniture,  while  another  leading  firm,  who 
have  recently    installed  nifxlern  and    com- 

{)l€te  plant  for  the  purpose  of  manufactur- 
ng  crepe  papers  of  all  kinds,  including 
decorative  crepe  papers  suitable  for  window 
dressing  and  all  kinds  of  advertising  mat- 
ter, will  display  a  complete  range  of  their 
products. 

In  the  Printing  Section  there  will  be  a 
number  of  the  large  printing  firms,  em- 
bracin  gall  the  different  prm-t^sses  of  print- 
ing for  the  production  of  works  of  art,  and 
commercial  printing,  such  as  catalogues, 
post<irs,  etc. 

The  ant  of  colour  printin*,'  in  the  United 
Kingdom  has  of  late  years  made  so  much 
progress  that  we  may  he  said  to  be  in 
advance  of  the  whole  world.  In  particular 
we  are  specially  predominant  in  the  three 
and  four  colour  processes,  and  there  are 
many  firms  with  hundreds  of  pretty  sub- 
jects in  various  sizes  suitable  for  use  as 
faney  box-tops,  calendar  tope,  advertising 
showcard  tops,  as  well  as  for  framing  or 
decorative  purposes.  The  smaller  nations 
have  neither  the  means  of  producing  good 
colour  work  nor  the  population  that  would 
make  such  production  a  commercial  selling 
proposition  ;therefore,  such  goods  are  im- 
ported. Germany  for  many  years  did  an 
enormous  trade  in  cheap  colour  reprodu;'- 
tion  for  the  above  purposes,  but  first  cost 
of  bl(K*,kmaking  and  printing  are  so  high 
now  that  German  firms  are  largely  selling 
old  subjects. 

United  Kingdom  firms  are  still  publish- 
ing, and,  bearing  in  mind  the  greater  in- 
terest to  the  Empire  of  British  scenes  and 
subjects  as  against  German  designs,  which 
usually  show  foreign  figurcvs  and  land- 
scapes, many  enquiries  for  these  lines  are 
amticipated. 


PLANNING    COMMERCIAL 
VICTORIES. 

Great  Display  (u-  Electrical  Exhibits  .\t 
Wembley. 

M(M*e  than  half  the  space  available  for 
electrical  engineering  exhibits  at  the  Briti.sh 
Empire  Exhibition  has  been  booked  already. 
In  this  section,  with  an  area  of  200,000 
square  feet,  organised  by  the  British  Elec- 
trical and  Allied  Manufacturers'  Associa- 
tion, there  will  be  a  mile  of  gangways  for 
the  visitor  to  walk,  and  nearly  two  miles  of 
stand  frontages  to  be  visited. 

The  electrical  industry  is  one  of  the 
youngest  of  the  great  industries  of  the 
world,  but  every  year  brings  new  inven- 
tions, developments  and  improvements, 
and  in  1924  the  public  will  realise  as  never 
before  what  this  industrs*  means  and  what 
it  offers  to  them.  It  is  clear  that  the 
organising  minds  intend  to  prove  to  the 
world  that  the  capacities  and  resources  of 
the  industry  are  co-extensive  with  the 
Empire  itself. 

Women  will  l>o  shown  what  electricity 
can  do  for  them  in  their  homes.  Electric 
labour-saving  devices,  electrical  appliances 
for  the  preparation  and  cooking  of  food, 
washers,  cleaners,  irons,  kettles  and  the  in- 
mmierable  appurtenam?es  of  the  modem 
home  will  be  demonstrated  in  infinite 
variety. 

.\mong  the  many  exhibits  of  interest  to 
the  technical  and  non-teolmieal  visitor 
alike  are : — 

Electrical  accessories,  accumulators, 
alternators,  bells,  batteries,  cables,  car- 
bons, controllers,  condensers,  dynamos, 
g»'nerators,  high  tension  fuses,  instrti- 
ments,  insulating  materials,  lamps, 
meters,  magnets,  motors,  models  of 
workshops,  power  plant,  rotary  con- 
verters, searchlights,  switchgear,  starters, 
telephones,  turbines,  transformers  and 
wiring  supplies. 

The  millions  of  visitors  to  Wembley  will 
be  shown  that  the  British  electrical  indus- 
try possesses  a  technical  ability  and  a 
manufacturing  capacity  which  maintain 
the  best  traditions  of  British  commerce, 
and  an  effort  will  be  made  to  educate  the 
public  and  to  create  in  them  the  desire  to 
p  )sse8s  the  many  advantages  which  the  use 
of  electricity  holds  out  to  them. 

To  set  up  this  mighty  monument  of  elec- 
trical achievement  before  the  world  for  six 
months  means  that  the  industry  is  planning 
great  commercial  victories  for  the  future. 


66 


THE   CHEMICAL    NEWS. 


FEBRUARY  2,  1023. 


A   NEW    SYSTEM    FOR    THE    LINEAR 

REPRESENTATION  OF  THE 

STRUCTURE  OF  ALL  ORGANIC 

COMPOUNDS. 

By  T.  Sherlock  Wheeler,  B.Sc, 
A.R.C.Sc.L,  A.I.C. 


(Continued  from  Page  66.) 

The  system  can  be  employed  in  writing 
equations.  It  can  also  be  used  in  conjunc- 
tion with  our  present  system  if  it  be  desired 
to  show  the  exact  course  of  a  reaction 
graphically,  so  that  it  may  be  apparent  at 
a  glance.  Much  space  oan  be  saved  in  this 
way,  and  there  is  no  loss  in  clearness.  The 
equation:  — 

(4-CH,.CH.,0H)   -H^O 
Ar.  VI.  1,  2  VI.  (5-CH;.CH;)  ->  Ar.  VI.  1,  2  VT.  4,  5  Al.  VI. 

illustrates  this. 

In  some  cases  it  may  be  desirable  for 
didactic  purposes  to  represent  a  chain  as 
part  of  a  closed  ring.  To  indicate  this,  the 
compound  is  described  a-s  if  the  ring  were 
closed,  and  the  fact  that  one  bond  is  miss- 
ing is  shown  by  a  bar  underneath  the  num- 
bers of  the  two  carbons  which  it  would  join. 

The  above  description  is  sufficient  to  en- 
able any  possible  type  of  ring  compound  to 
be  described.  One  further  example  may  be 
given :  XVIII.  is  the  probable  formula  of 
cinchonine.  It  is  Al.  VL'  (N-4)  4,  1  VI.  3, 
3'  VT  (0-4)  5  II.  2  Ar.  VI.  (N-4)  5,  6  VI. 
The  system  is  especially  fitted  for  dealing 
with  these  polynuclear  compounds  so  com- 
mon in  dye  chemistry.  Quinone,  pyridine, 
thiophene,  and  such  like  structures  are 
taken  to  come  unxler  the  heading  Ar,  but  if 
preferred  Al  can  be  placed  before  the  sym- 
bols for  the  rings  containing  them  and  the 
double  bonds  indicated. 

The  following  is  a  summary  of  the  sys- 
tem :  — 

(i)  A  "  structure  line  "  is  drawn, 
passing  in  ring  compounds  throug:h  the 
centres  of  rings  and  along  chains  joining 
rings.  In  open  chain  comipounds  the  lines 
pass  along  the  longest  chains,  and  then 
along  the  branches;  the  longer  branches  are 
included  as  far  as  possible  in  the  main 
structure  line. 

(ii)  Rings  are  numbered  clockwise 
from  the  extreme  left-hand  common 
carbon;  chains  are  numbered  in  the 
direction  of  the  structure  line  from  where  it 
joins  them;  common  carbons  are  included 
in  each  ring  and  chain  in  which  they  occur. 


(iii)  The  number  of  elements  in  a  ring  is 
shown  by  plain  Roman  numerals;  for  a 
chain  barred  Roman  numerals  are  em- 
ployed. 

(iv)  All  information  about  a  ring  or  chain 
comes  immediately  after  its  Roman 
numeral,  if  possible ;  where  it  is  necessary 
to  refer  back  to  any  ring  or  chain,  its  sym- 
bol is  labelled,  so  to  speak,  with  an  index. 

(v)  Substituents  come  after  the  number 
of  the  element  to  which  they  are  attached; 
non-carbon  elements  precede  the  number 
of  the  place  they  occupy. 

(vi)  The  extreme  left  and  then  the  ex- 
treme right  hand  carbons    common  to  two 


rings  are  shown  in  that  order,  between  the 
numerals  for  the  rings  by  their  numbers  in 


CHa. 


JM 


FEBBUARY  2,  1923. 


THE   CHEMICAL   NEWS. 


67 


the  first  ring.  The  single  oommon  carbons 
connected  with  chains  are  shown  in  a  simi- 
lar manner. 

(vii)  Ar.  shows  that  the  ring  or  rings  fol- 
lowing are  aromatic,  i.e.,  can  be  written 
with  a  centric  formula;  Al.  shows  them  ali- 
cyclic,  i.e.,  fully  reduced. 

(viii)  A  bar  under  the  numbers  of  two 
carbons  shows  that  the  link  jmning  them  is 
to  be  removed  after  the  compound  is  drawn 
as  indicated. 


(ix)  Stereo-chemical  torms  are  unaltered. 
Cis  and  trans  come  in  between  the  repre- 
sentations of  the  groups  or  elements  to 
which  they  refer.  Fischer's  system  is  used 
for  indicating  the  orientation  of  asymmetric 
carbons  in  sugars,  etc. ;  cis  and  trans  com- 
pounds can  also  be  shown  on  that  system. 

From  the  examples  given,  it  will  be  seen 
that  the  system  is  capable  of  indicating  any 
compound,  no  matter  how  complicated.  In 
Konie  cases  the  descriiption  is,  of  necessity, 
long,  but  it  is  never  hard  to  unravel  once 
the  few  simple  rules  are  known.  In  fact 
after  some  little  practice,  the  g^eral  struc- 
ture of  a  compound  is  apparent  at  a  glunce 
from  its  description,  while  to  describe  a 
compound  the  structure  line  need  never  Le 
more  than  drawn  mentally.  Where  tlure  ur<' 
several  w^iys.  of  describing  a  compound  on 
the  svst  m,  the  shortest  is  of  course  always 
to  be  preferred,  and  its  use  would  Ih^  fix<'d 
in  ipractice,  but  any  of  the  ways  available 
wiM  yield  up  the  formula  when  required.  It 
is  to  be  hoped  that  the  scheme  describ«»d 
will  find  a  ready  use  in  chemical  diction- 
aries, chemical  abstracts,  chemical  jour- 
nals, and  perhaps  advanced  text- books.  In 
elementary  text-books  nnd  all  such  cases 
where  obviousness  is  of  more  importance 
than  conciseness,  the  present  day  graphical 
formula  would  still,  of  course,  want  to  be 
given  directly;  having  to  "tranriate"  a  o-on- 
cisc  but  complete  method  of  representation 
might  iperhaps  confuse  a  beginner.  Al- 
though the  system  does  not  seek  in  any 
sense  to  name  the  compounds  described, 
yet  it  can  be  used  as  a  basis  of  a  system  of 
nomenclature.  This  aspect  of  the  matter 
^^ill  be  dealt  with  later. 

The  author's  thanks  are  due  to  Dr.  A.  M. 
Patterson,  of  Xenia.  Ohio,  for  his  helpful 
rriticism  of  the  above. 


NOTES  ON  THE  ACTIVE  PRINCIPLES 
OF  SOME   SOUTH  AFRICAN   PLANTS. 

By  Charles  F.  Jukitz,   M.A.,  D.Sc, 

F.R.S.S.Af.,  F.I.C,  Chief  of  Division  of 

Chemistry,    Department   of   Agriculture, 

Union  of  South  Africa. 

Up  to  the  present,  comparatively  little 
investigation  has  been  carried  out  by 
chemists  in  South  Africa  with  relation  to 
the  active  principles  of  South  African 
plants.  When  I  first  drew  public  atten- 
tion to  the  subject,'  after  alluding  thereto 
more  or  less  incidentally  in  many  succes- 
sive annual  reports,  practically  no  atten- 
tion had  l>een  given  to  it  outside  South 
Africa,  but  to-day  8U<di  names  as  those  of 
Power,  Salway.  liogerson,  Tutin,  Dunstan 
and  Holmes  testify  to  the  interest  which 
this  branch  of  South  African  iplant  chemis- 
try has  aroused  in  other  lands. 

Within  the  borders  of  the  Union  of  South 
Africa,  however,  the  matter  still  stands 
near  whiTc  it  stm>d  when  I  first  voiced  my 
plaint  in  1905,  and  the  chemical  investiga- 
tion of  the  poisonous  and  perhaps  phanna- 
cologically  valuable  principles  of  our  flora 
scarcely  advances  further  than  the  strict 
requirements  of  the  courts  of  justice  when 
Kaffir  "medicine  men"  are  being  tried  for 
culpable  homicide. 

Sixteen  years  have  passed  since  the  date 
of  my  first  i|)ul)lication  (alluded  to  above), 
and  on  four  subsi  <juent  occasions'  the  great 
desirability  of  making  a  special  feature  of 
this  phase  of  clumioal  research  in  South 
Africa  has  been  strongly  urged,  but  for  a 
long  time  it  seemed  vainly.  And  yet  it 
has  not  been  altogo>ther  in  vain:  Dr.  Rindl, 


'  '■  Some  niiim  reganUnrf  South  African 
Pharwacology,"  Trans.  S.A.  Phil.  Sac, 
Vol.  XVI.,  pp.  111-113. 

'  /?.  Marloth.  "  The  Chemistry  of  some 
vegetable  products  of  South  Africa," 
C.G.H.,  Agricultural  Journal,  1909,  pp. 
634-638. 

R.  Marloth,  "  The  Chemistry  of  South 
African  plants  nnd  plant  products,"  Cape 
Chemical  Society,  1913. 

C.  F.  Juritz,  "  South  African  plant 
poisons  and  their  investigation,"  Bept. 
S.A.  Assoc,  for  Adv.  of  Science,  1014.  pp. 
100-145. 

C.  F.  Juritz,  "  The  Urgency  of  a  definite 
fonrard  movement  in  the  studij  of  the 
active  principles  of  South  African  plants." 
S.A.  Medical  Record,  Nov.   13.   1015. 


68 


THE   CHEMICAL    NEWS. 


FEBEUARY  2,  1923. 


Professor  of  Chemistry  at  Grey  University 
College,  Bloemfontein,  has  definitely 
undertaken  as  a  subject  for  researcli  the 
study  of  South  African  pharmaoology 
from  a-  chemical  standpoint,  and  a  year  or 
two  ago  Dr.  J.  W.  C.  Gunn  was  appointed 
Professor  of  Pharmacology  at  the  Univer- 
sity of  Cape  Town,  and  he  has  since  under- 
taken systematic  determination  of  the  phy- 
siological action  of  plant  substances 
peculiar  to  the  flora  of  South  Africa. 

The  facilities  afforded  by  the  establish- 
ment of  a  fully  equipped  Department  of 
Pharmacology  of  the  University  in  the 
vicinity  of  the  laboratories  of  this  Division 
in  Cape  Town,  will  enable  the  two  institu- 
tions to  co-qperate  in  regard  to  the  investi- 
gation of  anygation  of  any  plant  supposed 
to  be  physiologically  active :  in  fact,  Prof. 
Gunn  has  already,  in  two  cases,  published 
the  results  of  experiments  which  have  been 
carried  on  in  his  laboratories,  while  such 
chemical  work  as  has  been  possible  was 
being  performed  in  the  laboratories  of  this 
Division.  This  will  appear  from  the  sub- 
joined nctes  on  three  South  African  plants. 

I. — Wild  Celery  [Peucedanum  galbanum 
(L.)] ,  Benth.  and  Hook. 
Some  time  ago  statements  regarding  the 
therapeutic  value  of  wild  celery  in  cases  of 
Bright 's  disease,  and  dropsy  resulting 
therefrom,  went  the  round  of  the  South 
African  press.  Instances  were  quoted  of 
persons  who  had  suffered  from  the  chronic 
disease  f.  r  years,  and  had  frequently  been 
surgically  tapped  witho'Ut  more  than  tem- 
porary relief,  but  who  had  been  restored  to 
health  after  a  few  months'  use  of  the  above 
iplant. 

Dr.  R.  Mar-loth,  in  his  "  Dictionary  of 
the  Common  Names  of  Plants,"'^  and  also 
in  his  "  Chemistry  of  South  African  plants 
and  plan  tproducts,"*  identifies  this  "wild 
celery"  with  Peucedanum  galbanum  (L.), 
Benth.  &  Hook  (Natural  Order  Umhelli- 
ferse),  and  in  the  latter  publication  makes 
the  following  further  reference  to  it :  — 

"  The  fresh  plant  contains  a  very 
volatile  essential  oil,  which,  when  ap- 
plied to  the  skin,  causes  severe  dermati- 
tis. Some  persons  are  so  sensitive  that 
the  mere  touching  O'f  the  leaves  will  pro- 
duce blistering  of  the  skin,  generally 
about  30  or  40  hours  afterwards,  al- 
though the  contact  itself  causes  no  irri- 
tation." 


1917,  p. 
1913,  p. 


19. 
12. 


On  acoouat  of  this  property  /the  plant  is 
also  very  well  known  vmder  the  name  of 
Blistering  bush."  It  is  common  on  the 
mountains  around  Cape  Town,  and  an  in- 
fusion of  the  leaves  is  largely  used  amongst 
the  coloured  classes  of  the  peninsula  as  a 
diuretic. 

An  investigation  of  the  fresh  green 
leaves,  kindly  supplied  by  Mr.  C.  R.  Ross, 
Conservator  of  Forests,  Western  Conser- 
vancy, was  undertaken  in  the  laboratories 
of  the  Division  of  Chemistry  at  Cape  Town 
by  Mr.  W.  J.  Coipenhagen,  steam  distilla- 
tion of  from  3  >to  8  kilos,  at  a  time  being 
can-ied  on  for  extraction  of  the  volatile  oil. 
The  quantity  of  the  latter  obtained 
the  fresh  leaves.  It  was  light  brown  in 
colour,  and  possessed  the  strongly  aromatic 
odour  which  characterises  the  plant.  The 
fo' lowing  physical  constants  were  found: 

Specific  ,g^vity  at  24°  C 0.847 

Refractive  index  at  40°  C 1.4742 

When  the  previously  steam-distilled  oil 
was  oolleoted  and  heated  to  85°  C,  it  dis- 
tilled over,  apparently  breaking  up  simul- 
taneously into  fractions. 

With  a  view  to  testing  the  supposed  vesi- 
cant properties  of  the  oil,  it  was  applied  to 
the  arms  of  a.  number  of  persons  without 
any  irritating  effect  being  noticeable,  either 
immediately  or  after  the  lapse  of  time.  The 
leaves,  both  fresh  and  dried,  were  similarly 
experimented  with,  also  without  any  blis- 
tering effects. 

In  order  to  permit  of  more  precise  phy- 
siologioal  tests,  some  of  the  volatile  oil  was 
sent  from  this  laboratory  to  the  Pharma- 
cology Department  of  the  University  of 
Cape  Town,  and  a  note  by  Prof.  J.  W.  C. 
Gunn  and  Dr.  E.  M.  K.  Gelling  on  their 
experiments  with  it  was  subsequently  pub- 
lished in  the  South  African  Medical 
Record.^  Some  of  their  conclusions  are 
here  quoted :  — 

"  The  volatile  oil  ...  has  a  per- 
sistent nauseating  taste,  but  is  not  spe- 
cially irritating  to  the  mucous  membrane 
of  the  mouth  or  stomach.  The  oil  was 
rubbed  into  the  skin  of  several  peoiple,* 
but  there  was  no  sign  of  irritation  apart 
from  the  initial  redness  caused  by  the 
rubbing. 

"  In  our  opinion,  the  irritant  proper- 
ties of  the  plant  are  not  due  to  this 
volatile    oil.     The    length    of    time    that 


'  Vol.  XVIII.,  1920,  p.  288. 

*  The  authors  are  not  referring  here  to  the 
similar  test  previously  applied^  in  the  labora- 
tories of  the  Division  of  Chemistry. 


FEBRUARY  2,  1023. 


THE   CHEMICAL   NEWS. 


69 


elapses  before  the  onset  of  dermatitis 
after  contact  with  the  planit  points  rather 
to  some  non-volatile  constituent  as  the 
cause. 

"  An  infusion    of  the  plant  is    some- 
times used  as  a  diuretic.       In    this    re- 
spect it  is  probably  as  efficient  as  buchu, 
and  could  be  used  as  a  cheap  substitute         i 
for  the    latter,  but  its  unpleasant    taste        i 
and  the  difficulty  in  handling  it  are  dis-        ' 
advantages. ' '  I 

There  are  several  South  African  species 
of  Feucedanuvi.  Harvey  and  Sonder  enu-  ; 
merate  some  two  dozen  (inclusive  of  Bubon 
and  Aruethumy ;  and  P.  galbanum  is  by  no  I 
means  the  only  species  which  yields  an 
essential  oil.  Dr.  Marloth**  states  that  the 
plant  commonly  known  a.s  wild  parsley  {P. 
tenuifvlium  Thumb.)  has  a  similar  effect  to 
that  prcxluced  by  P.  galbanum.  P.  gravc- 
olens  (L.),  Benth.  &  H<x>k,  also  yields  a 
volatile  (mI  (dill  oil),  and  its  fruit  has  for 
long  been  used  as  a  drug,  both  the  fruit 
and  the  extracted  oil  being  employed  as  aii 
aromatic  stimulant.  In  this  oDnnection  £. 
J.  Parry  saye,'  "  If  the  fruits  can  be  pro- 
duced in  quantity  in  Capo  Colony,  they 
should  form  a  most  useful  source  of  sup- 
ply." This  remark  wen  is  to  have  been 
proni|)ted  in  part  by  the  fact  that  J.  C. 
Umney  found  the  fruits  of  plants  grown  in 
South  Africa  to  be  slightly  larger  in  size 
than  those  grown  in  England,  and  to  con- 
tain a  slightly  higher  proiporticm  of  oil — 
11.0  per  cent.,  ae  compared  with  10.9  per 
cent. 

11. — Slanokop     (Uroinfa    macrockntra. 
Baker)  : 

A  quantity  of  bulbs  of  a  species  of  sliuig- 
kop  was  brought  to  the  laboratory  by  Mr. 
K.  F.  Wolff  from  Doomfontoin,  P.O.  Wil- 
helmshof,  Boshof,  O.F.S..  with  the  object 
of  ascertaining  its  value  as  a  tanning 
material.  The  poisonous  (pialities  of  some 
species  of  slangkoip  are  well-known :  after 
the  dry  season  the  first  green  vegetation  to 
appear  in  sight  is  the  young  shoot  of  this 
plant;  tiie  sheep  and  goats  nibble  it  off  and 
die,  and  hence  many  thousands  are  said  to 
be  lost  annually.     Mr.  Wolff  thought  that 

^  "  Flora  Capenais,"  Vol.  II..  ipp.  553- 
561. 

•  "  Dictionary  of  Common  Names  of 
planfa."  p    66. 

»  "  Chemistry  of  Essential  Oils,"  3rd  ed., 
1918,  p.  294. 


if  the  bulbs  could  find  useful  apphcation  in 
the  tanning  industry,  the  country-side 
would  simuLtaneously  be  delivered  from  a 
constant  menace  to  stock-life. 

There  are  several  South  African  species 
of  slangkoip,  or,  as  the  genus  called  by  that 
name  in  the  Transvsial^"  is  botanically 
known,  Urginea.  Not  only  are  many 
species  of  this  genus  poisonous,  but  other 
genera  of  the  Natural  Order  (Liliacee),  such 
as  Omithogalum  and  Boicica,  have  been 
paitaken  of  with  fatal  effects  either  to  man 
or  stock.  No  less  than  27  species  of 
Urginea  were  enumerated  by  Thiselton- 
Dyer  in  Flora  Capensis  (Vol.  VI.,  pp.  463- 
470).  One  of  the  best  known  species  is 
Urghiea  Burkei  Baker,  commonly  known 
as  the  Transvaal  slangkop,  and  presenting 
to  stock  prec^ely  the  temptation  already 
alluded  to  above.  Of  this  plant  Dr.  Mar- 
loth  says,  "  Nothing  is  known  about  its  in- 
gredients, and  the  antidotes  employed  are 
OMisequently  quite  empirical.""  Then 
there  are  the  purple  slangkop,  U.  san- 
guin-ea,  which  is  equally  poisonous  accord- 
ing to  Dr.  Marloth,  and  U.  altissima  Baker, 
or  magennan,  the  bulb  of  which  resembles 
the  Mediterranoiin  squill,  U.  maritima 
Baker,  in  its  action. 

U.  maritima,  which  is  found  not  only 
along  the  Meditirrsuiean  coast  but  also  in 
the  Cape  Peninsula,  contaiirs  a  number  of 
glucosides  and  other  bitter  principles,  such 
as  scillain  or  scillitin,  and  scillotoxin,  be- 
ionging  to  the  digitalis  group,  and  produc- 
ing effects  somewhat  similar  to  those  of 
digitalis  as  heart  poisons.  In  very  small 
doses  it  is  merely  expectorant  or  diuretic, 
but  in  larger  quantities  it  becomes  emetic 
and  purgative.  For  pharmaceutical  pur- 
poses the  bulb  of  this  plant  is  divested  of 
its  dry  membranous  outer  scales,  cut  into 
slices,  dried,  when  it  becomes  brittle  and  is 
easily  pfwdered.  The  dose  is  from  1  to  8 
grains  of  the  powder. 

On  U.  Burkei,  Mr.  J.  Burtt-Davy  wrote 
a  short  note  in  the  Journal  of  Industries," 
"mentioning  that  the  plant  is  acrid  and 
poisonous,  causing  inflammation  of 
stomach  and  intestines  and  paralysis.  He 
also  had  n  longer  account  of  the  plant  in 

'"  The  Cape  slangkop  is  quite  another 
plant — Omithoglossum  glaucum  —  which, 
however,  is  also  poisonous. 

"  "  Chemistry  of  South  African  plants 
and  plant  products":  Cape  Chemical 
Society,   1913,  p.  5. 

"  Jan.,  1920,  p.  72. 


to 


THE    CHEMICAL    ^EWS. 


FEBRUAEY  2,  1923. 


the  Eeport  of  the  Traasvaal  Department  of 
Agriculture  for  1903-4,  pp.  310-311,  with 
three  illustrations,  dealing  inter  alia  with 
the  distribution  of  the  plant,  the  season 
when  it  is  most  dangerous  to  stock,  the 
symptoms  of  poisoning  in  stock,  the  local 
remedies,  and  other  plants  liable  to  be  miB- 
taken  for  slangkop. 

The  late  Mr.  L.  H.  Walsh,  in  his  book- 
let on  "  South  African  Poisonous  Plants," 
has  two  half-tone  photographs  of  U. 
Burkei,  with  a  description  of  the  plant  (pp. 
31-32).  "  In  Griqualand  West  and  Bechu- 
analand,"  he  says,  "  numbers  of  sheep  die 
yearly  from  eating  it,  and  in  many  districts 
of  the  Transvaal,  notably  Klerksdorp,  its 
fatal  properties  aa-e  well  known. 
After  the  early  rains,  the  flower  spike 
appears  with  the  first  green  herbage,  and 
is  eaten  by  the  hungry  stock,  while  later 
the  leaves  make  their  a(ppearance,  and 
claim  fresh  victims."  At  the  close  of  his 
note,  Mr.  Burtt-Davy  remarked,  "  If  the 
acitiv'e  principle  contained  in  Urginea  Bur- 
kei should  prove  to  be  similar  to  that 
found  in  the  squill,  and  of  equal  value,  our 
native  bulb  might  not  only  replace  the  im- 
ported drug,  but  might  also  become  an 
article  of  export.  Incidentally  such  com- 
mercial use  of  the  plant  would  assist  in 
clearing  the  country  of  a  poisonous  plant 
detrimental   to  the    live-stock  industry." 

To  return  to  U.  macrocentra :  the  sipeci- 
mens  sent  to  the  Cape  Town  laboratory  by 
Mr.  Wolff  were  there  examined  by  Mr.  W. 
J.  Copenhagen.  The  bulbs  averaged  11 
cm.  in  diameter  and  380  gms.  in  weight. 
When  fresh  they  contained  66.36  per  cent. 
of  moisture,  and  the  proportion  of  tannin, 
determined  by  titration  with  potassium 
permanganate  in  the  presence  of  indigo- 
carmine,^^  amounted  to  0.53  per  cent,  of 
"the  fresh  bulb.  Obviously  there  is  not  much 
to  be  hoiped  for  from  such  an  article  as  a 
commercial  tanning  material.  The  bulbs 
were  therefore  minced  and  extracted,  with 
a  view  to  ascertaining  their  pharmacologi- 
cal potentialities.  On  extraction  of  the  air- 
dried  bulbs  (containing  10.37  per  cent,  of 
moisture)  with  alcohol,  after  acidifying  in 
the  usual  way,  Mr.  Copenhagen  obtained 
0.13  per  cent,  of  the  crude  active  principle. 
A  5  per  cent,  solution  of  this  in  50  per 
cent,  aqueous  alcohoil  was  prepared,  and  1 


^^  The  m.ethod  adopted  in  Leeds  Univer- 
sity Laboratory.  H.  R.  Proctor:  "Leather 
Industiies  Laboratory  Book,"  2nd  ed., 
1908,  p.  227. 


CO.  of  this  solution,  injected  subcutaneously 
into  a  guinea  pig,  caused  death  in  from  7 
to  10  minutes.  This  crude  active  principle 
formed  precipitates  with  picric  acid,  gold 
chloride,  and  iodine  in  potassium  iodide:  it 
reduced  Fehling's  solution  when  boiled 
therewith. 

The  following  colour-reactions  were 
obtained : 

Concentrated   sulphuric    acid — Brick   red 

to  violet. 
Frohde's  reagent — Green. 
Erdmann's  reagent — Pink  to  red. 
Mandelin's  reagent — Red    through     pink 

to  violet. 
Sulphuric    acid    Eind    potassium    dichro- 

mate — Pink  to  dark  brown. 
Greenish^*  enumerates  the  following  re- 
sults of  chemical  investigations  of  squill, 
U.  scilla  Steinh,  {U.  maritima  Baker) : 
"  The  constituents  of  squill  [he  says] 
are  imperfectly  known.  Merck  (1879) 
separa.ted  scillitoxin,  scillipicrin,  and 
scillin,  all  of  which  exhibit  glucosidal 
properties.  Scillitoxin  and  scillipicrin 
are  both  amoiiphous  and  act  npon  the 
heart,  the  former  being  the  more  active 
of  the  two;  scillin  is  crystalline,  but  it  is 
inactive.  Soillain  (Jarmerstedt,  1880) 
appears  to  be  a  purer  form  of  scillitoxin. 
Waliszewski  (1893)  separated  scillinin, 
schillipiorin  and  iscillamarin.  Kopaczew- 
ski  (1914)  isolated  scillitin  and  soilU- 
diuretin;  scillitin  (0.2  to  0.37  per  cent.) 
is  an  intensely  bitter,  purified  form  of 
scillitoxin  tmd  probably  the  active  con- 
stituent in  the  purest  condition  yet 
obtained." 

In  order  that  the  precise  pharmooological 
action  of  the  slangkop  bulbs  might  be 
tested,  some  of  the  latter  were  supplied  to 
Dr.  J,  W.  C.  Gunn,  Professor  of  Pharma- 
cology at  the  University  of  Cape  Town, 
Prof.  Gunn  has  recorded  the  results  in  his 
experiments  in  a  paper  read  before  the 
Royal  Society  of  South  Africa, ^'^  where  he 
sums  them  uip  by  saying  that  the  action  is 
tihe  same  as  that  of  the  digitalis  bodies,  a 
group  which  includes  a  number  of  sub- 
stances of  great  medicinal  value.  Prof. 
Gunn  thinks  dt  possible  that  slangkop 
might  replace  squill  in  South  Africa,  and  in 
fact  may  be  found  superior  to  the  latter, 

1*  "  Text  book  of  Materia  Medica,"  3rd 
ed.,  1920,  p.  388. 

i«  Trans.  Roy.  Soc.  8. A.,  Vol.  IX.,  Pt, 
11.,  1921,  p.  197. 

{To  be  Continued.) 


FEBEUARY  2,  1923. 


THE  CHEMICAL  NEWS. 


71 


THE  FORTHCOMING    "  BUSINESS 
EFFICIENCY." 

Now  that,  according  to  the  highest 
authorities,  trade  ifi  on  the  turn,  and  there 
are  unmistakable  signs  in  every  direction 
that  such  Ls  the  case,  business  men  all  over 
the  country  will  welcome^  the  unique 
opportunity  provided  .by  "  Business 
Efficiency  "  for  witness.ing  all  the  lat':»st 
ficienfcific  and  labour-saving  devices  fi«* 
faoilit-ating  business. 

Business  Efficiency  "  is  undoubtedly 
the  greatest  commercial  education  move- 
ment of  the  day,  and  will  denKmstrate  how 
one  man,  with  the  aid  of  modem  office 
appliance*;,  can  do  the  wf>rk  of  ten,  how 
maximum  efficiency  can  be  secured  at 
minimum  cost,  without  interfering  with 
existing  organisations,  and  ham  by  the  in- 
trfxiuotion  of  better  methods,  success  can 
bo  established  to  the  utmost  degree. 

This  epoch-making  event,  which  has 
been  promoted  to  help  along  the  commerce 
of  the  country,  will  be  of  al>sorbing  interest 
to  every  business  man  and  woman. 
Assembled  under  one  roof,  at  the  Central 
Hall.  Westminster,  from  February  7  to  17, 
will  be  found  the  world's  most  modem 
and  approved  methods  for  enabKng  busi- 
ness firms  to  'turn  out  more  work  at  less 
cost.  Mr.  Neville  Chamlierlain,  M.P., 
Postmaster-General,      will    officially     op?n 

BuKinese  Efficiency  "  on  February  7,  at 
12  o'clock. 

In  view  of  the  increased  cost  of  labour 
and  overhead  exipenses,  it  was  imperative 
that  some  move  of  this  kind  should  be 
initiated,  and  a«  "  Business  Efficiency  " 
was  so  successful  in  this  direction  last  year, 
it  was  decided  to  continue  it  again  on  a  far 
more  extensive  scale.  Cfm.sequently  more 
than  double  the  accommodation  has  been 
reserved  for  this  year's  effort. 

For  the  truth  is  that  more  than  ever  to- 
day the  world  wants  better  methods  and 
better  service.  The  business  prizes  go  to 
those  who  are  most  efficient.  Greater 
etTicieiu'v  is  what  builds  business  in  times 
like  the  present.  The  old  threadbare  ideas 
and  antiquated  methods  will  not  suffice, 
and  business  men  have  got  to  keep  up-to- 
date  all  the  time. 

"  Business  Efficiency  "  recognises  that 
improved  ideas  have  made  the  world  what 
it  is,  and  will  shape  the  world  of  to-morrow. 
It  is  a  co-operative  effort  of  business  men 
for  the  information  of  business  people  ex- 
clusively. 


Exiperience  has  proved  that  the  office  is 
the  brain  system  of  every  business  firm;  it 
is  the  nerve  centre  from  which  the  execu- 
tives direct  and  control  the  entire  estab- 
lishment, and  when  functioning  on  Busi- 
ness Efficiency  lines  radiates  efficiency  to 
every  department.  The  great  need  for  bet- 
ter methods  in  all  administrative  and  exe- 
cutive departments  of  commerce  is  not 
fully  appreciated.  How  to  reduce  unneces- 
sary labour  and  increase  individual  and 
collective  results  is  a  problem  every  busi- 
ness man  seeks  to  solve. 

"  Businees  Efficiency  "  shows  how  a  far 
greater  turnover  can  be  secured  for  every 
individual  firm,  how  the  costs  of  produc- 
tion can  be  lowered  in  both  office  and 
works,  and  how  future  dividends  can  be 
paid  out  of  savings.  This  is  the  psycholo- 
gical moment,  when  British  trade  is  reviv- 
ing, for  business  firms  to  take  advantage  of 
every  possible  appliance  which  will  speed 
up  production  in  every  department. 

There  are  device's  to  be  exhibited  which 
reveal  a  hundred  and  one  ways  of  conduct- 
ing business  more  efficiently  and  getting 
administrative  work  aocurattdy  and  scien- 
tifically done.  With  the  aid  of  these 
various  appliances  the  amoxmt  of  work  the 
individual  can  do  is  enormously  increased, 
and,  many  hours  are  thus  saved  from  rou- 
tine duties  for  more  creative  and  profitable 
work. 

Tin-  exhibits  range  from  the  very  latest 
telephone  syst<'ni,  by  means  of  which  two 
persons  in  different  fpoAn  of  an  extensive 
building  can  speak  to  each  other  from 
whatever  part  of  the  room  in  which  they 
happen  to  be  without  the  necessity  of  rais- 
ing the  mouthpiece.  This  alone  is  a  mar- 
vellous invention — worth  going  to  see. 

Another  amazing  example  of  efficiency  is 
the  latest  calculating  machine.  In  an  in- 
stant, by  a  shuffle  of  the  index  cards, 
ansAvers  to  every  conceivable  question  re- 
lating to  the  customer  can  be  obtained. 
Yet  a  further  innovation  is  the  complete 
office  printer,  which  can  be  oiperated  by 
junior  clerks,  and  turns  out  every  descrip- 
tion of  printing  quickly  at  50  per  cent, 
less  cost. 

All  the  ingenious  stamping  contrivances, 
machines  for  protecting  cheque-writers 
against  fraud,  all  the  modem  systems  of 
loose-leaf  books,  the  latest  carbons,  ribbons, 
typewriters  and  recorders  for  checking  piege 
work  can  be  seen.  In  fact  everything  that 
can  possibly  release  human  brains  and  in- 
telligence  for  work  which  is  not  mechani- 


72 


THE    CHEMICAL    NSlWS. 


FEBRUARY  2,  1921 


oal  has  been  included,  and  the  vaJuable 
time  and  expense  thus  saved  to  business 
firnis  is  almost  beyoml  calculation. 

A  word  about  the  piomotens — the  Office 
Appliance  Trades  Association — whose  mem- 
bership consists  of  men  who  realise  that  the 
country's  well-being  greatly  depends  upon 
the  advancement  of  efficiency  in  business. 

The  objects  of  the  Association  are  the 
linking  up  oi  the  activities  of  those  indus- 
tries which  have  already  done  so  much  to 
make  business  building  and  management 
easier  and  more  harmonious,  the  spreading 
among  British  business  peoiple  of  further 
knowledge  of  commercial  efficiency,  and 
the  general  improvement  of  modern  busi- 
ness conditions. 

The  Association  makes  no  profit,  for  its 
members  bear  the  expenses,  and  "Business 
Efficiency"  is  free  to  all  desiring  to  im- 
prove their  capacity  for  better  business. 
Whatever  the  type  of  business,  whether  a 
one-man  business  or  a  gigantic  organisa- 
tion, "Business  Efficiency"  will  show  how 
things  can  be  done  better  still.  It  will 
prove  of  invaluable  benefit  to  the  manag- 
ing director,  business  organiser,  business 
executive,  manager,  salesman,  foreman, 
and  all  who  are  keen  on  the  best  methods 
for  conducting  business  with  efficiency  and 
despatch. 

More  than  ever  to-day,  the  onus  for  the 
success  of  any  busineiss  falls  more  heavily 
upon  the  individual  member  of  the  staff,  in 
whatever  capacity  he  happens  to  serve, 
and  "Busines-s  Efficiency"  is  of  vital  in- 
terest to  every  business  man.  London's 
leading  authorities  on  commercial  efficdency 
vsdll  demonstrate  the  practical  application 
of  every  new  device,  without  any  obligation, 
and  admission  is  'by  invitation  or  presenta- 
tion of  business  card. 

To  those  desirous  of  forging  ahead  in 
business  and  anxious  to  take  full  ladvantage 
of  every  facility  that  will  help  in  this 
direction,  now  that  trade_  is  on  the  turn, 
"Business  Efficiency"  provides  a  very  real 
Qpport  unity. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Ordinary     Meeting — January     18,      1923. 
Sir  Charles  Sherrington.,  President,    in  the 
Chair. 
The  following  papers  were  read,  the  sum- 
maries here    printed  having  been    supplied 


by  the  authors  for  use  at  the  meeting:  — 

J.  Barcuoft,  F.R.S.  Observations  on 
the  Effect  of  High  Altitude  on  the  Physio- 
logical Processes  o  the  Human  Body. 

Three  principal  factors  appear  to  have  a 
positive  influence  in  acclimatization:  — 

(a)  The  increase  in  total  ventilation, 
which  usually  raises  the  alveolar 
oxygen  pressure  ten  or  twelve  milli- 
metres higher  than  it  would  other- 
wise be; 

(b)  The  rise  in  the  oxygen  dissociation 
curve  so  that  at  any  oxygen  pressure 
the  haemoglobin  will  take  up  more 
oxygen  than  before ; 

(c)  The  rise  in  the  number  of  red  cor- 
puscles, and  correspondingly  in  the 
quantity  of  haemoglobin. 

These  factors  were  provisionally  treated 
as  independent  variables.  In  reality  they 
are  not  so,  for  blood  can  be  made  arti- 
ficially to  rcvsemble  high-altitude  blood,  by 
shaking  out  the  CO3  and  then  withdrawing 
a  portion  of  the  plasma,  so  that  the  blood 
is  richer  in  corpuscles.  Suoh  blood  has 
been  found  to  give,  at  the  alveolar  COj 
pressure  of  the  Andes  (27  mm.  GOg  or 
thereabouts) :  — 

(1)  A  reaction  which  is  apparently  al- 
most unchanged,  or  even  more  acid, 
as  measured  by  the  ratio  of  com- 
bined to  free  CO^; 

(2)  A  more  alkaline  reaction  by  the  plati- 
num electrode ; 

(3)  An  oxygen  dissociation  curve  which 
rises  apparently  out  of  proportion  to 
the  change  in  reaction. 

Herein  would  appear  to  be  the  essence  of 
the  acclimatory  process.  The  possibility 
of  the  oxygen  dissociation  curve  altering 
owing  to  a  specific  loss  of  COj  appears  to  be 
ruled  out.  There  was  an  increase  in  the 
haemoglobin  value  of  the  blood  and  in  the 
red  cell  count  in  all  cases.  On  making  the 
ascent,  there  was  a  marked  increase  in  the 
number  of  reticulated  red  cells,  after  the 
descent  these  cells  fell  to  below  their  nor- 
mal percentage.  In  the  natives  the  ratio 
of  reticulated  to  unreticulated  red  cells  was 
not  greatly  increased,  but  the  absolute 
number  of  refcioulated  cells  per  cubic  milli- 
metre was  about  50  per  cent,  gi-eater  than 
nornial.  We  argue  a  hypertrophy  in  the 
bone  marrow.  There  were  no  nucleated  red 
cells.  The  increase  in  red  blood  corpuscles 
is  such  as  to  cause  an  absolute  increase  in 
the  amount  of  oxygen    in  each  cubic  centi- 


FEBRUARY  2,  1923. 


TMS  Cq^JIICAL  NEWS. 


73 


metre  of  blood  in  the  majority  of  cases,  in 
spite  of  the  decrease  in  saturation. 

A  number  of  mental  tests  of  the  ordinary 
type  were  performed  at  Ccrro  and  at  sea- 
level.  These  revealed  no  particular  men- 
tal disability  in  the  Andes,  but,  in  our 
opinion,  as  well  as  in  that  of  psychologists 
whom  we  have  consulted,  we  have  shown 
rather  that  our  tests  were  inadequate  than 
that  our  mental  efficiency  was  unimpaired. 

A  number  of  tests  were  made  for  the  pur- 
pose of  discovering  whether  the  pressure  of 
oxygen  in  the  blood  was  or  was  not  higher 
than  that  in  the  alveolar  air.  In  all  cases 
they  were  so  nearly  the  same  that  we  attri- 
bute the  passage  of  gas  through  the  pul- 
monary epithelium  to  diffusion. 

Prof.  E.  W.  MacBridk,  F.R.S.  He- 
marks  on  the  Inheritance  of  Acquired 
Characters.     (Verbal  conumiuication  only.) 

It  is  well  known  to  zoologists  that  during 
the  last  fifteen  or  twenty  yeatB  a  series  of 
exiperiments  have  been  carried  out  by  Di. 
Paul  Kammcrer  at  Vienna,  which  tend  to 
show  that  acquired  quaiitii's  or,  in  other 
words,  modifications  of  structure  induced 
by  modified  habits,  are  iriheritable.  The 
results  of  these  experiments  have  been  re- 
ceived with  much  scepticism,  both  here 
and  on  the  Continent,  and  the  bona  fides 
of  Dr.  Kammerer  has  been  called  in  ques- 
tion. 

One  of  the  most  interestinpr  ol  his  experi- 
ments was  in  inducing  Alyte$,  a  tond 
which  normally  breeds  on  land,  io  bre<'d  in 
water.  As  a  result,  after  two  generations, 
the  male  Alytes  developed  a  hwny  pad  on 
the  hand,  to  enable  him  to  gra«p  his  slip- 
pery partner. 

It  has  been  admitted  by  Kammerer^s 
critics  that  if  ho  could  demcMifltrate  this 
ipad,  he  wolud  to  a  large  extent  succeed  in 
estiihlishin  gthe  validity  of  his  reetiHs. 

This  summer,  at  my  request.  Mr.  J. 
(iua.stel,  of  Trinity  College,  Can)br.idge, 
when  in  Vienna,  int<'rvie\vi'<l  Kammerer, 
and  was  shown  by  him  one  of  these  modi- 
fied males.  Qua^tel  photographed  the  ani- 
mal, and  enlargements  from  his  photo- 
graphs are  now  shown.  Subsequently,  at 
my  request,  the  Zoological  Society  des- 
patched Mr.  E.  Boulenyer  on  a  visit  to 
Vienna.  He,  t<x>,  saw  the  modified  male, 
and  was  assured  by  Przibram,  the  head  of 
the  Biological  Institute,  that  all  Kam- 
mercr's  experiments  had  been  done  \mder 
his  (Przibrnm's)  supervision,  and  were  ipcr- 
fectly  genuine. 

C.  F.  Cooi'KK.  Ihiliichiiherixim  oxhomi 
(?  syn.   Indricuiherium    tunjuicum,  Borriss- 


yak.)  Communicated  by  Dr.  A.  S.  Wood- 
ward, F.R.S. 

Baluchitheriu  mosbomi  is  an  aberrant 
rhinoceros  of  such  unusual  size  as  to  be 
apparently  the  largest  known  land  mam- 
mal. The  remains  of  this  animal  were 
first  found  in  Baluchistan,  and  are  de- 
scribed in  the  present  Paper.  Subse- 
quently, further  fragments  have  been  found 
in  Turkestan,  and  quite  recently  more 
material,  as  yet  undescribed,  in  China. 

While  resembling  the  rhinoceroses  more 
mc««  than  any  other  of  the  Perissodaotyia, 
Baluchitherium  is  still  isolated  and  of  un- 
certain zoological  position.  There  are  cer- 
tain adaptations  to  weight  whicli  have 
brought  about  a  superficial  resemblance  in 
some  of  the  limb  IxMies  of  elephants.  There 
are  also  resemblances  in  some  of  the  foot 
bones  and  neck  \ertebrte  to  those  of  the 
horse,  which  are  less  easily  ex(plained,  ex- 
cept bv  the  hyi>ot^esi8  that  this  form  is 
desconded  from  a  small  eocene  form,  Tri- 
palpus,  which  likewise  shows  an  inter- 
mingling of  hoi-se  and  rhinoceros  charac- 
ters. In  some  structures,  notably  the  ex- 
cavation.><  of  the  vertebral  canal  to  ensure  a 
c^mibination  of  lightness  and  strength, 
Baluchitherium  stands  alone  among  mam- 
mala. 

J.  A.  GuNN  and  K,  J.  Franklin.  The 
Sympathetic  Imuervaiion  of  the  Vagina. 
Cwnmunicated  bv  Sir  Charles  Sherrington, 
P.R.S. 

H.  O.  Cannon.  On  the  Metabolio 
Gradient  of  the  Frog's  Eqg.  Communi- 
cated by  Prof.  E.  W.  MacBride,  F.R.S. 

Basis  WAR  Sen.  On  the  Relation  be- 
tween Permeability  Variation  and  Plant 
Movements.  Communicated  by  Sir  Wil- 
liam BayUss,  F.R.S. 

H.  L.  Duke,  M.D.  An  Enqtiiry  into  an 
Outbreak  of  Human  Trypanosomiasis  in  a 
"  Glosshia.  morxitans  "  Belt  to  the  East 
of  Mwama,,  Tanqanyika  Territory.  Com- 
municated by  Mr.  C.  Dobell,  F.R.S. 

Louis  DoLLO,  Sc.D.  Le  Centenaire  dea 
Iguanodons  (1822-1922).  Communicated 
by  Prof.  A.  C.  Seward,  F.R.S. 

Thursday,  January  26,  1923,  at  4.30  p.m. 

Papers  read :  — 

Prof.  A.  V.  Hill,  F.R.S.,  The  Potential 
Difference  occurring  in  a  Donnan  Equili- 
firium  and  the  Theory  of  Colloidal  Be- 
haviour. 

E.  F.  Armstrono,  F.R.S.,  and  T.  P. 
HiLDiTcH,  A  study  of  Catalytic  Actions  at 
Solid  Surfaces.       X. — The     Interaction    of 


74 


THE    CHEMICAL    NEWS. 


FEBRUAEY  2,  1923. 


Carbon  Monoxide  and  Hydrogen  as  con- 
ditioned by  nickel  at  relatively  low  Tem- 
peratures. A  Practical  Synthesis  of 
Methane. 

J.  HoLKER,  D.Sc,  The  Periodic  Opacity 
of  Certain  Colloids  in  progressively  increas- 
ing Concentrations  of  Electrolytes.  Com- 
municated by  Prof.  A.  V.  Hill,  F.R.S. 

E.  K.  RiDEAL  and  R.  G.  W.  Norrish, 
The  Photochemistry  of  Potassium  Perman- 
ganate. Part  I. — The  Application  of  the 
Potentiometer  to  the  Study  of  Photochemi- 
cal Change.  Part  II. — On  the  Energetics 
of  the  Photo-decomposition  of  Potassium 
Permanganate.  Communicated  by  Sir 
William  Pope,  F.R.S. 

E.  A.  Fisher,  Some  Moisture  Relations 
of  Colloids.  I. — A  Comparative  Study  of 
the  Rates  of  Evaporation  of  Water  from 
Wool,  Sand  and  Clay.  Communicated  by 
Prof.  A.  Smithells,  F.R.S. 

R.  Whytlaw-Gray,  J.  B.  Speakman,  and 
J.  H.  P.  Campbell,  Smokes,  A  Study  of 
their  Behaviour  a^  a  Method  of  Determin- 
ing the  Number  of  Particles  they  contain. 
Communicated  by  Prof.  A.  Smithells. 
F.R.S. 

R.  Whytlaw-Gray  and  J.  B.  Speakman, 
A  Method  of  determining  the  Size  of  the 
Particles  in  Smokes.  Part  IT.  Communi- 
cated by  Prof.  A.  Smithells,  F.R.S. 

R.  C.  Ray,  The  Effect  of  Long  Grinding 
on  Quartz  {Silver  Sand).  Communicated 
by  Dr.  M.  W.  Travers,  F.R.S. 


ABSTRACTS  OF  THE  PROCEEDINGS 

OF  THE  GEOLOGICAL  SOCIETY  OF 

LONDON. 

January  10,  1923. 

Prof.  E.  J.  Garwood,  Sc.D.,  F.R.S., 
Vice-President;  and  afterwards  Prof.  A.  C. 
Seward,  Sc.D..  F.R.S.,  President,  in  the 
chair. 

Prof.      William      .Johnson       Sollas, 

Sc.D.,   F.R.S.,   F.G.S.,     then  proceeded 

to  deliver  a  lecture    on  Man  and  the  Ice- 

Age. 

He  said  that,  thanks  to  the  researches  ot 
General  de  Lamothe,  Prof.  Deperet,  and 
Dr.  Gignoux,  the  Quaternary  System  now 
takes  its  place  as  a  marine  formation  m 
the  stratified  series. 

Four  ancient  coast-lines  of  remarkably 
constant  height  have  been  traced  around 
the  Mediterranean  Sea  and  along  the  west- 
em    shores  of  the    North  Atlantic    Ocean. 


These,  with  their  associated  sedimentary 
deposits,  form  the  successive  stages  of  the 
Quaternary  System :  namely,  the  Sicilian 
(coast-line  about  100  metres);  the  Milaz- 
zian  (coast-line  about  60  m.);  the  Tyrr- 
henian (coast- line  about  30  m.) ;  and  the 
Monastirian  (coast-line  about  20  m.). 

The  Sicilian  deposits  rest  unconformably 
upon  the  Calabrian  (Upper  Pliocene),  and 
in  their  lower  layers  contain  a  character- 
istic cold  fauna.  The  fauna  of  the  Milaz- 
zian  is  warm-temperate,  of  the  Tyrrhenian 
and  Monastirian  still  warmer,  for  they 
contain  numerous  species  of  mollusca  which 
now  live  off  the  coast  of  Senegal  and  the 
Canary  Islands. 

The  three  lower  coast-lines  correspond 
with  the  three  lower  river- terraces  of  the 
Isser  (Algeria),  the  Rhone,  and  the 
Somme.  Hence  it  may  be  inferred  that 
the  position  of  the  river-terraces  has  been 
determined  by  the  height  of  the  sea-level. 

The  lower  gravels  of  the  three  lower 
terraces  of  the  Somme  all  contain  a  warm 
fauna,  Elephas  antiquus  and  Hippopota- 
mus, ,and  thus  (like  the  corresponding 
marine  sediments)  testify  to  a  warm  cli- 
mate. The  climate  of  the  Quaternary  age 
was,  on  the  whole,  warm-temperate  or 
genial,  but  interrupted  by  comparatively 
short  glacial  intervals. 

The  outermost  moraine  (Mindel)  of  the 
Rhone  Glacier  is  associated  with  the  Mflaz- 
zian  terrace,  the  intermediate  moraine 
with  the  Tyrrhenian,  and  the  innermost 
moraine  (Wiirm)  with  the  Monastirian; 
except  for  their  serial  order,  these  associa- 
tions are  (in  a  sense)  accidental. 

It  is  now  possible  to  assign  then  Palseoli- 
thic  stages  of  human  industry  to  their 
place  in  the  Quaternary  System :  thus  the 
"Strepyan"  or  pre-Chellean  is  Milazzian  in 
age,  the  typical  Chellean — ^Tyrrhenian,  the 
evolved  Chellean,  Acheulean,  and  Lower 
Mousterian — early  Monastirian,  and  the 
Upper  Mousterian,  Aurignacian,  Solutrian, 
and  Magdalenian — later  Monastirian. 

The  coast-lines  of  the  Northern  Hemi- 
sphere appear  to  have  their  counterparts 
in  the  Southern  Hemisphere,  and  the  re- 
searches of  Dr.  T.  0.  Bosworth  in  Peru 
and  Prof.  G.  A.  F.  Molengraaff  in  the  East 
Indies  have  revealed  extensive  marine 
Quaternary  deposits  and  successive 
movements  of  the  sea-level. 

The  Quaternary  movements  are  probably 
due  to  a  general  deformation  of  the  globe 
involving  eustatic  changes  in  the  level  of 
the  sea. 


I 


FEBRUARY  2,  1923. 


THE   CHEMICAL   NEWB. 


75 


The  lecture  was  followed  by  an  interest- 
ing discussion,  in  which  the  following  gen- 
tlemen took  part :  Mr.  W.  Whitaker,  Mr. 
Walter  Johnson,  Mr.  S.  H.  Warren,  Prof. 
J.  E  .Marr,  Prof.  P.  G.  H.  Boswell,  Mr. 
H.  Dewey,  Mr.  K.  S.  Sandford,  and  the 
Secretary. 

At  the  meeting  on  Wednesday,  February 
7,  a  lecture  on  the  "Geological  Results  of 
the  Shackleton-Rowett  (Quest)  Expedi- 
tion" will  be  delivered  by  Mr.  G.  Vibart 
Douglas,  Geologist  to  that  Expedition. 

The  Annual  General  Meeting  of  the 
Society  will  be  held  on  Friday,  February 
16,  at  3  p.m.  The  Fellows  of  the  Society 
and  their  friends  will  line  at  the  Cafe  Royal 
(Regent  Street,  W.l)  on  the  same  day,  at 
7.15  for  7.30  o'clock. 


ROYAL  INSTITUTION. 
On  Tuesday,  January  30,  at  8  o'clock, 
Mr  ,.R.  D.  Oldham  began  a  course  of  two 
lectures  at  the  Royal  Institutiwi  on  "  The 
Character  and  Cause  of  Earthquakes";  on 
Thursday,  February  1,  Professor  I.  M. 
Heilbron  delivered  tne  first  of  two  lectures 
on  ' '  The  Photosynthesis  of  Plant  Pro- 
ducts," and  on  Saturday,  February  3,  Mr. 
J.  C.  Squire,  Editor  of  the  London  Mer- 
cury, commences  a  course  of  two  lectures 
on  "  Subject  in  Poetry,"  with  special  refer- 
ecne  to  contemporary  practice.  The  Fri- 
day evening  discourse  on  February  2  will  be 
delivered  by  Mr.  C.  F.  Cross,  ^  on  "  Fact 
and  Phantasy  in  Industrial  Sdenoe,"  and 
on  February  9  by  Sir  John  Russell  on 
"  Rothamsted  "  and  Agricultural  Science. 


THE  SOCIETY  OF  DYERS  AND 
COLOURISTS. 

A  meeting  of  the  Manchester  Section  of 
the  Society  was  held  on  January  19,  when 
two  papers  of  great  interest  were  read.  Mr. 
William  Marshall,  J.P..  F.I.C.,  F.C.S.. 
presided. 

The  Behaviour  of  Titanic  Acid  ioxrardtt 

Dyeatuffs,  -by  J.  K.  Wood,  D.Sc,  F.I.C. 

and  A.  M.  Morlev,  M.Sc.Tech.,  A.l.C. 

Dr.  Wowl.  in  reading  the  above-titled 
paper,  said  the  element  titanium  occurs  in 
the  fourth  group  of  the  periodic  classifica- 
tion, togothtr  with  silicon,  zirconium,  tin, 
and  other  elements.  These  elements  form 
hydroxides  which  are    aniiphoteric  in  char- 


acter, and  which  are  commonly  referred  to 
as  acids.  It  has  been  customary  to  con- 
sider these  substances  as  capable  of  exist- 
ing in  two  modifications,  known  respec- 
tively as  alpha  and  beta  acids,  and  showing 
a  considerable  difference  in  behavious  to- 
wards reagents.  Although  the  practice  has 
been  to  speak  of  c«ily  two  varieties  of  the 
various  acids,  the  facts  recorded  in  the 
literature  would  suggest  that  more  than 
two  modifications  are  obtainable  according 
to  the  methods  of  preparation  which  are 
emiployed.  It  is,  however,  extremely 
doubtful  whether  the  substances  referred  to 
are  definite  hydrates  of  the  oxide  of  the 
elements  in  question,  and  the  opinion  has 
gained  ground  in  recent  years  that  the  dif- 
ference between  the  so-called  modifications 
of  these  acids  is  really  due  to  a  difference 
in  size  of  their  primary  particles.  The 
ortho  acid,  now  commonly  referred  to  as 
the  alpha  variety,  is  considered  to  exist  in 
the  form  of  small  particles  which  are  more 
readily  attacked  hy  reagents  than  the 
larger  and  more  c(M3aplex  of  the  meta,  or, 
as  it  is  now  commonly  called,  the  beta 
acid.  If  the  difference  in  property  is  really 
due  to  the  size  of  the  particles,  it  will  be 
seen  that  this  opens  up  the  possibility  of 
the  existence  of  a  number  of  modifications 
of  the  acids  which  would  be  in  harmony 
with  the  behaviour  as  recorded  in  the 
literature.  It  has  iMig  been  known  that  it 
is  possible  for  the  alpha  nuKlifioations  of 
these  acids  to  be  transformed  into  the  beta 
varieties,  and  that,  in  turn,  the  beta  may, 
under  certain  conditions,  be  re-converted 
into  the  alfpha  varieties,  but  no  definite  ex- 
planation of  these  changes  and  of  the 
causes  which  operate  to  bring  them  about 
was  ofiered  until  a  lew  mcmths  ago,  when, 
ae  the  result  of  experiments  on  the  stannic 
acid«,  Mr.  Collins  and  himself  suggested 
that  the  gradual  change  in  the  structure 
and  properties  of  these  properties  might  be 
traced  to  the  amphoteric  character  of  the 
oxides  in  question. 

Mr.  Collins  and  himself  showed  by 
papers  published  last  year  that  the  hypo- 
thesis is  in  agreement  with  the  behaviour 
of  Stannic  Acids  imder  varying  conditions, 
and  they  also  suggested  that  the  isomerism 
of  the  analogous  compounds  of  titanium, 
zirconium,  and  other  elements,  might  be 
similarly  accounted  for.  Numerous  ex- 
periments which  have  been  made  with  Mr. 
Morlev  show  that  this  supposition  that  the 
explanation  of  the  isomensm  of  the  titanic 
acids  was  due  to  a  similar  cause  is  justified. 


76 


THE   CHEMICAL   NEWS. 


FEBRUARY  2,  1923. 


so  that  ia  regard  to  titamum  hydroxide  or 

titaniq  a^ids  it  may    be  assumed  that    oe 

tween  the  so-called  alpha    titanic  acid  a^d 

the  beta  titanio  acid,    ]ust  as  with  St^anmo 

Acids,    there  is  a    series  of    substances  J^t 

oraduallv     mcreasing    complexity  ot     their 

El%articles..and  that  tbere  is  reahy 

a    continuous    series    of  these    substance| 

aradually  increasing  in  beta  character  as  a 

Tocess  ^f  condensation    takes  pla<^  as  t^^^^^ 

result  of  the  titanium    hydroxide  function 

ng   n  two    oa^pacities.       TW«  ^^^^f^was 

ess  a  theoretical    statement    w^^^h  it  was 

neLsary    to  bear  in  mind    with  regard  to 

?hT;?e^nt  petition  of>nowledge^rega^dmg 

these  so-called  isomeric  acids.     O^^  Result 

of  a  process  of  condensation  would  be  the 

^adual  decrease  in  the  total  surface  of  the 

faSes,  because  by  the   fusk>n  owing  to 

fhp    nrnoess    of     condensation    ot    several 

sample  ^articles  together,    a  complex  par- 

de^    was    created,'  which    must    have    a 

smaller  surface    than  those  from  ^yhlch    it 

hTdten  formed.     Inasmuch  a.  adsorption 

is  a  surface  phenomenon    it  will  be  antici 

Dated  that,    other    things    being    equal,    a 

Ltple  of  titanic  a.id  having  a  pronounced 

beta    character    would    possess    a  jmauer 

adsorptive  capacity  than  one  m  which  the 

^ocess  of  condensation  had  proceeded  to  a 

^^TcSrable  number  of  experiments  in 
support  of  the  authors'  deductions  were 
exiplained. 

Investigatiori^  on  the  Constituents  of 
rI^  Cotton,  IV.,  by  Professor  t., 
Knecht,  Ph.D..  M.Sc.Tech  F-l-C 
and  G.  H.  Streat,  M.Sc.Tech. 

This  paper  was  then  read  by  Dr.  Knecht 
who  sta'te^  that  the  .title  of  the  paper  -s 
rather  a  comprehensive  one.     It  was  rea^^y 
a  secand    communication  on  cotton    wax 
In  an  account  of  the  systematic  exW^«n 
o?  the    bleached    cotton    yam  which    had 
been  heated  for  336  hours  in  ^  ^eakd  t^b^ 
at  93°,  it  was  stated    that  the  benzene  ex 
tracted  amounted  to  0  3,  -^^-^-J-^:^. 
water  also  0.6  per  cent  _     ^^^'ll^^'^f^. 
mation  of  the    assumption  that    these  ex 
Salrwere  due  to  treatment  m  ble^hmg 
was    obtained    at    he    time    by    extractmg 
o^rv^o    <m^v    Ecvptian    yarn    to    exhausiiou 
wTh  bST/ene  °  ften  bleaching  it     and  ex- 
teactin"    aVta  with  benzene,    when  a  not 
Ssaeraf,le  further  extract  was  cbtam:^. 
The  experiment  was  repeated  later  by  -teT 
nandfz!  and  it  was  found  -t  f  ^  \enzene 
but  also  alcohol  and  water  gave  turther  ex 


tracts    after    bleaching.       It.  ^^fJ'^'^^Z 
ascertained    that  cotton    which   had    been 
thoroughly    bleached  yielded,     after    being 
smLhfd  L  powder  on  an  --l    consider- 
able amounts  of  extracts.        further  wotk 
^n  th?s  subject    had  --.been  earned  out 
and   the     results     ge^^^rally  confirm    tho^e 
rpeviously    obtained.       Bncfly  stated,    the 
experiments  showed  that  extraction  of  the 
raw  cotton  with  benzene  on  y  removed  the 
w^  to    the  extent  of    about  one-half,    but 
Si?  the  fibre  suhstance    -/-t^^.^^i 
disintegrated    by  chemical   or    mechanical 
means     the  whole  of    the  wax  can    be  ex- 
ited,   and  is  then    f<>-d  to  amoun     to 
somewhat  over  one  per  ^^t.       A    further 
examination     of  cotton    wax  ^^a^    revealed 
the  presence  of  what  aPPf^^^  tj^^^^  ^^Z\n- 
rlpfinite    compound    which    diffeis    m  soiu 
bflTty    melting  point,  and  composition  from 
that  described  by  Schunck. 


GENERAL   NOTES. 

Abstract   of  evidence    gi;^^.   before    tj^e 
mr    G    S    W.  Marlow,  B.Sc,  F  I.O.),  on 

^'¥h:'issiS  secretary  gave  evid^ee  in 

should  be  defined,  and  suggested  (m  bnet) 
^rCtbnt  evidence  of  attainment    should  be 
bl  noLession  ?f  Fellowship    or  Associate- 
tto  of  one  o"   the  Institutes,  ot  a  Umver- 

t^w?S?J^Ce  "f'^e^uate  traiU J" 
Tose  subiects;  .(b)  that  exarmner.  shou  d 

have  had    '"'""fi^X^.SnersThould V 
^meCCrora^rtpSlirbody  of  chemists, 

^trrmphastrthe^^mportance    in    the 

Cu"nr?o%rcr?e'tenr  s 

&ty  o^^^^,„^- jrrre  was  ^o 
pointed  ou      however     t  ^^fi^iti^    „f 

provision  '"  t^".  JTrU^iity,  and  that  ga.s 
comipelenoe  and  ™P?"'»" /■  ,  ,  authori- 
examiners.  were  appointed  by^ocal^ 

ties  who,  m  many  cases. 


FEBRUABY  2,  1923. 


THE   CHEMICAL   NEWS. 


77 


tent  to  judge  of  the  qualifications  required 
of  gas  examiners.  He  then  related  the 
endeavours  the  Institute  of  Chemistry  had 
made  in  1920,  whilst  the  liill  was  before 
the  House  of  Commons,  to  ensure  the  in- 
sertion into  the  Act  of  such  definition,  and 
related  further  that  the  Institute  had  been 
unsuccessful  even  in  persuading  the  Board 
of  Trade  to  give  an  indication  (rf  the  nature 
of  the  qualifications  required. 

He  referred  to  the  fact  that  the  Gas 
Referees,  who  had  power  only  to  advise, 
had  issued  a  memorandum  for  the  informa- 
tion of  local  authorities,  in  which  some 
^idanoe  as  to  competence  and  impartial- 
ity had  been  given,  but  lu  remarked  that 
this  memorandum  contaijicil  phrases  which 
lacJted  definition,  and  tiien  fore  the  Insti- 
tutes of  Chemistry  and  of  Physioe  hud  en- 
deavoured to  provide  the  necessary  defini- 
tion, 

H(>  then  reviewed  some  of  the  a|)point- 
ments  which  had  already  been  made,  with 
a  view  to  showing  that  kx^al  authorities 
had  in  some  castas  made  unsuitable  ap- 
pointments. With  regard  to  the  appoint- 
ment of  whole-time  officers  o(  the  authori- 
ties (such  as  me<lical  officers  of  health,  in- 
spectors of  weights  and  measures)  he  sug- 
^sted  that  it  was  undesirable  in  the  public 
mterests  that  an  officer  should  be  appointed 
who  prima  facie  was  not  corrjjpetent,  ewn 
though  personally  he  might  possess  quali- 
fications which  might  be  deemed  sufficient, 
since  the  psychological  effect,  u^pon  the 
public,  of  indubitable  evidence  of  compe- 
tence was  important.  Moreover,  such 
persons  could  not  be  considered  impartial 
since  in  cases  of  doubt  they  would  be 
biassed  towards  giving  a  satisfactory  report 
in  view  of  the  fact  that  failure  to  maintain 
an  adverse  report  might  possibly  endanger 
their  major  a|)pointments. 

He  also  criticised  cases  in  which  local 
authorities  had  advertised  appototments  to 
tender,  and  suggested  that  pirscms  of  goixl 
professional  standing  would  l)e  unlikely  to 
apply  under  such  conditions. 

In  further  criticism  of  certain  aspects  of 
the  Act,  he  suggested  that  it  was  not  in 
fuxjordance  with  the  public  interests  that 
the  gas  examiners  should  Ih^  required  in 
certain  cases  to  give  notice  to  the  gas  com- 
panies of  the  time  at  which  they  proposed 
t  >  make  a  t-est,  and  further  that  for  the 
good  adminis-tration  of  the  Act,  it  was  de- 
sirable that  provision  should  be  made  for 
separate  "lock-U|p"  testing  stationa,  so  that 
there  might  be  no  doubt  as  to  whether  in- 
struments had  been  tampered  with. 


In  conclusion,  he  drew  particular  atten- 
tion to  the  desirabiUty  of  gas  examiners 
being  members  of  reputable  professional 
bodies  which  had  strict  rules  of  profes- 
sional conduct,  and  could  exercise  penal 
powers  upon  examiners  who  mere  guilty  of 
paitiality. 

In  reply  to  members  of  the  Committee, 
the  Assistant  Secretary  remarked  that  in 
order  that  provision  might  be  made  for  such 
regulations  as  to  competency,  the  Act 
would  require  amendment,  and  he  sug- 
gested that  the  lioard  of  Trade  or  the  Gas 
Referees  should  he  pveu  powers  similar  to 
those  possessed,  say,  by  the  Ministry  of 
Health,  in  the  case  of  public  analysts  under 
the  Sale  of  Foods  and  Drugs  Act,  to  pre- 
scribe regulations  as  to  oompetenoy. 

He  agreed  tliat  it  would  be  possible  to 
arrange  for  the  ad  hoc  examination  of  can- 
didates for  posts  as  gas  examiners,  such  ex- 
aminutio  nto  be  conducted  under  the  aus- 
pices of  the  Institutes,  or  alternatively  to 
provide  for  the  recogniticm  of  existing 
examinations. 

In  the  subsequent  evidence  of  witnesses, 
particularly  that  of  Mr.  Butterfield,  a  Gas 
R«'feree,  it  was  clear  that  the  Committee 
ha<l  grasped  the  imiportance  of  the  question 
of  the  competency  and  impartiality  of  the 
examiners,  and  also  of  the  other  matters 
mentioned  in  evidenoe. 

The  Chairman  of  the  Committee  re- 
marked to  Mr.  Butterfield  that  the  very 
wide  powers  given  io  the  Gas  Referees 
appeared  to  be  rcmdered  void  in  certain 
oases,  since  there  was  nobody  who  had  a 
power  of  veto  upi^n  the  appointment  of  in- 
competent examiners. 


TO  LIGHT  .\  TOWN  OF  100,000 
INHABITANTS. 

B.E.A,M.A,'8    £130,000  Offkr  of  Powkr 
Station  and  Plant  at  Wembley. 

From  one  source  alone,  enough  electric 
power  to  light  a  town  of  100,000  inhabit- 
ants will  be  supplied  to  the  British  Empire 
Exhibition  at  Wembley, 

We  are  officially  informed  that  the  Coim- 
cil  of  the  British  Electrical  and  Allied 
Manufacturers'  Association  have  offered  to 
supply  to  the  Exhibition  a  temporary 
power  staticm,  the  value  of  the  plant  for 
which  amounts  to  about  J&130,000,  The 
turbine  station  will  be  complete  with 
switchboards  and  subnstations.       They  are 


78 


THE  CHEMICAL  NEWS. 


FEBRUARY  2,  1923. 


also  prepared  to  supply  additional  generat- 
ing plant,  if  required,  amounting  in  value 
to  over  £50,000.  This  plant  will  be  lent  to 
the  Exhibition  on  terms  representing  only 
a  small  fraction  of  its  value. 

The  power  generated  in  this  station 
would  supply  a  town  of  100,000  inhabit- 
ants, or  it  would  light  a  60- watt  lamp 
every  hundred  yards  on  the  road  from 
London  to  Glasgow. 

The  blades  of  the  turbines  will  revolve 
at  a  speed  of  five  miles  a  minute.  While 
the  exhibition  is  open  they  will  travel  a 
distance  which  would  enable  the  world 
to  be  traversed  and  every  dominion  in 
the  Empire  to  be  visited  no  fewer  than 
twenty  times;  while  those  more  venture- 
some than  Jules  Verne  could  travel  to 
the  moon  and  back. 

Enough  steam  will  be  evaporated  in 
the  power  station  to  flood  the  stadium  to 
such  an  extent  that  the  oup  finalists 
would  have  to  play  the  game  up  to  their 
knees  in  water. 

Coal  to  be  consumed,  if  brought  in  one 
load,  would  require  a  train  over  two 
miles  long. 


UNIVERSITY  OF  PRAGUE. 

An  interesting  ceremony  took  place  on 
January  8,  1923,  at  the  Promotion  Hall  of 
the  Bohemian  (Charles)  University,  when 
the  degree  of  Doctor  of  Natural  Science 
was  conferred  by  Professor  J.  Sterba-Bohm 
upon  Mr.  J.  G.  F.  Druce,  M.Sc,  of  Lon- 
don. 

Mr.  Druce  had  presented  a  Thesis  en- 
titled, "  Contributions  to  the  Chemistry  of 
Organic  Tin  Compounds."  This  was 
accepted,  and  Mr.  Druce  was  called  to  the 
"rigorosum"  and  was  examined  in  General, 
Physical,  and  Inorganic  Chemistry  and  in 
Botany,  the  examinations  being  conducted 
in  English  and  French. 

Mr.  Druce  satisfied  the  examiners,  and 
passed  with  distinction,  and  thus  has  the 
honour  to  be  the  first  Englishman  to 
obtain  this  degree. 

In  his  speech  acknowledging  the  honour 
conferred  upon  him,  Mr.  Druce  referred  to 
the  achievements  of  Bohemian  scientists, 
mentioning  the  researches  of  Professor  B. 
Brauner  upon  Atomic  Weight  determina- 
tions and  other  important  investigations  in 
Inorganic  Chemistry.  He  hoped  that  other 
Enelish  students  would  visit  the  Bohemian 
University,  and  that  Czech  eifcudents  would 


visit  the  Universities  of  England.  In  this 
way  the  scientists  of  both  countries  would 
in  future  benefit  by  this  exchange.  The 
Rector      of      the      University       (Professor 

Horacek)  and  the  Dean  of  the  Faculty  of 
Science  (Professor  Domin)  expressed  simi- 
lar sentiments  and  hoipes. 


HYDROXY  STEARIC  ACID. 

By  L.  G.  Radcliffe  and  W.  Gibson. 

Hydroxy  stearic  acid  is  the  product 
formed  when  oleic  acid  is  sulphonated,  and 
by  appropriate  treatment  including  reerys- 
tallisation  from  alcohol,  the  acid  is  obtained 
as  crystals  M.P.  81°-82°  C.  Both  methyl 
and  ethyl  esters  can  be  prepared  by  treat- 
ing the  hydroxysteario  with  the  necessary 
alcohol  (pure)  and  dry  hydrogen  chloride. 
Methyl  ester  M.P.  46°  C.  and  ethyl  ester 
48.5°  C.  On  acetylation,  the  acid  gives  a 
white  powder,  M.P.  81-32°  C.  Attempts  to 
prepare  a  nitro  derivative  of  stearic  acid  by 
treating  bromo-stearic  acid  with  silver  ni- 
trate in  alcoholic  solution  were  unsuccess- 
ful. Direct  nitration  of  hydroxystearic 
acid  gave  a  greenish  yellow  crystalline  pro- 
duct, M.P.  83-83.5°  C,  and  containing  no 
nitrogen.  No  formula  can  be  suggested  for 
this  unknown  acid.  Other  nitration  pro- 
ducts are  a  yellow  oil  and  a  white  crystal- 
line solid,  M.P.  80-120°  G.—(J.  Soc.  Dtjera 
Col,  1923,  p.  4.) 


REVIEWS  ON 

Carotinoids   and   Related   Pigments. 

Year-Book  of  Pharmacy,  1922. 

Dictionary  of  Applied  Chemistry. 

By  John  Missenden. 

Cartinoids  and  Related  Pigments :  The 
Chromolipoids,  hy  Leroy  S.  Palmer, 
Ph.D.  Pp.  316.  New  York:  The 
Chemical  Catalog  Co.  Inc.,  19,  East  24th 
Street.     Price  $4.50. 

This  interesting  treatise  does  not,  as  do 
so  many  volumes  of  a  similar  order,  deal 
solely  with  the  phytochemical  aspects  of 
the  yellow-to-red  colours,  but  also  incor- 
porates the  carotinoids  obtained  from  or 
contained  in  the  vertebrates  or  inverte- 
brates. The  author  has  wisely  followed  M. 
Towett's  suggested  form  of  classification, 
thereby  maintaining  a  consistency  well  in 
keeping  with  a  difficult  series  of  com- 
pounds.      Towett    divided  the    carotinoids 


FEBRUARY  2,  1923. 


THE  CHEMICAL  NEWS. 


79 


into  two  categories;  the  CMiofcins  (i.e.,  sub- 
stances identical  or  isonuric  with  carotin, 
^40^^56*).  «nd  the  xant4io|)hylls  (i.e.,  sub- 
stances chemically  related  to  carotin). 

Extensive  lists  showing  the  organic  ori- 
gins of  the  carotins  and  xanthophylls  have 
been  introduced,  as  well  as  a  list  demon- 
strating the  sources  of  both  in  the  same 
plant  or  tissue.  They  are  very  exhaustive, 
and  improvements  upon  them  are  scarcely' 
possible.  Considerable  attention  has  also 
been  paid  to  the  comparison  between  the 
flower  xanthophylls  and  thr>se  contained  in 
Uk  yolks  of  eggs  and  the  blood-serum  of 
fowls;  and  Schunk's  8,pectn>so<^ic  investi- 
gations have  been  specially  quoted.  Spec- 
trophotographs  illustrating  the  wave- 
lengths of  absorption  bands  of  both  carotin 
and  xanthophyll  in  various  solvents  have 
been  reproduced.  At  the  end  of  the  volume 
are  comprehensive  indices  showing  authori- 
ties mentioned  and  subjects  dealt  with. 

There  is  one  great  fault  with  the  wwk : 
it  is  insufficiently  classified.     Reference  is 
difficult,     and     the     general     aiTangemcnt 
would,  perhaps,  prove  slightly  monotonous 
to  the    student.       It    is    very    exhau8ti\'e, 
however,    and  the  reasoning    m  clear    and 
soum^.     Above  all,  records  of  research  are 
strictly  up-t<>-date,  references  having  been 
made  to  studies  as  late    as  la«t  year;    for 
example,     Ha-shimato's     "  C.irotinoid    pig- 
mentation   of  the    skin    r<'siilting    from    a 
vegetarian     diet  "     (Joum.     Amer.     Med. 
A880C.,  LXXVIII..  1111).       As  a  complete 
review   of  alJ  that  is    at  present  known    of 
the  carotinoids,  no  better  treatise  could  be 
compiled,    and  it  fs    to  he  hoped    that  the 
author  will  endeavour  to  facilitate  reference 
through  the  text  in  future  editions. 

J.M. 
♦  WiUafatter  and  Mieg. 

Year-Book    of    Pharmacy    and    Tnns- 
actions    of    the    British    Pharmaceutical 
Conference,     1922.       I^ondon :    J.    &    A. 
Churchill,   7,   Great  Marlborough   Street 
W.C.     Price  128.  6d. 
This  book  has  again  bt^en  produce^!,  and 
again    it  brings    up  to  date    investigations 
made  during  a  year  in  pharmacy  and  chem- 
istry.    The     three   editors.     J.   O.  Braithe- 
waite     (Abstracts     from      Tapers),     Thoe. 
Strephenson,     F.R.S.E.     (New    Remedies), 
and  C.  H.  Hampshire,   B.Rc.  F.I.C.,    are 
to  be  congratulated  upon  the  discriminative 
care  they  have  exercised  in  their  respective 
compilations. 

Copious    revisionary     notes    liave     been 
a^ld«d  to    the  abstracts,    and    06ver    every 


branch    of    the    year's    research  that    has 
passed  the  c  !gnisance  of  the  Society.     Sipe- 
cial    recognition    is  due    to  the    numerous 
suggestions  cx)nt;iined  in  the  dispensing  sec- 
tion,  emphasis  having  been  laid  upon  the 
rendering  of  pivcipitates     easily   diffusible. 
Among  the  papers    read  during  the  course 
of  the  conference'  are  included  three  of  in- 
estimable impoitance,  "  Some  Characteris- 
Ucs  of  Wheat- St  arch."    by  T.    E.  Wallis, 
B.Sc.  (Lond.),  F.I.C. ;  "  A  Simple  Instru- 
ment    for    taking    Refractive    Indices     of 
Liquids,'        by       R.       Fouracre,        Ph.C, 
F.S.M.C. ;  and       The  Extraction    of  Qui- 
nine   and    Strychnine    from     Solutions    of 
varying  Hydrogen     Ion  Concentration :     A 
MvIIkkI   for  th(>   Separation     of  Strychnine 
from  Quinine,"    by  Norman  Evers,  B.Sc, 
F.I.C. 

The  annual  nprai  showed  an  increase  in 
membership  for  the  Society,  and  a  scheme 
was  recommended  f<M*  Committee  reorgani- 
sation.    The  book  not  only  shows  itself  in- 
valuable    and     indispensable     to    existing 
members,    but  should  certainly  be  on    the 
bookshelf  of  t-very  enterprising  pharmacolo- 
gist. J.M. 
A   Dictitwary    of    Applied    Chemistry, 
Vol.  IV.,  bv  SiK  Edward  Tiiokpe,  C.B., 
I.L.I)..  F.R.S.     Pp.  VIII.  +  740.     Lon- 
dfHi:  L'mgmans.  Green  &  Co.,  39,  Pater- 
noster How.  E.C.4.     1922.     Price  £3. 
This  volume  ei>ver8  the  ground  between 
L-acid  and  Oxydisilin,  and  im'^rip orates  the 
results  of  later  riscarch  in  every  branch  of 
Chemistrj'  in   this  section.        Many  promi- 
nent chemists  have  contribut^'d  to  it,  each 
one  an  authority    upon  his  particular    sub- 
ject. 

Specific  attention  has  In'en  paid  to  sub- 
stance^ of  wide  commcreial  utility  and  of 
pharmacological  urgency.  This  is  quite 
notable,  as,  in  the  construction  of  a  work 
of  this  description,  such  a  broad  outline  is 
seldom  attained. 

Two  interesting  papers,  one  Uipon 
Match"s  and  the  other  upon  Leather,  typi- 
fy the  tone  of  the  work.  These  papers  not 
only  give  data  solely  from  a  theoretical 
standpoint,  but  also  treat  at  some  length 
with  the  practical  sides.  Extensiveness 
has  been  accorded  such  subjects  as  the 
Lactones,  liOgwood,         Metallography, 

Methyl,  the  Naphthalenes,  Essential  Oils, 
and  Opium.  This  is  but  a  cursory  selec- 
tion, and  a  numU^r  of  others,  well  worthy 
of  eulogistic  mention,  could  be  quoted. 
E\ .  n  as  a  separate  factor,  the  volume  is 
admirable;  but  ;u?  one  of  a  series,  it  is  ex- 


80 


THE  CHEMICAL  NEWS. 


FEBRUARY  2,  1923. 


emplary.  Considering,  too,  the  excellence 
of  the  information  it  contains,  its  price  is 
most  reasonable,  and  in  no  way  to  be  re- 
garded as  a  bad  investment  by  those  who 
require  a  complete  survey  of  every  by-way 
in  Chemistry.  j.M. 


NOTICES  OF  BOOKS. 
Text  Book  of  Inorganic  Chemistry ,  by 
Dr.  J.  Newton  Friend,  D.Sc,  Ph.D., 
F.I.C.,  Carnegie  Gold  Medallist.  Pp. 
XXV.  +  367.  Second  Edition,  volume 
IX.,  Part  I.  London:  Messrs.  Charles 
Griffin  &  Co.,  Ltd.,  Exeter  Street, 
Strand.     1922.     Price  18s. 

lit  is  gratifying  to  find  that  a  second  edi- 
tion of  such  a  book  of  reference  as  this  by 
Dr.  Friend  has  been  called  for.  It  indicate 
that  this  series  of  text  books  supplies  a  real 
need. 

Most  of  the  few  errors  that  crept  into  the 
fipst  edition  have  been  corrected,  and  a 
summary  of  the  dates  of  issue  of  the  more 
important  journals  has  been  introduced. 

It  may  be  noted  that  the  equation  given 
on  page  233  for  the  preparation  of  Osmium 
cyanide,  does  not  balance. 

Among  ithe  many  and  useful  tables  given 
is  the  number  of  nickel  coins  cast  in  various 
countries.  The  information  oontainetl 
therein  may  be  trustworthy,  but  it  would 
be  interesting  to  know  who  is  responsible 
for  giving  the  currency  of  U.S.A.,  as  paras 
and  centisimos ! 

This  volume,  together  with  the  others  in 
the  .series,  will  be  widely  consulted  and 
used  by  students  and  also  by  experienced 
workers. 


Blearhinfj  Powder  and  its  Aciian  in 
Bleaching,' hy  R.  L.  Taylor,  F.I.C.  Pp. 
79.  Manchester  and  London:  John 
Hey  wood,  Ltd.     1922.     Price  4s.  6d. 

Mr.  Taylor's  book  has  been  based  upon 
his  contributions  to  the  theory  and  practice 
of  Bleaching,  since  1910.  These  are  repro- 
duced almost  in  the  form  in  which  they 
originally  appeared,  in  chronological  order, 
and  include  the  author's  important  investi- 
gations on  other  action  of  carbon  dioxide 
and  of  dilute  acids  on  bleaching  powder  and 
on  hypochloric  acid,  and  on  other  branches 
of  the  subject  as  well. 

It  will  he  a  convenience  for  students  and 
others  to  have  this  information  in  a  per- 
manent form. 


This  list  is  specially  compiled  for  the  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  (Jhanoery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade 
Marks,  and  Designs,  can  be  obtained  gratuitously. 


Latest  Patent   Applications. 

48 — Bader.     T.— Treatment      of     cellulose-acetate 
produets.    Jan.  1. 

78 — Metals    Production,      Ltd.— Leaching     copper 
rres  containing  slimes.    Jan.   1. 

478— Niohrl'on,  W.   E.— Manufacture  of  sulphuric 
acid.    Jan.  6. 


Specifications  Published  this    Week. 

190M3-DHnstan.  A.  E.,  Remfry,  F.G.P.— Treat- 
ment of  petroleum  and  other  liquid  hy- 
drocarbons. 

169725— Wendol  et  Tie  Les  Petits  Fils  De  F.  De.— 
Receptables  for  the  transportation  and 
preservation  of  air  or  other  gases  in  the 
liquefied   state. 

174.59.5— A kt-Ges  Fur  Anilin  Fabrikation.— Process 
dyeing  skins,   hairs,   and   the   like, 

190688^— Jarobson,  B.  H. — Manufacture  of  anhy- 
drous metal  chlorides. 


Abstract  Published  this  Week. 

Organic  Mercury  Compounds.  —  Patent  No. 
188376.— Messrs.  Fahlberg-List  &  Co.,  of  57,  Alt 
Salbke,  Sudost,  Magdeburg,  Prussia,  Germany, 
have  evolved  a  new  process  for  the  production  of 
aromatic   mercury   cyanide   compounds. 

They  are  prepared  by  treating  complex  mer- 
cury compounds  of  phenol  and  its  homologues 
with  alkali  cyanides  in  aqueous  solution,  or  by 
heating  phenol  and  its  homologues  with  mercury 
cyanide  in  alkaline  solution  or  with  mercuric 
oxide  in  alkali  cyanide  solution.  The  products 
are  efficacious  against  plant  diseases.  According 
to  examples  (1)  mercury  cresol  cyanide  is  obtained 
by  dissolving,'  mercuric  oxide  in  dilute  sulphuric 
acid,  adding  o-cresol,  boiling  the  resulting  pre- 
cipitate with  sodium  cyanide  solution  and  evapor- 
ating the  filtrate  in  vaciio;  (2)  o-cresol  is  boiled 
with  mercury  cyanide  and  dilute  sodium  hydrox- 
ide, and  the  mercury  cresol  cyanide  separated  by 
carbon  dioxide  or  dilute  acids;  (3)  mercury 
phenol  cyanide  is  prepared  by  boiling  phenol 
with  mercuric  oxide  in  sodium  cyanide  solution 
and  treating  the  cooled  solution  with  carbon 
dioxide  or  dilute  acids. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


FEBRUARY  9,  1923. 


THK   CHEMICAL   NEWS. 


81 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.     No.  8278 


THE  ISOLATION  OF  THE  OXIDE  OF 
THE  NEW  ELEMENT. 

At  the  meeting  of  the  Chemical  Society 
on  February  1,  1923.  Dr.  Ak-xander  Scott 
delivered  a  paper  on  "  A  Nt  w  Element  be- 
longing to  the  Fourth  (Iroup  of  the 
Periodic  System."  Its  oxide  rcwrabled 
thrwe  of  Titanium  and  Zirconium. 

He  had  discovered  it  in  a  black  sand 
from  New  Zealand,  where  large  quantities 
may  be  f>btained.  Upon  analysis,  Dr. 
Scott  found  that  this  sand  gave  a  residue 
insr>luble  in  sodium  hvdratt-.  The  residue 
was  partially  attecketl  by  sodium  bisul- 
phate. 

Bv  this  treatment  about  1 .4  grams  of  a 
solid  resembling  titanium  dioxide  were 
obtained.  It  was  difficult,  however,  to 
discover  a  method  for  the  dt  t^-rmination  of 
the  equivalent  of  the  metal  which  did  not 
iom\  salts  readily. 

It  was  eventually  converted  into  the 
double  potassium  fluoride  by  treatment 
with  potassium  carbonate  and  hydrofluoric 
acid. 

Dr.  Scott  announced  that  during  the  day 
(February  1)  he  had  coni[.!i  ted  two  ana- 
lyses of  this  double  fluoride. 

He  found  that  0,7203  gram  ol  the  salt, 
KjXF,,  gave  0.4507  gram  of  the  oxide,  XO,. 
This  result,  the  sum  of  two  determination?, 
indicated  that  the  element  had  an  atomic 
weight  of  175,  corresponding  with  an  atomic 
number  of  72. 

The  element  is  thus  identical  with  that 
announced  by  D.  Coeter  and  (1.  von 
Hevesy  from  the  results  of  their  examina- 
tion of  the  spectra  of  certain  zirconium 
ores. 

Its  oxide,  XOj,  which  was  exhibited  with 
specimens  of  the  sand,  was  cinnamon 
brown  in  colour,  which  Dr.  Scott  stated 
might  he  due  to  a  very  minute  trace  of 
ferric  oxide.  He  said  that  whilst  the  in- 
vestipntors  in  Denmark  had  only  observed 
the  spectrum  of  what  they  termed  Haf- 
nium, he  had  actually  a  quantity  of  the 
oxide. 

Sir  William  Tildon,  F.R.S.,  who  pre- 
sided, stated  that  Dr.  Scott's  discovery  was 
a  very  remarkable  one.  It  was,  perhaps, 
noteworthy  that  few  discoveries  of  new  ele- 
ments   had    been     communicated    to    the 


Chemical  Society.  Thus  when  Sir  William 
Crookes  discovered  thallium  in  1862,  he 
naturally  announced  his  discovery  in  The 
Chemical   Neics. 

Prof.  H.  E.  Armstrong,  who  also  rose  to 
congratulate  Dr.  Soott  upon  his  great 
achievement,  hoped  that  a  more  appro- 
priate name  couM  be  given  to  it.  It  was  a 
difficult  question  to  settle  the  point  as  to 
who  had  actually  discovered  the  new  cie- 
rnent.  It  had  developed  from  the  applica- 
tion of  Moeeley's  method,  whereby  we 
knew  there  was  a  blank  at  the  position  72. 

Prof.  Smithells.  who  conveyed  the  con- 
gratulations of  the  countrv  Fellows  to  Dr. 
Scott,  pointed  out  that  tTbis  was  the  first 
cftse  of  the  discovery  of  an  element  which 
had  actually  been  looked  for  and  found. 

-\t  the  same  meeting  of  the  Chemical 
Society,  two  other  papers  were  read : 

"  The  Derivatives  of  Tetrahydrocar- 
bazole,"  Part  II..  by  W.  H.  Perkin  and  S. 
O.  P.  Plant,  and  *  The  Chemistry  of  Poly- 
cyclio  Structures  in  relation  to  their  Homo- 
cyolic  Unsaturated  IsMnerides,"  Part  IV., 
^  C.  K.  Ingold.  K.  A.  Seeley,  and  J.  F. 
Tnorpe. 


A    NATIONAL    ASSET. 

The  Komaxce  of  a  War  Wixnino  Industry. 
By  Colmtr!  Sir  Arthur  Holhrooh,   M.P. 

Oas  has  proved  such  a  useful  servant  to 
the  general  public  that  the  present  seems 
an  opportune  time  to  state  a  few  facts 
which  stand  U>  the  credit  of  the  much 
maligned  gas  undertakings.  Eleven  vears 
ago,  the  cent<*nary  of  gas  as  an  illummant 
was  oelel)rated,  and  during  the  whole  of 
that  perio«l  its  history  was  o«»e  of  progress 
fnmi  publio  want  to  public  want.  Previous 
to  that  our  harder  living  forebears  had 
been  more  or  less  content  with  hard-won 
sparks  from  the  chafing  of  flint  and  8t<>el 
for  the  lighting  of  rush-lights  and  candles. 
The  clergy  of  many  churches  preached 
against  tne  intro<]uction  of  gas  into 
ciiurches  as  "  profane  and  contrary  to 
God's  laws." 

But  gas  lived  down  all  this  opposition 
and  became  what  it  is  to-day,  an  infjispens- 
able  adjunct  to  our  very  existence.  And 
the  reason  fw  this  lies  on  the  surface :  the 
needs  of  the  community  have  been  studied 
by  the  great  industry.  During  the  whole 
period  of  more  than  a  century's  service  to 
the  public,    the  best  brains  of  the  industry 


82 


THE    CHEMICAL    NEWB. 


FEBRUARY  9,  1023. 


have  been  engaged  an  improving    methods 
of  supply  and  cheapening  costs. 

Modem  science  has  revolutionised  the 
gas  industry  out  of  all  recognition,  and  in 
doing  so  has,  to  a  large  extent,  revolution- 
ised the  homes  of  the  people  by  a-dding  to 
their  comfort,  cleanliness,  and  convenience. 
Few  people  appreciate  the  national  value  of 
the  1,600  gas  undertakings.  The  country 
has,  perhaps,  no  greater  asset.  Time  was 
when  the  carbonisation  of  coal  was  carried 
out  with  only  one  objective — ^production  of 
ags.  To-day  there  is  hardly  any  trade  or 
manufacture  in  which  is  not  used  some 
substance  or  another  produced  by  the  dis- 
tillation of  coal  at  the  gas  works. 

Precisely  how  \^tal  and  how  necessary 
the  gas  undertakings  of  this  country  are 
was  demonstrated  during  the  war,  and  it 
can  be  truthfully  said  that  no  industry 
more  than  the  gas  industry  helped  to  win 
the  war.  The  products  of  gas  works  and 
gas  ovens  saved  the  Allies.  This  assistnnce 
took  the  form  of  the  production  of  snch 
necessary  products  as  benzol  and  toluol  for 
the  manufacture  of  high  explosives,  dyes 
and  motor  spirit,  sulphate  of  ammonia, 
creosote,  tar,  and  carbolic.  During  the  war 
one  gas  undertaking  alone  supplied  enough 
T.N.T.  material  for  the  manufacture  of 
lyddite  and  other  explosives  to  fill 
160,000,000  18-pounder  shells,  17,000,000 
gallons  of  oil,  and  13,000  tons  of  disinfec- 
tants. The  total  for  the  w4iole  industry 
ran  into  figures  representing  s.ix  times  these 
gigantic  totals. 

And  grs  has  its  uses  in  peace  no  less  than 
in  war,  altogether  apart  from  its  domes.bic 
utility. _  Germany  built  up  her  great  dye 
industry  by  working  up  the  by-products 
largely  obtained  from  England,  and  the 
dyes  resulting  from  these  by-products  were 
purchased  by  the  rest  of  the  world  from 
Germany,  who  reaped  a  rich  annual  harvest 
of  many  millions. 

If  England's  dye  industry  and  chemical 
trades  are  to  be  kept  in  existence,  the  gas 
industry  must  flourish.  Out  of  smaller 
services  rendered  to  the  State,  many  other 
industries  have  reached  the  peak  of  pros- 
perity. Not  so  the  British  gas  undertak- 
ings, which  were  seriously  handicapped 
during  the  war  and  have  had  tardy  help 
since  to  recover  their  lost  ground. 

But  few  people  realise  how  closely  coal 
'distillation  is  'bound  up  with  food  produc- 
tion. Vegetables  cannot  live  without  a 
proper  supply  of  nitrc^n,  and  before  the 
war  thi!s  country  imported  large  quantities 


of  nitrate  of  soda  for  this  and  other  pur- 
poses. This  supply  was  cut  off  during  the 
war,  so  the  gas  works  produced  increased 
quantities  of  sulphate  of  ammonia,  which 
serves  the  same  useful  purpose.  Without 
this  sulphate,  grass  and  grain  fields  would 
yield  but  very  poor  i-esults,  and  that  would 
mean  much  less  meat  and  corn  for  con- 
sumption. 

Allotment  holders  arc  indebted  to  gas 
works  for  the  gas  lime  which  is  so  detri- 
mental to  the  destructive  wire-worms.  Then 
there  is  naphthalene,  which  pioved  a  God- 
send to  the  men  at  the  front  b}'  helping 
them  to  exterminate  lice  and  other  vermin. 
And  when  "Tommy"  went  into  hospital 
there  came  to  his  aid  the  products  of  the 
gas  works  in  the  shape  of  aspirin,  phenace- 
tin,  and  antipyrine,  for  all  of  which  coal- 
tar  from  the  gas  works  is  responsible. 
Other  fi'itmds  in  every-day  life  which  ema- 
nate from  the  gas  works  include  sulphonal 
for  sleeping  purposes,  sal-volatile,  carbolic 
aoiil,  lyso!,  and  such  Hke  useful  things. 

And  so  the  wonderful  story  of  a  thousand 
and  one  uses  of  gas  and  gas  products  goes 
on.  It  is  a  worthy  record,  and  the  end  is 
not  yet,  for  the  industry  is  always  striving 
to  keep  abreast  with  modern  requirements, 
and  to  raise  the  standard  of  efiftciency.  The 
gas  indusrty  did  not  fail  the  nation  during 
the  war,  and  will  not  fail  the  nation  in  the 
piping  times  of  peace.  Given  fair  play — it 
asks  no  favour — its  history,  as  of  old,  will 
be  one  of  progress  from  public  want  to 
public  want. 


EMPIRE'S  RESOURCES  IN  THE  LESS 
COMMON  METALS. 

Professor  G.  T.  Morgan,  head  of  the 
Chemical  Department  of  the  University  of 
Birmingham,  is  the  President  of  the  Chemi- 
cal Society  of  that  University,  and  on 
Monday,  January  22,  he  delivered  his  Pre- 
sidential address  on  "  The  Empire's  Re- 
sources in  the  Less  Common  Metals." 
The  .attendance,  which  numbered  over  200, 
included  many  industrial  chemists  of  Bir- 
mingham and  the  Midlands. 

The  author  observed  that  in  his  Presi- 
dential address  of  last  year  ho  placed  be- 
fore tlhe  Society  a  survey  of  the  post-war 
problems  affecting  the  synthetic  colour  in- 
dustry. The  chief  reason  why  this  branch 
of  chemical  enterprise  has  become  a  so- 
called  "key"  industry  is,  in  his  opinion,  an 


I 


FERRUARY  0,  1023. 


THE   CHEMICAL   NEWS. 


83 


educational  one.  A  highly  developed  in- 
dustry in  coal  tar  products  leads  with  un- 
failing ci'rtainty  to  proficiency  in  other 
chfmioal  arts.  The  inter-dependence  of  all 
branches  of  chemical  trade  hae  been  de- 
monstrated up  to  the  hilt  by  the  develop- 
ment of  chemical  industry  in  Germany,  a 
country  where  faith  in  the  possibilities  of 
chemical  development  is  far  more  generally 
a<icopt<'d  than  in  any  other  civilised  nation. 

The  great  Rhenish  firms  are  something 
more  th&n  commercial  undertakings,  they 
are  technological  universities  of  the  highest 
grade.  It  is  largely  owing  to  tiie  educa- 
tional leaven  of  these  scientifically  directed 
enterprises  that  Germany  has  gained  her 
supremacy  and  prosperity  in  the  main 
branches  of  chemical  industry.  The  utili- 
sation of  atmospheric  nitrogen,  many 
mo<lem  metallurgical  processes,  scientific 
glassware,  synthetic  ruhl>or  and  t-he  highly 
profit4iblc  tradJDs  in  drugs,  photographic 
chemicals,  synthetic  tanning  mat<»rials. 
artificial  resins,  synthetic  emences  and 
other  fine  chemicals  have  arisen  a«  oft- 
B^hoots  of  the  scientific  industry  in  oo«l  tar 
dye  wares.  These  colour  factories  afford  a 
training  to  the  chemist  and  chemical  en- 
gineer which  at  present  is  hardly  to  l>e 
obtained  in  any  other  country  or  in  any 
other  branch  of  industry. 

In  short,  the  main  thesip  which  should 
be  pressed  on  the  attention  of  all  our  pub- 
lic men  and  leaders  of  industry  is  that  in 
regard  to  the  safeguarding  of  our  natural 
resources  in  materia  rhcmica  there  is  only 
one  strategic  chemical  front,  and  we  cannot 
fall  b>phind  in  any  particular  branch  of 
chemical  trade  without  grave  risks  of  k)sing 
ground  in  all  the  correlated  industries. 

Owing  to  the  wide  geographical  distribu- 
tion of  the  community  of  nations  known  as 
the  British  Empire,  these  countries  exhibit 
within  their  boundaries  striking  diversities 
of  gooloj^oal  structure  with  a  vwied  assort- 
ment of  mineral  deposits.  The  exploita- 
tion of  these  mineral  resources,  so  far  as  it 
has  progressed,  shows  that  the  Britiih 
Empire  ha«  a  very  generous  endowment  of 
the  common  and  precious  metals.  I'he 
possession  of  this  mineral  wealth  involves 
U8,  however,  in  the  grave  resiponsibility  of 
utilising  these  hidden  treasures  to  the  best  ) 
advantage.  We  must  give  a  faithful  ac- 
count of  our  stewardship,  otherwise  sooner 
or  later  the  task  will  be  undertaken  by 
others, 

A   comprehensive  study  of  inorganic    or        j 


mineral  chemistry  shows  us  that  each  ele- 
mentary type  of  matter  is  possessed  of  cer- 
tain oharacteristio  and  unique  properties 
which  are  not  shared  completely  by  another 
element,  even  when  the  two  are  closely  re- 
lated. Consequently  the  industrial  employ- 
ment of  any  clement  resolves  itself  ulti- 
mately into  finding  a  use  for  one  or  more  of 
its  unique  properties.  The  utilisation  of 
such  rare  elements  as  neon,  thorium  and 
vanadium  encoiu-ages  the  belief  that  ulti- 
mately some  employment  will  be  dis- 
covered for  all  the  elements  either  free  or 
in  a  state  of  combination. 

Professor  Morgan  referred  to  the  Empire's 
resources  in  the  precious  metals,  gold  and 
silver,  and  also  to  the  light  metals,  alu- 
minium, magnesium  and  berv'llium,  which 
are  of  special  interest  in  the  production  of 
light  alloys.  Ultra-light  alloys  are  now 
being  produced  by  the  Magnesium  Co., 
Ltd..  of  Wolverhampton.  The  metals  of 
the  less  common  earths  are  utili.sed  chiefly 
in  the  form  of  their  compounds.  Barium 
and  strontium  preparations  are  largely  de- 
rived from  British  sources,  and  the  world's 
requirements  for  thoria  and  oeria  employed 
in  the  incnndescent  mantle  industry,  are 
larg.'lv  supplied  from  the  extensive  '^ravan- 
core  (deposits  which  will  meet  the  demand 
for  many  years. 

The  favf>urable  situation  of  the  Empire 
in  regard  to  the  supply  of  tungsten 
minerals  should  place  us  in  a  premier  posi- 
tion for  mantifat^iiring  tungsten  steel,  but 
nevertheless.  Ix^fore  the  war,  Germany  con- 
trolled two-thirds  of  this  production,  the 
importation  of  German  tungst<^n  into  this 
country  having  an  annual  value  of 
£300.000.  This  unfavourable  position, 
which  exi.sted  up  to  July,  1915,  was  a  con- 
tributory cause  of  the  shortage  of  shell 
which  jeopardised  the  military  operations 
in  the  late  war.  He  regarded  the  produc- 
tion of  timgsten  steel  as  one  of  the  great 
triumphs  of  modern  metallurgy.  In  the 
development  of  our  mineral  resources  it  is 
essential  t'>  take  the  long  view.  Systematic 
research  is  needed,  even  on  chemical  ele- 
ments which  have  not  hitherto  received  in- 
dustrial application.  Zirconium  was  cited 
as  an  instance  of  a  metal  whio-h  has  so  far 
been  <*xamined  chiefly  by  German  and 
American  chemists,  the  English  contribu- 
tion to  this  branch  of  mineral  chemistry 
being  comparatively  small.  Cobalt  is  an- 
other examiple  of  a  metal  which  merits  in- 
creased  attention,     the  annual    production 


84 


THE   CHEMICAL    NEWS. 


FEBRUAKY  9,  1923. 


being  only  of  the  order  of  400  tons.  The 
chief  deposits  are  in  Ontario,  and  Canadian 
chemists  are  becoming  prominent  as  inves- 
tigators of  this  element.  Cobalt  is  a  metal 
with  a  future,  coaning  into  use  now  as  an 
alloy  metal  instead  of  being  restricted,  as  it 
was  until  recently,  to  employment  in  com- 
bination as  a  pigment  colouring  material. 
Cobalt  confers  hardness  and  durability  on 
aluminium.  There  is  a  world  famine  in  re- 
gard to  the  valuable  metals  of  the  platinum 
group,  owing  to  the  partial  failure  of  the 
Russian  supply.  These  metals  have  been 
detected  in  many  parts  of  the  British 
Empire.  Tasmania  has  furnished  osmium 
and  iridium,  whereas  the  Sudbury  nickel- 
oopper  ores  of  Ontario  have  yielded  notable 
quantities      of    platinum     .and    palladium. 

Referring  to  magnesium,  he  pointed  out 
that  the  metal,  which  has  exceptional  light- 
ness, is  permanent  under  ordinary  atmos- 
pheric conditions,  especially  when  free 
from  impurities.  Minute  quantities  of  suoh 
foreign  substances  as  alkalis  or  chlorides 
cause  local  granular  corrosion.  The  metal- 
lurgy of  magnesium  depends  on  electrolytic 
processes,  and  considerable  progress  in  this 
isolation  has  been  made  in  the  United 
States.  The  sudden  drop  in  the  number  of 
producers  and  in  the  output  is  due  to  the 
competition  of  the  German  product.  Ger- 
many controls  a  large  portion  of  Austrian 
magnesite,  and  owing  to  the  depreciated 
currency  it  can  sell  in  any  market  in  spite 
of  import  duties. 

On  the  subject  of  beryllium,  Professor 
Morgan  had  something  interesting  to  say. 
Owing  largely  to  the  scarcity  of  beryllium, 
miinerals,  comiparatively  little  headway  has 
been  made  in  the  isolation  of  beryllium,  al- 
though the  physical  constants  of  this  metal 
show  that  it  would  be  a  valuable  aid  in  the 
production  of  light  alloys,  providing  that  a 
sufficient  supply  of  its  minerals  was  forth- 
coming'. 

The  commonest  of  these  minerals,  beryl, 
is  an  acidio  silicate  of  beryllium  and  alu- 
mmium,  3BeO,  Al^Og,  OSiOj,  occurring 
both  in  tihe  old  world  and  the  new.  A  well 
known  deposit  exists  at  Limoges  in  France 
and  .considerable  quantities  have  been  noted 
in  New  Hampshire,  where  beryl  crystals  ot 
enormous  size  up  to  2|  tons  occur  native. 
Within  the  British  Empire  there  is  a  small 
nnexiploited  deposit  in  Glen  Cullen,  Co. 
Dublin.  It  is  also  found  in  the  former 
German  colony  of  S.W.  Africa.      Hitherto 


only  small  quantities  of  beryllium  metal 
have  been  produced.  The  first  difficulty 
encountered  in  the  metallurgy  of  beryllium 
is  the  separation  of  herylliinu  from  alumina. 

Beryl  is  an  acidic  felspar  like  orthoclase, 
and  accordingly    it  is    not  appreciably    at- 
tacked by  the  common  mineral  acids,    hy- 
drochloric, nitric  and  sulphuric   acids.      It 
is    opened    up,    however,     by    fusion    with 
caustic  alkali,    this  reagent  forming    alkali 
silicate  and  yielding    a  mixture    of  alumina 
and     beryllium     carbonate,         Subsequent 
treatment  with    dilute  sulphuric  acid  pre- 
cipitates silica.     The  filtrate  contains  iberyl- 
lium  and    aluminium  sulphate,    and  if  the 
alkali  used  in  the  fusion  contained  potash, 
a  good  deal  of  aluminium  sulphate  crystal- 
lises in  the  form  of  potash  alum  and  is  thus 
s  parated.      The    beryllium     remaining     in 
solution    as  the  more  soluble    sulphate    is 
separated  partially  from  the  remaining  alu- 
minium by  taking  advantage  of  its  solubil- 
ity  in  ammonium  carbonate,     this  reagent 
precipitating    aluminium    hydroxide.       By 
diluting  and  boiling  the  solution,   hydrated 
beryllia    is    precipitated  and    subsequently 
converted         into      the        basic       acetate. 
Be^O(CH3.C02)g,  a  co-ordination  compound 
of  considerable    stability    which,     although 
only   sparingly    soluble    in  water,    has    the 
remarkable   property  of    dissolving  in    such 
organic    solvents    as    acetone,    chloroform, 
benzene,    etc.       This    beryllium    derivative 
has  a  definite  melting  point,  and  when  pure 
can   be    sublimed    without    decompo'sition. 
These  singular  characteristics  render  it  use- 
ful in  the  final    separation  of  beryllia  from 
alumina. 

Two  other  processes  have  been  tried  with 
good  results,  in  Birmingham,  by  Mr.  T.  J. 
Hedley.  These  methods  are  based  on  the 
use  of  fluorides.  In  one  process  beryl  is 
heated  with  hydrogen  fluoride  and  ammo- 
nium fluoride  until  the  silicon  is  volatilised 
and  the  residue  contains  the  fluorides  of 
beryllium,  aluminium  and  iron.  The  second 
procedure,  a  French  process,  which  ob- 
viates the  use  of  poisonous  hydrofluoric 
acid,  consists  in  heating  the  finally  pow- 
dered mineral  with  sodium  silicofluoride. 
The  product,  on  lixiviation  with  water, 
gives  a  solution  containing  sodium  beryl- 
lium fluoride  only,  the  other  constituents 
remaining  as  sparingly  soluble  products. 
Whatever  process  was  employed,  it  was 
found  that  the  final  purification  is  best 
effected  through  the  basic  acetate. 


FEBRUARY  9,  1923. 


THE   CHEMICAL   NEWS. 


We  are  still  only  on  the  threshold  of  the 
metallurgy  of  beryllium.  The  purified  ace- 
tate must  be  converted  into  oxide  and 
and  fluoride  when,  by  an  electrolytic  pro- 
cess akin  to  that  employed  for  aluminium, 
the  metallic  beryllium  is  isolated.  Even  a 
moderate  supply  of  beryllium  or  ite  alloys 
with  copper  and  other  met^ils  would  be  an 
aid  in  aeroplane  and  airship  construction. 
Beryllium,  although  a  rniv  metal,  is  well 
worthy  of  the  serious  consideraticm  of 
chemists  and  metallurgists. 

Aluminium  is  the  only  fairly  plentiful 
metal  of  the  light  metai  gr.^ip;  some  of  the 
others,  such  as  scandium,  r,Mllium,  indium 
and  thallium  being  e.xc*  ssively  rare. 
.Yttrium  and  lanthanum  belong  to  the 
metals  of  the  rare  earths,  c  >inprlsing  some 
18  elements,  of  which  certainly  two  have 
met  with  industrial  application.  These  are 
thorium  and  cerium,  both  of  which  are  de- 
rived from  the  mineral  monsizite,  a  phos- 
phate containing  several  other  inetalM  of 
the  rare  earth  series. 

Having  regard  to  the  world's  production 
in  recent  years,    we  should  be  in  a  premier 
poeifcion  in  regard  to  the  production  of  in- 
candescent mantles,     the    manufacture     of 
which  utilises    the  thoria*and  a  small  pro- 
portion of  the  ccria.      Until  the  war,  how- 
ever, the  manufacture  of  those  mantles  was 
largely   a  German  and  Austrian  monopoly. 
The  Travancore    deposits  were  entirely   in 
the  hands  of    German    agents,  and  all  the 
mineral  obtained  was  exported    trotn  India 
to  Girmany.     During  the  war  these  enemy 
interests  were  eliminated  and  the  industry 
placed  on  a  satisfactory  basis  under  control 
f>f  British  oiipital.      These  Travancore  de- 
posits are  very  extensive.      They    are    tlie 
chief   source  of  thoria,    and  will    suffice    to 
meet  the  world's   requirements    for    many 
years.     As  by-iproducts  from  the  monazito 
concent;  ates,      ilmenite    (ferrous    tit>anate) 
and  zircon  (zirconium  silicate)  are  obtained. 
Both  are  s<'paratcd  from  inonazitc  by  elec- 
tionijurnetic  treatment.  These  by-products, 
which    contain    respectively    titanium    and 
zirconium,  may  come  to  have  an  economic 
value.     The  monazite  exported  from  India 
in  1918  was  2,117  tons,  valued  at  £58.820. 
.Mthough  Germany  is  now  i>hliged  to  pur- 
chase monazite  from  external  sources,   her 
activities  in  these  market,s    show  that    the 
trade  in  thorium  nitrate  and  inonnde«cent 
mantles  is  very  ipro6p)erous.       During  1021 
the  output  of  ineandeseent  mantles  in  Ger- 
many was  2,000,000  gross.     The  imports  of 
incandescent  mantles    from  Germany    into 


85 


Engla-nd  in  1291  were  63,756  gross,  or 
nearly  three  times  the  21,359  gross  im- 
ported in  1920.  The  value  of  the  larger 
import  was  £111.917.  In  1922,  evidence 
given  before  the  Committee  appointed 
under  Part  2  of  the  Safeguarding  of  Indus- 
tries Act  showed  that  of  four  thcwium  ni- 
trate factories  in  the  United  Kingdom  three 
were  closed  and  one  was  working  half  time. 
The  aales  in  Great  Britain  of  British  made 
iucandeaoent  mantles  was  444,000  gross  in 
1920,  but  only  280,000  gross  in  1921.  A 
certain  degree  of  support  is  afforded  to  the 
British  industry  under  the  Safeguarding  of 
Industries  Act,  but  a  repeal  of  this  measure 
would  expose  the  newly  created  industry  to 
the  full  force  of  German  competition.  This 
tidverse  factor  is  effective  largely  because 
of  the  depreciated  value  of  German  cur- 
rency and  the  great  difference  between  the 
internal  and  external  value  of  the  mark. 

Titanium  in  the  frjrm  of  its  oxide  (rutile), 
or  as  the  ferrous  compound,  ilmenite, 
FeO.TiO,,  is  widely  diffused,  and  is  among 
the  more  plentiful  elements  of  the  earth's 
crust.  There  is  as  yet  no  commercial 
method  for  producing  elemental  titanium. 
Difficulties  arise  owing  to  the  chemical 
activity  rf  the  element  and  its  high  melting 
point  (about  1,800°  C).  The  most  impor- 
tant use  of  titanium  lies  in  the  production 
oi  ferrotitanium  alloys.  There  are  two  of 
thesi>,  one  containing  carbon  (0.8  per  cent.) 
and  the  other  free  from  this  element.  They 
contain  r»  Hpeotivtiy  15  and  25  per  cent,  of 
tiUnium.  'Hiese  alloys  are  used  as  deoxi- 
dizers,  oxygen  and  nitrogen  scavengers,  and 
not  as  alloying  materials.  About  0.1  per 
cent,  of  titanium  in  the  form  of  the  Fe-C-Ti 
alloy  is  a<lded  to  the  steel  as  the  last  addi- 
tion before  pourinj^'.  and  ten  minutes  are 
allowed  to  complete  the  action  of  the 
titanium. 

Before  the  war  there  were  15  manufac- 
turers of  titanium  alloys  in  Germany,  3  in 
Great  Britain.  2  in  France,  and  several  in 
Sweden  and  Switzerland.  Titania,  TiOj.  is 
used  in  pigments;  titanium  white  (TiOj 
25%  -^  BaSO,  75'V.).  A  good  workable  glass 
may  contain  titania  replacing  silica.  \ 
batch  is  given  as  containing 
SiO,  24-69  parts  Na,CO,        29  part^;. 

TiO,  15-45      ..     Lime  7      ,, 

Borax  10 

Titania  was  utilised  long  l)efore  the  war 
as  an  alternative  refractory  material  to  sili- 
ca in  the  construction  of  crucibles.  Like 
silica,    it   withstands    sudden     changes    of 


86 


tMb  chemical  news. 


FEBEUARY  9,  1923. 


temperature  without  fracture,  and  being 
less  basic  it  is  less  readily  corroded  by  tJie 
basic  metallic  oxides  used  in  gi-avimetric 
analysis. 

Zirconium  and  its  compounds  are  a 
worthy  subject  of  chemical  research, 

Ziroonia,  which  has  a  high  melting  point 
and  low  conductivity  for  heat,  possesses  a 
low  copffioient  of  expansion,  and  withstands 
sudden  changes  of  temperature.  It  is  in- 
active towards  most  chemicals,  and  is 
scarcely  attacked  by  strong  acids,  alkaline 
fusion  mixture,  or  the  ordinary  fluxes  and 
slags. 

These  properties  point  to  the  value  of 
zirconia  as  a  refractory  material.  It  has 
been  employed  in  making  crucibles,  muffles 
and  combustion  tubes  which  are  gas-tight 
up  to  1,000°.  Zirconia  crucibles  have  been 
used  to  melt  pure  iron,  platinum,  and  tung- 
sten alloys.  Zirconia  linings  for  the  hearths 
of  steel  furnaces  are  very  durable.  It  is 
also  used  to  produce  opacity  in  glasses  and 
glazes.     In  medicine  it  has  been  substituted 


for  bismuth  nitrate  as  a  means  of  taking  X- 
ray  observations  of  the  alimentary  canal. 

In  this  connection,  Professor  Morgan 
mentioned  that  two  Danish  chemists 
claimed  to  have  discovered  a  new  element 
in  the  zirconium  minerals.* 

The  Professor  thought  he  had  said  suffi- 
cient to  show  that  there  was  sufficient  work 
to  be  done  by  all  chemical  students  from 
the  Birmingham  and  other  English  Univer- 
sities. They  cordially  welcomed  among 
them  Mr.  Piloher,  of  the  Institute  of 
Chemistry,  who  is  a  good  friend  of  chemists, 
and  has  done  much  to  diminish  unemploy- 
ment among  chemical  graduates. 

"  Although  chemical  industry  is  tem- 
porarily under  a  oloud  for  various  reasons," 
he  added,  "  the  outlook  is  not  bad  for  the 
adequately  trained  chemist." 


*  Dr.  A.  Scott  has  also  announced  the 
isolation  of  an  oxide  of  a  new  element  from 
a  similar  source. 


NOTES  ON  THE  ACTIVE  PRINCIPLES 
OF  SOME  SOUTH   AFRICAN  PLANTS. 

By  Charles  F.  Juritz,  M.A.,  D.Sc, 

F.R.S.S.Af.,  F.I.C,  Chief  of  Division  of 

Chemistry,    Department  of    Agriculture, 

Union  of  South  Africa. 


{Continued  from  Page  70.) 


IIL- 


-Mafeura   bean  (Trichilia   emetica 
Vahl)  : 

This  constitutes  the  seed  of  the  Cape 
Mahogany  (Dnich-Essenhout;  Kaffir-MW- 
Kuhlu),  one  of  the  most    magnificent  ever- 


green trees  in  the  forests  of  Pondoland, 
growing  to  a  height  of  80  feet,  with  a  leafy 
canopy  some  50  feet  in  diameter.  The 
seed  of  this  tree  has  of  late  years  acquired 
some  importance  as  a  source  of  oil  for  soap 
making,  and  attemipts  have  been  made  to 
utilise  the  cake  after  expression  of  the  oil 
in  a  manner  similar  to  that  adopted  for 
other  oil  cakes;  that  is  to  say,  both  for 
feeding  purposes  and  as  a  fertiliser.  The 
following  analyses  of  this  cake  have  been 
made  in  the  laboratories  of  the  Division  of 
Chemistry,  No.  1  at  Cape  Town,  Nos.  2,  3 
and  4  ;it  Pretoria: 


Moisture 

Ash         

Protein 
Oil 

Fibre       ...         ...     - 

Nitrogen-free  extract 
Nitrogen  ...    . 

Phosphoric  oxide 
Potash 


No.  1. 

No.  2 

No.  3. 

No.  4. 

11.98 

14.14 

22.93 

10.91 

17.12 

25.36 

29.79 

9.66 

30.38 

3.67 

3.93 

3.51 

3.00 

1.11 

1.17 

0.63 

0.57 

;_ 

1.84 

2.79 

2.19 

2.14 

FEBRUARY  0,  1923. 


THE  CHEMICAL  NEWS. 


87 


From  a  fertiloeing  j)oint  of  view  the  article 
is  not  of  very  high  grade,  but  it  may  be 
worth  applying  to  hungry  soils,  poor  in 
humus,  and  therefwe,  incidentally  lacking 
in  nitrogen.  As  a  fertiliser  it  would  not  be 
profitable  to  transport  it  any  distance,  and 
it,  moreover,  possesstjs  certain  defects  as  a 
fertiliser  inherent  in  its  hi^h  oil  content. 

The  poisonous  nature  of  the  seed  is  not 
as  definitely  settled  as  it  might  be.  Dr. 
Marloth  observed'*  regarding  the  genus  Tri- 
chilia,  "The  seeds  contain  much  oil:  that 
of  T.  emetica  is  edible,  while  the  oil  of  T. 
Dreyei  is  employed  by  the  natives  only  for 
greasing  their  bodies."  Of  course,  it  is 
quite  possible  that  the  oil  may  be  edible 
while  other  constituents  of  the  bean  may  be 
{>oiiionous.  Dr.  Marchand,  in  his  article 
on  "  Fertilisers  "  in  the  July,  1918,  issue 
of  the  South  Afriian  Journal  of  Industries, 
remjwks  that  "  the  cake  left  after  the  ex- 
pression of  the  oil  is  useleiw  us  a  stock  food, 
as  it  contains  a  poisonous  princi|)le,"  and 
he  quotes  an  investigation  by  Mr.  J.  S. 
Jamieson,  F.l.C,  oa.  the  subject."  But 
Mr.  Jamieson  undertook  the  investigation 
not  of  the  entire  seed,  but  only  of  the  hark 
and  8."  d-oi'  of  T.  emetica  (U'cause  the  Rev. 
A.  'J'.  B.yiint  had  descrilx-d  that  bark  as 
very  poisonous),  and  statcni  in  his  opening 
paragraph  that  the  "  absence  of  toxic  symp- 
toms on  administering  it  to  "guinea  pigs  up- 
holds the  view  that  it  is  not  poisonous." 
Mr.  Jamieson  also  states  that  he  mixed 
about  10  grams  of  the  jut  from  the  seeds 
with  mealie  meal  and  ailunnist^'red  it  to  a 
guinea  pig  with  no  toxic  effect  or  symptoms. 
"  The  bark  of  T.  emetica,"  he  isayw.  "which 
is  known  to  the  Natal  Kaffir  as  the  um-^ 
Khulu,  is  used  as  a  purgative  medicine." 
From  the  bark  he  extracted  a  rather  rcfnic- 
tory  resin,  to  the  Large  proportions  of  which 
he  ascribed  the  purgative  action  of  the 
bark.  Mr.  Jamieson 's  paper  contains  no- 
thing whatever  to  warrant  the  inference 
that  the  8ee<l  either  before  or  after  extrac- 
tion of  the  oil  is  in  any  way  {>oifl(mou8.  On 
the  other  hand.  1  am  infonned  by  Mr.  L. 
H.  Hyman  that  the  results  of  numerous  ex- 
periments show  the  cake  from  undecorti- 
catcd  seeds  to  be  extremely  toxic,  and  to 
cause  death  invariably  when  fed  to  guinea 
pigs.     Natives,  he  tells  me,  consume  large 


'•  "  The  Chemistry  of    S.A.  plants    and 
])lani  products,"  p.  11. 

"  Repf.  HA.  Assoc,  for  Adv.  of  Science, 
1010,  p.  496. 


quantities  of  the  decorticated  kernel    with- 
out any  apparent  hannful  effect. 

The  Rev.  A.  T.  Bryant,  in  his  paper  on 
Zulu  medicine  and  medicine  men,'*  includes 
um-Khulu  (T.  emetica)  in  a  list  of  plants, 
of  which  he  says  "  all  of  the  following 
should  b©  labelled  at  any  rate  as  dangerous, 
many  of  them  being  most  certainly  fatally 
pmsonous,  and  that,  with  some  constitu- 
tions, even  in  minute  quantities."  "  It 
must  be  recolltHsted,  however,"  he  adds, 
"  that  everj-  part  of  a  plant  is  not  always 
equally  poisonous ;  that  the  noxious  proper- 
ties are  not  at  all  seasons  equally  great,  and 
that  they  may  at  times  be  oompTetely  re- 
moved or  neutralised  by  the  method  of 
medicinal  preparation."  (p.  12).  Further 
on,  he  says,  "  The  i-Xolo  or  um-Khulu  (T. 
emetira)  is  a  tree  poeseseing  very  powerful 
medicinal  properties,  amongst  others  those 
of  a  purgative.  A  piece  of  the  bark,  of  the 
length  and  brea^lth  of  two  fingers,  is  pul- 
verised and  mixed  into  two  teacu,paful  of 
hot  water  as  an  enema,  in  which  form  this 
drug  is  usually  julrainistered."  There  is 
no  reference  by  that  author  to  any  poison- 
ous properties  of  the  aeed. 

In  my  own  paper  on  "  South  African 
Pharmacology,"!  (fTrorw.  S.A.  Phil.  Soc, 
Vol.  XVI.,  p.  117)  I  referred  to  another 
species  of  Trichilia  (T.  Dregeana  E.  May). 
A  Kaffir  woman  at  Port  St.  John's  died 
after  using  as  im  enema  a  decoction  said  to 
have  Iwen  made  from  the  latter  plant,  but 
the  examination  did  not  lead  to  any  definite 
result. 

Dr.  T.  R.  Sim  states'*  that  "  the  seeds, 
which  are  striking  obieots,  and  may  be 
gathered  in  bushels  under  old  fruiting  trees, 
are  not  eaten  by  birds  or  monkeys,  and  are 
not  u«ed,  so  far  as  I  can  learn,  in  Pondo- 
land  or  Transkei,"  but  he  also  quotes 
Oliver"  as  sayiuf?.  "  The  oil  and  tallow 
obtained  from  the  seeds,  Dr.  Kirk  states, 
are  valuable,  and  may  be  had  in  quantity. 
The  oil  is  used  in  cookery." 

FVom  all  the  above  it  will  be  seen  that 
the  alleged  poisonous  character  of  the  de- 
corticated seed  has  no  very  definite  scienti- 
fic evidence  to  rest  upon,  although  the  shell 
or  ca;pHule  thereof  is  apparently  poisonous. 


'•  Annals  of  the  Natal  Museum,  Vol.  II., 
Pt.  I.,  1909. 

»*  "  Forest  Flora  of  C-ipc  Colony,"  1906, 
p.  161. 

*•  "  Flora  of  Tropical  Africa." 


88 


THE   CHEMICAL    NEWS. 


FEBBUAEY  9.  1923. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 

Ordinary  Meeting,  January  25,  1923. 

Sir  Charles  Sherrtngton,  President, 

in  the  Chair. 

The  following,  papers  were  read,  the  sum- 
maries here  printed  having  been  supplied 
by  the  authors  for  use  at  the  meeting:  — 

Prof.  A.  V.  Hill,  F.R.S.  The  Poten- 
tial Difference  occurring  in  a  Donfian 
Equilihriuvi  and  the  Theory  of  Colloid 1 1 
Behoiviour. 

Loeb    has     shown    experimentally     that 
there    is  a  potential    difference  between    a 
ojTToidal  solution  of  a  protein  and  a  crystal- 
loid solution  with  which  it  is  in  equilibrium 
across  a    membrane,     impermeable  to    the 
protein,  but  permeable  to   the  other  bodies 
involved.      This    P.D.  varies    in  the    same 
general  manner  as  the  osmotic  pressure,  the 
viscosity  and  the  swelling,    when  the  con- 
centration   of  hydrogen    ions  or  of  salt    is 
changed,    and    the  manner  of  variation    of 
the  P.I),  can  be  deduced,  in  general,  from 
the    theory     of    the     DoniMtfi    equilibrium; 
hence  it  is  concluded  by  Loeb  that  the  Don- 
nan  equilibrium  is  the  basis  of  the  colloidal 
properties  of  protein  solutions.     While  the 
probability   of  this  conclusion  is  admitted, 
it  is  pointed  out  here  that  one  of  the  chief 
arguments  employed  in  its  favour  by  hoeh 
is  incorrect.       Loeb  shows   that    the  P.D. 
observed  experimentally  agrees  very  exactly 
with  that  "calculated"  from  the  difference 
in  hydrogen    ion    concentration,    also    ob- 
served experimentally,  and  concludes    that 
this  supports  his  theory.       As  a  matter  of 
fact  the  equality  he  has  observed  is  a  neces- 
sary consequence    of  the  manner  in  which 
his  observations  were  made,  and  of  general 
thermodynamical  reasoning,  and  is  indepen- 
dent   of  any  theory  of    the  mechanism    by 
which  the  P.D.  is  produced. 

E.  F.  Armstrong,  F.R.S. ,  and  T.  P. 
HiLDiTCH.  A  Study  of  Catalytio  Actiqns  at 
Solid  Surfaces.  X. — The  Interaction  of 
Carbon  Mo-nomde  and  Hydrogen  as  condi- 
tioned by  Nickel  at  relatively  Low  Tem- 
peratures. —  A  Practical  Synthesis  of 
Methane. 

Attempts  to  produce  formaldehyde  or 
methyl  alcohol  by  passage  of  a  mixture  of 
carbon  monoxide  and  hydrogen  over  nickel 
at  temperatures  220-280°  C.  have  been  so 
far  unsuccessful,  but  it  was  observed  that 
under  these  conditions  a  mixture  of  equal 


volumes  of  the  two  gases  was  largely  trans- 
formed into  methane  and  carbon  dioxide : 
2C0  +  SH^  =  CO2  +  CH,. 
This  action  has  hitherto  escaped  notice, 
although  it  affords  the  simplest  and  most 
economical  means  of  producing  methane  in 
quantity,  since  a  suitable  gas  mixture 
exists  in  ordinary  commercial  water-gas 
when  the  latter  has  been  freed  from  cata- 
lyst poisons  by  removal  of  sulphur  com- 
pounds. 

The  process  is  available  for  the  prepara- 
tion of  pure  methane,  or  for  partial  conver- 
sion of  the  original  gas  mixture,  yielding  a 
gas  enriched  to  any  desired  degree  in 
methane. 

The  action  is  at  first  sight  anomalous, 
because  it  involves  simultaneous  oxidation 
and  reduction  of  CO  under  entirely  reducing 
conditions.  The  experimental  data  obtained 
are  so  far  definitely  against  any  inter- 
mediate formation  of  formaldehyde  or 
methyl  alcohol,  but  are  compatible  with  a 
combination  of  what  is  usually  known  as 
the  "  water-gas  reaction  ":  — 

CO  +  H^O  =  00^  +  H,, 
with  the  normal  hydrogenation  process :  — 
CO  +  3H2  =  OH^  +  H^O. 
Thus,  of  two  volumes  of  water-gas  (2C0 
+  2H2),  one  molecule    ol  carbon  monoxide 
and  a  molecule    of  water    (either    moisture 
present  in  the  gases  or  catalyst,  or  formed 
by  initial     normal  hydrogenation    of    some 
monoxide)  interact    and  yield    a    molecule 
each  of  carbon  dioxide  and  of  hydrogen,  the 
latter,     with  the   balance   of  hydrogen  pre- 
sent in  the  original  gas,  furnishing  sufficient 
hydrogen  for  the  normal  hydrogenation    of 
a  second  molecule  of  carbon  monoxide. 

J.  HoLKKR,  D.Sc.  The  Periodic  Opacity 
of  certoiin  Colloids  in  progressively  increas- 
ing Cor»cenfratio(ns  of  Electrolytes.  Com- 
municated by  Prof.  A.  V.  Hill,  F.R.S. 

In  stud;\ing  the  effect  of  electrolytes  on 
colloids  it  was  found  that,  as  the  concentra- 
tion of  the  electrolyte  was  increased,  the 
opacity  of  the  crystal  lo-eolloidal  solution 
varied  in  a  periodic  manner. 

The  method  of  testing  the  effect  of  com- 
mon salt  on  the  typical  emulsoid  colloid, 
serum,  may  be  described.  Into  each  of  a 
series  of  tes't-tubes  was  pipetted  0.5  oc.  of 
undiluted  scrum.  To  each  tube  was  then 
added  2  oc.  of  solution  of  sodium  chloride, 
which  progressively  increased  in  concentra- 
tion in  each  successive  tube.  The  tubes 
were  then  shaken  and  placed  in  a  thermo- 
stat at  40°  for  four  hours.  At  the  end  of 
that  time  the  opacity  of  the  solution  was 
determined  by  a  new  method. 


FEBRUARY  9,  1923. 


THB   CHEMICAL   NEWS. 


89 


It  was  shown  that  the  periodic  pheno- 
menon is  a  general  one.  It  is  given  by  col- 
loids of  both  the  emulsoid  and  suspensoid 
tyipe,  and  by  animal,  vegetable,  and  mineral 
colloids.  It  is  also  given  by  certain  mix- 
tures of  simple  aqueous  solutions  of  in- 
organic salts,  e.g.,  by  a  "buffer"  solution  of 
phosphates  to  which  arc  added  progres- 
sively increasing  concentrations  of  calcium 
chloride. 

Emulsoid    colloids    ti^nd     to  give     many 
oscillations  of  low  amplitude       Suspensoid 
colloids  tend  to  give  few  oscillations  of  high 
amplitude. 
II  For  a  given  set  of  conditions  the  pheno- 

«*  menon  tends  to  be  more  rei)roduoible  with 
emulsoid  than  with  suspensoid  collcMds. 
When  tlie  degree  of  aggir;,';ition  of  a  col- 
loid is  such  that  precipitaticm  is  imminent, 
reproducibility  is  markedly  diminished. 

The  phenomenon  is  not  .in  c^tical  inter- 
fcrcnc*!  of  the  light  scattticd  by  colloidal 
particles,  but  is  a  definite  oscillatory  change 
in  the  physical  condition  f>f  those  particles. 

K.  K.  RiDEAi.  and  K.  (i.  W.  Nokrisii. 
The  Photochemistry  of  PoUisHium  Perman- 
(jannte.  Part  I. — The  Aiii>luaiion  of  the 
Potenti4>meter  to  the  Study  of  Photochemi- 
cal Change.  Part  11. — Oti  the  Energrticn 
of  the  Photo-decftmposition  of  PotisHium 
Permanganate.  C(»ximunicat<'a  by  Sir  Wil- 
liam Pope,  F.ll.S. 

The  electrode  potential  of  potassium  per- 
manganate undergoes  a  change  (oa  O.'io 
volt)  when  illuminated  with  ultra-violet 
light  from  the  mercury  vapour  lamp,  and 
recovers  slowly  in  the  dark.  This  change  is 
correlated  with  a  photoohi  niicnl  decom- 
position of  the  p(>nnanganiit  appar- 
ent by  the  separation  of  a  i>;  ,  -•  of  the 
composition  K3O  .  2MnOj,  and  the  fornia- 
tion  of  a  sol  of  MnOj,.  llliimination  estab- 
lishes a  photochemical  stationary  state, 
KC)H  being  simultaneously  pKKluced  by  the 
decomposition,  and  remove<l  by  combina- 
ti(m  with  the  colloi<lal  MnO,.  This  in- 
volve* an  alteration  of  the  Ph  of  the  solu- 
tion, which  causes  the  elect rtnle  potential 
changis.  From  curves  obtain*  d  the  decom- 
position was  shown  to  be  monomolecular 
over  the  range  of  conccntrntiMis  investi- 
gated, and  from  them  it  was  inqpoesible  to 
calculate  the  veWxjity  constant  by  two  in- 
dependent methods,  the  values  ol)tained 
bein<^'  in  gfKxl  agreement  with  that  obtained 
by  direct  analysis  of  the  decomposing  solu- 
tion. 

The  decomposition    of  acidified    perman- 
ganate under  identical  conditions  is  d  zero 


order,  the  change  in  type  of  reaction  being 
due  to  non-formation  of  colloid.  The  photo- 
sensitivity of  mixtures  of  permanagante  and 
oxalio  acid  is  investigated,  and  the  results 
emb  ;died  in  a  discussion  of  the  mechanism 
of  the  decomposition  of  the  permanganate 
ion.  Attention  is  drawn  to  the  use  of  the 
potentiometer  for  detecting  and  measuring 
photo:!hemical  change  almig  the  lines  indi- 
cated in  this  paper. 

The  ulti  a- violet  absorptiwi  spectrum  of 
potassium  permanganate  is  investigated, 
and  the  photf>active  ra<liation  shown  to  lie 
in  this  region.  Evidence  is  given  for  con- 
sidering the  Hg  line  at  3128  AU.  as  the 
chief  agent.  llie  absorpticMi  of  radiant 
energy  was  detei rained  quantitatively;  the 
result  obtained  i^  in  agreement  with  t^c 
Einstein  Law  of  Photochemical  Equivalent, 
a  result  of  nipeeial  intt-rest  as  the  first  in- 
stance of  its  application  to  solutions. 

E.  A.  FisHKK.  Some  Mointurc  licIationH 
of  Colloids.  Part  I. — A  Comparative  Study 
of  the  Hates  of  Evaporation  of  \\':iter  from 
Wool,  Sand,  and  Clay.  C(/mmimicated  by 
Pio  .  A.  Smithells,  F.K.S. 

A  comparative  study  of  the  rates  of 
evaporation  of  water,  umler  u(>m,parable  and 
rigidly  controlled  conditions,  from  a  wool 
fabric,  quartz  sand,  silty  <soil  and  heavy 
clay  subHoil.  h  is  l>een  ouried  out. 

The  curves  obtained  by  plotting  rates  of 
evaporation  af»ainst  water  contents  are,  in 
the  cjises  dealt  with,  discontinuous  and  very 
different  from  the  ccMTCstponding  smooth 
vapour- ]>re8sure  curves.  Each  portion  of 
the  rate  ourve  can  be  expressed  by  a  simple 
tyipe  of  equation  connecting  rate  of  cvapora- 
t:on  with  water  content.  Various  factors 
affecting  the  rat*-  of  evaporation  are  dis- 
cussed m  some  detail. 

The  rate  curves  obtained  are  similar  in 
ty|K?  in  the  oases  of  wool  (wholly  colloidal 
with  a  cellular  structure),  quartz  sand 
(wholly  non-colloidal  with  a  granular  struc- 
ture), silty  soil  (notoriously  feeble  in  col- 
loid pro|>crties).  and  heavy  clay  sub-soil 
(typically  colloidal  in  behavi  tur).  The  con- 
clusion is  drawn  that  the  forces  holding  the 
water  are  essentially  similar  in  all  four 
oases,  and  that  colloid,  merely  as  such,  has 
no  charjicteristic  rate  of  evaporation  ourve. 
It  is  only  when  certain  physico-chemical 
factors  are  operative,  as  in  the  case  of  gela- 
tin, that  the  relatively  simple  type  of 
evaporation  curve  is  not  followed. 

The  shrinkage  of  clay  has  a  charact.(>ristic 
effect  on  the  evaporation  curve,  which  can 
be  allowed  for  in  the  equation  of  rate,  lliis 


90 


THE   CHEMICAL   NEWS. 


FEBRUARY  9,  1923. 


effect  is  entirely  absent  in  wool,  as  in  sand 
and  silt,  and  it  is  concluded  that  the  so- 
called  shrinkage  otf  wool  on  drying  is  really 
a  deformation  and  not  a  volume  shrinkage. 

An  attempt  is  made  to  exiplain  the 
vapour-pressure  relationships  of  wool  on 
the  basis  of  capillarity ;  the  absorption  of 
water  hy  wool  is  attributed  primarily  to  a 
filling  up  of  fine  pores  of  various  shaipes  and 
sizes,  and  that  the  vapour  pressures  of 
wool-water  systems  are  determined  by  the 
diameters  of  the  pores  that  are  full  of  water. 

R.  Whytlaw-Grav,  J.  B.  Speakman,  and 
J.  H.  P.  Campbell.  Smokes.  Part  I. — A 
Study  of  their  Behaviour  and  a  Method  of 
Determining  the  Number  of  Particles  they 
contain.  Communicated  by  Prof.  A. 
Smithells,  F.R.S. 

A  study  has  been  undertaken  of  highlj^ 
dispersed  and  dilute  smokes,  consisting  of 
solid  ipai'ticles  of  ultra-microscopic  size, 
with  the  object  of  discovering  whether 
these  systems  present  any  analogy  in  be- 
haviour to  the  solid-liquid  systems  of  col- 
loidal solutions. 

The  smokes  were  produced  (a)  by  the  arc 
disohargie  in  air,  (b)  by  volatilisation  and 
condensation,  (c)  by  chemical  action.  In 
each  case  highly  dispersed  systems  of  very 
minute  particles  could  be  obtained. 

As  a  first  line  of  attack,  a  method  of 
counting  with  an  ultra-miorosco])e  of  the 
slit  type  the  number  of  particles  in  a  given 
volume  has  been  worked  out,  and  it  has 
been  found  that,  starting  from  the  moment 
after  dispersal,  the  life-history  of  a  smoke 
falls  into  two  main  iperiods :  — 

(a)  An  unstable  period  in  which  the 
number  of  particles  diminishes 
rapidly  with  time. 

(b)  A  stable  period  in  which  the  decrease 
in  number  is  slow. 

During  the  first  period  the  increase  in 
size  is  very  marked,  and  it  is  shown  that 
these  changes  are  not  due  to  evaporation, 
but  to  a  process  of  aggregation,  whioh  pro- 
duces complexes  of  different  structure  de- 
pending on  the  nature  of  the  dispersed 
substance. 

R.  Whytlaw-Gray  and  J.  B.  Speakman. 
Smokes.  Part  II. — A  Method  of  Determin- 
ing the  Size  of  the  Particles  they  contain. 
Communicated  by  Prof.  A.  Smithells, 
F.R.S. 

A  filtration  method  has  been  devised 
which  enables  the  concentration  in  weight 
of  the  suspended  solid  matter  in  these 
rapidly  changing  smokes  to  be  determined 
with  an  accuracy-  of  about  3  per  cent. 


A  given  volume  of  smoke  (usually  1  litre) 
is  filtered  through  small  tubes  containing 
asbestos,  and  the  increase  in  weight  is  as- 
certained by  means  of  a  micro-balance  sen- 
sitive to  0.0002  mgm.  The  process  of  fil- 
tration takes  about  five  minutes.  Curves 
have  been  obtained  showing  the  variation 
in  weight  concentration  of  the  smoke  over 
periods  of  from  0  to  6  hours.  Knowing  the 
weight  and  the  number  of  the  particles  in  a 
given  volume,  the  average  mass  of  a  smoke 
particle  at  different  periods  can  be  calcu- 
lated and  the  gi'owth  followed  in  a  quanti- 
tative manner.  Assuming  the  density  of 
the  particle  to  be  that  of  the  substance  in 
bulk,  the  average  radius  can  be  evaluated. 

All  the  weight-concentration  curves 
show  an  initial  rise,  and  this  fact,  in  con- 
junction with  ultra-microscopic  observa- 
tions, renders  it  probable  that  all  these 
clouds  contain  in  the  (Mirly  stages  a  large 
number  of  invisible  particles  of  a  micro- 
scopic size. 

R.  C.  Ray.  The  Effect  of  Long  Grinding 
on  Quartz  [Silver  Sand).  Communicated 
by  Dr.*  W.  M.  Travers,  F.R.S. 

It  is  found  that  when  quartz  (silver 
sand)  is  ground  for  a  long  time,  the  density 
of  the  ground  substance  is  lower  than  the 
one  which  has  not  been  subjected  to  grind- 
ing. The  fall  of  density  shows  that  as 
much  as  25.7  per  cent.  O'f  the  material  is 
converted  from  the  crystalline  to  the 
vitreous  condition.  This  value  agrees 
fairly  with  that  aiTived  at  from  the  deter- 
mination of  the  molecular  heats  of  solution. 

Papers  Read  on  February  8,  1923. 

Prof.  L.  Bairstow,  F.R.S.,  Miss  M.  B. 
Cave,  and  Miss  E.  D.  Lang.  The  Resist- 
ance of  a  Cylinder  m.oving  in  a  Viscous 
Fluid. 

G.  I.  Taylor,  F.R.S.  The  Motion  of 
Ellipsoidal  Particles  in  a  Viscous  Fluid. 

L.  F.  Richardson.  Theory  of  the  Mea- 
surement of  Wind  by  shooting  Spheres  up- 
ward. Communicated  by  Dr.  G.  C.  Simp- 
son, F.R.S. 

Papers  read  in  title  only. 

Prof.  W.  E.  Dalby,  F.R.S.  Further  Re- 
searches on  the  Strength  of  Materials. 

L.  C.  Jackson  and  Prof.  H.  Kamerlingh 
Onneh,  For.  Mem.  R.S.  Investigations  on 
the  Paramagnetic  Sulphates  at  TjOw  Tem- 
peratures. 

Ij.  C.  Jackson  and  Prof.  IT.  Kamerlingh 
Onnes,  For.  Mem.  R.S.  Investigations  on 
the  Paramagnetfsm  of  Crystals  at  Low 
Teniperaturea. 


FiiBKUAliY  9,  1923. 


THE   CHEMICAL   NEWS. 


91 


Ernest  Wilson.  On  the  k>H69fiptihiUty 
of  feebly  Magnetic  Bodies  as  affected  by 
Tension.  Communioated  by  Prof.  O.  W. 
Hichardaon,  F.li.S. 

W.  D.  WoMERSLEY.  The  Specific  Heats 
of  Air,  Steam,  and  Carbon  Dioxide.  Com- 
municated by  Sir  Dugald  Clerk,  F.li.S. 


THE  CHEMICAL  SOCIETY. 

Bye -Law  8  Relating  to  the  Election  of 
President,  Officers,  and  Council. 

V. — Of  the  Ccmstitution  of  the  Council. 

The  Council  shall  consist  of  the  Presi- 
dent, not  more  than  twelve  Vice-Presidents, 
the  Treasurer  and  Secretaries,  and  eighteen 
Ordinary  Members.  They  shall  cmiduct  the 
business  of  the  Society  and  may  fill  any 
casual  vacancy  in  their  number  until  the 
next  Annual  General  Meeting.  The  Pre- 
sident, Trejwurer  and  the  Secretaries  shall 
be  termed  the  officers  of  the  Society. 

An  election  to  fill  vacancies  shall  bo  held 
annually  in  manner  hereinafter  provided, 
and  the  result  of  the  election  shall  be  de- 
clared at  the  Annual  General  Meeting.  The 
retiring  members  shall  n(;t  be  eligible  for 
re-election  until  after  the  kpse  of  one  year. 

VI.— Of  the  Election  of  the  Council. 

In  the  month  of  January  a  list  shall  l»e 
prepared  by  the  Council  of  the  vacant 
pUioi^s  in  the  Council  which  fall  due  to  be 
filled  at  the  .\nnual  General  Meeting.  This 
list  shall  be  read  at  an  Ordinary  Scientific 
Meeting  in  January,  and  shall  be  published 
in  the  Proc*edings.  The  Council  shall  at 
the  same  time  and  in  the  same  manner  in- 
timate the  names  of  the  person^  whom  it 
proposes  to  nominate  for  1  ~  of  Pre- 

sident,   Treasurer  and   Se<  should 

then*  be  a  vacancy  in  any  of  these  offices, 

A  nomination  for  any  v.icancv  among  the 
officers,  Vice-Presidents  or  Ordinary  Mem- 
Ikts  of  Council  may  be  made  in  writing 
signed  by  at  least  twenty  Fellows,  and 
must  be  received  by  the  Secretaries  at  the 
Society's  Rooms  not  latter  than  the  four- 
tei'uth  day  of  Februiu^.  Every  nomination 
must  relate  to  one  vacant  place  only,  and 
must  be  accompanied  by  a  sifined  declara- 
tion by  the  n()minee  that  he  us  willing  to 
aoc/Oipt  office  if  elected.  Nominations  may 
be  mofio  also  by  the  Council. 

The  Council  shall  prepare  the  list  of 
nominations  for  the  vacant  places,  which 
shall    include    all    candidates    duly    nomi- 


nated. This  list  shall  be  read  out  by  the 
Chairman  at  the  first  Ordinary  Scientific 
Meeting  in  March,  and  shall  be  thereupon 
publicly  suspended  in  the  Society's  Rooms, 
and  if  the  number  of  nominations  does  not 
excee<l  the  number  of  vacancies,  the  per- 
sons nominated  shall  be  declared  duly 
elected  at  the  Annual  General  Meeting 
without  any  vote  being  taken. 

li  more  candidates  are  nominated  than 
there  are  vacant  places,  the  Secretaries 
shall  poet  to  each  Fellow  usually  resident 
in  the  United  Kingdom  a  ballot  paper  con- 
taining a  list  of  the  vacancies  for  which 
there  is  a  ccmtest  and  of  the  candidates 
nominated  therefcw,  dLstiuguishing  those 
who  are  nominated  by  the  Council,  and 
stating,  in  the  case  of  candidates  for  the 
places  of  Ordinary  Members  of  Council, 
how  many  are  to  be  elected  who  are  resi- 
dent within  fifty  miles  from  Charing  Cross, 
and  how  many  beyond  that  radius,  and  the 
date  by  which  the  ballot  papers  must  be 
receivcMl  in  order  to  be  oounted. 

In  the  event  of  a  ballot  being  required, 
two  Fellows  shall  be  appointed  scrutators 
at  the  first  Ordinary  Scientific  Meeting  in 
March  to  assist  in  tne  subsequent  counting 
of  votes.  In  the  event  of  either  w  both  of 
these  scrutators  being  unable  to  act,  it 
shall  be  in  the  power  of  the  President  to 
appoint  substitutes. 

On  some  day  previous  to  the  Annual 
General  Meeting  the  voteg  shall  be  counted 
by  the  scrutators,  with  the  assistance  of 
(Mie  of  the  Secretaries,  and  the  scrutators, 
together  with  the  Secretary,  shall  ipreparo 
and  sign  a  report  to  the  Council.  A  state- 
ment of  the  votes  cast  for  each  candidate 
shall  be  presented  -at  the  Annual  General 
Meeting,  and  the  Chairman  shall  declare 
the  names  of  those  duly  elected. 

In  any  case  of  equality  of  votes  for  two 
or  more  candidates,  the  Cotmcil  shall  de- 
cide which  of  the  candidates  shall  be 
deemed  elected. 

XI. — Of  the  Ordinary  Members  of  Council. 

The  term  of  office  of  Ordinary  Members 
of  Council  shall  l)e  three  years.  If,  before 
the  expiry  of  this  period,  an  Ordinary 
Member  has  been  nominated  for  any  other 
position  on  the  Council,  this  nomination,  if 
accepted,  shall  he  deemqd  to  create  an 
additional  vacancy  in  the  list  of  Ordinary 
'Members  of  Council. 

The  Ordinary  Members  shall  be  elected 
in  such  wise  111  it  nine  shall  be  resident 
within  a  ratlins  r^f  fifty  miles  from  Charing 
Cross  and  nine  beycmd  such  radius. 


92 


I'HE   CHEMICAL   NEWS. 


PEBRUAEY  9,  1923. 


XX. — Temporary  Bye- Law. 
These  Bje-Laws  shall  come  into  force  on 
the  first  day  of  June,  1920. 

Notwithstanding  anything  hereinbefore 
to  the  contrary,  the  Council  which  is  in 
office  when  these  Bye-Laws  come  into  force 
shall  be  deemed  to  be  the  Council  of  the 
Chemical  Society  until  the  Annual  General 
Meeting  in  M^arch,  1921.  It  shall  be  the 
duty  of  this  Council  to  make  an-angements 
for  the  election  of  the  Council  for  1921-1922 
in  conformity  with  the  foregoing  Bye-Laws, 
and  the  terms  of  office  of  Members  of  Coun- 
cil elected  at  the  first  annual  election  after 
these  Bye-Laws  come  into  force  shall  be 
determined  as  follows:  — 

Of  the  twelve  Vice-Presidents,  two  of 
each  class  shall  retire  at  the  end  of  one 
year  and  two  of  each  class  at  the  end  of  two 
years. 

Of  the  eighteen  Ordinary  Members,  three 
of  each  class  shall  retire  at  the  end  of  one 
year  and  three  of  each  class  at  the  end  of 
two  years. 

The  Council  shall  determine,  by  arrange- 
ment or  by  ballot,  which  shall  be  the  retir- 
ing members  of  each  class  for  each  year. 

The  Annual  General  Meeting  of  the 
Society  fc*  the  election  of  officers  and 
Council,  and  other  business,  will  be  held 
on  Thursday.  March  22,  1923,  at  4  p.m. 


THE  CHEMICAL  SOCIETY. 

Burlington  House, 

Piccadilly,  London,  W.l. 

Notice  is  hereby  given  that,  in  accord- 
ance with  the  Bye-Laws,  the  following 
vacant  places  in  the  Council  fall  due  to  bt 
filled  at  the  Annual  General  Meeting  of  the 
Society  on  the  22nd  day  of  March,  1923:  — 

President,  one  vacancy. 

Vice-Presidents  who  have  filled  the  office 
of  President,   two  vacancies. 

Vice-Presidents  who  have  not  filled  the 
office  of  President,  three  vacancies. 

Treasurer,   one  vacancy. 

Ordinary  Members  of  Council — 

(a)  Town  Members  (i.e.,  those  living 
within  a  radius  of  50  miles  from  London), 
three   vacancies. 

(&)  Country  Members  (i.e.,  those  living 
beyond  a  radius  \>i  50  miles  from  London), 
three  vacancies. 

The  Council  has  n  ^minated  Professor  W. 
P.  Wynne  to  the  office  of  President.  It  has 
also  nominated  Professor  J.  F.  Thorjpe  to 
the  office  ol  Treasurer. 


(In  October  last,  the  Council  appointed 
Prof.  J.  F.  Thorpe  as  Treasurer  until  the 
next  Annual  General  Meeting,  to  fill  the 
vacancy  caused  by  the  retirement  of  Dr.  M. 
O.  Forster.  It  also  appointed  Dr.  J.  T. 
Hewitt  as  Vice-President  until  the  Annual 
General  Meeting  to  fill  the  vacancy  amongst 
the  Vice-Presidents  caused  by  Prof.  J.  F. 
Thorpe's  appointment  as  Treasurer.) 

Fellows  are  reminded  that  nominations 
for  any  of  the  above  vacancies  may  be 
made  in  writing,  signed  by  at  least  twenty 
Fellows,  and  must  be  received  by  the  Sec- 
retaries at  the  Society's  Rooms  not  later 
than  the  14th  day  of  February,  1923.  Every 
nomination  must  relate  to  one  vacant  place 
only,  and  must  be  accomipanied  by  a  signed 
declaration  by  the  nominee  that  he  is  will- 
ing to  accept  office  if  elected. 

Forms  of  nomination  can  be  obtained  on 
application  to  the  Assistant  Secretary. 

The  names  of  the  Members  of  Council 
who  retire  at  the  Annual  General  Meeting 
on  the  22nd  March,  1923,  and  who  are  in- 
eligible for  re-election  to  the  same  office 
until  alter  the  lapse  of  one  year,  are  as 
follows :  — 

President :    Sir  James  Walker. 

Vice-Presidents  who  have  filled  the  office 
of  President:  Professor  H.  E.  Annstrong 
and  Professor  W.  H.  Perkin. 

Vice-Presidents  who  have  not  filled  the 
office  of  President:  Professor  F.  S.  Kipping 
and  Professor  S.  Smiles. 

Ordinary  Members  of  Council — 

(a)  Town  Members :  Professor  A.  J.  All- 
mand,  Mr.  F.  H.  Carr,  and  Professor  J.  M. 
Thomson. 

(b)  Country  Members :  Professor  T.  S. 
Patterson,  Mr.  W.  Rintoul,  and  Professor 
R.  Robinson. 

James  C.  Philip, 
Irvine   Masson,        Secretaries. 
26th  January,    1923. 


SOCIETY  OF  GLASS  TECHNOLOGY. 

Prof.  W.  E.  S.  Turner,  D.Sc,  President, 
presided  at  the  meeting  of  the  Society  of 
Glass  Technology,  held  in  Sheffield,  on 
Wednesday,  January  17. 

A  very  cordial  welcome  to  the  meeting 
was  given  to  Mr.  H.  L.  Dixon,  of  Pitts- 
burgh, U.S.A.,  who  was  at  present  visiting 
Eurotpe.  He.was,  said  Prof.  Turner,  well- 
known  not  only  in  America,  hut  also  in 
England   and  on  the   Continent.        He  had 


FEBRUARY  9.  1923. 


THE    CHEMICAL    NEWS. 


93 


built  nearly  all  the  glass  furnaces  in 
America. 

The  first  paper  presented  to  the  uieeting 
was  by  Dr.   W.  H.  Hatfiuld,    and  entiti-d 

Stainless  Steel,  with  some  Consideration 
of  it«  Application  to  the  Glass  Industry." 
At  the  outset,  Dr.  Hatfield  stated  that  he 
did  not  know  sufficient  of  the  glass  industry 
to  do  anything  more  than  suggest  some 
directions  in  which  stainless  ^el  might  hi' 
useful.  He  remarked  that  the  most  impor- 
tant property  of  stainless  steel  was  its  re- 
sistance to  corrosion  and  to  o.xidisation. 
The  resistance  to  ordinary  corrosion  was 
not  of  much  interest  to  glass  technologists, 
but  its  resistance  to  oxidisation  at  high 
temperatures  was  of  consiihrable  interef^t, 
especially  from  the  fact  that  at  high  tem- 
peratures it  scaled  much  less  than  ordinary 
steels.  Stainless  steel  had  such  different 
properties  from  ordinary  steel  that  it  must 
be  studied  as  an  entirely  different  material 
from  many  points  of  view. 

After  demonstrating  how  nitric  acid 
rapidly  attacked  wdinary  steel  but  left 
stainless  steel  unaffected.  Dr.  Hatfield  said 
that  stainless  steel  could  now  be  made 
direct  into  castings,  while  gheet  steel, 
which  wa«  very  malleable,  could  also  be 
made.  The  making  of  sheet  steel  was  a  de- 
velopment of  the  last  twi>  years.  Then, 
again,  it  could  be  diawn  into  tubes,  so  tine 
that  hypodermic  needles  were  now  largely 
made  from  stainless  tubes.  Turbine  blades 
had  been  successfully  turned,  and  in  this 
case  the  steel  was  brought  into  contact  with 
steam  at  high  temperatures.  He  showed 
pieces  of  tu:bine  hiades  that  had  been  in 
use  eighteen  tnonths  and  still  retained  their 
special  properties.  These,  he  compared  to 
f>r(iiuary  nickel  steel,  which  lost  so  much 
material  that  they  had  censed  t^o  function 
properly.  Practically  all  the  turbine  manu- 
facturers had  adopted  st.iinless  steel  as 
being  the  most  effective  material  for  the 
manufacture  of  blades. 

Stainless  steel,  he  went  on,  was  an  alloy 
of  iron  and  chromium.  It  contained  from 
12  to  14  per  cent,  of  chromium.  The  car- 
bon content  varied  a  little  with  the  different 
types  of  stainless  steel,  but  for  general 
purposes  might  be  considered  to  be  about 
0.30  per  cent.,  which  was  very  similar  to 
ordinary  structural   steel. 

Dr.  Hatfield  showed  by  lantern  slides  the 
action  of  various  corrosive  and  oxidisinji 
influences  on  stainless  steel.  They  were 
able  to  make  a  stainless  steel  which  would 
be  impervious  to  sodium  sulphate,  though 


some  ty4)es  of  stainless  »tec\  were  liable  to 
be  affected  by  continued  contact  with  it. 
He  showed  micrographs  illustrating  the 
structure  of  various  special  steels,  such  aL 
nichrome  and  tautiron.  The  former,  he 
said,  resisted  oxidising  influences  and 
maintained  its  >trength  at  high  tempera- 
tures. Tantiron  was  not  ductile,  but  rela- 
tively hard  and  brittle  like  cast  iron. 

With  regard  te  the  glass  industr}-,  he 
considered  that  stainless  steels  could  be 
considered  as  alternatives  for  those  now 
used,  from  two  standpoints,  which  were  the 
resistance  to  scaling  and  its  strength  at 
high  temperatures.  Stainless  steel  had  u 
high  tensile  stnugth,  equal  to  the  best 
alloy  steels,  had  a  high  fatigue  range,  and 
miglit  Im?  iiardeiud  and  teujpered.  There 
were  many  directions  in  which  the  material 
might  Im>  useful,  the  most  notable,  in  his 
(j||)inion,  bt  in^'  toi  narison  and  blow  moulds. 
Many  parts  of  ft cder  devices  might  be  use- 
fully produci'd  in  such  material,  as  might 
also  blowing  irons,  rolls,  belt  conveyers, 
lelir  chain  pins,  and  other  things,  including 
knives  for  cutting  viscous  glass.  The  ends 
of  blowpifM-s  might  very  well  be  made  of 
stainless  stc-el.  Brushes  which  had  to  be 
made  of  wire  could  well  be  made  cf  stain- 
less steel. 

Explaining  rec»nt  developments  in  the 
use  of  this  st4>el,  Dr.  Hatfield  said  that 
where  a  highlv  ftolished  surfaet  was  needed, 
stainless  steel  was  admirable  for  the  pur- 
pose. Indeed,  several  firms  were  produc- 
ing scientific  mirrors  from  this  material. 

A  discussion  followed,  in  which  the>re 
took  part  the  President  (Prof.  W.  E.  S. 
Turner).  Major  V.  F.  Gloag,  and  Messrs. 
.1.  H.  Davidson,  W.  C.  Snowdon,  R.  Hem- 
inguay,  and  (i^^y  Simpson. 

Replying  to  tlie  discussion.   Dr.   Hatfield 
said  that  the  question  of  a  g(K)d  surfa<!e  was 
answered  by  th*-    manufacture  of  the  mir- 
rors he  had  referred  to.     He  thought  stain- 
less steel  woulil  do  very  well  in  muffle  lehrs. 
Stainless  steel  could  be  welded  without  any 
d'fii  ulty  to  stainless  steel  or  ordinary  steel, 
but  a  good  deal  depended  on  the  skill  of  the 
smith  employed.       He    thought    that    the 
moulds     used     in    glassmaking    were     too 
heavy.     Stainless  steel  e/)uld  withstand  the 
proc^ess  of  crushing  and  also  ordinary  wear 
and  tear  as  well  as  most  materials.  He  was 
not  able  to  answer  questions  with  regard  to 
comnarative  costs,  but  the  cost  of  stainless 
steel  was  something  approaching  the  iprice 
of  cheap  high  speed  steel.     It  was  a  special 
steel,  and  not  a  cheap  steel,    but  the  cost 


94 


was  not  prohibitive.  The  expense  was  al- 
ways justified  when  used  in  those  indus- 
tries where  its  special  properties  were  an 
advantage  over  other  materials. 

The  second  ;paper  was  entitled  "  Some 
Measurements  of  the  Viscosity  of  Glasses 
near  their  Annealing  Points,  and  a  critical 
Review  of  some  recent  literature  on  the  An- 
nealing of  Glass,"  by  S.  English,  M. Sc. 

Mr.  English  showed  that  contrary  to  the 
general  opinion,  strain  in  glass  could  not 
always  be  detected  bv  examining  the  glass 
in  polarised  light,  an^  that  the  most  sensi- 
tive position  was  that  in  which  the  direc- 
tion of  the  strain  in  the  glass  was  at  45°  to 
the  plane  of  polarisation  of  the  light.  In 
discussing  strain  viewers,  the  lecturer 
dealt  with  the  defects  in  design  of  a  strain 
viewer  recently  put  on  the  market,  and 
showed  that  with  a  strain  viewer  of  this 
tyipe  it  was  very  easy  to  obtain  misleading 
indications  of  the  presence  of  strain.  Re- 
viewing the  statements  made  concerning 
the  advantages  accruing  from  the  use  of  a 
selenite  or  quartz  plate  in  CMinection  with 
the  analysing  Nicol  prism,  it  was  shown 
that  the  claim  made  by  one  author  that  the 
selenite  plate  was  more  sensitive  than  plain 
crossed  niools  was  only  true  when  a  very 
poor  source  of  light  was  used,  and  that  a 
further  claim  made  by  another  author  to  be 
able  to  distinguish  between  tension  and 
compression  stresses  by  the  use  of  such  a 
plate  was  entirely  untrue. 

Details  of  the  measurements  of  the 
mobility  of  various  types  of  glasses  from 
the  annealing  temperatures  through  a  range 
of  150°  were  given,  and  it  was  shown  that 
the  rate  of  change  of  mobility  of  the 
glasses  at  their  annealing  points  was  ap- 
proximately constant,  most  of  them  requir- 
ing a  rise  of  temperature  of  9°  to  cause  a 
doubling  of  the  mobility.  In  some  cases 
this  temperature  interv^al  rose  to  as  much 
as  11°.  At  temperatures  of  100  or  150° 
above  the  annealing  points  the  temperature 
interval  required  to  double  the  mobility  was 
generally  rather  longer  than  that  required 
at  the  annealing  points.  Curves  were 
shown  indicating  that  the  mobility  of 
glasses  is  not  a  true  logarithm's  function 
of  the  temperature,  and  that  a  point  of  in- 
flection in  the  curves  will  probably  be 
found  at  temperatures  rather  higher  than 
those  included  in  the  present  range.  It 
was  also  suggested  that  the  well-known 
working  properties  of  lead  glasses  and  other 
soft  glasses  are  determined  more  by  the 
rate  of  radiation  of  heat  than  by  rate  of 
change  of  viscosity  with  temperature. 


THE  CHEMICAL  NEWS. 


FEBRUARY  9,  1923. 


During  the  forenoon,  by  the  courtesy  of 
the  directors,  members  had  the  privilege  of 
visiting  the  works  of  Messrs.  Thos.  Firth  & 
Soils,  Ltd.,  Sheffield,  where  they  saw 
various  processes  in  the  manufacture  of 
stainless  steel. 

THE   INSTITUTE  OF  CHEMISTRY   OF 
GREAT  BRITAIN  AND  IRELAND. 

Pass  List  :     January  Examinations,  1923. 

The  following  Associates  have  passed  the 
examination  for  the  Fellowship,  in  branch 
E,  The  Chemistry,  including  microscopy, 
of  Food  and  Drugs  :  — 

Two  candidates  were  examined;  both 
passed : 

Hawley,  John  William,  B.Sc.  (Lond.). 

King,  John. 

The  following  candidates  have  passed  the 
examination  far  the  Associateship  :  — 

Current  Regulations :  in  General  Chemis- 
try :^ 

Fifteen  candidates  were  examined ;  seven 
passed : 

Bender,  Gustave  William,  University 
College,  London. 

Cattle,  Alfred  Philip,  East  London  Col- 
lege. 

Lomax,  James,  College  of  Technology, 
Manchester, 

Madden,  Frank  Cox,  University  College, 
London. 

McKean,  John  Brown,  Paisley  Technical 
College. 

Powell,  Cyril  John,  University  College, 
Nottingham. 

Reynolds,  Thomas  Edward  Stewart, 
University  College,  London. 

Regulations  prior  to  1920;  in  branch  (a), 
Mineral  Chemistry:  — 

Two  candidates  were  examined;  both 
passed : 

Dallimore,  Thomas  Warwick,  Chelsea 
Polytechnic. 

Smith,  William,  University  College,  Not- 
tingham. 

Regulations  prior  to  1920;  in  branch  (d), 
Organic  Chemistry :  — 

Three  candidates  were  examined;  all 
passed : 

Hansford,  Mitchell  Harold,  Blackburn 
Technical  College. 

Tadman,  Vernon  Thorpe,  University  Col- 
lege,  Nottingham. 

Taylor,   George,   University  College,  Not- 
tingham. By  Order  of  the  Council, 
Richard  B.  Pilcher, 

Registrar  and  Secretary, 
30,  Russell  Square,  London,  W.C.I. 
26th  January,  1923. 


FEBRUARY  0,  1923. 


THE  CHEMICAL  NEWS. 


05 


APPARATUS  FOR  THE  RECOVERY  OF 
BROMINE  FROM  SOJ)IUM  HYTO-    - 
BROMITE 

By  C.  H.  Collings. 

Erratum. 

P.  57,  third  line  of  third  paragraph  of 
first  column:  after  the  words  "with  tho 
evolution  of  free  Br,"  insert  "  a  constant 
stream  of  air-bubbles." 


P_..- 


The  above  illustration  shows  the  appara- 
tus used. 

A,  acid  c"p;  W.  waste-cup;  H,  soda  sol. 
cup;  HJ,  hypobromite  jar  supports  on  WS, 
with  delivery  la^p  HD;  MC.  mixing-cham- 
ber; V.  valve;  I,  air  inlet:  BD,  bromine  de- 
livery tube;  P,  connection  with  aspirator 
or  pump;  R.T  receives  n^siduum  from  tho 
operation  in  MC,  and  is  cTiiptied  when  full 
through  RD  at  O. 


NOTICES  OF  BOOKS. 
Common    Science,     by    Carleton     W. 

Wastiburnr.     Pp.  XV.  '+  390.    London  : 

G.   Bell  &  Sons,   Ltd.,    Portugal  Street, 

W.C.     1023.     Price  4s.  fid. 

A  collection  of  answers  to  about  2,000 
questions  asked  by  children  forms  the  foun- 
dation of  this  book. 

These  questions  were  selected  from  those 
asked  by  several  hundred  children  in  upper 
elementary  grades.  They  were  sorted  and 
'Classified,  and  from  them  this  course  was 
•constructed.       The  aim  has  been  to  select 


simiple  and  striking  experiments  and  illus- 
trations which  will  stimulate  and  maintain 
the  children's  interest  in  the  subject. 

The  assumption  that  the  scientific 
method  can  be  taught  to  children  by  mak- 
ing them  carry  out  uninteresting  quanti- 
tative exiperiments  in  an  effort  to  obtain 
results  that  correspond  with  those  in  a 
text-bocJc  can  be  considerably  ovor-rat'Cd. 

In  the  present  volume,  exercises  are 
selected  to  illustrate  the  scientific  prin- 
ciples of  Gravitation,  Molecular  Attraction 
and  Capillarity,  CMiservation  of  Energy, 
Heat,  Radiant  Heat  and  Light,  Sound, 
Magnetism.  Electricity,  and  Chemical 
Change  and  Chemical  Action. 

The  volume  is  intended  for  young 
pupils  who  are  studying  elementary  science, 
and  should  be  useful  to  their  instructors  as 
well."  J.G.F.D. 


Inorganic  Chrmuttry,  by  O.  S.  Nkwth, 
F.I.C.,  F.C.S.     New'  and    enlarged  edi- 
tion.   Pto.  XIII.  +  772.     London:  Long- 
mans,   Green  A  Co.,    Paternoster    Row, 
E.C.     1928.     Price  Ss. 
The    continued    poipularity    of    Newth's 
"Inorganic  Chemistry,"    as  evidenced    by 
the>  constant  issue  of  new  editions,    is  not 
difficult  to  understand. 

The  book  is  just  the  type  which  appeals 
to  those  tutors  who  tflke  students  to  the 
Matriculati'.n  and  Intermediate  Science 
stages. 

It  also  appeals  to  students  who  are 
largely  left  to  their  own  initiative  to  acquire 
an  efenientary  knowledge  of  chemistry. 
Tliis  may  be  due  in  some  measure  to  the 
fact  that  the  author's  aim  has  been  to  in- 
clude deseriptifvMs  of  as  many  experiments 
as  is  consistent  with  the  correct  prcsenta- 
ti<Mi  of  the  theoretical  matter. 

It  may  be  urj^M-d  that  the  time  has  come 
for  such  a  volume  to  be  entirely  re- written, 
but  this  does  not  necessarily  apply  to  such 
a  subject  as  elementary  inorganic  chemis- 
try, especially  if  the  important  new  de- 
velopments are  indicated. 

This  text-book  will  doubtless  continue  to 
be  used  in  many  schools  and  other  insti- 
tutes by  those  students  for  whom  it  is 
intnde^.  J.G.F.D. 

We  have  received  from  Messrs.  Adam 
Hilger,  Ltd.,  75a,  Camden  Road.  London, 
X.W.I,  a  copy  of  the  second  edition  of 
their 

Optical  Mcthoch    in    Control    and    Re- 
search Laboratories,  by  J.  N.  Goldsmith, 


96 


THE  CHEMICAL  NEWS. 


FEBRUARY  9,  1923. 


Ph.D.,  M.Sc,  F.I.C;    S.  Judd  Lewis, 
D.Sc,  F.I.C.,  Ph.C;    and  F.  Twyman, 
F.Inst. P.  Vol.  I.,  pp.  56  +  IV.  +  plates. 
This  volume,  which  costs  Is.  6d.,  or  Is. 
8d.  post  free,  deals  with  Sipeotrum  Analy- 
sis,     Absorption    Spectra,      Refrncjtometry, 
and  Polarimetry. 

In  the  preface  it  is  rightly  pointed  out 
that  there  is  a  tendency  to  lose  sight  of 
the  deeper  significiince  of  physical  proper- 
ties when  they  are  merely  used  for  identifi- 
cation or  other  technical  purposes.  This 
tendency  should  be  guarded  against,  and 
this  has  certainly  been  the  policy  of  Messrs. 
Hilger,  who  have,  from  time  to  time,  pub- 
lished valuable  information  concerning 
th  r  instruments  and  the  physico-chemical 
applications  for  which  these  may  be  em- 
ployed. 

In  the  present  pamphlet,  Seotion  I.  deals 
with  Spectroscopy  and  analysis  by  Emis- 
sion Spectra.  The  use  of  spectrum  analy- 
sis has  been  very  considerably  extended 
during  the  last  decade.  Recent  applica- 
tions are  very  numerous,  as  is  indicated  by 
the  references  quoted.  Section  II.  gives 
an  account  of  Absorption  Spectra  and  Spec- 
tre-photometry. Section  III.  is  devoted  to 
fhe  Refractometer  and  its  uses;  and  finally 
Section  IV.  deals  with  the  Polarimeter. 
These  sections  are  all  followed  by  lists  of 
references  to  the  important  and  cognate 
publications  on  these  subjects. 

The  pamphlet  is  thus  seen  to  be  of  con- 
siderable value  to  the  users  of  these  physi- 
cal instruments. 

The  Association  of  British  Chemical 
Manufacturers,  166.  Piccadilly,  W.l, 
have  sent  us  an  Official  Directory  of 
Members  icith  a  Classified  list  of  their 
Manufactures. 

This  directory  should  assist  buyers  of 
chemical  products  at  home,  in  the  colonies, 
and  abroad.  There  are  keys  to  the  index  in 
French,  Spanish,  Italian,  Portuguese  and 
German,  which  considerably  enhance  the 
utility  of  this  directory,  copies  of  which 
may  be  purchased  at  the  offices  of  the  Asso- 
ciation, price  10s.  6d. 


BOOKS  RECEIVED. 

Seifen  IJnd  Eiweissstoffe,  von  Martin  H. 
Fischer  unter  Mitarbeit  von  George  D.  Mc- 
Lauglin  und  Marian  0.  Hooker.  Autori- 
sierte  Deutsche  Ausgabe  von  Dr.  Johann 
MuTALA.  Pp.  188.  1922.  Dresden  and 
Leipzig:  Verlag  von  Theodor  Steinkopff. 
4s.  3d. 

A  Text -Book  of  Inorganic  Chemistry,  by 


G.  S.  Newth,  F.I.C,  F.C.S.  Pp.  XIU.  + 
772.  New  and  enlarged  edition,  1923. 
Mesisrs.  Longmans,  Green  &  Co.,  39,  Pater- 
noster Row,  E.C.4.     8s. 

Outlines  of  Theoretical  Chemistry,  by 
Frederick  H.  Getman,  Ph.D.  Pp.  VIII. 
+  625.  Third  Edition,  1922.  Messrs. 
Chapman  Sc  Hall,  11,  Henrietta  Street, 
Covent  Garden,  W.C.2.     18s.  6d.  net. 

Qmstions  and  Probhms  in  Chemistry, 
by  Floyd  L.  Darrow.  Pp.  VII.  +  177. 
1923.  Me=srs.  G.  Bell  &  Sons,  Ltd.,  York 
House,  Portugal  Street,  W.C.2.  3s.  6d. 
net. 


This  list  is  si>ecially  compiled  for  the  Chemical 
News,  by  Messrs.  Bayner  &  Co..  Rogistered  Patent 
Asrents,  of  5,  Chancery  Lane,  Ijondon,  from  whom 
all  information  relating  to  Patents,  Trade 
Marks,  and  Designs,  can  he  obtained  gratuitously. 

Abstract  Published  this   Week. 

Lead  Sulphate.— Vatent  No.  180160.— The  inven- 
tion is  related  to  a  process  described  in  Si>ecifi- 
cation  5299/15,  granted  to  Messrs.  J.  Gitsham  and 
TT.  R.  Evershed,  of  175.  George  St.,  Launceston, 
Tasmania,  wherein  sulphate,  sulphite,  and  oxide 
of  lead  iire  obtained  directly  from  the  native  sul- 
phide by  volatilising  the  latter  in  an  electric 
furnace.'  The  present  invention  aims  at  the  pro- 
duction of  a  product  free  from  sulphide,  oxide, 
or  unchanged  sulphide.  The.  finely  crushed  ore, 
which  may  have  been  previously  concentrated, 
falls  in  regulated  quantities  from  a  feeding  ap- 
paratus through  the  guide  tubes  on  to  the  elec- 
trodes of  the  furnace.  These  are  arranged  in 
pairs,  and  are  placed  about  nine  inches  above 
the  floor  of  the  furnace.  About  five  feet  al>ove 
the  arcs  is  an  atmospheric  intake  communicating 
through  a  bifurcated  flue  with  a  fan  chamber.  A 
fan  induces  a  current  of  air  over  the  furnace 
shaft,  and  the  fan  chambers  deliver  into  spray 
boxes,  wherein  the  fumes  are  subjected  to  the 
action  of  water  sprays  delivered  from  a  per- 
forated pipe.  A  chimney  assists  the  flow  of  air 
and  fumes  through  the  apparatus.  The  water 
containing  the  reaction  products  passes  through 
launders  into  vats,  where  it  may  be  warmed  and 
agitated  bv  steam  pipes  placed  on  the  floor  of 
each  vat.  The  finelv  cru-^hed  sulphide  falls  on  to 
the  arcs,  and  is  at  once  volatilised.  The  vapours 
rise  up  the  furnace  shaft  into  the  current  of  air 
passing  through  the  top  of  the  furnace,  and  are 
then  oxidised.  The  reaction  products,  having 
been  delivered  into  the  vats,  they  are  agitated, 
and  free  acid  may  be  added  if  nec<>ssary,  to  con- 
vert any  sulphites  or  oxides  present  into  sul- 
phates. The  agitation  serves  to  float  any  sul- 
•phide  that  Wav  have  escaped  volatilisation.  This 
is  skimmed  off.  dried,  and  retreat'^d.  The  re- 
maining liquor  is  neutralised  with  lime,  and  the 
sulphates  finally  allowed  to  settle,  decanted,  and 
dried  for  use  as  a  pigment. 

Messrs.  Rayn«r  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  ofiicial  price  of  le.  each. 


FEBRUARY  16,  1923. 


THE   CHEMICAL   NEWS. 


97 


THE  CHEMICAL  NEWS. 

VOL.   CXXVI.     No.   3279. 


PASTEUR. 

On  Friday,  February  2.  a  lecture  was 
delivered,  in  French,  under  the  auspices  of 
the  Alliance  Franpaise,  by  Doctor  Pasteur 
Vallery-Radot,  Mddecin  des  Hqpitaux  de 
Paris,  in  the  rooms  of  the  Royal  Society, 
Burlington  House.  The  Chairman  was  Sir 
Charles  Sherrington,  President  of  the 
Royal  Society. 

The  lecturer  was  the  grandson  of  the  great 
scientist,  and  had  lived  with  him  in  his 
youth ;  he  stated  that  auicmg  all  the 
homages  paid  to  him  on  the  occasion  of  the 
hundredth  anniversary  of  his  birth,  none 
would  be  dearer  to  Pasteur  than  that  Eng- 
land is  paying  him  this  month,  because  it 
is  the  land  of  Jcnner  and  Lister,  and  be- 
cause here  he  found  his  warmest  partisans 
and  some  of  his  greatest  friends. 

Before  Pasteur,  medicine  knew  nothing 
of  the  cause  of  virulent  illnesses;  surgeons 
dared  no  longer  operate,  infection  was  the 
fear  (  f  maternity  hospitals,  the  industries 
baaed  on  fermentation  were  powerless, 
herds  were  dying  fast.  In  40  years,  Pas- 
teur'.«.  genius  changed  all. 

At  22  he  already  ranked  as  a  great  scien- 
tist, and  from  his  study  of  crystals  he  was 
led  to  study  fermentation,  and  whence  he 
touched  on  the  question  of  the  "  spon- 
taneous generation  of  life." 

He  was  a  man  who  liked  to  obtain  re- 
sults, and  he  showed  at  once  how  the 
various  industries  could  benefit  bj'  his 
studies  on  fermentation ;  he  thus  gave  prac- 
tieal  help  to  the  wine,  beer,  dairy,  vinegar, 
and  bread  industries;  in  a  word,  all  that 
touches  the  necessities  of  life  benefited 
through  his  work. 

In  1865  he  began  the  study  of  the  plague 
which  was  ruining  the  silk  industry,  and 
succeeded  in  discovering  the  microbe 
which  killed  the  silkworms.  He  then 
turned  to  help  medicine  and  surgery.  Tn 
1877  he  studied  that  disease,  anthrax, 
which  was  killing  cattle  in  such  a  quan- 
tity at  this  time;  then  fowl  pestilence,  or 
chiqken  cholera.  He  was  dominated  by 
the  idea  of  saving  humanity  from  epidemic, 
and  was  led  to  the  discovery  of  vaccination 
by  experiments  carefully  done.  Microbes 
were  thus  transformed  from  an  instrument 
of  death  into  an  instrument  of  preservation. 


Pasteur  studied  rabies,  and  had  there  to 
fight  hard  against  opposers  who  calle<i  him 
a  murderer  on  account  of  his  experiments 
on  animals. 

The  work  of  Pasteur  is,  by  its  logical 
linking  and  it«  incalculable  consequences, 
one  of  the  most  wonderful  productions  of 
man's  genius;  he  had  an  extraordinary 
imagination,  but  he  tempered  it  by  the 
most  strict  experimentation.  This  is  parti- 
cularly exemplified  by  his  researches  upon 
disymmetry. 

But  if  Pasteur  was  great  by  the  mind,  he 
was  as  great  by  the  heart.  Modesty  was 
his  great  characteristic.  To  his  father  and 
mother  he  gave  thanks  for  what  life  had 
given  him.  His  work  and  his  home  life 
were  closely  linked  because  Madame  Pas- 
teur was  his  help  in  every  moment. 

He  closely  bound  together  the  love  of  his 
country  to  his  love  for  humanity.  He  often 
said  that  if  Science  had  no  country,  the 
scientist  should  have  one.  His  ideal  was 
to  see  humanity  lead  to  peace  by  the  aid  of 
science. 

His  grandson,  a  medical  man  by  profes- 
sion, is  also  a  distinguished  biologist;  he 
has  given  special  attention  to  the  study  of 
hypersensitiveness  in  asthmas  urticairc, 
and  its  gradual  or  sudden  cure  by  the  swal- 
lowing before  meals  of  a  certain  dose  of 
peptone  in  tablets.  He  is  also  very  deeply 
int«>rested  by  the  study  of  kidney  troubles. 

Mr.  A.  Chaston  Chapman,  President  of 
the  Institute  of  Chemistry,  proposed  the 
vote  of  thanks,  and  expressed  the  opinion 
that  the  thanks  of  the  audience  were  d>ie 
to  the  lecturer  for  his  clear  exposition  of 
the  aohievements  of  his  grandfather.  As  a 
chemist,  be  was  specially  interested  in 
Pasteur's  chemical  achievements,  by  which 
he  commenced  his  illustrious  career. 

The  vote  was  R<^oonded  by  Prof.  Martin, 
and  was  carried  with  acclamation. 


THE  RARE  EARTHS  AND  THEIR 

METALS. 

II. — Modified  Methods  of   Separation. 

Bo  John  Missenden,  B.Sc. 

{Coniiniird  from   Page   55.) 

(a)  Apart  from  periodic  classification, 
which  may  only  he  considered  for  the  evolu- 
tion of  new  lines  of  research,  the  rare 
earth  metals  may,  for  all  practical  pur- 
poses, be  divided  into  two  groups : 


98 


THE    CHEMICAL    NEWS. 


FEBRUARY  16,  1923. 


(a)  The  cerium  group:   Ce,  La,  Pr,    Nd, 
(Di),  Dip,  Gd,  Sm,  etc.; 

(b)  The  yttrium  group:    Y,  Yb,   Sc,  Lu, 
Ho,  Er,  Tr,  Tm,  etc. 

The  division  of  the  metals  depends  upon 
the  solubility  in  a  saturated  solution  of 
potassium  sulphate  of  the  double  potassium 
salt  having  the  general  formula,  R2(S0.,)3. 
SKjSOj,  group  (a)  being  precipitated. 

(b)  The  main  method  of  effecting  a 
separation — specifically,  in  the  case  of 
splitting  up  a  complex  earth — is  by  the 
fractional  precipitation  with  ammonia.  The 
process,  while  standardised  more  or  less, 
admits  of  some  variation,  and  discrimina- 
tion has  been  difficult.  In  simple  analysis 
(i.e.,  where  an  unknown  earth  ha-s  to  be 
examined)  the  elimination  of  a  certain 
amount  of  tedium  seems  barely  possible. 
Where,  however,  a  known  earth  is  applied 
to  the  extraction  of  a  specified  oxide,  by  a 
careful  examination  of  these  variations,  a 
really  convenient  process  has  been  found, 
and  may  serve  for  general  adoption  in  the 
laboratory.  It  is  not  put  forward  as  a 
suitable  proces-s  for  separations  on  a  con- 
siderable scale,  however,  for  two  reasons : 
firstly,  ammonium  salts  are  split  up  by 
ipraseodymia;  and,  seccmdly,  the  hydroxides 
are  difficult  to  isolate. 

(c)  The  fractionation  referred  to  is  based 
on  Dro?sbach's  explanation  (Ber.  Deut. 
Chem.  Ges.,  1902,  XXXV.,  2826).  He 
boiled  the  specimen  earth  in  an  ammonium 
salt,  rendering  soluble  the  more  basic 
metals  by  displacing  the  ammonia.  Pre- 
cipitation, stage  by  stage,  then  takes  place 
from  the  complex  solution. 

Where  the  earth  contains  large  quanti- 
ties of  ntrates  in  natural  form — this  is  the 
rule  rather  than  the  exception — it  is  as  well 
to  precipitate  slowlv  by  the  usual  method 
of  ammonium-fractionisation.  When  the 
bulk  of  the  natural  nitrates  have  been 
dealt  with,  resort  should  be  made  to  the 
ammonium-salt  method  of  Drosisbach.  The 
most  basic  metals,  i.e.,  lanthanum,  neody- 
mium,  praseodymium,  gadolinium,  and 
samarium,  are  left  in  the  filtrate  after  the 
first  process. 

The  continuation  of  the  separation  is 
engineered  by  repeating  the  fractionisation, 
this  tie  dissolving  the  hydrides  in  dilute 
hydrochloric  acid  (not  concentrated,  as  has 
been  described  in  another  work)  of  0.125 
strength,  on  excess  of  analine  being  added. 
Ammonia  is  then  admitted  to  the  solution 
dron  by  drop,  and  a  quite  accurate  frac- 
tionisation of  those  earths  which  are  least 
soluble  in  analine  hydrochloride  results. 


{d)  The  double  ammonium  nitrates  of 
the  R(N03)3.2NH,NO,.4H30  order  were 
submitted  to  a  crystal lisation  process  by 
Welsbach,  who  produced  the  two  compo- 
nents of  didymium  by  this  process.  The 
most  soluble  fractions  were  found  to  be  the 
metals  of  the  yttrium  group.  Drossbach 
[Ber.  Deut.  Chem.  Ges.,  1902,  XXXVIII., 
2823)  discovered  a  n.ethod  whereby  praseo- 
dymium and  neodyniium  ccmld  be  more 
speedily  obtained,  and  it  is  a  variation  of 
the  above.  The  difficulty  of  effecting  a 
separation  between  lanthanum  and  didy- 
mium was  overcome  by  Denis  and  Tjomon 
(Jotim.  Amer.  Chem.  Soc,  1915,  XXXVII.. 
131),  who  resorted  to  fractional  electrolysis. 
The  separation  of  other  earths  will  be 
found  in  a  table  of  general  reference  at  the 
end  of  this  section. 

(e)  l^unsen  devised  the  original  method 
of  separation  by  nitrate  ignition.  The  prin- 
ciple of  this  process  is  briefly  the  fusion  of 
a  series  of  nitrates  in  complicated  mixture, 
scandium  having  the  lowest  melting  point 
of  the  yttrium  group,  and  yttrium  the 
highest.  More  energetic  applications  of 
heat  cause  decomposition  of  the  nitrates  in 
chemical  mixture  over  the  same  range. 
Undecomposed  matter  is  removed  in  each 
case  by  dissolving  in  water,  and  the  pre- 
cipitate freed  by  filtering. 

(/)  With  regard  to  the  content  of  the 
rare  earths,  Sir  William  Crookes,  following 
a  line  of  study  parallel  to  that  of  Nilson 
and  Kriiss,  arrived  at  a  remarkable  conclu- 
sion. Nilson  and  Kriiss  carefully  examined 
the  absorption  spectra  of  the  metallic  ni- 
trates obtained  from  a  wide  range  of  earthy 
specimens,  and  observed  that  the  intensity 
of  the  absorption  bands  for  different  speci- 
mens was  not  identical.  Crookes,  examin- 
ing the  phosphorescent  spectra,  upheld  this 
quite  feasible  opinion.  The  different  phos- 
phorescent spectra  of  the  two  separate 
basic  fractions  of  yttria  is  a  case  in  point, 
the  two  analyses  each  having  their  own 
characteristics. 

(g)  A  complete  separation,  applicable  to 
many  of  the  rare  earths,  is  described  as 
under.  It  is  a  modification  of  S.  J.  John- 
stone's method  for  the  constitutional  deter- 
mination of  monazite  [Journ.  Soc.  Chem. 
Ind.,  1914,  XXXIII.,  55),  incorporating  in- 
vestigations by  Mosander,  whose  work  in 
obtaining  ceria  is  mentioned  in  I.  (d)  of 
this  treatise. 

The  earth  to  be  examined  is  completely 
dissolved  in  concentrated  sulphuric  acid, 
the  ratio  of  the  acid  to  the  earth  being  as 
3:1,  and  poured  into  200  oc.  (or  even  more) 


I 


FEBRUARY  16,  1923. 


THE   CHEMICAL    NEWS. 


99 


of  distilled  water.  The  precipitate  is  taken 
i+way,  and  the  process  upon  it  repeated  two 
or  three  tinaes,  the  final  washing  taking 
place  tot  several  hours.  The  remaining 
liquid  is  poured  into  500  cc.  of  weak  am- 
monia solution,  and,  after  half  an  hour, 
250  cc.  of  hydrochloric  acid  solutiwi 
(strength  0.1)  is  added  slf,\vly.  12  g.  of 
ammonium  oxalate  (compare  the  wwks  of 
Glaser)  will  commence  precipitation.  Hero 
is  the  main  deviation  from  Johnstone's 
method.  When  precipitation  has  stopped, 
the  residue  should  be  taken  from  the  solu- 
tion, reprecipitated  and  thoroughly  cleansed 
in  distilled  water.  2  more  p.  of  the  oxa- 
late; added,  and  the  next  precipitated  in  a 
like  manner;  and  so  on,  in  2  g.  operations, 
until  precipitation  ceases.  There  will 
prf>hably  be  six  or  seven  grades  of  in- 
solubles.  (In  the  examination  of  pyro- 
chlor  by  this  method,  nine  separate  pre- 
cipitates were  made.  The  first  three  were 
mixed  together  for  the  extraction  of 
thf>rium,  and  the  remainder  put  aside  for 
further  investigation.  Originally.  10  grams 
of  ipyroi'-hlor  were  used,  and  gave  the  re- 
sults found  on  p.  54  of  the  (Item.  Newit, 
Vol.  CXXVI.,  very  nearly.*) 

A  part  of  these  insolubUs  can  be  re- 
dissolved  in  hydrochloric  acid  Tsay  1  g.  <^ 
insoluble  to  85  cc.  of  a  0.1  solution  after 
contentration  treatment),  and  the  whole 
made  up  to  250  cc.  by  the  n<ldition  of  water 
and  sufficient  ammonia  to  neutralise.  8  g. 
of  sociium  thiofiulphate  is  then  added  to 
the  former  liquid  at  h  oiling -point,  the 
whole  being  immediati^lv  c(M>led  to  10*  C 
below  the  point  of  ebullitir»n,  and  allowed 
to  simmer  for  three  days  or  more  (the 
longer  time  causing  the  whole  of  the 
thorium  to  combine  with  the  sulphate,  thus 
eliminating  further  treatment  with  nitric 
acid  afterwards). 

The  filtrate  is  now  heated,  nnd  the  water 
distilled  off.  The  residue  is  dissolved  in  20 
CO.  of  hydrochloric  acid,  mnde  up  again  to 
250  cc.,  and  oxalic  precipitation  again 
takes  place  to  free  the  sulphate.  This  pre- 
cipitate  is  treated  precisely  as  explained  by 
Johnstone  from  here  to  the  end  of  the 
yttrium-earth  extractions. 

*  PijrochloT  was  eTamined  after  ike  com- 
pilation of  the  table  vicntioncd,  and  a  note 
.us  to  its  composition  will  he  added  at    the 
''tnd  of  this  section.     A  brief  description  of 
llanthaino-tanialUe     ivill       appear     shorfly. 
[Rc.f.:  I.  (h).] 


In  the  division  of  the  cerium-earths  (i.e., 
ceria,  lanthana,  and  didymia,  etc.),  the 
processes  of  Mosander  aie  closely  followed. 
Greater  care  is,  however,  exercised,  in  pre- 
cipitatirm  and  purification.  Lanthana  and 
didymia  are  also  precipitated  as  oxalates, 
and  treated  with  nitric  acid.  The  melting 
point  of  mixed  lanthanum  and  didymium 
nitrate  is  about  i'2H°  C.  when  the  mixture 
is  in  equal  proporticMis.  The  molten  liquid 
resolidifies  in  crystalline  form,  which,  on 
boiling  with  10  parts  of  water,  throws  down 
the  basic  salt.  The  soluble  portion  is  frac- 
tionally separated,  as  has  been  previously 
described. 

(h)  The  metal  oeltium  has  an  oxide 
whose  basic  strength  is  between  scandia 
and  butecia,  which  is  not  as  basic  as 
neovtterbia  (Bhunenfeld  and  Urbain, 
Compt.  Ren4i.,  1914.  CLIX.,  828). 

( I)  References  :  — 
CVItium:    Urbain:   (Comptes  Rend.,    1911, 

CLII.,  Ibl). 
Cerium :    Schtitzenberger    (Compt.     Rend., 

1895,  CXX..  008). 

Brauner   (Chcm.     News,     1896,     LXXI., 

288). 
X  nlenHkidld  (Pogg.  Ann.,  1861.  CXIV., 
612). 
Docipitini :    Delafontaine    (Compt.     Rend., 

1878,  LXXXVIII..  578). 
Dysprosium:   CUve    (Joum.    Chcm.    Soc, 

1896.  i.,  476). 

Erbium  :  Lecoq  de  Boisbaudran  (see  Dana). 
Lecoq  de  Boisbaudran     (Compt.    Rend., 

LXXXVIII..  328). 
Ga^lolininm  :  Mari<,Miac  (/Inn.  Chim.  Phys., 

1880  [V.].  XX.,  686). 
Holmium  :  S.  I.  Levy  {The  Rare  Earths). 
Lanthanum :   Muthmann  and    Rolig    (Ber. 

Deut,    Chem.      Qes.,     1898,      XXXI., 

1718). 
Drosebach  (ibid.,  1902.  XXXV..  2826J. 
Luteoium:    Urbain    (Compt,   Rend.,    1907, 

CXLV.,  769). 
Welsbach     (Monkish.       Chem.,       1918, 

XXXIV.,  1713). 
Neodymium :     Baskerville    and     Stevenson 

(Journ.     Amcr.      Chem.     Soc,     1904, 

XXVL.  54). 
Praseodymium  :  Schc^ele  (Ber.  Deut.  Chem. 

Ges.,  1899,  XXXII.,  409). 
Mever     (Zeitsch.    anorg.     Chem.,     1904, 

3^LI.,  94). 
Scandium:  Nilson  (Ber.  Deut.  Chem.  Qes-, 

1879,  XII..  554). 
(ibid.,  1880,  XII 1.,  1439). 


100 


THE   CHEMICAL    NEWS. 


FEBRUARY  16.  1923. 


Samarium:    Boisbaudran     {Compt.   Rend., 

LXXXVIII.,   323). 
Terbium:    Kriiss    {Zeitsch.   arwrg.     Chem., 

1893,  IV.,  26). 
Thulium-      Welsbach     {Monatsh.     Chem., 

1913,   XXXIV.,  1713). 
Ytterbium:  Marignac  {Compt.  Kenrf.,  !«/», 

LXXXVIL,  578).  „     ,        ,oqo 

Yttrium:      Cleve     {Compt.     Rend.,     18«^, 

XCV.,  1125). 

{j)  Note  on  the  Composition!  of  PyrocUor. 

The  '^ipecimen  was  obtained  from  Impila- 
ko  in  Finland,  and  bore  much  resemblance 
to  that  examined  by  Rammelsherg.  Un- 
fortunately, the  total  of  the  constituents 
only  reached  98.72.  The  specimen  con- 
tained 55  per  cent,  of  niobium  pentoxide, 
10  52  per  cent,  of  titanium  dioxide,  8.1  per 
cent,  of  thorium  dioxide,  6.37  per  cent,  ol 
cerium  sesquioxide.  The  amount  of 
thorium  dioxide  noted  on  the  table  (p.  o4) 
for  this  earth  is  10.98  per  cent.,  not  10.47. 

(To  he  continued.) 


THE   ACTION  OF  POTASSIUM 
CYANir>E     ON  MONOCHEORAMINB. 

By  W.  F.  Short,  M.Sc,  A.I.C. 
The  cyanamide  required  for  an  investi- 
gation of  the  interaction  of  its  hydrochlor- 
ide with  phenolic  substances  (Short  and 
Smith,  T.  1922,  CXXL,  1803)  was  not 
available  from  the  usual  sources.  The  in- 
teraction between  potassmm  oyanide  and 
monochloramine  was  examined  m  the  hope 
that  cyanamide  would  be  produced  accord- 
ing to  the  equation  : 

KCN  +  NH.Cl  =  KCl  +  NH3:0N. 
Ra^chiff    (Vevh.-  Ges.     deut.     Naturforsch. 
Aetze    1907,  II.,  120)    states    that    mono- 
chloramine reacts    with  potassium  cyamde 
in   aqueous  solution    to  produce     cyanogen 

chloride  and  -«^«^<>^i^^,b"V  I Y VTll'^^Tol 
Cannipzaro  (Ann.  1851.  ^XXVIII.,  229) 
have  shown  that  these  substances  react  to 
produce  cyanamide,  it  was  anticipated  that 
bv  employing  suitable  experimental  condi- 
tions cyanamide  would  be  the  mam  pro- 
duct. Instead  of  the  anticipated  result, 
the  interaction  led  to  the  formation  of  di- 
cyanimide,  a  new  substance  recently  de- 
s,cribed  by  Franklin  (J.  Amer.  Chem.  Soc 
1922  XLIV.,  497),  who  prepared  it  by 
fusing  sodamide  with  melon  or  by  i^iting 
eodimn  cyanide  with  mercuric  cyamde. 


The  interaction  of  potassium  cyanide  and 
monochloramine  takes  place  according  to 
the  following  equation : 
2KCN+2NH,C1  =  2KC1+NH3+NH(CN),. 
It  seems  probable  that  the  dicyammide  is 
produced  by  the  interaction  of  cyanogen 
chloride  with  cyanamide,  these  substances 
being  first  produced  according  to  the 
equations:  ^         ^^^^    ^, 

^  HON  +  NH3CI  =  NH3  +  ON^Cl 
KCN  +  NH.Cl  =  KCl  +  MH,-CN. 

Experimental. 

A  solution  of  sodium  hypochlorite  con- 
taining approximately  one  gram  molecule 
per  litre  was  prepared  by  passing  chlorine 
into  an  ice-cold  solution  of  slightly  more 
than  two  gram,  molecules  of  caustic  soda 
in  a  litre.  To  this  solution,  one  equivalent 
of  ammonia  in  semi-normal  solution  was 
slowly  added  by  means  of  a  capillary  tube. 
One  equivalent  of  potassium  cyanide  in 
concentrated  solution  was  then  added  m  a 
similar  manner.  The  admixture  of  these 
reagents  was  carried  out  in  a  tiask 
immersed  in  a  freezing-mixture  the  tem- 
perature being  maintained  below  &  ^. 
After  standing  for  five  hours^  m  an  ice- 
chest,  ammonia  was  added  m  sufhcient 
quantity  to  retain  in  solution  the  silver 
cyanide  produced  on  the  subsequent  addi- 
lion  of  silver  nitrate.  A  precipitate  of 
glistening  white  crystals  quite  distinct  from 
silver  cyanide  in  appearance  was  produced 
These  crystals  were  collected,  washed  with 
a  little  water,  and  thoroughly  dried  m  air. 
They  darkened  superficially  on  exposure  to 
sunlight.  Strong  ignition  produced  a  mix- 
ture of  silver  and  silver  chloride. 

0.2015  gram  left  a  residue  of  OloJ,^ 
grams  on  ignition.->(AgN(GN), :  AgCl^ 
Ag  +  AgCl  requires  0.2015  gram ->  0.1596 
o-iam)  The  residue,  after  treatment  with 
nitric  and  hydrochloric  acids  weighed 
0.1816  gram,  whence  Ag  =  67.82  per  cent 
(AffN(CN), -AgCl  requires  Ag  =  bb.Ui  per 
cent )  A  determination  of  the  nitrogen 
content  by  Kjeldahl's  method  gave  N  = 
13.0  per  cent.  (AgN(CN),  •  AgCl  requires 
N   =   13.25  per  cent.). 

Hydrogen  chloride  in  ether    deconnposed 
this  double  compound,  thus: 
2HCl.AgN(CN)..AgCl^=^^^^^^.^^^_ 

It  was  found  that  dicyanimide  hydrochlor- 
ide could  be  titrated  with  potassium  hy- 
droxide using  phenolphthalem  as  indicator. 

(^^^^^^-^^^^dJjfNK^KCl.HA 


FEBRUAKY  16,  1923. 


THE   CHEMICAL   NEWS. 


101 


Biuret  was  produced  by  warming  the  hy- 
drochloride with  water.  Cold  hydrochloric 
acid  oonvert'Cd  the  silver  compound  into 
cyanocarbamide,  NHj :  CO  •  NH  •  CN,  char- 
acterised by  its  copper  salt.  By  treating 
the  silver  compound  in  aqueous  susipension 
with  hydrogen  sulphide,  removing  the  sil- 
ver sulphide  and  concentrating  the  solution 
in  vacuo,  a  jelly-like  mass  separated  out. 
This  appeared  to  consist  for  the  greater 
part  of  an  insoluble  amorphous  polymer  of 
dicyanimide.  On  neutralising  a  dilute 
aqueous  solution  of  dicyanimide  with  caus- 
tic soda  and  adding  silver  nitrate,  a  bulky 
white  precipitate  of  the  true  silver  deriva- 
tive, AgN(CN)j,  is  obtained. 

I  have  tf>  thank  Mr.  R.  Gardner,  B.Sc, 
for  assistance  in  carrying  out  the  prelimi- 
nary experimental  work. 

Chemical  Laboratories, 
University   College, 
Auckland,  N.Z. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


HIE  ROYAL  SOCIETY. 

Thuksday,  February  1,  1923,  at  4.80  p.m. 
The  following  papers  were  read:  — 

Prof.  O.  W.  Richardson,  F.R.S.  The 
Magnitude  of  the  Qyromagtictic  Ratio. 

This  note  discusses  various  possibilities 
as  to  why  this  ratio  has  the  value  m/e  in- 
stead of  2  m/e,  the  value  calculated  on  the 
turning  electron  orbit  theory  of  ndagnetism 
of  the  Lnngevin  type,  and  suggests  that  the 
discrepancy  is  due  to  the  rotation  of  the 
atomic  nucleus.  In  the  case  of  iron  it  ap- 
pears that  the  effective  electron  orbits 
possess  altogether  two  quanta  of  angular 
momentum  per  atom  and  the  nucleus  a 
single  quantum  of  angular  momentum  on 
this  view. 

Sir  Richard  Paget,  Bart.  The  Pro- 
duct of  Artificial  Vowel  Sounds-  Commu- 
nicated by  Sir  William  Bragg,  F.R.S. 

Experiments  were  made  with  plasticenc 
resonators  to  imitate  resonances  heard  by 
the  writer  in  his  own  voice  when  breathing 
various  English  sounds.  The  first  models 
were  made  in  rough  imitation  of  the  oral 
cavity,  and  were  found  to  give  two  double 
resonances. 

Experiments  were  made  with  these 
models  to  ascertain  the  effects    of  various 


alterations  of  form  on  the  natural  reson- 
ances of  the  model  when  tapped  or  blown 
through.  The  models  were  then  tuned  by 
appropriate  alterations  of  form  to  give 
resonances  similar  to  those  heard  in  b 
(earth)  and  a  (calm)  in  the  writer's  voice. 
They  then  gave  recognisable  breathed  vowel 
sounds  when  blown  through  a  small  orifice 
at  the  back. 

An  artificial  larynx  was  made  by  means 
of  a  rubber  strip  laid  edge-wise  across  a 
flattened  tube,  and,  when  blown  through 
this  larynx,  the  models  gave  recognisable 
voiced  vowels. 

Further  experiments  indicated  that  the 
oral  cavity  behaves  in  every  case  as  two 
Helmholtz  resonators  in  series,  and  the  re- 
maining vowel  sounds  were  reproduced  by 
forming  two  separate  resonators  joined  to- 
gether in  series,  and  made  of  such  capacity 
suid  size  of  orifices  as  to  allow  for  mutual 
reacti(m  of  resonators  on  their  respective 
res(Miant  pitch. 

In  one  case  the  vowel  sound  u  (who)  was 
apparently  produced  by  a  single  resonator 
when  blown  by  mouth  through  an  artificial 
larynx.  It  was  found  that  the  vowel  sound 
was  due  to  the  fact  that  the  mouth  cavity 
acted  as  a  second  resonator,  i.e.,  that 
vowels  may  be  produced  by  two  resonators 
in  series  with  a  larynx  between  them.  Cer- 
tain vowel  sounds  in  the  mouth  can  be 
changed  into  others  by  adding  a  resonant 
capacity  on  to  the  mouth. 

With  a  single  cylindrical  resonator,  and 
with  an  ovoid  resonator,  it  was  foimd  that 
when  blown  throuf,'h  by  means  of  a  small 
orifice  at  the  back  two  or  more  resonances 
were  given,  some  bore  correct  pitch  rela- 
tion to  one  another  to  give  certain  vowel 
sounds,  i.e.,  a  single  tubular  resonator  may 
act  as  two  resonators  in  series. 

Two  resonators  in  parallel,  blown  by 
means  of  a  single  lurynx  with  a  bifurcated 
passage,  produced  vowel  sounds  indistin- 
guishable from  resonators  in  series. 

F.  Simeon.  The  Carbon  Arc  Spectrum  in 
the  Extreme  Ultra-Violet.  Communicated 
by  Prof.  A.  W.  Porter,  F.R.S. 

The  results  of  this  investigation  may  be 
stated  as  follows:  — 

(1)  The  arc-spectrum  of  carbon  has  been 
shown  to  give  lines  in  the  Lyman  region  at 
1194,  945,  858,  687,  661,  640,  599  and  595, 
whioh  have  not  been  previously  observed, 
and  which  correspond  with  prominent  lines 
in  the  "hot-spark"  spectrum  studied  by 
Mi  I  Ilk  an. 


102 


THE   CHEMICAL   NEWS. 


FEBRUAEY  16,  1923. 


(2)  Grroups  of  lines  have  been  found  at 
1657,  1560,  1335,  1329,  1260,  1194,  1175, 
1036  and  651,  of  which  those  at  1329,  1260, 
1194,  1036  and  651  do  not  seem  to  have 
been  observed  by  any  other  worker,  and 
that  at  1657  has  not  been  completely  re- 
solved heretofore. 

(3)  A  new  determination  o  fwave-length 
has  been  made  of  the  prominent  lines  in 
the  carbon  arc-spectrum. 

Papers  Read  in  Title  Only. 

Prof.  J.  Joly,  F.R.S.  Pleochroic 
Haloes  of  Various  Geotogical  Ages. 

Prof.  H.  A.  Wilson,  F.R.S.  The  Motion 
of  Electrons  in  Gases. 

H.  Hartridge.  The  Coincidence  Method 
for  the  Wave-length  Measurement  of  Ab- 
sorption Bands.  Communicated  by  Prof. 
J.  N.  Langley,  F.R.S. 

(1)  Measurements  of  the  absorption 
bands  of  pigments  by  means  of  the  ordinary 
spectroscope  are  found  to  be  inaccurate 
because  of  the  breadth  of  the  bands  and 
the  indefiniteness  of  their  margins. 

(2)  The  adjustment  of  two  similar  ab- 
sorption bands  into  coincidence  is  found  to 
be  effected  with  considerable  accuracy.  If 
then  a  spectroscope  is  designed  in  which 
two  spectra  are  seen  side  by  side  on  looking 
down  the  eyepiece,  but  reversed  in  direction 
with  one  another,  the  mea?iu'enienb  of  the 
mean  wave-length  of  the  absorption  bands 
can  be  accurately  carried  out. 

(3)  The  optical  construction  of  the  instru- 
ment is  described  in  Section  3. 

(4)  The  method  of  calibrating  the  micro- 
meters of  the  spectroscope  are  described, 
and  experimental  values  are  given  to  show 
the  accuracy  obtained. 

(5)  The  method  for  the  quantitative  esti- 
mation of  pi^^ents  by  the  wave-length 
measurement  of  their  absorption  bands  is 
described.  The  estimation  is  shown  to  de- 
pend on  the  movement  of  the  bands  which 
occurs  when  the  concentration  of  one  pig- 
ment changes. 

(6)  An  example  of  the  method  is  given, 
namely,  the  estimation  of  the  percentage 
saturation  of  blood  with  CO  gas  by  the 
measurement  of  the  wave-length  of  the 
a- absorption  band.  The  accuracy  of 
measurement  is  found  to  be  approximately 
0.7  A.U. 

(7)  Sources  of  error  in  the  method  are 
considered,  and  probable  accuracy  of 
measurement  discussed.  The  probable 
error  in  setting  two  absorption  bands  inEo 
coincidence  is  found  but  little  greater  than 
that  of  setting  two    sharp  black  lines  into 


coincidence,  or  of  making  one  line  bisect 
the  area  between  two  others. 

A.  Berry  and  Lorna  M.  Swain.  On  the 
Steady  Motion  of  a  Cylinder  through  In- 
finite Viscous  Fluid.  Communicated  by  H. 
W.   Richmond,  F.R.S. 

This  paper  offers  another  partial  solution 
of  the  problem  of  the  motion  produced  by 
a  cylinder,  moving  with  uniform  velocity 
through  infinite  viscous  fluid.  The  so- 
called  "inertia"  terms  are  neglected  and  a 
solution  is  found  which  satisfies  the  bound- 
ary condition®  on  the  cylinder  and  makes 
the  velocity  only  logarithmically  infinite  in 
one  direction  at  infinity.  The  relative 
velocity  increases  comparatively  slowly 
with  the  distance  from  the  cylinder  and  the 
solution  may  be  expected  to  give  a  fairly 
good  approximation  to  the  motion  at  small 
distances  from  the  cylinder. 

In  the  first  place  the  problem  is  solved 
by  treating  the  elliptic  cylinder  as  a  limit- 
ing case  of  the  ellipsoid.  The  solution, 
which  in  the  case  of  the  ellipsoid  satisfies 
the  boundary  conditions  and  those  at  infin- 
ity, leads  to  a  solution  for  the  elliptic  cylin- 
der, which  has  the  velocity  at  infinity 
logarithmically  infinite  in  one  direction. 
The  plane  laminse,  both  along  and  perpen- 
dicular to  the  stream,  are  considered  as 
limiting  cases,  and  further,  the  motion 
due  to  the  circular  cylinder  is  deduced  as  a 
special  case  of  the  elliptic  cylinder. 

Secondly,  the  solutions  for  the  elliptic 
and  circular  cylinders  are  obtained  directly 
from  the  equations  of  motion. 

Finally,  stream-lines,  curves  showing 
variation  of  velocity  along  stream-lines  and 
curves  of  constant  velocity  are  drawn  for 
three  limiting  cases. 

Some  numerical  results  are  given  to  show 
how  slowly  velocity  does  increase  with  dis- 
tance from  the  cylinder.  From  these  vA'c 
are  able  to  conclude  that  it  is  probable  that 
the  theory  represents  the  facts  fairly  accu- 
rately for  some  considerable  distance  from 
the  cylinder. 

W.  Jevon.  The  Line  Spectrum,  of  Chlor- 
ine in.  the  Ultra-Violet  {Region  A3354-2070 
A).  Communicated  by  Prof.  H.  C.  Plum- 
mer,  F.R.S. 

(1)  Observations  of  the  spectrum  of  the 
CI  discharge  tube,  which  have  not  hitherto 
extended  lower  than  A  3276  A  (Eder  and 
Valenta)  have  been  continued  as  far  as 
A  2070  A,  by  means  of  10-feet  grating  and 
quartz-prism  spectrographs. 

(2)  Wave-lengths  and  wave-numbers  of 
nearly  200  newly  observed  CI    lines  are  re- 


FEBRUAKY  16,  1923. 


THE  CHEMICAL  NEWS. 


103 


corded,  together  with  the  effects  of  varia- 
tions of  capacity  on  the  intensities  of  more 
than  100. 

(3)  The  constant  differences  (Av)  40.4, 
67.1,  107.5,  found  by  Paulson  in  pairs  and 
triplets  above  X  3276  A  recur  in  a  few  pairs 
below  that  point.  The  significance  of  these 
separations  in  relation  to  the  analysis  of 
the  sipectrum,  however,  appears  doubtful, 
since — 

(o)  There  is  no  apparent  regularity  in  the 
intensities  of  the  lines  involved ;  and 

(b)  No  triplets  having  these  separations 
been  detected  in  the  region  under  in- 
vestigation. 

M.  H.  Evans  and  H.  J.  Gfx)rob.  N«^ 
on  the  Adsorption  of  Bases  by  Solids  and 
the  Thickness  of  the  Adsorbed  Layer. 
Communicated  by  D.  L.  Chapman,  F.R.S. 

The  authors  have  determined  the  amount 
of  carbon  dioxide  adsorbed  by  unit  surface 
of  glass,  at  a  pressure  approximating  to 
one-sixth  of  an  atmoeiphere,  and  their  re- 
Hults  are  in  agreement  with  the  assumption 
that  the  carbon  dioxide  is  condensed  on  the 
surface  of  the  glass  in  a  liquid  layer  hav- 
m^  a  thickness  equal  to  between  five  and 
six  tines  the  diameter  of  the  mcJeculo  of 
the  giis. 

H .  Kinbining  this  result  with  the  pub- 
lished figures  of  Mulfaith  {Ann.  d-  Physik, 
1900,  Vol.  III.,  p.  828)  on  the  relative  ad- 
sorption by  glass  of  the  gases — acetylene, 
nitrous  oxide,  carbon  dioxide,  sulphur  di- 
oxide and  ammonia — they  deduce  that  at 
the  same  pressure  these  gases  are  adsorbed 
by  the  surface  to  such  an  extent  that  if 
they  were  present  as  liquid  layers,  the 
thicknesH  of  the  layers  would  vary  from  (in 
the  cas«,'  of  acetylene)  three,  to  (in  the  case 
of  ammonia)  forty  molecular  diameters. 

A  direct  determination  of  the  degree  of 
a<l&(>rption  of  NH,  made  by  them  furnished 
a  value  which  was  of  the  same  order  as  that 
calculated,  as  above,  from  Miilfarth'a  data. 

The  results  are  in  disa-^ement  with 
Langmuir's  recent  generalisation  that  the 
forces  of  attraction  exerted  by  a  surface  do 
not  extend  to  a  distance  ^^^reater  than  the 
diameter  of  one  molecule. 

Prof.  li.  Bairstow,  F.R.S. .  Miss  B.  M. 
Cave,  and  Miss  E.  D.  Lano.  The  Resist- 
ance of  a  Cylinder  moving  in  a  Viscous 
Fluid. 

The  equations  of  motion  of  a  viscous 
fluid  in  the  approximate  form  proposed  by 
Oseen  have  been  taken  as  a  basis  for  new 
calculations  sn  the  resistance  of  cylinders. 
Calculations  are  given  in  the  paper  for  the 
resistance  of  a  circular  cylinder,  and  for  the 


surface  friction  along  a  plane.  In  the  case 
of  the  circular  cylinder  experimental  infor- 
mation obtained  at  the  N.P.L.  is  wholly 
suitable  ior  the  purposes  of  comparison 
with  the  present  calculations.  A  resistance 
eo-efficient  is  found  which  is  about  30  per 
cent,  greater  than  that  observed  at  the 
limit  of  the  range  of  observation. 

The  calculations  represent  an  extension 
of  the  solution  by  Lamb  from  values  of 
Reynolds'  number,  i.e.,  Vdjv,  which  are 
small  (0.2  approx.)  to  values  which  may  be 
as  great  as  desired;  the  comparison  with 
experiment  is  first  made  with  Ud/v  =  12. 
The  only  approximation,  other  than  per- 
centage accuracy  of  computation,  is  that 
reprewnted  by  Oseen's  form  of  the  equa- 
tions of  moticHi ;  it  is  proposed  to  attempt 
the  calculation  with  the  full  equations  pro- 
posed by  Stokes  in  order  to  account  for  the 
remaining  30  per  cent,  difference. 

Calculations  for  the  plane  show  singu- 
larities at  the  edges,  but  lead  to  a  resist- 
ance which  is  in  rough  agreement  with  ex- 
periment. Exact  comparison  is  not  pos- 
sible because  the  experiments  were  not  car- 
ried out  under  conditions  which  sufficiently 
approach  two-dimensiwial  flow. 

The  analysis  has  been  extended  to  cover 
the  calculation  of  the  resistance  of  a  cylin- 
der of  any  form  for  the  same  approximate 
diffenmtial  equation.  Whereas  the  circular 
cylinder  and  plane  have  been  treated  by 
analytical  metnods,  it  appears  tnat  graphi- 
cal methods  are  required  for  the  more 
general  boundary  form. 

G.  I.  Taylor,  F.R.S.  The  Motion  of 
Ellipsoidal  Particles  in  a  Visfous  Fluid. 

Tne  experiments  here  described  were 
Undertaken  in  order  to  test  experimentally 
an  unproved  hypothesis  recently  introduced 
by  Dr.  G.  B.  Jeffery.  The  hypothesis  was 
that  ellipsoidal  particles  immersed  in  a 
moving  viscous  fluid  would  swsume  certain 
definite  orientations  in  relation  to  the 
motif>n  of  the  fluid.  It  was  found  that 
ellipsoidal  particles  made  of  aluminiuc  and 
immersed  in  water  glass  do  in  fact  take  up 
the  positions  indieated  by  Dr.  Jeffery,  but 
they  take  a  long  time  to  get  to  those  posi- 
tions. During  the  time  in  which  the  par- 
tich'S  are  gradually  approaching  their  final 
positions  they  oscillate  in  the  way  indicated 
m  Dr.  Jeffery 's  analysis. 

Prof.  W.  E.  Dalby,  F.R.S.  Further 
Researches  on  the  Strength  of  Materials. 

This  paper  describes  my  recent  researches 
on  the  strength  of  materials,  and  is  in  con- 
tinuation of  papers  published  in  Proc.  Hoy. 


104 


THE   CHEMICAL    NfeWS. 


FEBEtJABY  16,  1923 


Soc,  A,  vol.  86,  and  vol.  88,  and  in  Phil. 
Trans.,  A.  vol.  221. 

The  papers  describe  first,  a  new  appara- 
tus hj  means  of  which  an  alternating  load, 
push  and  pull,  can  be  applied  to  a  test 
piece  in  such  a  way  that  the  curves  of  load 
and  elastic  extension  are  recorded  photo- 
graphically. Two  records  are  shown,  the 
one  in  which  a  test  piece  was  broken  down 
in  tension,  and  the  other  in  which  a  similar 
test  piece  was  broken  down  in  compression. 
The  immediate  deduction  fi-om  the  re- 
cords is  that  the  yield  in  tension  and  com- 
pression is  substantially  the  same,  and  that 
the  modulus  of  elasticity  is  the  same.  But 
the  point  of  greater  interest  is  that  alternat- 
ing load  is  met  by  alternating  response. 
When  a  load  of  either  sign  is  removed  the 
response  is  elastic,  but  imperfectly  so. 
When  a  load  is  re-applied,  but  of  opposite 
sign  to  the  load  removed,  the  response  is 
mainly  plastic.  This  alternating  response 
to  alternating  loading  is  discussed  in  the 
light  of  the  experiments  of  Ewing  and 
Rosenhain  and  the  recent  researches  of 
Carpenter. 

The  fact  that  Carpenter  has  found  the 
elastic  properties  of  an  ordinary  test  piece 
reproduced  in  a  test  piece  turned  from  a 
single  crystal,  definitely  ehmmates  the 
amorphous  network  and  allows  the  discus- 
sion to  be  based  on  the  fact  that  elastic 
property  resides  mainly  in  the  crystalline 
structure. 

Many  points  requiring  investigation  are 
noted.  A  new  instrument  is  then  described 
by  means  of  which  an  alternating  torque 
and  elastic  twist  are  recorded  photograiphic- 
ally.  A  record  is  shown  from  which  it  is 
seen  that  alternating  torque  is  also  met  by 
an  alternating  response  in  shear.  Reference 
is  then  made  to  the  possibility  of  predict- 
ing a  practical  fatigue  limit  from  these 
diagrams. 

Lbwis  F.  Richardson.  Theory  of  the 
Measurement  of  Wind  by  Shooting  Spheres 
Upward.  Communicated  by  Dr.  G.  C. 
Simpson,  F.R.S. 

During  the  last  fifteen  years  a  vast 
i»3r.-»unt  of  information  concerning  upper 
wind  has  been  obtained  on  occasions  when 
the  air  was  clear  enough  to  allow  a  small 
rubber  balloon  to  be  seen  through  a  theodo- 
lite. Some  observations  of  wind  above  fog 
or  low  cloud  have  been  made  by  tethered 
balloons  carrying  instruments,  or  by  the 
method  of  sound  ranging;  but  these  obser- 
vations are  very  scajity. 


The  new  method,  the  theory  of  which  is 
here  described,  is  independent  of  visibility. 
A  steel  sphere,  about  the  size  of  a  pea  or  a 
cherry,  is  shot  upwards  from  a  gun,  which 
is  not  rifled.  The  gun  is  inclined  from  the 
vertical  towards  the  advancing  air,  and  the 
tilt  adjusted  by  trial  until  the  returning 
sphere  falls  very  close  to  the  gun.  The 
tilt  is  then  some  measure  of  a  weighted 
average  of  the  wind,  in  the  region  extending 
from  the  ground  up  to  the  maximum 
height  attained.  This  height  is  found  from 
the  time  of  absence  of  the  sphere,  which  is 
recorded  by  a  stop-watch. 

The  observation  of  the  tilt  and  time  is 
reipeated  for  greater  and  greater  heights  in 
succession.  The  result  may  be  said  to  de- 
pend upon  a  set  of  weighted  averages  of 
wind  up  to  successive  heights;  and  the 
problem  is  to  undo  the  averaging  process, 
and  so  find  the  wind  at  each  level.  A  con- 
dition of  the  problem  is  that  the  computa- 
tion of  the  winds  should  not  occupy  the 
observer  for  more  than  about  fifteen 
minutes. 

Mathematically  speaking,  the  problem 
involves  a  "  linear  integral  equation  of  the 
first  kind."  This  is  solved  approximately 
by  transforming  it  into  a  moderate  number 
of  algebraic  simultaneous  equations.  The 
error  due  to  the  finiteness  of  the  number  of 
these  equations  is  studied  by  varying  the 
number. 

In  the  general  part  of  the  theory  it  is 
necessary  to  make  an  approximation  which 
fails  at  the  vertex  of  the  trajectory.  So  for 
the  sake  of  observations  in  which  the  im- 
portant part  of  the  path  is  near  the  vertex, 
there  is  given  either  a  special  and  suffi- 
ciently correct  theory  or  else  a  correction 
to  the  general  theory. 

Ernest  Wilson.  On  the  Susceptibility 
of  Feebly  Magnetic  Bodies  as  affected  by 
Tejision.  Communicated  by  Prof.  O.  W, 
Richardson,  F.R.S. 

The  experiments  demonstrate  that  when 
magnetite  is  subjected  to  tensile  stress 
ranging  from  about  50  to  130  kgm.  per  sq. 
om.  as  a  maximum,  the  susceptibiHty  for  a 
given  value  of  the  magnetic  force  at  first 
increases  and  then  decreases  as  the  specific 
load  continuously  increases,  and  exhibits  a 
reversal  point  as  in  iron.  The  magnetic 
force  at  which  the  percentage  increase  in 
permeability  has  a  maximum  value  is  less 
than  the  magnetic  force  at  which  maxi- 
mum susceptibility  occurs.     The  specimens 


I 


FEBRUAKY  16,  1923. 


TSS  C'HEMICAL   NEWS. 


106 


teeted     have     widely     different    structural 
characteristics. 

Papers  Read  in  Title  Only. 

L.  C.  Jackson  and  Prof.  H.  Kamerlingh 
Onnes,  For.  Mem.  R.S.  hivestigations  on 
the  Paramagnetic  Sulphates  at  Low  Tem- 
peratures. 

L.  C.  Jackson  and  Prof.  H.  Kamerlingh 
Onnes,  For.  Mem.  R.S.  Investigations  on 
the  Paramagnetism  of  Crystals  at  Low 
Temperatures. 

W.  D.  Womersley.  The  Specific  Heats 
of  Air,  Steam,  and  Carbon  Dioxide.  Com- 
municated by  Sir  Dueald  Clerk,  F.R.S. 

D.  W.  Dye.  The  Valve -maintained  Tun- 
ing Fork  as  a  Precision  Time  Standard. 
Communicated  by  Sir  Joseph  Petavel, 
F.R.S. 

An  investigation  has  been  made  oi  the 
variations  in  frequency  of  a  valve-main- 
tained tuning  fork,  when  aIt<'ration8  were 
made  in  various  quantities  which  might  be 
expected  to  cause  variations  in  frequency. 
The  following  quantities  were  varied:  — 

(a)  Temperature. 

{h)  Anode  voltage  and  filament  bright- 
ness. 

(c)  Capacity  connected  in  parallel  with 
grid  and  anode  windings  respectively. 

(d)  Polarising  inugnetic  field  strength. 

(e)  and  (/)p]nergv  taken  from  the  system 
and  the  method  of  doing  this. 

(g)  Effective  mass  of  different  parts  of 
the  mounting  and  orientation  of  the 
fork  and  mounting  in  space. 

In  addition,  various  valves  were  tried 
and  absolute  measurements  made  of  the 
frequency  in  terms  of  a  standard  clock,  to 
a  high  order  of  accuracy. 

Thv  conclusions  arrived  at  were  as  fol- 
lows: The  valve-maintained  fork  is  steady 
in  frequency  to  a  degree  beyond  that  re- 
quired for  most  purposes.  The  most  serious 
cause  of  variation  of  frequency  is  that  due 
to  temperature.  The  temperature  must  be 
kept  constant  to  0°.l  C.  if  accuracy  to  one 
part  in  a  hundred  thousand  is  required.  By 
the  use  of  a  special  steel  known  as  "elin- 
var,"  having  very  small  temperature  co- 
efficient of  elasticity,  it  is  probable  that 
the  variation  of  frequency  with  tempera- 
ture could  be  reduced  to  one-tenth  that  of 
ordinary  steel  forks. 

The  other  factors  causing  variation  of 
frequency  are  not  thomselvcs  variable  with- 
out attention  to  an  extent  which  would 
cause  a  variation  of  more  than  a  very  few 
piirts  in  a  hundred  thoiisnnd.  By  suitably 
choofling  the  capacities  and  the  anode  volt- 


age of  batteries  of  +  10  per  cent,  will  cause 
a  change  of  only  about  one  part  in  a  million 
in  frequency. 

By  observation  of  care  in  the  adjust- 
ments of  the  factors  affecting  frequency,  it 
is  probable  that  sufficient  accuracy  would 
be  attainable  to  observe  diurnal  variations 
in  the  rates  of  standard  clocks,  and  per- 
haps in  the  value  of  "  g." 

[The  abstracts  are  provided  by  the 
authors  of  papers,  and  are  not  to  be  com- 
municated to  any  journal  for  publication 
untU  after  the  meeting.] 

At  the  meeting  on  February  22,  the 
Bakerian  lecture  will  be  delivered  by  G.  I. 
Taylor,  F.R.S.,  and  C.  F.  Elam,  on  "  The 
Distorticm  of  an  Aluminium  Crystal  during 
a  Tensile  Test." 


ROYAL   INSTITUTION  OF  GREAT 
BRITAIN. 

Albbmarlk  Strebt,  Piccadilly,  W.l. 

Saturday,  February  17.  —  Sir  Ernest 
■RCTHBRFORD,  LL.D.,  D.Sc,  F.R.S., 
M.R.I. ,  Prof,  of  Natural  Philosophy,  on 
Atomic  Projectiles  and  their  Properties. 
(Lecture  I.) 


THE  CHEMICAL  SOCIETY. 

Ordinary   Scientific  Meeting,   Thursday, 
Fbbruary  15,  1928,  at  8  p.m. 

The  following  papers  were  read: — 

Spituicens :  Its  Oxidation  and  decompo- 
sition.— A.  Chaston  Chapman. 

Investigationj<  on  the  dependenae  of  ro- 
tatory power  on  chemical  constitution. 
Part  XIX. :  The  rotatory  and  refractive  dis- 
persion ofd-y-nonyl  nitrite. — R.  H.  Piok- 
ARD  and  H.  Hunter. 

Investigations  on  the  dependence  of  ro- 
tatory power  on  chemieal  consfitxition.  Part 
XX.  :  The  rotatory  dispersive  powers  of 
oxygen  comxponnds  containing  the  secondary 
ootyl  radicle. — H.  Hunter. 


PHYSICAL  SOCIETY  OF  LONDON. 

Procekdinos  at  the  Meeting  held  on 

January  26.  1923,  at  the  Imperial  College 

OF  Science. — Alexander    Russell,   M.A., 

D.Sc,  IN  THE  Chair. 

A  paper  on  A  Supposed  Relationship  be- 
tween Sunspot  Frequency  and  the  Potential 


106 


THE   CHEMICAL    NEWS. 


FEBRUAEY  16,  1923. 


Gradient    of    Atmospheric  Electricity    was 
read  hy  Dr.  C.  Chree,  F.R.S. 

Abstract. 

In  a  recent  paper  in  Terrestrial  Magnet- 
ism, Dr.  L.  A.  Bauer  draws  the  conclusion 
that  both  the  range  of  the  diurnal  inequal- 
ity of  atmospheric  electricity  potential 
gradient  and  the  mean  value  of  the  element 
for  the  year  increase  and  diminish  with 
sunspot  frequency.  This  conclusion  was 
based  on  observational  data  from  the  Ebro 
Observatory,  Tortosa,  Spain,  between  1910 
and  1920. 

The  present  paper  investigates  the  sub- 
ject more  mathematically,  employing  Kew 
electrical  data  from  two  periods  of  years, 
in  addition  to  the  Ebro  data  utilised  by 
Dr.  Bauer.  Magnetic  data  from  Kew  Ob- 
servatory for  the  same  periods  are  similarly 
treated,  so  as  to  have  parallel  results  from 
an  element  for  which  the  sunspot  relation- 
ship is  generally  admitted. 

The  results  obtained  are  on  the  whole 
not  incompatible  with  Dr.  Bauer's  conclu- 
sion, but  they  indicate  that  if  a  relationship 
of  the  kind  supplied  exists,  the  sunsipot 
influence  must  be  very  much  less  in  the 
case  of  atmospheric  electricity  than  in  that 
of  terrestrial  magnetism. 

Discussion. 

Dr.  A.  Russell,  in  expressing  the  thanks 
of  the  meeting  for  an  interesting  and  in- 
structive paper,  said  that  few  realise  the 
very  high  value  of  the  potential  gradient 
which  normally  characterises  their  physical 
environment,  and  which  may  have  impor- 
tant biological  effects,  not  only  in  connec- 
tion with  electro-culture,  but  also  in  human 
psychology.  The  "correlation  coefficient" 
which  Dr.  Chree  introduced  was  not 
familiar  to  all  physicists,  and  appeared  to 
be  of  ver^  great  interest  as  a  test  of  the 
inter-relation  of  different  phenomena. 

A  paper  on  A  Further  Improvement  in 
the  Sprengel  Pump,  by  J.  J.  Manley, 
M.A.,  Research  Fellow,  Magdalen  College, 
Oxford,  was  taken  as  read  in  the  absence 
of  the  author. 

Abstract. 

The  paper  relates  to  a  further  improve- 
ment in  the  pump  described  in  the  "Pro- 
ceedings" of  the  Society,  Vol.  XXXIV., 
page  86,  which  is  designed  to  avoid  irregu- 
larities due  to  air  skins  on  the  inner  sur- 
faces of  the  apparatus.  The  present  im- 
provement consists  in  means  for'  providing 
a  mercury  seal   during    periods  when     the 


pump  is  out  of  use,  whereby  the  formation 
of  fresh  air  skins  is  prevented. 

A  paper  on  Null  Methods  of  Measure- 
ment of  Power  Factor  and  Effective  Re- 
sistance in  Alternate  Current  Circuits  hy 
the  Q^iadrant  Electrometer,  was  read  by 
D.  Owen,  B.A.,  D.Sc,  F.Inst.P.,  Sir 
John  Cass  Technical  Institute,  London. 

Abstract. 

Zero  methods  are  proposed,  and  expres- 
sions derived,  for  the  measurement  of 
power  factor  and  effective  resistance  of  al- 
ternating current  loads.  The  methods  are 
extended  to  high  tension  circuits. 

The  effect  of  "electrical  control"  of  the 
needle  of  the  quadrant  electrometer  is  dis- 
cussed, and  it  is  showTi  that  the  usual  form- 
ula for  the  instrument  is  applicable  only 
when  the  needle  is  maintained  at  its 
mechanical  and  electrical  zero.  The  fur- 
ther advantages  of  null  methods  are 
emphasised. 

Illustrative  tests  are  recorded. 

Discussion. 

Dr.  E.  H.  Rayner  congratulated  the 
author  on  his  valuable  additions  to  the 
many  uses  of  the  Quadrant  Electrometer. 
This  wonderful  instrument  was  invented 
over  half  a  century  ago  by  Lord  Kelvin, 
but  was  still  unsurpassed  in  its  utility, 
being  applicable  to  the  accurate  measure- 
ment of  power,  insulation,  phase-angles, 
and  many  other  quantities.  The  speaker 
took  the  opportunity  fo  point  out  some  de- 
tails as  to  which  care  is  necessary  in  the 
practical  use  of  the  Electrometer.  (1) 
With  high  voltages  the  mechanical  force 
on  the  needle  is  considerable  and  may  bend 
it,  leading  to  inconsistent  results  at  low 
power  factors.  (2)  Referring  to  Fig.  1  of 
the  paper,  the  high  resistance  AO  generally 
has  an  appreciable  distributed  capacity, 
with  the  result  that  the  voltage  across  MO 
is  not  in  phase  with  the  current.  If  con- 
ditions permit,  the  easiest  remedy  is  to 
take  as  much  current  along  OA  as  possible ; 
for  instance,  if  the  current  in  this  branch 
be  1/20  ampere,  the  power  facti>r  in  a 
common  case  would  be  0.1  or  0.2  per  cent., 
but  on  increasing  the  current  to  1  ampere 
the  phase  lag  might  become  negligible.  A 
similar  error  has  to  be  contended  with 
where  a  step-down  transformer  is  used,  as 
shown  in  Fig.  5,  and  it  must  be  remem- 
bered that  for  small  phase-angles  an  error 
of  a  few  minutes  of  arc  may  represent  a 
large  percentage  error.       (3)  An  extremely 


t'EBRUAKY  16,  1923. 


THE   CHEMICAL   NEWS. 


107 


important  point  when  high  voltages  are  a^- 
phed  to  the  needle  is  that  the  faces  of  the 
quadrants  should  be  perfectly  flat.  To  this 
end  they  should  be  ground  on  cast  iron 
after  they  have  been  fixed  in  place. 

Mr.  G,  L.  Addenbrooke  referred  to  his 
papers  published  in  the  Electrician  in  1901 
as  relevant  to  some  of  the  points  raised  by 
the  author.  He  added  that  it  is  convenient 
to  arrange  a  switch  whereby  the  .point  P, 
Fig.  1  of  the  paper,  may  be  WMinected  at 
will  to  the  point  0.  In  this  way  the  in- 
strument may  be  converted  into  an  am- 
meter. He  had  used  detlectional  methods 
because  they  permitted  "  seeing  what  was 
going  on." 

Dr.  A.  Russell  congratulated  the  author 
on  discovering  so  many  theorems  and 
applying  them  so  usefully,  and  expressed 
appreciation  of  Dr.  Kayner's  he]{>ful  sug- 
gestions. 

Capt.  R.  Dunshoath  (communicated): 
This  paper  is  very  opportune  at  Ohe  present 
time,  when  so  many  investigate^  are  seek- 
ing the  best  meth(xi  of  nu'asuring  dielectric 
tosses,  and  is  full  of  useful  suggi-ntions.  I 
do  not  agree  with  the  author,  however,  that 
it  is  desirable  to  eliminate  both  voltmeter 
and  ammeter.  His  methods  give  power 
factor  only,  but  a  figure  for  actual  watts 
lost  is  generally  required.  Also,  due  to  the 
in4)ortance  of  the  dependence  of  power 
factor  and  losses  on  voltage,  it  is  usual  to 
decide  at  the  commencement  of  ft  to^t 
what  voltage  shall  be  adopted,  and  n  volt- 
meter is  essential.  The  ammeter  is  not  so 
necessary  as,  having  V,  N',  and  R,  In 
formula  (4),  the  value  of  the  current  fol- 
lows at  once.  Proceeding  in  this  manner 
cos  <f,  is  obtainable  without  the  use  of  the 
cumbrous  equation  (6).  It  is,  of  course, 
necessary  to  switch  one  side  of  the  volt- 
meter from  0  to  B,  but  this  is  a  simple- 
matter. 

I  notice  that  Dr.  Owen  estimates  the 
error  of  the  figure  obtained  fw  phase  angle 
on  a  1/xF  condenser  at  nbout  16  per  cent. 
Much  smaller  condens4'r8  than  this  are 
usual  in  certain  branches  of  industrial 
work,  and  it  would  be  interesting  to  know 
the  sensitivity  of  the  instrument  used,  and 
what  sort  of  accuracy  might  be  expected  if 
the  method  were  applied  to  capacities  of 
the  order  of  0.01/mF. 

The  author  fin  reply  to  the  discussion) : 
The  remarks  of  Dr.  Rayner  will  be  valued 
by  ipractical  workei-s.  The  question  of 
phase  error  in  the  shvint  resistance,  and 
methods   of   compensation   have    also  been 


treated  by  Orlich  and  Schultze.  Mr.  Ad- 
denbrooke's  desire  to  follow  what  was  going 
on  by  watching  the  deflection  was,  of 
oourse,  quite  natural.  In  the  present 
methods  this  could  always  be  done  in  the 
preliminary  tests  by  slipping  P  into  coinci- 
dence with  0  (see  Fig.  1);  for  the  final 
reading  the  zero  balance  would  confer  a 
distinct  gain  in  accuracy.  In  reply  to 
Capt.  Dunsheath's  inquiry,  the  sensitivity 
of  the  electrometer  used  in  the  tests  quoted 
was  such  that  with  100  volts  on  the  needle 
and  one-tenth  of  a  volt  across  the  quad- 
rants the  deflection  was  about  60  mm.  at  a 
metre  scale-distance.  This  could  have 
been  multiplied  three  cw  four  times  pos- 
sibly. Measurements  on  a  O.Ol/x  F  conden- 
ser could  be  eonduoted  with  much  the 
same  accuracy  as  those  with  l/xf ,  since  the 
resistance  R  could  be  increased  in  inverse 
prt^ortio  nto  the  capacity. 

A  Demonstration  of  an  Electro-Capillary 
Relay  for  Wired  Wireless  was  given  by 
Majok  C.  E.  Prince,  O.B.E. 

The  relay  is  intended  for  use  with  a  call- 
ing device  in  connection  with  high- 
frequency  currents  acting  as  carrier  waves 
for  telephony  over  power-mains.  The  high- 
frequenoy  current  is  rectified  and  passed 
through  a  thread  of  mercury  which  is  con- 
tained in  a  capillary  tube,  and  is  in  contact 
at  each  end  with  a  quantity  of  acid,  plati- 
num wires  by  which  the  current  enters  and 
leaves,  bein^j  immersed  in  the  latter.  The 
passage  of  the  current  causes  the  mercury 
thread  to  move,  and  it  was  suggested  many 
years  ago  by  Wheat  stone  that  this  thread 
might  be  made  to  oUmi  an  electric  circuit; 
l)ut  practical  difiioulties  prevented  the  suc- 
cessful application  of  the  idea.  In  the 
p'.esent  invention  the  capillary  tulx;  is 
arranged  horizontally  on  a  beam  which,  as 
soon  as  the  mercury  moves,  over-balances 
in  consequence  of  the  weight  of  the  latter 
and  closes  the  circuit  of  a  call  bell  or  lamp. 
To  pri'vent  the  evaporation  of  the  acid  the 
oups  containing  it  are  connected  by  a  fur- 
ther capillary  tube  which  serves  to  equalise 
the  pressure,  and  the  tube  in  which  the 
mercury  threat!  lies  is  widened  at  its  middle 
point  to  fwni  a  chamber  for  the  reception 
of  bubbles  and  other  obstructicwis  which 
may  have  got  into  the  tube  before  sealing. 

The  circuit  arrangements  make  provision 
for  the  restoration  of  the  mercury  to  its 
original  position  whether  the  call  be 
answered  or  not.  In  series  with  the  thread 
and  with  a  rectifier  is  arranged  a  condenser 
in  which  the  charge  that  has  passed  round 


108 


THE    CHEMICAL    NEWS. 


FEBRUARY  16,  1923. 


the  circuit  is  stored,  and  after  the  call  this 
charge  is  sent  through  the  niercury  and 
acid  in  the  reverse  direction.  The  required 
discharge  is  effected  bj  contacts  which 
short-circuit  the  rectifier  when  the  switch- 
hook  is  raised,  but  if  the  call  be  unanswered 
the  same  result  is  produced  more  slowly  by 
a  high-resistance  leak. 

The  instrument  will  respond  to  currents 
of  4  or  5  or  even  2  microamperes,  and  will 
function  during  long  periods  without  atten- 
tion. Its  sensibility  was  demonstrated  by 
passing  through  it  the  voice-current  from 
the  secondary  of  a  microphone  transformer, 
and  subsequently  the  current  from  a  single 
dry  cell  in  series  with  the  body  of  the  de- 
monstrator. If  the  leak  resistance  be  small 
enough  Morse  signals  will  fail  to  effect  a 
call  in  consequence  of  the  leakage  which 
takes  place  during  the  intervals  between 
the  signal  elements,  while  a  series  of  long 
dashes  will  nevertheless  be  effective  and 
can  be  used  as  a  call  signal. 

The  cause  of  the  movement  of  the  mer- 
cury is  obscure,  and  the  phenomenon  is  of 
some  interest  to  physicists.  The  total 
movement  appears  to  be  proportional  to  the 
coulombs  which  pass,  so  that  the  arrange- 
ment might  be  used  as  a  quantity  meter 
for  small  currents,  such  as  voice  currents. 

Notice  to  Fellows. 
Fellows  who  have  not  already  done  so 
are  kindly  requested  to  forward  informa- 
tion in  regard  to  change  of  address,  or  of 
title  or  degree,  not  later  than  March  1 
next  to 

Mr.  F.  E.  Smith,  F.R.S., 

Redcot,"  St.  James's  Avenue, 
Hampton  Hill,  Middlesex. 


ABSTRACTS   OF    THE   PROCEEDINGS 
OF  THE  GEOLOGICAL   SOCIETY  OF 

LONDON. 
January  24,   1923,  Prof.  A.  C.   Seward, 
Sc.D.,  F.R.S.,  President,  in  the  Chair. 

The  following  communications  were 
read :  — 

0)1  Reptilian  Remains  from  the  Karroo 
Beds  of  East  Africa,  by  Sidney  Henry 
Haughton,  B.A.,  D.Sc,  F.G.S.  (Read  by 
Dr.  A.  Smith  Woodward,  F.R.S.,  Pres. 
L.S.,  F.G.S.) 

Three  specimens  of  a  small  fossil  were 
found  by  Mr.  F.  P.  Mennell,  F.G.S.,  in 
black  shale  in  the  middle  of  Karroo  Forma- 
tion, near  Tanga,  on  the  coast  of  Tangany- 
ika Territory.     Two  are  well  preserved,  and 


are  now  described  in  detail.  They  repre- 
sent a  new  genus  and  species  of  aquatic 
reptile,  in  general  appearance  much  like 
Mesosaurus,  but  differing  in  its  shorter 
neck,  thinner  ribs,  relatively  larger  and 
more  massive  fore-limb,  the  presence  of  a 
large  rounded  sternum,  and  of  only  four 
distal  carpal  and  tarsal  bones  instead  of 
five.  It  is  perhaps  more  closely  related  to 
Yoiingina,  and  may  be  regarded  as  an 
aquatic  adaptation  of  that  type.  If  so, 
the  shale  at  Tanga  is  approximately  of  the 
same  age  as  the  Middle  Beaufort  Beds  of 
South  Africa. 

Glacial  Succession  in  the  Thames  Gatch- 
ment-Basin,  by  the  Rev.  Charles  Overy, 
M.A.,  F.G.S. 

This  paper  is  intended  to  establish  a  de- 
finitive succession-grouping  for  high-level 
gravels  of  the  Thames  catchment-basin, 
analogous  to  that  adopted  for  the  valley- 
gravels  proper.  The  necessity  for  this 
arises  from  the  present  confused  system  of 
nomenclature,  and  the  lack  of  correlation 
between  different  areas.  It  is  indispensable 
to  the  establishment  of  the  Glacial  Succes- 
sion. 

The  Kennet  Stages  of  H.  J.  Osborne 
White  are  dealt  with,  and  an  analysis  is 
given  of  the  Plateau-Gravels  of  Oxford- 
shire :  the  grading  of  these  with  reference 
to  river- level,  establishes  a  simple  correla- 
tion with  the  Kennet  Stages. 

The  author  advocates  the  adoption  of  a 
norm  series  with  effective  nomenclature  for 
the  Berkshire-Oxfordshire  area :  namely, 
PPPP  PPP  If 

••-350'     -•-SOO'     ■'-265'     ■'^230'         "'■210'     ^260'    '"ISS"        ^^ 

this  norm  series  is  represented  in  the 
Hamipshire  and  London  areas,  succession- 
grouping,  according  to  this  scheme, 
possesses  high  significance. 

Grading  and  analysis  in  the  Hampshire 
and  London  areas  result  in  the  establish- 
ment of  the  norm  series  for  the  whole  river- 
system.  In  this  way  light  is  thrown  on 
such  vexed  questions  as  the  age  of  the  Gor- 
ing Gap,  the  mode  of  description  of  the 
Plateau-Gravels,  Glacial  Succession  in  the 
Thames  Pasin,  and,  finally,  on  the  bearing 
of  the  distribution  of  Drift  constituents  on 
the  history  of  the  Thames  river-system. 

The  author  claims  to  furnish  definite 
evidence  for  the  course  of  the  pre -Pleisto- 
cene Thames,  for  the  continuity  of  the 
Evenlode,  Goring  Gap,  Henley  Gorge, 
Colne-Lea  divide,  and  Essex-coast  system. 
He  is  able  to  correlate  the  deposition  stages 
with  recognised  Glacial  Epochs,     and  con- 


FEBRUARY  16,  1923. 


THE   CHEMICAL   NEWS. 


109 


eludes  with  deductions  as  to  the  age  and 
succession  of  the  iniipkinentiferous  gravels 
of  the  Thames  and  its  tributaries. 


BOROUGH    POLYTECHNIC 
INSTITUTE. 

Distribution  of  Phizes  by  The 
Attorney-Gkneral. 

The  Attorney-General,  the  Rt.  Hwi.  Sir 
Douglas  McGurel  Hogg,  P.C,  K.C.,  M.P., 
distributed  the  prizes  at  the  Borough  Poly- 
technic on  Friday,  February  2.  The  Chair- 
man of  the  Governors  (Mr.  J.  Leonard 
Spioer)  presided.  In  introducing  the 
Attorney-General,  Mr.  Spicer  referred  to 
the  pleasure  it  gave  all  those  connected 
with  the  work  of  polyttchnics  that  in  Sir 
Douglas  Hogg  they  welcomed  nne  whose 
whole  life  had  passed  in  the  polytechnic 
atniosphen'  and  tradition.  Sir  Douglas 
Hogg's  father,  Mr.  Quintin  Hogg,  had  been 
the  founder  of  the  Polytechnic  in  Regent 
Street,  and  Sir  Douglas  himself  had, 
throughout  his  life,  been  associated  with 
that  Institute. 

Sir  Douglas  Hogg,  in  his  address,  after 
referring  to  the  great  loss  suffered  through 
the  death  of  Lord  Kinnaird  by  all  those  in- 
terested in  the  ^outh  fjf  London,  described 
the  origin  an<l  aims  of  the  great  f)olyt<-ohnic 
movement  which  had  taken  shape  in  the 
formation  80  years  ago  of  such  institutes  as 
the  Borough  Pf>lytechnic.  With  regard  to 
the  work  of  the  Institute,  he  said  it  was  not 
their  desire  to  turn  out  a  number  of  half- 
fledged  amateurs  to  compete  with  the  men 
in  the  workshops,  but  by  technical  instnic- 
tion  to  enal  le  those  in  the  workshops  to 
make  themselves  more  efficient  and  to 
make  greater  progress  in  the  industry  to 
which  they  belonged.  He  was  sure  that 
the  policy  which  had  actuated  the  Gover- 
nors in  supplementing  the  experience  of 
the  workshop  by  this  technical  instniction 
was  a  sound  one,  as  was  the  policy  of  select- 
ing teachers  who  themselves  had  know- 
ledge of  their  industries. 

It  was  very  gowl  to  see  that  the  women's 
side  of  the  Borough  Polyte6hnic  was  so 
strong.  Some  of  the  activities  of  the 
Borough  Polytechnic  were  unique  in  this 
part  of  England;  the  School  of  Bakery  and 
Confectionerv-  had  no  parallel  in  the  South- 
Eastern  Counties,  and  the  Department  of 
Painters'  Oils,  Colours  and  Varnishes  re- 
presented a  highly  specialised  and  very 
valuable  piece  of  technological  work.  The 
Borough  Polytechnic    was  to  be  congratu- 


lated on  the  way  in  which  it  had  enlisted 
the  help  of  associations  of  employers,  ex- 
pert trade  conunittees,  trades  unions,  and 
associations  of  employers  in  order  to  keep 
its  work  closely  related  to  the  current  needs 
of  industry.  In  addition,  however,  to 
purely  technical  instruction,  the  social  side 
of  the  Institute  was  a  very  strong  one;  it 
was  concerned  even  more  with  the  educa- 
tion of  good  citiaens  than  with  the  produc- 
tion of  expert  craftsmen. 

Principal  Bispham,  in  his  report,  pointed 
out  that  both  in  quality  and  bulk  the  work 
of  the  session  under  review  was  a  record 
one  for  the  Institute,  and  an  altogether 
worthy  tribute  to  the  former  Princiipal, 
Mr.  C.  T.  Millis,  who  had  just  retired. 

Other  speakers  were  Mr.  F.  A.  Strauss, 
M.P..  the  Mayor  of  Southwark,  Mr.  D. 
Clifford  Highton  (Vice-Chairman  of  the 
Govemoi-s).  .Mr.  P.  M.  Evans  (Clerk  of  the 
Clothworkers'  Company),  and  Mr.  F.  W. 
Mills  (Chairman  of  the  Students'  Electoral 
Committee). 

OBITUARY  NO'l^S. 

The  Late  Mr.  W.  Woolley,  J. P., 
OP  Blackburn. 

Great  regret  has  Ix'en  caused  at  Black- 
bum  through  the  death  of  Mr.  W.  Woolley, 
J.P.,  of  the  Bungalow,  Meins  Road,  in  that 
town,  at  the  age  of  •'>8  years.  He  was  the 
head  of  the  firm,  J.  Woolley,  lyt-d.,  manu- 
facturing clieniists,  and  had  Ix'en  seriously 
ill  for  a  few  weeks.  In  th«'  hope  of  bring- 
ing about  an  improvement  in  his  condition, 
two  transfusions  of  blood  were  resorted  to. 
Tn  each  of  these  cases  his  sf>ns  volunteered 
to  undergo  the  operation,  the  last  being 
only  a  few  hours  before  Mr.  Woolley 's 
death,  when  the  required  quantity  of 
bloofl  was  given  by  a  younger  son.  Mr. 
Harold  Woolley,  who  is  at  the  Agricultural 
College,  Preston. 

Mr.  W.  Woolley's  early  life  was  spent 
in  Preston.  All  his  Hfe  he  was  connected 
with  the  Weslevan  body,  and  he  filled  all 
offices  open  tr>  laymen  in  the  circuit.  He 
hal  also  worked  for  and  held  responsible 
'p  >Hitions  in  relation  to  the  Blaokbum  Free 
Church  Council,  the  Sunday  School  Union, 
and  the  Band  of  Hope  Union,  For  six 
years  he  was  a  member  of  the  Blackburn 
Town  Council.  In  November,  1916,  he 
w.os  made  a  Justice  of  the  Peace  for  the 
Borough  of  Blackburn.  He  has  left  a 
widow  and  three  sons. 


110 


THE  CHEMICAL  NEWS. 


FEBRUARY  16,  1923. 


Professor  William  von  Rontgen,  the 
discoverer  of  X-rays,  has  died  at  Munich  at 
the  age  of  seventy-eight. 

Though  a  German,  he  was  educated  in 
Holland  and  Switzerland,  taking  his  doc- 
tov's  degree  at  Zurich  in  1869. 

After  holding  minor  appointments,  he 
settled  at  Wurzburg  as  Professor  of  Physics 
in  1885,  and  later  became  director  of  the 
Physical  Institute,  Munich,  a  post  he  re- 
signed four  years  ago  on  account  of  ad- 
vancing age.  He  applied  mathematics 
to  practically  every  branch  of  physics,  and 
while  at  Wurzburg  he  discovered  the 
Rontgen  rays,  or,  as  he  called  them  because 
of  their  character,  the  X-rays.  That 
ep^ch-making  discovery  was  the  result  of  a 
series  of  experiments  he  conducted  in  1895 
on  the  phenomena  resulting  from  the  pas- 
sage of  electricity  through  the  vacuum 
tuibes  invented  by  Sir  William  Crookes. 
The  tube  was  enclosed  in  an  opaque  case, 
and  Rontgen  was  astonished  to  find  that 
certain  radiations  from  the  tube  passed 
through  the  case  and  caused  a  fluorescent 
effect  on  objects  outside. 

With  the  caution  of  the  true  scientist, 
Rontgen  was  in  no  hurry  to  announce  his 
discovery,  but  concentrated  on  a  long  series 
of  confirmatory  experiments.  More  than 
a  year  later  he  felt  justified  in  making  pub- 
lic his  sensational  discovery. 

His  other  physical  researches  are  of  in- 
terest mainly  to  scientists,  but  the  dis- 
covery of  ihe  X-rays  has  assured  his  name 
a  permanent  place  in  the  roll  of  those  men 
of  science  who  have  wrested  secrets  from 
nature  of  inestimable  value  to  the  world  at 
large. 


GENERAL    NOTES. 


THE  DEITECTION  AND  ESTIMATION 

OF  SMALL  QUANTITIES  OF 

ARSENIC. 

Joint  Meeting  of  the  Society  of  Public 

Analysts  and  the  Nottingham  Section 

OF  THE  Society  of  Chemical  Industry. 

For  the  first  time  in  the  history  of  the 
two  Societies,  a  joint  meeting  of  the  Society 
of  Public  Analysts  and  of  the  Nottingham 
Section  of  the  Society  of  Chemical  Indus- 
try has  been  held.  On  January  17  more 
than  50  of  the  members  of  the  Society  of 
Public  Analysts  went  to  Nottingham  to 
take  part  in  the  discussion  on  the  methods 
of  estimating  arsenic,  and  were  entertained 
at  dinner  by  the  local  section  prior  to  the 
discussion  which  took  place  in  the  Lecture 


Theatre  of  Nottingham  University  before  a 
crowded  audience. 

The  chair  was  taken  by  Mr.  Burford, 
Chairman  of  the  Nottingham  Section,  and 
the  discussion  was  opened  by  Mr.  A.  Chas- 
ton  Chapman,  F.R.S.,  who  described  his 
experience  during  the  last  25  years  with 
the  zinc-acid  process,  and  gave  an  outline 
of  his  proct'duie,  more  particularly  in  the 
use  of  cadmium  to  render  the  zine  sensi- 
tive. 

He  was  followed  by  Mr.  Wilkie,  Secre- 
tary of  the  Nottingham  section,  who  de- 
monstrated the  use  of  his  electrolytic 
method  of  estimating  arsenic,  in  which  the 
reversibility  of  the  reaction  was  prevented. 

The  next  speaJier  was  Dr.  Monier- 
Williams,  who  showed  an  electrolytic 
Marsh  apparatus  modified  from  that  in  use 
in  the  Govei-ument  Laboratory. 

Major  Trotman  was  of  the  opinion  that 
the  prel  minary  treatment  of  the  material 
was  the  crucial  point  of  the  estimation.  He 
advoL-ated  the  calling  of  a  conference  to 
discuss  the  standardisation  of  methods  of 
estimating  arsenic. 

Mr.  H.  Droop  Richmond  attributed  the 
want  of  sensitiveness  of  the  zinc  in  the 
zinc-acid  method  to  the  presence  of  iron, 
and  Mr.  J.  Webster  described  an  exiperi- 
ment  indicating  that  the  total  amount  of 
arsenic  in  a  large  organ,  such  as  the  liver, 
was  correctly  estimated  by  multiplying  the 
amount  found  by  a  factor. 

Mr.  Jenson,  Dr.  Dyer,  and  Mr.  Weaver 
also  joined  in  the  discussion,  and  Mr.  P.  A. 
Ellis  Richards  (President),  and  Mr.  E.  R. 
Bolton  (Secretary)  expressed  the  thanks  of 
the  Society  of  Public  Analysts  for  the  hos- 
pitality which  had  been  sh  ;wn  to  them  by 
the  Nottingham  section. 


ROYAL  INSTITUTION. 
On  Tuesday,  February  13,  at  3  o'clock, 
Professor  A.  C.  Pearson  delivered  the  first 
of  two  lectures  at  the  Royal  Institution  on 
"Greek  Civilisation  and  To-day":  (1)  "The 
Beginnings  of  Science";  (2)  "  Progress  in 
the  Arts."  On  Thursday,  February  15, 
Professor  B.  Melvill  Jones  began  a  course 
of  two  lectures  on  "  Recent  Experiments 
in  Aerial  Surveying,"  and  on  Saturday, 
February  17,  Sir  Ernest  Rutherford  will 
commence  a  course  of  six  lectures  on 
"  Atomic  Projectiles  and  their  Properties." 
Th '  Friday  evening  discourse  on  February 
16  will  be  dehvered  by  Professor  A.  V.  Hill 


FEBRUARY  16,  1023. 


THE  CHEMICAX  NEWS. 


Ill 


on  "  Muscular  Exercise,"  and  on  February 
23  by  Professor  A.  S.  EddingtMi  on  "  The 
Interior  of  a  Star." 

A  General  Meeting  of  the  members  of 
the  Royal  Institution  was  held  on  February 
5,  Sir  James  Criohton-Browne,  Treasurer 
and  Vice-President,  in  the  chair.  The 
d-  aths  of  Uord  Kinnaird  and  the  Hon.  R. 
G.  Parsons,  members,  and  of  Professc*  G. 
Lem^>ine  and  G.  Lunge,  honorary  members 
of  the  Institution,  were  reported,  and  reso- 
lutions of  ccmdolenoe  with  the  families 
were  passed.  The  special  thanks  of  the 
members  were  returned  to  Dr.  Ernest 
Clarke,  for  his  donation  of  £100  to  the 
Fund  for  the  Promotion  of  Experimental 
Research,  and  to  Sir  Huinphry  Rolle8t<«i 
for  his  gift  of  Sir  Humphry  Davy's  h(xi(M'- 
ary  diplomas.  Mr.  and  Mrs.  Maonab  were 
elected  members. 


IRISH  CHEMISTRY  STUDENTS  AT 
BIRMINGHAM. 
Recently  the  Senate  and  Council  of  the 
University  of  Birmingham  received  a  re- 
quest from  the  Royal  College  of  Science, 
Dublin,  to  make  provision  at  Birmingham 
University  for  eight  senior  students  of 
chemistry  who  wish  to  do  laborat<H7  work, 
the  commandeering  of  their  alma  mator 
by  the  Free  State  authorities  having  madr 
it  impossible  for  them    t  ;  '  te    their 

studies  in  Ireland.     The  i  arrange- 

ments were  made  for  their  reception,  and 
all  pf  them  are  now  working  under  the 
supervision  of  the  Dean  of  the  Faculty  of 
Science'  in  tlio  Chemical  Department  at  the 
new  University  buildinps  at  Edgbaston. 
From  an  tvcademic  point  of  view  the  hard 
necessity  which  has  comipilled  these  gentle- 
men to  cross  St.  George's  Channel  is  to  be 
deplored,  but  Midlanders  will  feel  some 
satisfaction  in  the  thought  that  it  was  their 
university  which  was  selected  by  those 
competent  to  judge  when  ttie  question  of 
transmigration  was  considered. 

At  a  meeting  of  the  Council  of  the  Insti- 
tution of  Electrical  Enp^ineers,  held  on 
February  1,  the  following  resolution  was 
passed :  — 

"  That  in  view  of  the  present  state  of 
trade  and  employment,  the  Council  re- 
quest members  who  place,  or  who  advise 
upon  the  placing  of  orders,  to  specify,  as 
far  aK  ipraeticable,  that  the  plant  and 
material  ordered  shall  be  of  British 
manufaoturr  " 


NOTICES  OF  BOOKS. 

Organic  ChemiBtry,     or  the   Chemistry 
of  the  Carbon-  Compounds,     by    Victor 
vox     RiCHTER,    edited     by      Prof.     R. 
Ans$:hutz  and  Dr.  H.  Meerwein.     Vol. 
III.     Heterocyclic    Compounds.       Trans- 
lated from  the  Eleventh  German  Edition 
by     E.     E.     FouRNiER    D'Albe,    D.Sc, 
A.R.C.Sc.     Pp.  XVIII.  +  326.  London: 
Kegan  Paul.  Trench  Trubner  &  Co.,  Ltd. 
1923.     Price  25s.  net. 
The  publication    of  this  volume  on    the 
heterocyclic  organic  comipounds   completes 
the  translation    of    the    eleventh    German 
edition  of  Rirhfrr,  which  appeared  in  1912. 
There  is  undoubtedly  a  demand  for  this 
translation — long  overdue — but    it  is    very 
regrettable  that  the  impw-tant  work  accom- 
plished   by  many    eminent  workers    since 
1912  is  missing  from    the  latest  edition  of 
this    widely-consulted    compilation.       This 
is  very  noticeable,  for  instance,  in  the  sec- 
tion on  Vegetal)le  Alkaloids,  which  is  by  no 
means  up-to-date. 

.\nother  exasjierating  feature  of  this  edi- 
tion is  that  references  to  the  original 
memoirs  of  authors  outside  Germany  are 
to  the  Chemisrbea  Zeritralblntf.  Authors' 
names  are  also  seldom  given.  The  same 
applied  to  Vol.  II.,  reviewed  in  The 
Chemical  News  (1922,  CXXIV..  226).  April 
21. 

Thus,  in  the  present  volume,  the  refer- 
ence on  p.  89  to  Moureu  and  Lazenneo's 
synthesis  of  pyrazolone  is  C.  1906.  II.,  484. 
Py man's  researches  on  histidine  and  Lusk's 
work  on  amino-aoids  are  quoted  in  the 
same  manner.  Examples  of  this  kind  could 
be  further  multiplied. 

The  intention  in  the  original,  evidently, 
was  to  assist  German  readers,  but  it  would 
surely  have  been  worth  while  to  introduce 
French,  English,  American,  and  other 
original  references  in  this  translation. 

Apart  from  these  drawbacks  the  volume, 
which  is  well  indexed,  will  serve  a  useful 
purpose  until  it  is  superseded  by  a  subse- 
quent editiwi.  J.G.F.D. 

Seifen  und  Eiweisssioffe ,  von  Dr. 
Martin  H.  Fischer  unter  Mitarbeit  von 
G.  D.  McLaughlin  und  Marian  O. 
Hooker.  Autorisierte  Deutsche  Ausgabe 
von  Dr.  Joiiann  Matdla.  Pp.  188  +  37 
plates.  Dresden  and  Tveipzig:  Verlag 
von  Theodor  SteinkopfT.  1922.  Price 
48.  3d. 
Dr.   Matula's  German  translation  of  the 


112 


THE  CHEMICAL  NEWS. 


FEBRUARY  16,  1923. 


work  of  Dr.  Fischer  aud  his  collaborators 
will  bring  to  the  notice  of  Central  European 
scientists  the  researches  and  ideas  of  these 
American,  physical  and  biological  chemists. 

After  an  introduction  on  the  preparation 
of  soaps,  the  systems  soap -water,  soaip- 
alcohol  are  considered,  together  with  cases 
of  colloidal  soap  solutions  in  non-aqueous 
solvents. 

Then  follows  an  account  of  colloidal 
phenomena  in  general,  from  which  the 
author  proceeds  to  the  study  of  colloidal 
proteins,  the  behaviour  of  which  he  con- 
siders analogous. 

The  proteins  and  their  derivatives  have 
been  investigated  in  this  manner  in  order 
to  arrive  at  a  better  understanding  of  their 
biological  significance. 

Part  II.  gives  the  author's  version  of  the 
preparation  of  soaps  from  the  standpoint 
of  colloid  chemistry,  in  which  the  hydra- 
tion theory  is  supported. 

In  Part  III.  analogies  are  adduced  be- 
tween the  behaviour  of  soaps  and  albumin- 
ates and  organic  tissues. 

Part  IV.  is  by  way  of  a  supplement,  con- 
taining physico-chemical  data  of  various 
series  of  acids  of  importance  in  soap- 
making. 

So  far  as  the  reviewer  is  able  to  judge, 
the  translation  has  been  well  done,  and  al- 
though the  views  expressed  are  not  always 
those  generally  accepted  and  understood, 
this  edition  should  be  well  received. 

J.G.F.D. 


This  list  is  specially  compiled  for  the  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chanoery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade 
Marks,  and  Designs,  can  be  obtained  gratuitously. 

Latest  Patent  AppUeatwns. 

901— Chemical    &   Metallurgical   Corporation,  Ltd. 
— Acid-resisting  tanks,   etc.    Jan.   10. 


1775— Phopal   Produce     Ti-ust,     Ltd.— Process     for 

obtaining  oxalic  acid  or  its  salts.    Jan.  19. 
1674— Clayton     Aniline     Co.,     Ltd.— Treatment  of 
^6— Cowburn.     A.     W. — Production     of     concen- 
trated  sulphuric  acid.    Jan.   10. 
734 — Roucka,   E. — ^Apparatus      for   measuring    and 
transmittinif  values  of  physical   or   chemical 
quantities.    Jan.   9. 
1673 — Alcock.  H.  E. — Manufacture     of  phosphoric 

acid.    Jan.  18. 

acetyl  cellulose  in  alkaline  liquids.    Jan.  18. 
1301— Frink,     K.     L. — Producing     alumina       and 

glass-making'   salts.    Jan.   15. 
1G66 — Nolx^l,  h.  A. — Process  for  removing  nitrogen 

from  metal  and  alloys.    Jan.  18. 
1680 — Vaiitin,    C     T.     J. — Extraction     of     copper 

from   its  ores.    Jan.  18. 
1787— V.L.    Oil     Processes,     Ltd.  —  Treatment    of 

mineral  oils.    Jan.  19 

Specificatious   Published  this   Week. 

190783— Barton.  G.  V.,  and  Lead  Products  Syndi- 
cate, Ltd. — Apparatus  for  the  manufac- 
ture of  lead  oxide. 

190754— Foster.  A.  B.— Process  of  treating  hydro- 
carbon oils  and  tare. 

190923 — Linde  Air  Products  Co. — Process  and 
apparatus  for  the  separation  of  gaseous 
mixtures. 

190961— Mueller,  M.  E.— Method  of  recovering  hy- 
drocyanic acid  from  gas. 

191117 — Howland.  A.— Analysis,  synthesis,  ar- 
rangement, and  notation  of  colours,  and 
apparatus  thereof. 

191122— Abbott  Laboratories. — Production  of  cer- 
tain esters  of  aromatic  acids. 

191129— Adeltanado,     L.— Manufacture     of     super- 

fhosphates  and  manure, 
'urner,    W.   L.— Manufacture     of     metals 
and     metallic     alloys     by     the       alumino- 

4-  V)  rv  J*  TjT  J  p    01*00  6SS 

184760— Caspar,  C.  H.— Process     of  distilling    and 

concentrating  liquids. 
191215— Dieterich,   H.— Process     of  manufacturing 

oxide  of  iferium. 
191233— Soc.     of     Chemical     Industry     in  Basle.— 

Manufacture     of  derivatives    of   Dihydro- 

isoquinoline. 
191305— Soc.  of     Chemical     Industry     in     Basle.— 

Manufncture  of   azo-dyestufls. 
191318— Cross,    R.— Process    for    converting    hydro- 

carl>on  oils  into  oils  of  lower  boiling  point. 

Abstract  Published  this   Week. 

Titanium  dioxide;  vanadium  compounds.— 
Patent  No.  189700.— Mr.  E.  E.  Dutt,  of  7,  Vicarage 
Gate,  Kensington,  London,  has  developed  a  pro- 
cess for  the  treatment  of  the  residues  of  certain 
bauxites  after  they  have  been  first  treated  by  the 
Bayer  process  for  the  production  of  titanium  di- 
oxi'de  and  vanadium  compounds.  The  residues, 
after  washing,  are  dissolved  in  hydrochloric  acid 
to  yield  a  solution  containing  about  100  grm. 
titanium  chloride  per  litre.  Any  considerable 
excess  of  acid  is  then  neutralised,  the  iron  is  re- 
duced, and  alkali  acetate  added  to  the  solution 
in  amount  equal  to  one-tenth  of  the  titanium 
chloride  present.  The  solution  is  boiled  to  pre- 
cipitate titanium  dioxide,  and  almost  coniplefcely 
neutralised.  The  filtrate  is  treated  with  barium 
salts  to  prec'pitate  barium  vanadate,  which  may 
be  used  in  the  preparation  of  other  vanadium 
compounds. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


FEBRUARY  23,  1923. 


THE   CHEMICAL   NEWS. 


lis 


THE  CHEMICAL  NEWS. 

VOL.  CXXVL      No.  ;^280. 


SUBSTANCES  DISS<:)LVE1)  IN  RAIN 
AND    SNOW. 

By  H.  8.  J.  FRIES. 

Cf>iisid(ni.hlo  int€Ht*»t  has  been  ahown 
throughout  thiC  country  on  Uu-  determina- 
tion of  the  charactor  and  quflutity  of  sub- 
stances dissolved  in.  jiaia  and  snoiw.  The 
accom^panving  article  is  a  icontinuation  of 
the  winalj-BtH  <:f  rain  .and  snow,  which  has 
been  cmrrird  on  at  Cornt<ll  (>>llege  for  a 
number  of  ^oare. 

The  -saimplos  that  w<<re  anialused  were  col- 
lected in,  enanK-lware  f^ms  n«^ar  the  oentr«' 
oif  the  town.  The  t(j(wn  of  Mount  Vernon 
is  seventeen  miles  fiom  Cedar  Rapid*»,  th** 
ne»ro«t  mnnufucturing  cenrtre,  aod  the 
town  itself  has  no  industries  of  its  own. 

Fortfy'-imet  sn.mf)l<'K  of  rain  and  imow  wrro 
f'ol'eated  and  analysed.  Diiriiig  tlie  perio4l 
from  S^^ptem^X'r  19.  1021.  to  .J\>ne  2.  1922, 
tliere  wa*  a  tcAal  pnt-ipitatioa  of  17.46 
inchoe  of  rain,  includiavg  snows.  Twelve 
inches  of  ^now  wt%v  tnkcn  to  equal  one  inch 
cii  raiji. 

The  totn.1  pound!*  of  nitratc*4  per  acre 
were  1.074.  In  ordrr  to  <lri«rmin£»  the 
number  of  poimds  of  eftch  siil>stane<>  thai 
fe'!l  per  acre,  wo  took  220,()0(>  pounrls  to  be 
the  w<'ight  <jif  ome  inch  f>f  rain  (vn  one  acre. 
We  found  there  w.f«?  0.183  poundJs  of  ni- 
trites ptT  acrt'.  The  total  p^arnds  of  free 
anamonia  per  acne  were  1.813.  The  total 
poumls  of  albiDininoid  aiiunjnia  per  acre 
wen^  1.327.  The  prccipitviiion  ol  sulphates 
as  SOj  was  0.6919  pounds  pei*  aone.  The 
total  pounds  of  chlorine  as  chlorides  wa>« 
7.942  per  acre. 

These  analyses  were  cairied  on  under 
ordinarjr  laboraA^or^'  conditions,  at  the 
same  tame  avoiding  unacia^s.ary  contami- 
nation during  prooesaes.  'I'he  "samples 
were  analysed  as  soon  after  their  colleotion 
as  possible. 

It  is  rather  interesting  to  note  that  the 
rainfall  during  the  lattrr  part  of  Octf>her. 
and  t*he  laittcr  p«rt  of  Fobr^iMry,  wam  ap- 
proximately the  «ame.  and  the  highest 
point  n  ached  in  ejach  month  was  exiactly 
the  same.  Also,  tho  rainfall  during 
December  and  April  was  appro.xinaately  tho 
same,  ag-ain  reaching  tftie  same  high  point 
in  waterfall  This  same  phenftmrnon  was 
agiain  ol)SCrved  tq  be  found  for  tho  months 


Oif  November  and  Maroh.  The  high  point 
for  theee  two  months  was  0.50  and  0.52 
inches  respectively. 

Grafa.<ful  acknowlit^meut  is  made  of 
the  kind  awiitiatanee  and  suggestions  of  Dr. 
Xiclv)las  Kni>jht  in  eaarj'ing  on  this  work. 

Cornell  College, 

Moun$  Vcnion,  Id^uxb. 
Jafiuary  20,  1923. 


A  METHOD  FOR  THE  NAMING  OF 
ALL  ORGANIC  COMPOUNDS. 

By  T.  Sherlock  Wheeler,  B.Sc, 
A.R.C.Sc.L,  A.I.C. 

The  "  structure  line  "  system  for  re- 
presenting the  constitution  of  organic 
o.^tnpoiinas.  descril^ed  by  the  author  in  The 
Chemical  NeuH,  January  19  and  2fi,  and 
Febniary  2  (1923.  ('XXVI.  327r)-6-7),  is 
the  basis  of  this  new  nomenclature  system, 
and  in  describing  the  latter,  the  compounds 
I..  II.,  III.,  etc..  of  the  preceding  artide 
will  be  referred  to  by  the  same  Roman 
numbers. 

Comp')und  I.  {Chemical  Newit,  1923. 
CXXV.,  p.  83)  is  on  the  "structure  line" 
system  represented  by  Ar.  VI.  2,  8  IV.  2, 
8  VI.  4.  5  VI.  2.  3  IV.  and  its  derived 
name  is  hexar-2.  3-tetrar-2,  8-hexar  -4, 
.'S-hexar  2,  3-t«'trar.  The  number  of  car- 
bons in  a  ring  shown  by  the  Roman  nu- 
merals in  the  representation  is,  in  the 
name,  replaced  by  the  corresponding  Greek 
number  followed  by  "-ar."  or  "-al."  re- 
spectively, according  as  the  ring  is  aroma- 
tic or  aliphatic.  Chains  are  shown  by  add- 
ing "-  an."  to  the  Greek  number  corres- 
{>onding  to  the  barred  Roman  numeral  in- 
d  eating  the  chain.  The  termination  is 
ado- t^d  because  the  barred  Roman  numer- 
als represent  fundan)entally  waturated 
hydrocarbon  chains,  and  "an"  is  the 
usual  termination  for  such  chains. 

.\II  the  rules  for  the  representations 
apply  to  the  nani(>s.  Thus  everything 
about  a  chain  or  ring  comes  in  brackets 
immediately  after  its  name;  in  the  chain  or 
ring  are  included  all  elements  linked  to 
two  carbons,  and  these  are  shown  bj'  their 
names  before  the  miniber  of  the  place  they 
occupy:  the  names  of  groups  and  elements 
attached  to  one  carbon  oome  after  the 
number  of  that  carbon.  Double  bonds  are 
called  "en"  triple  "in"  as  is  usual.  These 
syllables  precede  the    number  of  the    ele- 


114 


THE    CHEMICAL    NEWS. 


FEBRUARY  23,   1923. 


ment  from  which  the  double  or  triple  bond 
starts.  It  is  better  not  to  incorporate  these 
syllables  in  the  chain  name,  as  is  done  at 
present,  because  with  several  double  and 
triple  bonds  confusion  arises.  Branches 
in  the  structure  line  are,  in  the  name, 
given  after  the  names  describing  the  main 
line,  dashes  being  used  for  identification 
purposes  as  before.  The  longest  chain  or 
ring    system    is  the    one  along    which,    or 


Number  of 
Compound 
(in  loc.  oit.)  Representation. 

II.        Ar.  VI.  (I-NO2,  4-NHJ2,  3  V. 
(4  =  H2)2,  8V.  (2  =  H2)  3,  4  IV. 
(N-2). 

III.       Ar.  VI.  3,  4  VI.'  2,  3  VI."  2,  3 
VI.;  4',  5/  VI.;  4",  5"  VI. 

IV.  Ai.  n.  3  V. 

V.  Al.  III.  2"TV.'  4  IV. ;  2''nT. 

3  v.;  3' "TIT.  (3 -Br.) 

VI.  IT.'  5  IVT;  4'  IlT.  (3- CI.) 

VII      IT.   (0-3  N-7,  5-CI,  9  =  0,  9- 
OH,  A'.) 


VIII.   V.  (S-3,  3  =  0.) 


IX.  iX  (A«  «)  5  IV. 

X.  Al.  VI.  2,  3  VI.  2,  5  iTl  (N-2, 
2-Me.) 

XI.  Al.  VI.  1,  4  XIV. 

XII.  Ar.  VI.  2,  3  VI.  5,  6  VI. 

XIII.  Al.  VI.  2,  3  VI.  5,  6  VI. 

XII.     Al.  VI.'  2,  3  VI.  5,  4'  V" 

(fully 
reduced) 


through  which,  the  structure  line  first 
passes,  and  the  main  structure  line  is  made 
as  long  as  possible.  Also  Latin  numbers 
are  alwa.3^  used  to  show  recurrences  of 
groups,  elements,  etc.,  in  order  to  prevent 
ambiguity  with  the  Greek  numbers,  cis, 
trans,  and  asymmetric  compounds  are 
shown  as  in  the  representation  system. 

As  the  system  of  representation  has  been 
fully  described,  the  method  of  nomencla- 
ture will  be  clear  from  the  following:  — 


Name. 

Hexiar-(l-nitr(>,     4 -amino) -2,  3-pentar- 
(4  -  bi-hydro-)-2,    3    pentar-(2-bi-hydro) 

-  3 ,  4  -  tetrar  -  (nitrogen  -  2 . ) 

Hexar-3.  4  -  hexar'-2  3  -  hexar"  -  2,  3- 
hexar;  4',  5'  hoxar;  •}"  5"  hexar. 

HexnI-3-pontal. 

Trial  -  2  -  tetran'  -  4  -  t<>tral;  2'  -  trian 

-  3  pental;  3'  -  trian  -  (3-bix>mo.) 

Nonan'  -  5  -  t-etran ;  4'  -  trian  -  (3  -  chloro.) 

Nonan  -  (oxygen  -  3,    nitrogen -7,     5    chloro, 
9-oxy,  9 -hydroxy,  en -7.) 

Pentar- (sulphur- 3,   3-oxy.) 
(Note) :   Doubly-linked  sulphur  correspond- 
ing to  "oxy"  might  be  called  "  thio. " 

Nonan-(bi-en-5  :  8)- 5- tetran. 

Hexal-2,  3-hexa.-2,    5     trian -(nitrogen - 
2,  2 -methyl.) 

Hexal-1,  4  -  tetradeoal . 

Hexar -2,  3 -hexar- 5,  6  hexar. 

Hexal-2,  3-hexaI-5,  6-hexal. 

Hexa1'-2,   3  hexal-5    4'-pentan. 


FEBRUARY  23,  1923. 


THE   CHEMICAL    NEWS. 


Number  of 
Compound 

(in  l(jc.  cib.) 


115 


Representation. 


Name. 


XIV.    iT*    (1.4  =  (OH)^,    1:4  ^  O.,     Tetran - ( 1 : 4 -  bi-hydro,    l:4-bi-oxy.  en    '2 
A*,  1  trans  4.)  '      1  trans  4.) 


XV.       V.  (2 -Br.  trans  3  NO^  A- 
or 

+ 

T.  (2 -Br.,  a-NO^  A*). 


Penban- (2-bromo-trans  3-nitro,  en   2) 
or 

4 

Pentan-(2  bromo,  3  nitro  en -2.) 


x.x,.     ■^rr    ,^   ^    -  .,  S  Hexan-(2:3:5- ter    hydroxy,      4- hydroxy, 

^^^-   J^-i^--^J^^^(^>^^h,^~   (OB),  i:6-bi  hydroxy.)  "         ^  ^        ^ 

l:6=(OH)2)  QP 

or  +  +  -  + 

■••  +  -+  Hexan-(1:2:8:4:5:6-   sexi  hydroxy.) 

\T  (l:2:3:4:5:0a|{OH,)  J        J  > 

+ 

__"*'"  Tetran- (2 -chloro,  8-  bromo,  en -2.) 
XVII.  IT.  (2-C18-Br  A=.  ^ 


XVIII. 
Probable,  form- 
ula of  cineh- 
onine. 

Al.  VI.'  (N-4)  4,  1  VI.  8,  8' 
"VT.  (0-4)  5TI.  2  Ar.  VI.  (N-4) 
6,  6  VI. 

These  examples  ji^iven  will  suffice  to  show 
that  the  flvstem  can  supply  a  sysiematrc 
name  for  any  compound,  no  matter  how 
complex,  provided  it"*  structure  be  known. 
It  is  fundamental  in  principle  since  taking 
no  account  of  the  classes  of  compoimds,  it 
names  them  simply  on  the  ba««is  of  struc- 
ture, chains  or  rin^.  It  la  especially  suit- 
able for  abstractinj?,  indexinfif  and  record- 
inpf  purposes ;  no  longer  will  it  be  necessary 
t'>  give  the  graphit%al  formula  of  a  com- 
pound after  its  name.  Ifc  marks  anothor 
advance  in  the  writing  of  chemical  formula* 
which  passed  years  ago  from  the  old  type 
system  to  the  graphical  linking  system,  and 
then  stood  still.     The  new  method  has  the 


llexal'- (nitrogen -4) -4.  l-hexal-8.  8'- 
hexan  -  (oxygen -4)  -  5-dian  -  2  -  hexar 
-(nitrog«^n-4)-6,  6-hexar. 


double  advantage  of  enabling  a  compound 
to  be  named  frcmi  its  formula,  or  alterna- 
tively the  formula  can  be  deduced  from  the 
name. 

In  The  Chemir<il  News,  1021.  CXXII.. 
122,  the  author  iput  forward  a  logical 
scheme  for  the  naming  of  the  fundamental 
groups  of  orgimic  chemistry.  That  scheme 
is  very  easily  fitted  into  the  above ;  it  only 
neceesitaies  an  alt(  ration  in  the  termina- 
tions and  in  the  names  of  some  of  the 
grouper.  In  the  same  paper  are  indicated 
methofls  by  which  a  new  system,  such  as 
fche  above,  could  be  introduced  into  the 
science  of  chemistry. 


[Contribution  fr<im  the  Department  of 
CiiKMisTRY,  Cornell  Univrrsity.] 

GERMANIUM.     IV.— GERMANIUM 

TETRA-IODIDE.' 

Bv  L.  M.  Dfnnis  and  F.  E.  Hance. 

(From   the  "  Journal  of  fhr  American 

Cheinica'   Society/'    Deremher,    1922.) 

Winkler"     prepared      germanium     tetra- 
ifwlide  by  heating    ipulvenilont    germanium 


in  vapour  of  iodinr  that    was  carried  over 
the  metal  by  a  slow    ourreni  of  eiarbon  di- 

'     The     inveHtiifntion     ttpim     which     thin 

article  in  haned  was    supported  by  a(  cfrant 

from   the     Uechschrr    Fo\in)Hati(M    for    the 

idvarurement   of   Research,    established  by 

August  Hechscher  at  Cornell  Vviversity. 

»  Winkler,  J.  prikt.  Chem..  CXTJI  (N.S. 
84),  177.  1886. 


116 


THE    CHEMICAL    NEWS. 


oxide.  He  found  it  necessary  to  sublime 
the  produot  repetate'dly  in  carbon  dioxide  to 
reonove  free  iodine.  He  describes;  the  sub- 
stance 'a«  highl^^  hygroscopic,  of  orange 
colour,  j^ellow  when  powdered,  possessing 
a  melting  point  of  144°,  land  aippearing  to 
boil  between  350°  and  400°.  He  gives  the 
results  of  an  anal\'^'i.s  of  the  comipound, 
and  adds  thiat  L.  F.  Nilson  found  that  ger- 
manium tetra-iodide  did  not  di.ssooiat^  up 
to  440°,  but  showed  considerable  dissocia- 
tion at  658°. 

Tihe  preserut  investigaition  describes  the 
preparation  and  further  study  of  thi'S  sub- 
set ance. 

Preparation. — Powdered,  crystalline  ger- 
manium was  pliaced  in  alundum  boats 
which  were  'then  inseiited  in  a  tuibe  of  Jena 
glaiss  lying  in  an  elecitric  combustion  fur- 
nace. A  thermometeiT  wais  laid  in  the  com- 
buiation  tube  beside  the  'boaits.  The  portion 
of  the  tube  projecting  beyond  the  furnace 
was  drawn  down  to  fi.Tnall  diameiter  at  7 
points  10  om.  lajpart.  Each  constrict' on 
was  packed  with  glass  wool.  Into  the  other 
end  of  the  combustion  tube  was  inserted 
the  neck  of  a  500  co.  glass  retort  containing 
purified  iodine.  The  tubulus  of  the  retort 
was  joined  to  an  apparatus  that  supplied 
pure,  dry  carbon  dioxide.  An  asbestos  box 
was  built  around  the  reitort,  and  this  was 
heated  from  the  outride  to  a  te-mperature 
sufficaenitly  'high  to  keep  the  retort  filled 
with  vapour  of  iodine.  The  introdaietion  of 
iodine  into  the  combustion  tube  was  regu- 
lated by  the  rate  at  which  carbon  dioxide 
was  paeised  through  the  retort. 

All  'air  in  the  apparatus  was  first  dis- 
ipliaced  by  carbon  dioxide,  land  then  the  re- 
tort land  tube  were  gradually  heated.  Union 
of  germanium  and  iodine  began  at  212". 
When  the  temperature  .had  risen  to  250°, 
there  appeared  in  the  hot  tube  just  before 
it  emerged  from  the  furnace  a  deipoisit  of 
yellow  and  red  crystals.  At  360°  very  rapid 
combination  of  gefrmianium  land  iodine  took 
place,  and  the  ®ublimiate  isteadily  increased 
until  there  had  collected  a  considerable  de- 
posit of  yellow  crystafe  just  beyond  the 
boat,  and  beyond  these  a  m^asis  of  orange- 
coloured  crystals  on  the  upiper  side  of  th^^ 


FEBRUARY  23.   1923. 

tube  and  a  ruby-red  liquid  along  the  bot- 
tom of  the  tube. 

The  operation  was  continued  for  30 
hours,  and  at  intorvals  during  the  \x\n  the 
product  that  had  formed  was  caused  t/O 
sublime  through  the  constrictions  beyond 
the  fiunace  by  gently  heating  the  tube 
with  a  Bumsen  flange.  It  was  noted,  how- 
ever, that  as  the  sublstance  was  driven 
througli  the  succeissdve  con,strictions,  its 
colour  gi-arluallv  changed  from  bright  red 
(Mullikeu's  Colour  Standard''  R.  Shade  2) 
to  a  chocolate -brown  (R.  0.  Shade  2).  In- 
aismuch  as  tJiis  change  of  coJour  indiicated 
that  the  germanium  tetra-iodide  under- 
went decomposition  when  sublimed,  the 
experiment  was  repeated  with  a  tube  that 
was  not  constricted,  and  the  red  liquid 
which  collected  jusit  within  and  beyond  the 
hea'ted  p;vrt  of  the  combustion  tube  was 
allowed  to  cool  in  the  tube  at  the  end  of 
the  run  , which  wais  of  70  houns'  duration. 
It  solidified  to  a  mass  weighing  about  50  g. 

Durinig  this  run  there  appeared  on  the 
wajilsi  of  the  tube,  between  the  last  boat 
and  the  red  tet.ra-iodi<le,  a  deposit  otf  light 
yellow  orysitals  that  were  found  to  be  ger- 
manous  iodide,  G'el2.  The  crystals  were 
of  the  hexagonal  system  with  external 
angles  of  120f.  The  compound  will  be 
fully  deacribed  in  a  Later  article. 

Amihjsis. — Portion)s  of  the  red  product 
were  weighed  in  porcelain  crucibles  and 
were  moi(s,tened  with  wa.ter.  Cone,  nitric 
acid  was  added,  and  the  contents  of  each 
crucible  was  evaporated  to  diryness  on  a 
steam  cup.  A  few  drops  of  oono.  sulphuric 
acid  were  added,  the  acid  w'as  carefully 
fumed  off,  and  the  crucible  was  then  heated 
to  about  900°.  The  residual  germanium 
dioxide  was  then  weighed. 

For  the  determination  of  iodine,  samples 
were  disisolved  in  water,  0.1  N  (solution  of 
silver  nitrate  was  islowly  added,  and  the 
liquid  wais  vigorously  shaken  until  the  yel- 
low precipitate  collected  and  the  super- 
natant liquid  became  clear.  About  3  cc.  of 
cone,  nitric  acid  and  a  few  oc.  of  a  solution 
of  lammonium  ferri  calum  were  then  added, 
and  the  exces®  of  silver  was  titrated  with 
potassium  thiccynate  solution. 


Wt.  of  Gel, 

Wt. 

of  Ge 

Wt. 

of  I 

Calc. 

Found 

Calc. 

Found 

G. 

G. 

G. 

G. 

G. 

0.1975 

0.02468 

0.0243 

1.085P) 

0.13565 

0.1357 

0.1790 

0.02237 

0.0225 

0.1329 

0.0166 

0.0165 

0.2015 

0.1763 

0.1761 

0.2067 

0.1809 

0.1807 

FEBRUARY  23,  1923. 


THE   CHEMICAL    NEWS. 


117 


Melting  Point. — The  moasureraents  were 
made  with  a  "Tycos"  Precieion  Thermo- 
meter, nitrogen  fiHed.  range  100°  to  155", 
The  apparatus  was  that  described  by 
Dennis,*  whiidh  was  filled  with  cone,  sul- 
phuric acid.  The  sample  wa«  placed  in  a 
small  melting-point  tube  that  was  attached 
to  the  thermometer,  ami  the  sulphuric  acid 
was  then  heated  ab  such  nite  as  to  cause  a 
rise  of  1°  per  minute.  The  yeJlow,  pow- 
dered,  germanium  tetra-dcdide  assumed  an 
orange  tint  as  the  temperature  rose,  and 
at  132°  iA  beoame  deep  red  in  colour.  It 
melted  sharply  to  a  ruby -coloured  liquid  at 
144°.  Repetition  of  the  experiment  gave 
the  '$*aTue  resuli  ae  did  a  ^hird  determina- 
tion in  which  was  employe<l  an  AiLBchiit/ 
thermometer  tbab  bad  bet>n  correoted  by 
the  Bureau  of  Standards. 

Crystal  Form. — A  crystal lographic  ex- 
amination of  the  substance  wag  kindly 
nwkfle  for  us  by  Professor  A.  C.  Gill,  of  the 
Deipartment  of  Mineralof^y.  The  crystals 
were  (prepared  by  slow  and  careful  «ublinin- 
tion  in  a  currenit  of  dry,  warm  air.  Thoy 
were  found  to  be  regular  ()c<tHhedroii9;  the 
plan*'  angles  were  60°.  indicatine  that  they 
ii(^lr>n4?  to  the  regular  system.  The  crysi^ln 
HlH>we<l  no  double  n>fractif>n. 

Specific  Gravity. — In  searching  for  a 
liquid  metlium  in  which  th<'  specific  gravity 
of  gennanium  teira-iodide  nii^'ht  be  deter- 
mined, ita  behaviour  toward  more  than  20 
inorganic  or  organic  liquids  was  investi- 
gated. In  every  oaee  the  substance  wa» 
dissolved  or  decompowod  by  the  liquid.  (See 
Chemical  Prx>perti<^.) 

Since  the  tetrachloride  and  tetrabromide 
of  germanium  hml  been  found  to  be  un- 
affedted  by  cone,  sulphuric  acid  at  rriom 
temperature,'  the  behaviour  of  the  tetra- 
iodide  to\^wd  thi«  acid  wias  examined,  and 
it  was  found  that  at  room  temperature  no 
visible  change  could  Ih«  obs*  rved  in  the 
subfitance  «£<er  flubmersion  in  the  acid  for 
24  hours  Con«eq\ien«tly.  cone,  sulphuric 
acid  was  need  in  the  determination  of  the 
fiipecifio  gravity  of  the  compound.  Pure 
germanium  tetra-indide  was  prepared  in  the 
form  of  pelle*B  by  spreading  the  powdered 
subftbanoe  lalon^  the  inside  of  a  long  tube  of 

»  Mnllrhcn,  "  Idrntificatidn.  of  Pvrr  Or- 
ga-tiio  C(mip(mnds,"  J(ihn.  Wiley  and  Sons, 
1903.  Vol.  I.  ^ 

*  Dennit,    J.    Ind.    Enq.    Chem..    1920. 

XII..  366. 

"  See  Demtin  amd  Hnncc,  Jour.  Avicr. 
Chem.  Soc,  1022.  XLIV.,  209. 


Jena  glass  and  melting  it  in  a  partial 
\acuum.  The  temperature  was  kept  below 
150°.  When  the  eoinpound  melted,  it 
coalesced  into  small  globules  about  3  mm. 
in  diameter.  A  pycnxwneter  of  5  cc.  capa- 
city waa  weighed,  was  then  half  filled  with 
the  pelfcts  of  the  tetra-iodide,  and  was 
again  weighed.  Cone,  eulphuric  acid  was 
now  run  in  until  the  sample  was  completely 
covered,  and  the  air  oiooluded  in  the  pyo- 
nometer  was  then  removed  by  placing  the 
bottle  in  a  vacuum  deaiooatw  and  exhaust- 
ing the  air.  The  pycnometor  wae  then 
filled  with  sul|phuric  acid  and  was  again 
weighed.  The  eptn-ifio  gravity  of  the  eul- 
phuric acid  at  the  s^vme  temperature  waa 
determined  with  the  aitme  pycnometer. 
Two  determixiatioii£  at  26°  gave"  4.322  and 
4.821.     Henoe  dg    =  4.3215. 

Colour  of  Qermaniitm  Tetra-iodide. — At 
room  te^nperature,  fused  germanium  tetra- 
iodide  in-  lump  fonn  ie  of  the'  colour  of 
coral,  the  precise  shade  being  "  O.  R.  Nor- 
mal."* When  powdered,  it  has  an  orange 
colour  •'  O.  Y.  Nonual." 

The  compound  in  lumip  form  shows  at 
various  tciiipenatutvtt  the  coloura  listed 
below. 

Temp.        Colour.  Mu  I  liken. 

- 185°    Canary-yell(»w  O. 

-  6(f    Bufif  Y.O. 

-  l(f    Orange  O.Y. 
^  85°     Salmon  Y. 

+  50°     Briok-red  O.K. 

+  90°     Red  R. 

+  144°     Ruby-fed  R.O. 

SubUmathfu  of  Gvrmunium   Tetra-iodide. 

About  5  g.  nf  the  subatanoe  was  placed 
in  a  tr**-tube;  in  the  neck  of  the  tube  was 
iasert«Hl  a  cork  that  carried  a  thertTiometer 
anrl  inlet  and  outlet  tubes  of  glass.  The 
iest-tnibe  waa  immersed  in  an  oil-bath,  and 
a  slow  current  of  dry  air  was  passed 
through  the  tub<\  The  oil  was  slowly 
heated.  At  110°  a  yellow  vapour  appeared 
in  the  upper  portion  of  the  tube,  and  as  the 
teonperat'ure  rose  beyond  this  point  a  finely 
oryfjititlline,  j-ellow  powder  collected  on  the 
tube  wall.  When  the  tetra-iodide  had 
rcjiched  a  temperature  aHghtly  above  its 
melting  point  (144°),  sublimation  was  rapid. 
The  heating  wa«  then  stopped,  ami  the 
tube  was  allowed  to  cool  slowly.  At  the 
conclusion  of  the  experiment  a  mass  of 
quite  large,  orange -coloured  oryshale  had 
collected  on  the  s-teiu  of  the    thermometer 


•  MuUiken'g  Colour  Standards.     Ref.  3. 


118 


THE    CHEMICAL    NEWS. 


FEBRtFAEY  23,  1923. 


and  the  uBsublimed  residue  in  the  tube  was 
of  ruby-red  oolour.  lit  is  thus  aippaxent 
that  when  germanium  tetra- iodide  is  care- 
fully heated  in  a  current  of  air  to  a  tem- 
perature but  slightly  •above  its  melting 
point  it  isublimes  without  deicomposition. 

Nilson  and  Petter&son  have  stei^tod^  that 
the  compound  "  exist*  undecomposed  in 
the  gaiseols  condition  at  440°  but  dissociates 
ait  higher  tempeirature."  They  base  this 
sitatement  upon  the  result  of  a  determina- 
tion of  the  vapour  density  of  the  compound 
when  it  was  volatilised  at  440°  (via,pour  of 
sulphur).  They  obtained  a  Vapour  density 
of  20.46,  the  theorotioal  vapour  density 
being  20.0.  Our  observations  during  the 
preparation  of  germanium  tetra-iodide 
seemed,  however,  to  indicate  that  the 
compound  is  disisoL'iated  when  he'ated  to 
temperatures  appreciably  above  its  melting 
ipoint.  To  gain  definite  informiation  upon 
this  question  glass  tubes  1  m.  long  and  10 
mm.  wide  were  sealed  at  the  lower  end  and 
were  inserted  in  vei'tiaal  position  into  an 
electric  heating  fura.ice  to  a  distance  of  20 
am.  The  tubes  were  then  heated  to  a  tem- 
perature of  445°,  and  a  small  open  tube 
containing  gernmnium  tetra-iodide  was 
dropped  into  each.  In  a  few  minutes  a 
reddish  brown  vapour  appeared  in  the  long 
tube®  just  -above  the  top  of  the  electric  fur- 
nace, and  shortly  thereafter  dark-coloured 
crystals  were  deposited  on  the  inner  walls 
of  the  tube  at  a  distance  of  about  8  cm. 
ahove  the  top  of  the  furnace.  The  heating 
was  continued  or  some  time  at  a  tempera- 
ture between  442°  and  448°,  and  the  tubes 
were  then  cooled  and  removed  from  the 
furnace.  The  eiystalline  deposit  8  cm. 
above  the  furnace  was  identified  as  free 
iodine.  Just  at  the  top  of  the  furnace  there 
was  «,  deposit  of  yellow  crystals,  which 
proved  to  be  germanium  tetra-iodide.  Mid- 
way between  the  bottom  of  the  tube  and 
the  top  of  the  furnace  there  was  a  deposit 
of  oanary-yellow  crystalline  plates  of  ger- 
manium di-iodide. 

A  small  quantity  of  germanium  tetra- 
iodide  wasi  plia.ced  in  a  tube  of  Jena  glass 
which  was  then  sealed  and  was  gradually 
heated  in  an  electric  combustion  furnace  to 
a  teniiperature  of  440°,  Dissociation  re- 
sulted, land  iodine  amounting'  to  over  5  per 
cent,  of  the  weight  of  the  tetra-iodide  wa.s 
set  free. 

(To  be  continued.) 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


''    Nilson    and     Pettersson,     Z.     physik. 
Chem.,    887,  I.,  36. 


THE  ROYAL  SOCIETY. 

Thursday,  February  15,  1923,  at  4.30  p.m. 

Eapers  read :  — 

E.  E.  tSPEYER. — Researches  upon  the 
Larch  Chcrmes  {Cnaphalo'pes  strobiloibius, 
Kalt.),  and  their  Bearing  upon  the  Evoiu- 
tioiv  f)j  the  ChermesiuiB  in]  general.  Com- 
municated by  Prof.  G.  C.  Bourne,  F.R.tS. 

(1)  An  alternation  of  form  is  tlie  normal 
course  of  biological  development  in  all 
Chermesince. 

(2)  This  alternation  breaks  down  at  a 
certain  point  in  the  life-cycle  of  Cnti<pha- 
lopes  strobilobius,  Kalt.,  the  numerical  pro- 
portions of  one  form  to  another  produced 
in  tilie  same  generation  showing  the  period 
at  which  failure  in  the  alternating  mechan- 
ism takes  place. 

(3)  The  Progrediens  type  of  Cnwphailo'pes 
strobilobius,  Kalt.,  is  potentially  a  winged 
form,  and  is  not  a  true  dimoiphism  of  the 
Sistens  type.  This  applies  also  to  all 
Cherniesince  in  which  either  or  both  of  these 
types  occur. 

(4)  The  Sexuales  are  different  morpho- 
logicially  from  all  other  generations.  They 
are  held  to  be  a  new  production  in  evolu- 
tian. 

(5)  Species  which  are  purely  partheno- 
genetic  have  ceased  to  develop  from  an  evo- 
lutionary point  of  view,  and  show  itihe  prob- 
able course  of  evolution  in  the  various 
genera. 

(6)  Migration  from  one  species  of  Conifer 
to  another  is  responsible  for  a  duplication 
in  the  series  of  form-alternating,  partheno- 
genetic  generations;  the  series  upon  one 
Conifer  has  become  morphologically  differ- 
ent from  that  on  the  other  through  the 
action  of  natural  selection  in  two  different 
environments. 

(7)  In  existing  species  with  two  hos-t- 
plants,  that  portion  of  the  cycle  wtiioh  now 
takes  place  upon  the  definitive  host-plant, 
has  arisen  through  a  (atii,mulus  given  by  a 
recent  return  to  sexuality,  this  accounting 
for  the  linking  up  of  the  two  cycJes  and  a 
duplication  of  the  series  of  parthenogenetic 
generations. 

(8)  Under  these  circumstances  the 
theories  of  "  parallel  series  "  and  "  poly- 
morphy  "  (become  obsolete. 

Ct,  V.  Anrep. — The  Irradiation  of  Condi- 
tioned Reflexes.  Communiciated  by  Prof. 
E.  H.  Starling,  F.R.S. 


FEBRUARY  23,  1923. 


THE  CHEMICAL  NEWS. 


119 


The  exiperiineiits  were  performed  with 
tactile  conditioned  reflexes,  the  parotid 
gland  being  taken  as  ihe  effector  organ. 
The  following  facte  were  established:  — 

(1)  The  textile  reflexes  estabKshed  on 
one  side  of  the  animal  irradiate  without  a 
measurable  decrecneiit  into  the  obher  side 
of  the  animal. 

(2)  There  is  a  progressive  deorement  in 
the  conditioned  reflex  during  it«  in'adiation 
over  each  of  the  two  aides  of  t(he  animal. 

(3)  The  conditioned  inhibition  is  in 
broad  Kfliiits  a  cruder  form  of  inhibition 
than  tihe  differential  inhibition. 

(4)  The  irradiation  of  the  conditioned  in- 
hibition follows  in  the  main  Hnee  the  rules 
ci-t;ib!iished  for  the  irradiation  of  the  differ- 
ential inhibition  and  that  of  the  reflex  it- 
self. 

(5)  The  inhibitory  processes  previously 
established  are  temporarily  inhibited  during 
the  development  of  a  new  inhibition. 

(6)  The  short  trace  reflexes  take  an  intor- 
n>ediate  position  between  the  simultaneous 
and  the  long  trace  reflexes. 

Papers  Read  in  Title  Only. 
M.  Dixon  and  H.  E.  Tunnicliffb. — Thr 
Dx'uhition    of    Reduced    Qluthaihione    and 
other  Sulphydryl  Cctmjjtynnda .     Communi- 
ojited  by  Prof.  F.  G.  Hopkins,  F.R.8. 

(1)  A  study  has  been  marie  of  the  sul- 
phydryl compounds :  reduci^d  gluthathione. 
cystein  and  thioglyooHic  acid.  The  reduc- 
tion of  methylene  blue  by  these*  w  in  each 
case  an  aut'ocatalytio  reaction. 

(2)  The  active  agent  pro^lucing  <tiiJ8  cata- 
lysis is  the  disulipnide  form  R  .  S  .  8  .  R. 
All  the  disulphidee  atudicd  poepsese  the 
j)ower  of  catalysing  the  reduction  by  each 
of  ihe  sulphydryl  compounds. 

(8)  Evidence  is  advanced  in  support  of 
the  hypothesis  that  a  more  nctive  addition 
compound  of  R  .  SH  witJh  R'.  S  .  S  .  R'  \h 
fo'rmed. 

(4)  It  is  sAiown  by  three  methods  that 
the  disulphide  compounds  also  catalyse  the 
oxid^ition  of  the  sulphydryl  ct^mpounds  by 
atmosplierio  oxygen.  The  fonn  of  the  re- 
action curves  is  not  autocataljiic,  but  an 
exiplanation  for  this  is  suggested. 

(5)  The  reaction  velocity  in  the  cases  of 
glutathione  and  cystein  shows  a  sharp  opti- 
mum at  a  pH  of  7.4.  ThioglycoUic  acid 
does  not  show  this. 

(6)  Tlie  influencf^  of  various  fiactors  on 
tht'  reaotion  is  described. 

(7)  The  l>earing  of  these  resulta  on  the 
conception  of  thJo  function  of  glutathione 
and  related  compounds  in  tissue  oxidation 
processes  is  discussed. 


J.  C.  Bramwell,  R.  J.  S.  McDowALL, 
and  B.  A.  McSwiney. — The  Variation  of 
Arterial  Elasticity  with  Blofpd  Pressure  in 
Man.  Communicated  by  Prof.  A.  V.  Hill, 
F.R.S. 

A  method  is  described  by  which  the  ex- 
tensibility of  an  artery  in  living  man  may 
be  measured  at  all  internal  pressures  up  to 
the  diastolic  pressure.  As  Ln  the  case  of  an 
isolated  artery,  the  extensibility  decreases 
as  the  internal  pressure  is  increased. 

L.  J.  Harris.— On^  the  Existence  of  an 
Unidentified  Sulphur  Orouping  in  the  Pro- 
tein Molecule.  Part  I. — On  the  Deriioiura- 
tiofi'  of  Proteins.  Part  II. — OA  the  Estinui- 
tion  of  Cystine  hu  certaitk  Proteins.  Com- 
municated by  Prof.  F.  G.  Hopkins,  F.R.S. 

Results  obtained  by  nuny  workers  in  the 
past  point  to  the  existence  of  an  undis- 
covered sulphur  linkage  in  certain  proteins. 

A  studj  has  been  made  of  t)he  conditions 
under  which  the  grouping  reactive  to  nitro- 
prusside  is  liberated  from  ovalbumin  and 
other  proteins,  and  of  its  survival  in  the 
proteose,  pefvtone  and  polypeptide  mole- 
cule. 

The  production  of  this  reactive  group  is 
an  essential  feature  of  the  denaturation  of 
ovalbumin  and  certain  other  proteins. 

The  chemical  nature  of  precipitation,  de- 
oatunation,  and  coagulation  is  discussed. 

It  is  suggested  that  the  nitroprusside  re- 
action, attributed  by  Arnold  to  cystein, 
ma,y  be  dua  to  the  presence  of  a  grouping 
of  the  thiopeotide  type. 

A  new  metnod  has  been  employed  for  the 
gmvimetric  eatimatioa  of  cystine  in  pro- 
teins. The  results  indicate  that  whereas 
in  serum  albumen  the  cystine  accounts  for 
no  lees  than  89  per  cent,  of  the  total  sul- 
phur content,  in  ovalbumin  86  per  cent,  of 
the  sulphur  still  remains  to  be  accounted 
for. 

PreJiminary  work  has  been  started  on  the 
isolation  of  sulphur  bodies  from  the  degra- 
dation products  of  protein. 

N.  B.  Lauohton. — Reflex  Contraelums 
of  the  Cruraln  Muscle  in  the  Decerebrate 
and  Spin<il  Frog.  Communicated  by  Sir 
Charles  Sherrington,  P.R.S. 

(1)  In  the  decerebrate  frog  there  was  a 
prolonged  tonic  aftor-efifect  in  the  contrac- 
tion of  the  cruralis  muscle  on  reflex  stimu- 
lation of  the  ipsilateral  sciatic  nerve.  No 
such  tonic  efiEeot  was  observed  in  the  cru- 
ralis muBcle  of  the  spinal  preparation  on 
stimulation  of  the  same  nerve. 

(2)  A  shorter  l«.t<^nt  period  and  a  more 
rapid  increment  of  height  were  marked  in 
the  spinal  preparations. 


120 


THE    CHEMICAL    NEWS. 


FEBRIJAEY  23,  1923. 


(8)  During  spinal  shocik  the  heigiht  of  the 
reflex  oantraction  in  the  spinal  frog  is  not 
maximal. 

(4)  In  50  per  cent,  of  the  experiments 
the  height  of  the  myogram  wias  gre.ater  in 
the  deicerebrate  than  in  the  spinal  prepara- 
tions. In  the  other  50  per  cent,  of  the  ex- 
periments, the  height  of  the  contraotions 
was  greater  in  the  ispinal  than  in  the  tle- 
eerebrate  frogs. 


The  Bakerian  Lecture  was  delivered  on 
Thursday,  February  22,  at  4.30  p.m.,  by 
G.  I.  Taylor,  F.R.S.,  and  C.  F.  Elam,  on 
The  Distortion,  of  ain  Alu.ininium  Ci-ystal 
durirug  a  Tensile  Test. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 
The  Annual  Genera-l  Meeiting  of  the 
Society  was  held  at  the  Chemical  Society's 
Rooms,  Burlington  House,  on  Wodnesdtay, 
Feibruary  7,  when  tihe  President,  Mr.  P.  A. 
ElLis  Richards,  delivered  his  annual 
address. 

The  following  were  elected  as  Officens 
and  Councdl  for  the  ensuing  year:  — 
President:  P.  A.  El liis.  Richards. 
Past-Presidenis,  Sesving  on  the  Council 
(Limited  by  the  Society's  Articles  of  Asso- 
ciation to  8  in  number) :  Leonard  Arch- 
butt,  A.  Chas'ton  Chapman,  Bernard  Dyer, 
Otto  Hehner,  SamueJ  Rideal,  Alfred 
Smetham,  E.  W.  Voeloker,  J.  Augustus 
Voel'ckeir. 

Vice-PresiderUs :     F.  W.   F.  Amaud,    F. 
H.  Carr,  G.  W.  Monier-Williams. 
Hon.  Treasurer:  Edvv^ard^  Hinks. 
Hon.  Secretary:   E.  Ri^ghardis  Bolton. 
Assistant  H&n.  Secretary:  R.  G.  Pelly. 
Other  Members  of  Cmincil :     H.  Ballan- 
tyne,     S.  F.    Burford,    S.    Elliott,    B.    S. 
Evans,   E.  M.   Hawkins,   Harri  Heap,     H. 
F.  E.  Hultton,  Andrew  More,  A.  E.  Parkes, 
W.  R.  Schioeller,    G.  R.  Thompson,    J.  F. 
Tocher. 

At  tJhe  Ordinary  Meeting  on  February  7, 
1923,  held  ai  the  Chemical  Society's  Rooms, 
Mr._  P.  A.  Ellis  Richards  (President)  in  the 
chair,  cerii£ciates  were  read  for  the  firs^t 
time  in  favour  of: — Messrs.  Josetph  .John 
B^a^lies,  A.R.C.Sc,  A.I.C.,  D.I.C.,  Samuel 
Gordon  Stevenson,  A.I.C.,  Richard  Wil- 
liam Sutton,  B.Sc.Te-eh.  (Manch.),  A.I.C., 
Laurence  Bamett  Timmis,  M.Sc.Tech. 
(Manch.),  A.I.C.,  Alfi'ed  Edward  Johnson, 
B.Sc.  (Lond.),  F.I.C.,  A.R.C.S.I.,    Ernest 


Victor  Jones,  F.I.C.,  PVancis  Kenelm 
Donovan,  B.Sc.  (Land.). 

Cei'tiiaoatcis  were  read  for  the  second 
time  in  favour  of: — Mest&rs.  George  Henry 
Applejard,  F.I.C.,  James  Walter  Black, 
B.Sc.  (Lond.),  Ai-thur  William  Starey, 
A.R.C.S.,  B.Sc.,  A.I.C..  John  M^atthew 
Wilkie,   B.Sc.    (Lond.),    F.I.C. 

The  fo.llo^\^ng  were  ejected  membtu's  of 
the  Socdety  : — ^Meissrs.  Henry  Aldous  Brom- 
ley, Walter  Horace  Clulow,  William  Pien- 
derleiith  Lowellen  Hope,  B.Sc.  (Edin.), 
A. I.e.,  Robert  Faraday  Tnnes,  F.I.C, 
Osman  Jones,  F.I.C,  Alan  Wesit  Stewart, 
D.Sc.  (Brux.),  A.I.C,  William  Heaton 
Thorns. 

The  following  papei^  were  read:  — 
Notes  on  the  Examination  of    Preserved 
Meats,  etc.,  by  Osman  Jones,  F.I.C 

Titanium  in  Nile  Silt,    by  E.  Griffiths- 
Jones. 

Abstracts. 

Notes  on  the  Ezaniinatiu'n  of  Preserved 
Meats,  etc.,  by  Osman  Jones,  F.I.C.  The 
author  stated  that  the  presence  of  a  trifvce 
of  zinc  chloride  in  the  tin  container  (which 
soonetiimes  arises  through  the  use  of  this 
salt  as  a  sioldering  flux)  caused  a  more 
raipid  absoi^ption  of  tin  by  the  food  con- 
tents, and  that  the  use  of  sealing  fluid 
containing  a  high  boiling  point  solvent 
Claused  a  disagreeablei  fla.vour  to  ha  im- 
parted to  the  food  material.  Methods  for 
the  detection  of  sooch  a  solvent  were  given. 
The  absorption  of  tin  by  the  meat  contents 
of  a  can  was  found  to  be  the  gi'eatest  at 
the  time  of  processing  and  almost  to  cease 
after  about  four  months.  The  author  also 
mentioned  a  teislt  for  Agar  in  the  presence 
of  gelatine  :  a  dilute  solution  of  iodine  in 
potassium  iodide  gives  ,a  crimson  colour 
with  Agar,  while  with  gelatine  an  orange 
eoloured  precipitate  is  produced. 

Titardum  in  Nile  Silt,  by  E.  Griffiths- 
Jones.  The  -author  has  examined  silts  from 
various  pairts  of  the  Nile,  and  determined 
the  Titanium  by  a  colorimeitric  method 
after  freeing  the  sample  from  silica. 
Amounts  varying  from  1.3  to  2.55  per  cent, 
of  titanium  oxide  on  the  dried  silt  were 
foimd,  but  an  examination  of  Egyptian 
straw,  a  likely  source  of  titanium,  only 
showed  0.4  per  cent,  of  titanium  oxide  on 
the  ash. 


FEBEUAKY  23,  1923. 


THB   CHEMICAL   NEWS. 


121 


THE  INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

Paper  read  at  the  Royai  Sooietj  of  Arts 
on  Tuesday,  Februaiy  13,  1923,  at  5.30 
p.m. : 

Some  Practical  Notes  oni  Oil    Pumping, 
by  G.  W.  E.  Gibson,  Member  "  Koniiiklijk 
Instituut    van  Ingeoieurs  "    (The   HagucV 
Member  "Soci^t^  de  Chcmie  Industritil< 
(Paris). 


ROYAL  INSTITUTION"  OF  GREAT 
BRITAIN. 

Saturday,  February  24. — Sir  Ernest 
RuTHERKOuD,  LL.D.,  D.Sc.,  F.R.S., 
M.R.I.,  Prof,  of  Natural  Philoeophy,  will 
dttliver  his  second  lecture  on  Atomic  Pro- 
jectiles and  their  Properties. 


THE  CHEMIC.\L  SOCIETY. 

On  Thureday,  February  22.  1923,  at  8 
p.m.,  at  the  Institution  of  Mi^olianioal 
EngineeoB,  SU>rey's  Gu>U\  S.W.I.  Princi- 
pnlJ.  C.  Irvine, 'C.B.E.,  F.R.S.,  doJivorPd 
hift  lecture,  entitled,  Some  Constilutidtnal 
Prohlems  of  Carbo-Hydrnfc  Chemistry. 

At  the  Ordinary  Sdi^ntific  Meeting  of 
the  diemioal  Society  on  ThuDBday,  Feb- 
ruary 15,  In  addition  i<>  the  papers  nn- 
nounoed  or  reading,  Dr.  A.  Soott.  F.IJ  >.. 
loade  a  abatement  with  niferenoe  to  his  m- 
voetigations  on  "  The  Oxide  ol  a  New  Ele- 
ment "  (eee  The  Chemical  News,  this  vol 
p.  81). 

He  announced  that  ('<-r-t<'r  and  Hevcsy 
had  found  no  trace  of  Hainium  in  the  sam- 
ples ol  sand  which  he  had  sulmutted  to 
them  for  examination. 

Bohr,  however,  stottxl  that  from  tiis 
spectrum  analysts  he  fouii  dlines  which  did 
not  correspond  with  any  known  element. 

It  is  tliu!^  possiible  Uiat  two  new  elements 
have  been  discovered. 


THE  INSTITUTE  OF  METALS. 
The  Annual  (^^noral  M<'<  ting  of  the  In- 
stitutt'  of  Mcitals  will  bo  hold,  by  kind  per- 
mission, in  the  house  of  the  Institution  of 
Mechjvnioal  Engineers,  SUa-ey's  Gat<?, 
We«tininster.  S.W.I.  <*n  Wednesday  or.d 
Thursday,  March  7th  and  8th,  1923.  "  The 
meetin<;  will  commonco  at  10  a.m.  oach 
day,  ooncluding  not  later  than  5  p.m.  On 
March  7th  the  annual  dinner  of    the  Insti- 


tute will  be  held  ab  the  Trocadero  Restaur- 
ant, Piooadilly  Cirous,  W.l,  at  7.30  for  8 
p.m. 

May  Lecture. 
After  the  Annual  General  Meeting  the 
next  gathering  of  members  will  take  place, 
as  previously  announced,  on  Wednesday, 
May  2,  at  the  Institution  of  Mechanical 
Engineers,  at  8  p.m.,  when  Dr.  W.  Rosen- 
HAiN,  F.R.S.,  will  deJiver  the  annual  May 
lecture,  hia  subject  being,  The  Inner  Struc- 
ture of  Alloys. 

Anwual  Autumn  Meeting. 
The  Annual  Autumn  Meeting  of  the  In- 
stitute will  be  hoki  at  Manchester  in  Sep- 
tember. Further  announcements  regard- 
ing bo4;h  the  above  meetings  will  be  made 
at  a  Iflter  date. 


INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 

An  extra  meeting  wtas  held  on  Thursday, 
February  22,  1928,  «t  6  p.m.,  when  Dr.  H. 
W.  Nichols  delivered  .a  lecture  on  Trans- 
oceanic WirelesH  Telephony,  followed  by  a 
diacuasion.  Mi.  B.  Welbourn  exhibited 
two  oinematogiaph  films  on  "  The  Eleotri- 
fication  ol  the  C  hicrago,  MiJwaukee  and  St. 
Paul  Railroad  Company." 


ROYAL    MlCliOSCOPK'AL    SOCIETY. 

A  meeting  of  the  Society  was  held  on 
WodncBday.  Fcl>niary  21.  lat  7.45  p.m.  The 
following  ix^pers  were  ri'-jid  and  discussed : 

Prof.  Sir  William  Maduock  Baylihs, 
D.Sc.  F.H.S..  F.R.M.S.  :  MicroscojncaL 
Stainintf  ami  ColUiids. 

Mr.  a.  Mallook,  F.R.S.  :  Note  on  the 
Resolving  Pmcvr  and  Definition  of  Optical 
Instruments. 


SOCIETY  OF  GLASS  TECHNOLOGY. 

A  meeting  <xf    the  Society    was  held    in 

.Vrmstroiig    Collof^,    Newcastle-upon-Tyne, 

on  Wpdnf«d«y.    Fe*)ruary  21.  1923. 

The  following  papers  were  read  :  — 

Orqanising  jm  Production  from  Pot  Fur- 

nncfH,   bv   W     W.     Waruen,     A.M.I.C.E., 

\.m.i.e!e. 

The  Effect  <>f  Boric  Oxide  'on  the  Melt- 
iutj  and  Workiiuf  of  Qlass,  by  ¥.  W.  Hop- 
kin.  B.Sc,  an<i  Prof.  W.  E.  S.  Turner, 
D.Sc. 


122 


THE    CHEMICAL    NEWS. 


FEBRUARY  23,  1923. 


So<me  Physieal  Pro*peHies  of  Boric 
Oxide- Contoiinik^g  Glasses,  by  Violet  Pim- 
BLEBY,  B.Sc,  S.  English,  'M.Sc,  and 
Prof.  W.  E.  S.  Turner,  D.Sc. 

By  the  ooiuirtesy  of  the  Directors,  a  visit 
has  been  arranged  to  the  works  of  Mesisrs. 
Le.mington  Glacis  Works.  Ltd.,  Lemington- 
on-Tyne,  on  Wednesday  morning,  Feb. 
21,  1923.  The  works  aie  engiaged  in  the 
manufacture  of  electric  liamjp  bulbs  and 
tusbong,  the  former  both  by  hand  and  by 
machine.  The  furnaces  include  a  re- 
cently-installed 10  pot  Hermansen  Recuper- 
ative Furnace.  A  24-arm  Westlake  bulb 
miachine  is  in  operation. 


FUEL  PROBLEMS. 

On  February  6,  an  open  meeting  of  the 
Birmingham  and  Midland  Section  of  the 
Sociiiety  of  Oheimioa.l  Industry  was  held  at 
the  University  of  Birmingham,  on  "  Fuel 
Problems."  Dr.  E.B.  Maxted,  Chairman 
of  the  Section,  who  presided,  pointed  to 
the  close  reliationship  of  fuel  and  fuel  prob- 
lems to  the  chemiaal  industry.  From  a 
national  isitandpoint  our  aim  should,  he 
said,  l)e  to  make  most  effective  the  utilisa- 
tion of  coal. 

Mr.  Edgar  C.  Evans,  F.LC.  (London) 
emphaisised  the  need  for  fueH  problems  be- 
ing considered  fro.m  a  national  standpoint. 
Although  our  coalfield's  were  geographically 
crowded  togetlher  in  a  very  'small  larea,  it 
was  la  maltiter  fior  surprise  that  so  few  lat- 
tenapts  had  'been  made  to  co-ordinate  coal- 
field problems.  Work  was  being  done  in 
the  varions  research  Inboratories  oi  the 
oonntry  on  the  constitution  of  ooal,  and 
work  had  been  and  wais  being  done  lat  in- 
dividual coillieriee,  on  tftie  pairticuLar  prob- 
lems of  those  collieries,  but  very  little  had 
been  achieved  towards  co-ordinating  the 
mass  'of  individual  work  available,  and 
drafting  in  general  term's  a  scheme  of  re- 
seiaroh,  a  method  of  lattacik  which'  would 
be  national  and  not  local  in  its  n-espects. 
Ther.*e  was  necessity  for  the  production 
through ou|t  the  country  of  a  standard  blast 
furnace  coke.  He  believed  that  the  prob- 
leon  of  excessive  moisture  in  coke  would 
eventually  'be  solved  by  the  adoption  of 
continuous  vertical  retorts  in  which  the 
coke  \^ould  be  evolved  inside  the  oven,  so 
that  t'he  only  moisture  in  the  miaterial  when 
it  reac!]r(d  the  furnaces  would  be  that 
picked  up  em  route.  The  sulphur  q\ie.stion 
wa's  becoming  acute  in  some  coalfields.  In 
certain  cases,  supplies  of  high-class  coking 


coal  free  from  sulphuir  were  getting  very 
scarce,  and  any  method  of  removing  it  from 
the  remaining  seiams  would  be  extremely 
valuable.  Sulphur  could  exist  in  coal,  in 
one  or  other  of  tftiree  forms — ^as  pyrites,  as 
organic  sulphur  and  as  inorganic  sulphur. 
If  it  existed  as  pyrite  sulphur  it  could  be 
reduced  very  often  by  crushing  the  coal  to 
'a  10  or  20  mos'h  size  and  treating  it  in  a 
fine  coal  ciieaning  plant.  In  some  oa^ses 
organic  sulphur  could  be  very  largely  re- 
duced by  fractional  distillations  in  a  cur- 
rent of  steam.  He  had  made  a  large  num- 
ber of  teisit-s  on  different  coals  in  a  small  re- 
tort of  about  1  ton  a  day  ctapacity,  in  which 
ca rb on i Station  of  the  coal  was  effected  in  a 
current  of  supei-heated  inert  gas.  In  some 
cases  where  steam  was  used  as  the  heajting 
medium,  considera-ble  reduction  of  the  sul- 
phur content  had  been  effected,  but  in 
other  in-stances  no  (improvement  whatever 
took  place.  There  was  an  enormous  qpen- 
ing  for  smokeless  fuel  production  on  a  big 
scale  in  England,  and  the  gias  in<lustry  was 
logically  the  one  that  should  take  up  the 
question.  As  an  ex'ample  of  the  posisibili- 
tiesi  to  the  gas  industry  of  the  prelimiruary 
treatment  of  coal,  he  cited  the  following 
test:— 1  ton  of  coal  'at  750°  C.  gave:  70 
per  cent,  of  coke  contaming  5  per  cent,  of 
volatiles  of  a  free  hurning  chanacter;  53  to 
54  lbs.  of  sulphiate  of  ammonia;  15  igals.  of 
tar;  4  gals,  of  light  oil;  and  17,000  to  18,000 
c.f.  of  gas,  of  a  oalorific  value  of  437 
B.T.U.s  iper  cubio  foot,  the  gas  not  con- 
taining more  than  10  per  cent,  of  GO.  A 
high  yield  was  not  inconsistent  with  51  low 
carbonising  teanperature  and  the  produc- 
tion of  a  high -class  smokeless  fuel.  A 
natifjnal  view-point  would  go  a  long  way, 
said  Mr.  Evans,  to  clear  up  some  great 
difficultiis.  The  question  was  prin^arily 
one  of  co-ordimation  of  the  research  of  the 
c  )untry.  A  chain  of  research  stations  was 
required  at  the  various  coalfields;  eiach 
should  specialise  dn  its  own  problems.  Coal 
owners  and  iron  and  steel  manufacturers 
should  be  on  the  governing  body  of  the 
stations,  and  there  should  also  be  gas 
engiineei-s  and  fuel  consumers.  The  work 
should  be  linked  up  with  Miat  of  the  uni- 
versities, and  he  suggt^sted  that  the  Fuel 
Research  Board  should  be  the  central  body 
and  00- ordinate  researches  into  a  .general 
policy. 

Dr.  E.  W.  Smith  (F.T.G.),  London,  said 
he  was  of  the  opinion  that  gas  undertak- 
ings should  not  only  supply  suitable  gas  at 
a  low  price,  but  "should  develop  the  produc- 


FEBRUARY  23,  1923. 


THE   CHEMICAL   NEWS. 


123 


tioo  uud  gale  of  «mokeIes6,  free  bummg 
solid  fuel,  suitable  for  domostio  and  indus- 
trial purposes.  The  net  value  of  the  coke 
available  for  sale  on  a  gas  works  was  very 
hfctle  different  from  tlie  net  value  of  tlie  gas 
made  on  the  works.  It  was,  therefcwre,  well 
worth  while  impo-oving  tlie  quality  of  this 
so-called.  "  by-iproduct, "  and  enhancing  itte 
value  as  much  a»  poeeible.  A  number  of 
undertakings  aertainlj  'did  screen  and  grade 
their  ooke,  and  keep  the  water  cocitent 
down  to  -a  reasonable  figure,  but  more 
oouUl  verj-  well  be  dono.  There  is  room 
for  much  to  be  done  in  this  direotioQ. 
Tliere  was  a  growing  pubUc  feeling  that 
"smoke"  mu^t  eventually  be  ediminatcd. 
All  types  of  <K>aI  should  be  made  available 
ior  the  {production  of  gas.  and  smokeless 
solid  free  burning  fuel.  How  could  thi«  be 
attained?  By:  (1)  Coal  cleaning;  (2)  coal 
blending;  (3)  coal  briquetting;  (4)  coaJ  bri- 
queiite  carbon i>;at ion,  and  the  produotioQ 
of  gtiB  and  fre<'  burning  Rmr>kol<w8 
briqueWos.  This  would  be  done,  and  the 
cycle  of  operattons  would  be  made  to  pay 
as  compared  with  (presenl  gas  works' 
methods. 

Dr.  Smitli  expressed  surprise  at  the 
actdon  taken  by  somebody  in  raising  the 
CO  br^c  in  la  neiw^paper  oocPBspoQdence. 
The  net  result  ol  the  newspaper  stunt  bad 
been  an  incrcanc  in  the  number  of  people 
who  preiforred  Uio  "gas  way"  to  end  tih«'ir 
livce.  Ignonancc  wa«  at  the  bofatc/iii  of 
much  of  this  outcry.  It  waa  well  t'luO,  the 
gii8  iiulustry  wa«  well  established,  otherwise 
when  it  was  found  that  winsless  cnthuKinstn 
wore  court inj;  dangens  of  explosions  and 
fires  by  o«rthing  their  equipments  to  ga« 
pipes,  somebody  might  demand  an  inquiry 
by  unbiased  men  of  the  hkiiest  soientiHc 
atijunments  to  advise  the  %oai^  of  Trade 
whether  it  was  any  longer  safe  for  gas  to 
be  distriibuted  in  houses  in  ircMi  pipes.  It 
had  no<t  been  shown  ttiat  there  had  been 
diirin<?  the  last  y«'ar  monr>  aocidental  deaths 
from  CO  poisoning  than  previously;  acd- 
dontnl  gias  ])oisoning  cases  were  not  more 
prevalent  in  districts  where  the  CO  was 
high  tlian  where  the  CO  was  low,  and  it 
had  be<'n  shown  \hat  tJure  was  no  more 
CO  in  toNvns'  g)as  generally  at  any  time  diir- 
ing  the  last  15  years.  Whifet  it  was  im- 
portant to  increase  the  efficiency  of  produc- 
tion of  fuel,  it  was  more  imiportant  to  in- 
creas*^'  the  efficiency  of  the  iitili.<»Ation  of 
fuel.  That  had  been  done  in  connection 
with  lightinp:  nnTl  gas  fiivf^,  but  much  more 
required  to  be  dorwe  in  connection  with  in- 


dustrial heatmg  furnaces,  and  in  regwrd  to 
these  he  advocated  further  reeearoh  work 
as  to  insulating  matei-ials,  conductivity  tkf 
re^naotories,  the  best  means  of  attaimng 
flame  temperatunee,  the  value  aud  limits  of 
regeoieration,  tire  relative  values  of  radiant 
heat  iind  thermal  efficiencies  of  stundaxd 
types  of  furnaces  in  use.  He  believed  that 
the  proeec-'utiou  of  such  a  researdi  would 
amply  repay  the  Institution  of  Gas 
Engineers. 

An  interesting  discussion  followed. 


UNION  OF  SOUTH  Al'KICA— DEPARl- 
iVlENT  OF  AGRICULTURE. 

liBPORT  OF  THE   DlVISlUN   OF  CUEMISTUY    FOR 

THE   Yeah  Ended  30tii  June,   1922. 

Chief  of  Divmivn:  C'huj*.  F.  Juritz,  M.A. 

D.Sc,  F.l.C. 

1.     Organiiaaiioiu — The    most    impoitaut 
function  of  the  year  has  been  that  of  lay- 
ing fouudoiiUons  for  the  cloKei*  co-oporation 
of  tile  sections  uf  the  Division    located  in 
variouji  parts  of  the   Union.       Tliis  oauuot 
be  aohierved  all  at  once,    but  a  few    select 
phases  of  work  will    be  brought  into    line 
step  by  step.      Some  of  these  will  be  enu- 
merated lat<r  <>u.       The  guiding  principle 
bus  been  the  resoJutkm  adoipted  at  a  con- 
ference oolK'd   by  the    Socrcttu-y   for  Agri- 
culture of  liL-ads  of  divisions  tmd  principals 
of  agricultural  aohools    (shortly  betfore   the 
tweJve  mouths  under  report),  viz.,  that  the 
control     aud     guidance    of   research     work 
should  be  vcst^  d  in  the  chiefs  of  divisions, 
and    tbat   the     services    of    the    technical 
ottioeiM    {i.e.,  in.  thia  case  the  chemists)  at 
the  schools  should  be  utilised  to  Uhe  great- 
est extent  pijtssible    to  assist  the  heads    of 
<livi«ions.         The    reJatiuns     between      the 
chemists  at  the  schools    and  the  Chief    ')i 
the  Division    in  regard    to  research    work 
would  therefore  reat  upon  tihe  basic  prin- 
X9tple    that  the    former    sliould    act    in    a 
directive  oapacity,  in  consutltcution  witii  the 
principal  of    the  school  concerned,     in  re- 
si>eot  of  any  work  to  be  carried  out  by  any 
partkuJar  chemist. 

At  Grootfontein  the  Division  has  in  Mr. 
A.  Iia^iead  an  othcer  of  it;?  own  :  he  advises 
Ithe  principal  on  miktbers  pertaining  to  the 
school's  chemical  seotioin,  and  in  return 
the  school  Uibortutories  ari^  at  his  disposal 
for  the  puri)<)s«'8  of  the  Division.  On  the 
r>ther  hand,  the  chemist  belonging  to  the 
bohool  staff  assists  in  the  work  of  the  Divi- 


124 


THE   CHEMICAL   NEWS. 


FEBRUAR'y  23,  1923. 


teion  as  far  as  passible,  subsidiarily  to  the 
exigencies  of  the  school's  own  require- 
ments. On  this  basis  the  relations  be- 
tween the  various  chemical  laboratories  of 
the  Department  have  been  made  closer, 
but  fa  further  rapprooheanent  will  be  needed 
before  .a  coherent  unit  is  evolved.  Mean- 
while, conisolidation  is  being  proceeded 
with  fi.rs(t  where  most  urgently  needed. 

The  Pretoria  laboratory  is  wholly  under 
the  control  of  the  Division.  A  great  deal 
of  the  work  there  carried  on  hitherto  has 
consisted  of  soil  investigation. 

The  ^eatest  difficulty  is  in  regard  to 
retsearch  work.  There  the  supervision  of 
the  Chief  of  the  Division  embraces  the 
la.boratorie&  attached  to  the  sohools  as  well 
as  those  directly  connecfed  with  the  Divi- 
sion. The  fulieeit  and  most  willing  co- 
operation from  prinoipals;  and  chemists  is 
given  in  the  endeavours  to  bring  about  co- 
ordination, but  development  must  not  be 
forced.  At  present  measures  are  taken 
continuously  to  inform  each  institution  of 
the  progress  of  research  work  at  every  one 
of  the  others,.  This  makes  for  mutual  in- 
terest and  solid artity  of  aim.  Several  prob- 
lems have  arisen  and  have  been  dealt  with 
in  a  Siaitiefactory  and  uniform  manner,  that 
previously  would  either  have  been  disiposed 
of  as  the  individual  institution  first  con- 
fronted therewith  thought  fit,  or  letft  in 
aibeyance  until  a  .ohemfets'  conference 
could  consider  it. 

With  the  importtant  matlteir  of  the  agri- 
cultural soil  survey  of  the  Union  little  pro- 
gress has  been  made.  It  is  impossible  for 
the  Chief  of  the  Division  to  giive  the  sur- 
vey the  undivided  attention  which  is  es- 
sential, and  Mr.  Stead,  Senior  Chemist  of 
the  Division,  w^ho  vvnas  placed  in  charge 
thereof,  was  pre\'ented  hy  other  duties  and 
prolonged  illness  from  assuming  that 
ciharge.  The  work  will,  it  is  confidently 
(lioped,  soon  be  commenced. 

2.  Commission  Work. — During  the  year 
the  Chief  of  the  Division  served  on  com- 
mittees appointed  to  investagiate  the-  (prob- 
leans  airiisiing  from  the  need  of  cheap  indus- 
trial alcohol,  and  to  inquire^  into  the  mat- 
ter of  the  destruction  of  prickly-pear. 

From  October,  1920,  until  well  into  the 
year  under  report,  Mr.  Steiad  was  virtually 
seconded  for  service  a8  a  mecmber  of  the 
Dirought  Commission.  The  first-hand 
knowledge  of  the  country  and  its  .problems 
and  conditions  gained  in  the  course  of  this 
inquiry  should  prove  of  great  value  to  the 
Division. 


3.  Publicatio'ns. — The  following  papers 
by  officers  of  the  Division  were  published 
during  the  twelve  months:  — 

A.  Stead : 

"The  Value  of  the  Paddoclv  System," 
Journ.  Dept.  Agric,  Vol.  III.,  No.  2, 
August.  1921,  pp.'  131-135. 

B.  J.  Smit: 

"Representative   Transvaal    Soils:     The 

Xorite    Black    Turf,"     Jonirn.      Dept. 

Agric.  Vol.  II.,  No.  4,  Ootober,  1921, 

pp.  337-342. 
"The  Uses  of    Tobacco  Waste,"    Journ. 

Dept.  Agric,  Vol.  IV.,  No.  3,  March, 

1922,  pp.  267-271. 

C.  F.  Juritz: 

"  The  Nicotine-Content  of  South  African 
Tobacco,"  Journ.  Dept.  Agric,  Vol. 
IV.,  No.  6,  June.  1922,  pp.  552-562. 

"  The  Submarine  Phosiphates  of  the 
Agulhas  Bank,"  8. A.  Journ.  of  Indus- 
tnes.  Vol.  IV.,  No.  10,  November, 
1921,   pp.  863-865. 

"  Baciterial   Production  of  Motor  Fuel," 
.S..4.   Johirn.   of  Industries,    Vol.     IV., 
No.  11,  December,  1921,  pp.  905-910. 
B.  de  C.  March  and  : 

"  On   the  Volumetric     Determination    of 
Piio6,phoriio    Oxide,"     8. A.     Jourru.     of 
8cience,  Vol.   XVII..    Nos.  3    and    4, 
July,  1921,  pp.  259-268. 
W.  J.  Copenhagen  : 

"  Studying  our  Marine  Resources,"  8. A. 
Jonirrn.  of  Industries,  Vol.  V.,  No.  4, 
April,  1922,  pp.  160-163. 

Extracts  from  the  Reports  of  the 

Division's  Officers  in  Charge  at 

Capetown,  Grootfontein,  ano  Pretoria.. 

1. — Caspeiowru:    Chief  of  the   Division. 

(a)  Antdytical  Work. — During  the  year 
477  samples  of  Various  kinds  were  ana- 
lysed. Of  these,  the  analyse©  of  salt, 
brine,  bittern,  etc.,  were  performed  for  the 
purpose  of  a  general  survey  of  the  salt- 
pans of  the  Union;  and  an  invesitigation 
into  the  nicotine -content  of  various  types 
and  qualities  of  tobacco  grown  in  the 
Union  was  undertaken  in  connection  with 
the  produdtion  of  a  satisfactory  tobacco  ex- 
tnaot.  An  analysis  of  ash  from  tobacco 
stems  yielded  17.8  per  cent,  of  potash. 

With  the  exception  of  seventeen  sampU^s 
of  guiano  and  a  few  analyses  of  limestone, 
practically  all  the  fertilisers  analysed  were 
in  connection  with  the  Fertilisers,  Farm 
Foo'ds,  and  Pest  Remedies  Act. 

As  usual,  several  analyses  of  Govern- 
ment guano   were  made,    and  a    series    of 


FEBRUARY  23,  1923. 


THE    CHEMICAL    NEWS. 


125 


comparftfcive  analyses  of  the  produce  of  the 
different  islajids  are  also  in  progress.  liime- 
stwio  from  Saidanha  'Ba.y  crushed  for  use 
as  rgriculturaJ  lime  was  found  to  contain 
36.3  per  oent.  of  oarbon.  dioxide,  correfi- 
-ponding  to  82.5  per  cent,  of  calcium  oar- 
(booate.  Some  limestone®  and  supposed 
pha«{>hatic  deiposktis  from  Dassen  Island 
were,  examined,  but  the  results  were  not 
promising. 

A  special  report  on  the  subject  of  the 
change  in  bhe  com^oHitioii  <A  basic  sln^  wns 
furnished,  also  one  on  the  aJWed  poison- 
ous .character  of  basic  slag  and  other  fer- 
tilisers. 

An  invedig<aitioD  was  commenced,  and  is 
being  o^>nt4mied,  in  reigaad  to  ihc  relation 
between  the  degree  of  ripeoees  of  grapes 
and  their  sugar-content  to  (heir  suitability 
for  ex2>ort. 

^  A  resttrioted  axwount  only  of  soil  investi- 
gation could  be  carried  out.  A  sandy  soil 
Ifrom  the  Celedon  District  wae  examined 
•and  found  to  be,  ««  puch  soiVs  usually  are, 
indifferently  supplied  with  humus,  Ictw  in 
moi#(ture-re<«ining  poi\er,  and  poor  in 
plant-food .  Two  samples  o(  virgin  sandy 
Ic  «in«  from  Klipheuvel  were  abo  defkrient 
in  organic  matter,  nitrogtm,  ond  wator-n- 
itainin^  .power  as  well  as.  in  organic  phint- 
•food.  Some  soils  from  a  farm  at  De  Dooms 
(proved  to  be  rather  hrak.  containing  about 
0.25  \Hvr  cent,  of  sodium  salts.  A  similar 
(proportion  was  found  in  one  out  of  three 
«oil»>  obtained  froim  a  farm  in  the  irrigHblo 
nrotfi  of  the  OliCants  Rivor,  V-an  Rhyns- 
dopf).  A  very  brak  soil  from  Middolburg. 
Transvaal,  was  examined.  It  oonimined 
0.56  per  loent  of  sotlium  salt??.  A  de*^  vir- 
gin 8f)il  of  good  humi  it,  rich  in 
tiitroj^en,  and  with  a  sn  .-y  moisture- 
retaining  power,  wtn«  received  from  the 
•Cere*;  District,  but  itis  supply  of  uiorf^anic 
plant-food  ooiild  only  l)e  described  as 
mo<ler«t4'.  Teni  jroiils  from  the  Cnndock 
Divisifsn  were  examined  in  connection  with 
the  construotion  of  an  irrigation  dam. 

The  occurremce  of  collar*oit  in  citrus 
t>re<»<  in  the  Clmnwilliani  Dl«»triot  led  to  an 
examination  of  the  soil  for  brak  salts  and 
acidity.  In  neither  retspoofc  was  the  salt 
in  any  wiay  at  fault.  The  use  of  liquid 
•hydrocyanic  acid  for  tho  defttruc»tion  of 
yKHsts  on  fruit  trees  led  to  an  investigation 
Kjf  the  chanaot-er  of  the  liquid  oommeroially 
Applied  for  tho  purpoee  and  the  mode  of 
its  manufaobure. 

The  only  snmple  of  water  that  requiree 
any  sipecial  remark  was  one  from  Bel Wi lie, 


(r-sted  for  salinity  in  connection  with  its 
prqpo-ed  use  in  dairying.  It  contained 
61.2  i)ai-t'8  of  dissolved  .^tlt«  i^er  100.000. 
M,>nsisting  almoat  entirely  of  sodium 
chJoride. 

As  to  plant  products,  a  sample  of  Senecii^ 
from  Newlands  was  examined  in  connec- 
tion with  it^  use  «b  a  j)oultj'y  food.  Some 
guinea  ffrat^s  from  Somerset  liiast  was  also 
ItinaiMsed  witli  a  view  to  being  utilised  as 
tfbdder.  Several  pknts  were  examined  for 
ihoir  essential  oil  content,  and  the  con- 
stants of  tiiose  oils  determined.  Experi- 
iiirnts  were  carried  out  to  aaoert«.in  whether 
pricJtly-pear  sections  contain  any  saponin 
lor  i)ectin  substances  which  covild  cause  it 
ito  >«ict  as  a  "spreader"  in  insecticide 
twashee,  but  nothing  definite  could  be 
elicited.  Lt  wb9  also  sought  to  ascertain 
whetlier  prickly-pear  mucilage  could  par- 
<tially  replace  gelailine  if  added  when  a  solu- 
iioHi  of  the  latter  was  ja«<t  below  setting 
consistency.  In  this  respoot,  too,  tho  re- 
sults were  of  n  negative  nature. 

In  connix?tioii  with  experiments  at  El- 
senburg  on  U\  <Hng  pig«  with  tho  reeddue  of 
«nai/.e  from  wlvich  .alcohol  had  been  pre- 
•pannl  and  distilled  off,  angU^-Be<5  of  mcalie 
tmenl  befon'  and  after  tnpatmeat  wfje 
-oarried  out. 

(b)  ToaricxUogical  TVork.  —  Oooasional 
cases  d  8uppr»ied  poinoning  of  8*ocl<  woro 
vHubtnitbed  fnr  examination. 

Several  «amplee  of  strychnine  wore  re- 
ceivtKl  at  various  time«.  with  the  cf)mplaint 
♦that  they  had  been  found  ineffective  for 
wild  anim«l  poisoning.  In  every  case  the 
UiHicle  w««4  foimd  perfectly  pure,  and  tho 
•fatilt  m\i«i  lie  in  the  compounding  of  the 
Ibaii. 

The  deposition  <rf  crystals  in  drums  of 
erjncentraied  sodiiun  arsenite  solution,  was 
inquired  into,  jind  aitrteinition  given^  to  the 
numerous  untoward  resn-lts  of  the  careless 
•or  malioioue  u.se  of  the  arseniojtis  om ployed 
{n  otvhaixi  apraving  and  stock  dipping. 

(o)  MicrohioJagical  Work. — In  connec- 
tiofu  with  tihe  coounercial  mjinufncture  of 
•acetone  and  alcohol  from  such  cultures  as 
maize  or  sweet  potottoes,  a  bacillus  oapable 
of  effecting  the  oooviewion  of  maize  was 
bbbained  by  the  kindness  of  the  Rockefeller 
Institute,  and  cultures  were  preipared  for  a 
/large-scale  prodixotioc  of  these  articles, 
but  the  pkint  was  not  located  in  a  8uitabi<^ 
environment,  and  was  subsequently  broken 
up. 

Pure  cultures  of  cei<(iain    soil   organisms 
were  prooiired    from  the  Lister    Institute. 


126 


THE  CHEMICAL  NEWS. 


FEBRUARY  23,  1923. 


and  sub-cultures  of  -fcheee  were  preipared 
land  distributed  aanongsit  a^^ulturisibs  foi' 
experimeufcal  pui-poscis.  Further  samples 
of  soil  froffn  different  paiita  of  the  Union 
were  sent  to  Eothamsjted  for  the  study  of 
isoil  protozoa.  Experitoientis  in  soil  inocu- 
lation were  initiaited  on  several  £arms  in 
the  south -western  diistniats. 

(d)  Dairy  Industry  Act. — Under  the  pro- 
visions of  this  Act,  all  milk  .and  cream  test- 
ing a(pplian,oea  ,offered  for  sale  within  the 
Unioai  have  to  be  tested  for  .accuracy  of 
graduation  and  dimensions,  and  marked  in 
a  Government  laboratory.  This  practice 
was  continued,  and  616  articles  examined 
during  the  year.  They  comiprised  447  Bab- 
cook  ore>ajn  bottleis,  72  JBabcock  milk 
llK,ittles,  and  97  pipettes.  Of  these,  46.9 
per  cent,  were  rejected,  viz.,  50.1  per  cent, 
of  the  cream-test  bottles,  86.1  per  cent,  of 
the  milk-teist  battles,  and  3.1  per  cent,  of 
the  pipettes. 

(e)  Co-nsultathmi  Work. — On  frequent 
ocoasions  reports  had  to  be  furnished  on 
miiscellaneous  abteitracit  question's  submitted 
for  adviice,  siuch  as  the  manuring  of  sandy 
grass  lands,  horns  as  a  fertiliser,  preser- 
vation of  foodstuffs,  etc. 

^.—Groiotfontem:   A.  Stead,  B.Sc,  F.CS. 

Most  of  the  period  was  occupied  by  the 
officer  in  charge  in  serving  a®  a  .member  of 
ith©  Drought  Inquiry  Coonmission  or  on 
leave  of  absence.  Other  work  included  the 
iuiSipection  oif  manuirial  exjperiments,  of 
brak  land  at  Uitenhage,  of  prickly-pear 
Stprajing  tests,  of  brak  in  an.  orcbard  near 
Criadjock,  the  compilation,  of  a  ccanprehen- 
siv©  report  on  brak  for  the  Department  of 
Mines  and  Irudusitries  (still  in  progress),  in- 
vestigiation  of  the  feeding  of  sheep  on 
prickly-pear  as  the  main  portion  of  their 
dieit,  invesitigation  of  farmeins'  experienice  in 
the  Graaff-Eeinet  District  regarding  the 
utilisation  of  Agave  amcricana  as  a  stock 
food,  experimental  feeding  of  prickly-pear 
to  cows  and  oxen,  .and  continu'ation  of 
shciep-feedinig  experimenrt/s. 

In  connection  with  the  report  on  brak, 
referred  to  above,  the  method's  adopted  for 
reclaiming  bnak  land  neiar  Robertson  were 
iruspected.  and  led  to  a  recommendation 
that  the  Division  of  Chemistry  should  en- 
gage in)  such,  operations  as,  for  inst>ance,  at 
Klipdrift,  where  the  well-known  efforts  of 
'the  late  Mr.  J.  P.  Manais  had  failed. 

A  consideraM©  amount  of  work  of  an 
advisiory  and  consulting  naitvire  w^s  also 
done. 


3. — Pretoria:   B.  de  C.  Marchalmd,  B.A., 
D.Sc. 

(a)  Analytical  Work. — The  samples  re- 
ceived for  analysis  or  /examination  com- 
prised: — Soils  and  sub-soils,  146;  fertili- 
sers, 115;  dairy  products,  20;  tobacco,  16; 
\mter,  15;  miscellaneous,  69;  total,  381. 
Of  the  soil  siampleis,  54  were  taken  by  offi- 
tcers  ,of  the  Diviision  in  iconnection  with  in- 
vositigational  work.  The  only  other  soil 
samjples  which  call  for  any  comment  were 
<five  isent  in  by  the  Postal  Depart-ment  in 
(Oonneotiom  .with  the  rapid  corrosion  of  atay 
rod's  and  .plates.  This  was  a>scribed  to  al- 
(kaline  salts  in  the  soil-  Prevenitive  mea- 
•sures  were  suggested. 

(b)  Dairy  Glassivarc. — Tllie  total  number 
of  pieces  tested  was  932,  consisting  of 
Bahcock  cream  bottles  583,  B.abcock  milk 
bottles  277,  pipettes  72.  The  percenibage 
rejected  las  inloorreot  wa®  four. 

(c)  Investigations. — In  addition  to  the 
conitin nation  of  others,  investigations  were 
commenced  on  the  physiicial  properties  of 
soils,  the  influence  of  various  factors  on 
the  citric  solubility  of  the  phosphoric  oxide 
iu'  basic  slag,  anjd  tho  determination  of 
"available"  potash  in  soils. 

The  trials  of  various  methods  for  the 
determinatioin  of  phosphoric  oxide  in  ferti- 
lisers were  compleited,  and  the  results  for 
the  siample  of  biasic  slag  experimented  on 
were  published  in  the  Journal  of  the  South 
Afritcan  Chemical  Institute,  Vol.  V.,  No. 
1,  p.   16. 

(d)  Pot  Experiments.  —  In  conncotion 
with  certain  of  the  investigations  in  hand, 
pot  experiments  on  a  sm^all  scale  were 
oommeaiced. 


NOTICES  OF  BOOKS. 

Outlines  of  Theoretical  Chemistry,  by 
F.  H.  Getman,  Ph.D.  Third  edition, 
thoroughly  revised  and  enlarged.  Pp. 
VIII.  +  625.  New  York :  Wiley  &  Sons, 
Inc.  London:  Chapman  &  Hall,  Ltd., 
Henrietta  Street,  Covent  Garden.  1922. 
Price  18s.  6d.  net. 

Getman's  Outlivies  of  Theoretical  Chem- 
istry is  on©  of  the  best  of  those  deisigned  to 
meet  the  requirements  of  students  follow- 
ing courses  of  physiical  chemistry.  It  is 
also  a<  Very  useful  guide  and  help  for  those 
engta.ged  in  giving  such  covirses. 

k  working  (but  elementary)  knowledge  of 
chemistry  and  physics  is  naturally  assumed. 
The  matter  is  w©l.l  arranged,     and  the    re- 


FEBRUARY  23,  1023. 


THFi  CHEMICAL  NEWS. 


127 


suits  of  rewnt  researches  have  been  incor- 
porated witfti  the  subject  matter  in  a  very 
sabisfa-otory  manner. 

YiiU'h  civapte-r  in  foJlo\vc<l  by  a  set  of  ques- 
tions which  should  enable  the  student  to 
grasp  the  tiubject  thoroughly. 

The  author  has  evidently  spared  little 
effort  in  s«ijurching  the  literature  for  the 
in)pr>rtiMnt  advances  thai  Iwive  beon  made 
since  the  earlier  editions  appeared,  and  this 
iss^ue  .slio^ild  iprove  as  useful  a»  the  previous 
on  66. 


(1)  8ec4)nd  Year  College  Chemistry. 

(2)  Lahoratory  Mamial  to  accompany 
Second  Year  CoUrqr  Chemistry,  by  Wil- 
liam H.  CiiAPiN.  "  Fp.  XI.  +  311  and 
Vn.  +  112.  N(vw  York:  Wiley  &  Sons. 
Inc.  Tiondon :  Chiiipman  &  Hall,  Ltd., 
Henrietiba  Street,  Covent  Garden,  W.C. 
1922.     Price  15s    net  and  7s.  6d. 

The  trend  of  chemical  science  at  the  pre- 
sent tdnie  is  reflecfced  by  the  coatenfas  at 
advanced  t/exithwilcs,  and  is,  eapeoially  in 
AnK-rica,  diret-^ed  towards  a  study  of  the 
fundamental  principles  rather  than  with 
th<'  object  of  nddinpf  to  the  alremdy  im- 
mense store  of  facts  and  methods. 

The  present  volumes  by  Prof.  Chapin  in- 
dicaU'  this  in  no  uncert^'iin  manner,  and 
they  are  larg'eJy  devotod  to  an  acooxmt  of 
the  Chemioiftl  Laws  and  thoir  exiperimental 
bans. 

The  impnrtAncc  of  suitnble  and  reliable 
textboolds  of  this  kind  cannot  be  over- 
emphaaised,  since  the  average  student,  in 
his  first  and  early  years,  is  confronted  with 
a  mctsR  of  d<\8criptive  matter  and  particular 
facts  mixed  up  haz/ily  in  his  mind  with 
those  theories  and  generalisations  with 
which  they  are  aasociated. 

Another  good  feature  of  the  theoretical 
volume  is  the  adoption  of  the  histoncal 
me+hod  otf  treatonent.  This  has  led  the 
author  to  introduce  nfVrences  and  bri'^f 
footnotes  dealinjf  with  the  scrientists  whofle 
achievements  are  beinp  discuflsed  in  the 
text.  One  or  two  of  these  require  envenda- 
tion,  however. 

The  same  volume  contains  a  prefatory. 
"  Sugpe«tod  Course  of  Study,"  in  which 
the  n  nth  or  indicateip  that-  the  test  <' ovens  a 
year's  work  f32  weelcs),  and  the  Laboratory 
Mnnvial  oan  be  used  to  cover  the  same 
period.  All  the  experiments  described  are 
stated  to  hnve  been  tested  with  several 
olaases  of  students. 

Tn  the  (preface  to  the  Tiahoratory  Com- 
panion the  author  rightly  insists  on  the 
importance  of  tho  p^irefnl     and  correct  use 


of  the  laboratory  note-books.  It  often 
happens  that  a  student  is  able  to  derive 
more  knowledge  froim  an  unsucco'ssful  ex- 
periment than  from  suocGiSisful  ones  carried 
out  oaBually  and  written  up  in  an  unsatis- 
factory manner. 

Together,  these  volumes  will  be  found 
quite  BuitaWc  for  those  students  for  whom 
they  are  intended.  Those  in  charge  of 
lahoratory  clat^ises  will  find  the  appendices 
to  the  experimental  volume  of  use  in 
planning  the  work. 


Organic  F^ynthcses.  an  annual  publi- 
cation of  sati-sifactory  methods  for  the 
p<req>aratioii  of  organic  chomioals.  James 
RuYANT  CoNANT,  Edito«--in -Chief .  Vol. 
TL.  pp.  VI.  +  100.  New  York:  Wiley  & 
Sons,  Inc.  London:  Chapman  &  Hall, 
Ltd.,  Henrietta  Street,  W.C.  1922. 
Price  7s.  6d.  net. 

The  publication  of  thus  series,  one 
volume  of  which  is  to  appear  each  year, 
has  been  undertaken  by  certain  chemists  in 
order  to  rrwike  their  detailed  directions  for 
the  (pr&paration  of  various  organic  ehemi- 
oals  avniUble  in  a  permanent  form. 

The  high  cost  of  chemicals,  nnd  also  the 
difficulty  of  obtaining  suppHes  of  even 
ordinary  organic  rengents  <luring  the  war 
anu«x<d  many  researchers  to  prepare  their 
own. 

.\s  frequently  happens  in  such  cases,  the 
methods  deisj'ribed  in  convpendia  and  those 
given  in  the  litenatupe  were  often  found  to 
be  \msuitablo  or  at  least  capable  of  modifi- 
cation and  improvement  with  regard  to 
yield,  c^  nnd  facility  of  preparation. 

The  resuHis  published  in  this  series  of 
" pamphlotiR"  give  the  experiences  and  final 
methods  arlopto^i  by  well-known  re*searrh 
workejTs  in  certain  Americein  Universities, 
and  those  of  the  Enstman  Ko<lak  Co.  and 
Parke  Davis  Co. 

The  authors  do  not  claim  that  their 
methods  are  ideal,  btit  all  have  been  tesite<l 
by  other  experienced  organic  che.mistfl. 

Notes  are  appended  to  the  methods  gdvjn, 
and  the  original  references  are  quoted. 

Undoubtedly  the  metiho'lis  of  preparation 
for  the  25  bodies  described  will  be  found 
9atis.factory,  but  it  >s  siirprising  tliat  the 
aiithors  have  retained  ft  slight  modification 
of  Skrnup's  Quinoline  synthesis,  involving 
two  ateam  distilTations,  although  in  their 
Notes  they  mention  the  simpler  method  of 
E.  de  Barry  Bamett  (The  Chemical  News, 
1920.  CXXL,  205).  Their  selection  seems 
to  rest  upon  the  fact  that  the  chemists  who 
tested  the  two  prooesees  obtained  better  re- 


128 


THE  CHEMICAL  NEWS. 


FEBRUARY  23,  1923. 


suite    with    the   older    one — an.   experience 
contrary  to  th^at  of  the  present  writer. 

These  volumes  (Vol.  I.  appeared  early 
last  year,  see  The  Chemical  News,  1922, 
CXXIV.,  174)  should  be  available  in  all 
refeirencQ  libraries,  .and  they  should  be  oon- 
suJited  by  chemiats  wishing  to  know  of  re- 
liable and  siinnple  processes  for  the  prepara- 
tion of  moderate  quantities  of  the<se  re- 
agents. J.G.F.D. 


BOOKS  RECEIVED. 

Handbook  on  Petroicam,  by  Captain  J. 
H.  Thomson  and  Sir  Boverton  Redwood. 
Pp.  XIX.  +  342.  1922.  Meissrs.  Charles 
Griffin  &  Co.,  litxJ.,  Exeter  Street,  Strand, 
W.C.2.     12&.  6d.  net. 

Organic  Syntheses,  bv  James  Bryant 
CoNANT  and  Others.  Pp^  VI.  +  100.  Vol. 
II.  1922.  Messns.  Chapman  &  Hiall,  Ltd., 
11,  Henrietta  Street,  Covent  Garden, 
W.C.2.     7s.  6d.  net. 

Dyes,  and  their  Applicaxtion  to  Textile 
Fabrics,  by  A.  J.  Hall,  B.Sc.  (Lond.), 
F.I.C,  F.C.S.  Pip.  118.  1923.  Sir  Isaac 
Pitman  &  Sons,  lid.,  Parker  Street,  Kings- 
way,  W.C.2.     3s.  net. 

A  Method  for  the  Identification  of  Pure 
Organic  Compo^unds,  bv  Samuel  Parsons 
MuLLiKEN,  Ph.D.  Pp.  VI.  +  238.  Vol. 
IV.  1923.  Messrs.  Chapman  &  Hall, 
Ltd.,  11,  Henrietta.  Street,  Covent  Gar- 
den, W.C.2.     30s.  net. 


RAPID  EiSTIMATION  OF  IRON   AND 

ALUMINA. 

By  F.  Lucchesi. 

The  iron  and  alumina  are  precipitated  to- 
gether with  annmonaa  in  tlie  presence  of 
ammonium  chloride.  The  precipitate  is 
well  washed  and  dissolved  in  a  known  vol- 
ume of  semi-normal  sulphuric  acid.  A  few 
drops  of  meitihyl  orange  solntion  is  now 
added,  and  the  uncombined  acid  titrated 
with  isemi-normal  caustlio  soda.  Then,  by 
difference,  one  can  arrive  at  the  amoimt  of 
acid  used  in  combining  with  the  iron  and 
alumina.  A  little  concentrated  H2SO4  is 
added  to  the  solution,  and  the  iron  reduced 
with  HgS  and  subsequently  titrated  with 
deci-normal  KMnO^.  From  the  two  titra- 
tions the  lamounts  of  iron  and  aluminium 
oxides  can  be  calculated. — {GiofioXe  di 
chim.  Ind.  App.,  1923,  p.  14). 


after  four  notcible  exhibation&  boom  years 
have  followed,  although  lean  yeai^s  hsd 
preceded  those  exhibitions 


The  February  issue  of  the  Empire  Ex- 
hihitio,n\  Neivs,  the  organ  of  the  British 
Empire  Exhibition,  draws  attention  to  the 
fact,   which  statistics    have     proved,    tliat 


This  list  is  specially  compiled  for  the  Chemical 
News,  by  Messrs.  Rayner  &  C<1.,  Registorpd  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade 
Marks,  and  IJesigns,  can  be  obtained  gratuitously. 

Latest   Patent   Applications. 
1980— Lland,   W.— Production     of     alkali   salts     of 

higher   fatty  acids.    Jan.   22. 
207ft— Rusberg,   P.— Manufacture    of     alkali     thio- 

sulphate.    Jan.  23. 
2339— Soo,     of     Chemical     Industry     in     Basle.— 

Manufacture  of  dye-stufie.    Jan.  25. 

Specifications  Published  this   Week. 

19141"- -Kulns,  C,  and  Pauling,  C— Process  for 
the  manufacture  of  resinous  products  of 
condensation  from  phenol  and  formalde- 
hyde. 

171367 — Melamid.  ^r.  M. — Process  of  producing 
hydrocarbons  of  relativply  low  boiling 
point  from   tar  oils. 

191582^ — Had  Inn,  R.  —  Recovery  of  aluminium 
chloride. 

191680— Federal  Phosphorus  Co.— Production  of 
phosphoric  acid. 

176785— Simon ,  T. — Mannfactnre  of  magnesium 
carbonate  from  dolomite. 

190995 — Legeler.  Dr.  E. — Process  for  the  manufac- 
ture of  sulphur  proto-chloride. 

Abstract  Published  this  Week- 
Recovery  of  hydrocarbons  and  sulphur  from. 
Coal  GflW.— Patent  No.  190203.— Pad ische  Anil'in  & 
Soda  Fabrik;  Ludwigshafen-on-Rhine,  Germany. 
Coal  or  coke-oven  gas,  previously  freed  from 
tar,  cyanogen  rompounds,  and  part  of  the  ammo- 
nia content,  is  passed  at  ordinary  or  slightly 
raised  temperature  throngh  a  number  of  towers 
containing  active  charcoal,  such  as  is  obtained 
by  charrinur  wood  with  zinc  chloride.  In  the  first 
towers,  all  the  benzene  hydrocarbons  are  ab- 
sorbed; in  the  next  towers,  the  hydrogen  snlphide 
is  removed  in  the  state  of  free  sulphur,  after  a 
sufficient  amount  of  oxygen-containing  gas  with 
or  without  ammonia  has  been  added;  finally,  if 
desired,  the  ethylene  hydrocarbons  are  absorbed 
in  the  last  towers.  By  employing  an  arrange- 
ment of  interchangeable  towers,  the  process  may 
be  conducted  in  a  continuous  manner.  Organic 
sulphur  compounds,  if  present,  are  retained  in 
the  first  towers  along  with  the  benzene  hydro- 
carbons; any  hydrocyanic  acid  present  becomes 
converted  into  ammonium  thiocyanate,  and  is 
also  deposited  in  the  first  towers.  The  etliylene 
may  be  freed  from  ammonia,  before  or  after 
absorption,  by  washing  with  aqueous  sulphuric 
acid  or  other  acid.  Instead  of  absorbing  ethy- 
lene as  such  in  the  last  towers,  it  may  be  con- 
verted into  ethylene  compounds  by  interaction 
with  halogens.  &c.,  in  .the  presence  of  the  active 
charcoal,  and  these  compounds  are  then  retained. 
The  absorbed  substances  are  removed  at  inter- 
vals, for  instance,  by  extraction  with  a  solvent  or 
by  expulsion  with  steam. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


MARCH  2.  1923. 


THE    CHEMICAL    NEWS. 


129 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.     No.   3281. 


RUBBER    VULCANISATION. 

The  importance  of  the  new  rubber 
"accelerators"  just  perfected  by  Britiish 
chemist«  has  been  explained  by  Major  Lefe- 
bure,  who  is  responsible  for  the  develop- 
ment department  of  the  British  Dyestuffs 
Corporation. 

He  stated,  in  an  interview,  that  the  use 
of  rub})er  was  greatly  restricted  until  about 
eighty  years  ago,  when  Hancock,  Goodyear, 
Parkes  and  other  pioneers  discovered  that  it 
acquired  some  very  valuable  properties 
when  vulcanised,  that  is,  when  associaled 
with  sulphur.  It  was  only  then  that  rub- 
ber began  to  come  into  its  own ;  yet,  up  to 
some  ten  years  ago,  if  rubber  was  needed  to 
combine  with  sulphur  in  this  way.  a  tem- 
perature of  140  degrees  Centigrade  or  more 
was  required.  For  a  thicker  article  like 
ebonite  or  vulcanite,  this  temperature  had 
to  be  maintained  for  many  hours. 

About  ten  years  ago,  it  waa  discovered 
that  by  adding  from  a  quarter  per  cent,  to 
one  per  cent,  of  certain  synthetic  organic 
chemicals  to  the  rubber  the  time  of  vulcani- 
sation was  reduced  from  one-half  to  one- 
eightieth,  according  to  the  size  of  the  ar- 
ticle and  the  nature  of  the  synthetic  organic 
chemical  used.  The  process  was  termed 
acceleration,  and  it  is  no  exaggeration  to 
say  that  the  use  of  synthetic  organic  chemi- 
cals in  this  way  has  been  a  landmark  in  the 
development  of  the  rubber  industry.  The 
consequences  are,  in  the  first  place,  a  very 
appreciable  reduction  in  the  amount  of 
steam  required  in  vulcanisation,  which 
means  a  marked  lowering  of  cost.  The  use 
of  small  percentages  of  synthetic  organic 
chemicals  introduces  an  entirely  new  con- 
trol factor  into  rubber  manufacture. 

In  America,  where  the  rubber  industry  is 
so  highly  developed,  there  are  very  few 
rubber  articles  which  are  not  made  by  the 
use  of  those  accelerators,  but  in  England  we 
have  been  slower.  An  important  new  fea- 
ture has  now  come  into  the  situation.  These 
accelerators  are  all  synthetic  organic  chemi- 
cals which  are  either  actually  intermediates 
in  the  dyestuffs  industry,  or  can  easily  be 
made  from  such  intermediates.  We  have 
perfected  products  with  special  suitability 
for  different  types  of  rubber.  Up  to  within 
a  year  ago  it  was  fairly  true  to  say  that  the 


I  British  rubber  industry  was  largely  depen- 
I  dent  on  chemicals  from  foreign  sources  for 
this  purpose.  There  were  certain  excep- 
tions. Rubber  manufacturers  were  even 
using  chemicals  under  trade  names  without 
knowing  what  the  chemicals  were  or  with- 
out being  sure  that  they  could  rely  on  get- 
ting them,  in  say,  a  year's  time  if  they 
wanted  to  repeat  them  for  any  particular 
department  of  their  work.  Now  that  the 
British  chemical  industry  has  taken  on  the 
production  of  them,  it  will  be  possible  to 
j  supply  the  rubber  industry  with  satisfactory 
proaucts  for  all  types  of  rubber  production. 
Certain  important  results  follow.  For 
example,  the  range  for  useful  articles  in 
rubber,  although  wide,  has  been  seriously 
limited  owing  to  the  fact  that  rubber  Las 
had  to  be  vulcanised  at  140  degrees  Centi- 
grade and  over  a  long  period  of  time.  Many 
materials  which  would  probably  comipound 

3uite  satisfactorily  with  rubber  under  less 
rastic  heat  treatment  have  had  to  be  ruled 
out  because  of  that  high  temperature.  The 
possibility  is  now  in  sight  of  using  such  pro- 
ducts and  a  good  range  of  colours,  for  rub- 
ber flooring,  hot-water  bottles,  and  so  on, 
is  also  made  possible. 


THE    INFI.UENCE    OF   THE    ATOMIC 
NUCLEUS    UPON  VALENCE,    ORIEN- 
TATION AND  THE  INDTTCED 
POLARITY  OF  ATOMS. 
By  Hbkhert  Henstock. 

That  the  hypothesift  of  the  Induced 
Polarity  of  Atoms  is  eminently  practical, 
explaining,  as  it  does,  many  hitherto 
obscun-  and  often  apparently  unrelated 
phenomena,  becomes  more  and  more  evi- 
dent as  its  applications  in  various  direc- 
tions are  brought  to  light.  Up  to  the  pre- 
sent, with  one  exception,  there  does  not 
appear  to  be  any  attempt  to  explain,  or 
attribute  any  imderlying  cause  to  this 
alt<^mate  polarity.  The  exception  referred 
to  is  that  of  Kermack  and  Robinson  (Tranti., 
1922,  CXXI.,  427).  who  a*;sign  the  cause  to 
the  number  of  electrons  in  the  outer  layers 
of  the  atoms  and  not  to  a  precise  definition 
of  their  supposed  arrangement  in  space. 
This  explanation  is.  however,  only  a  par- 
tial truth  and,  as  will  be  shown  later,  does 
not  apply  to  alternate  but  to  another  kind 
of  polarity. 

The  the<M'y  thai  induced  polarity  can 
alter  the  sign  or  the  electrical  eflfeet  of  an 
atom,  presupposes  some  easily  alterable  at- 


130 


THE   CHEMICAL    NEWS. 


MARCH  2,  1923. 


tribute  of  that  atom,  an  attribute  which 
does  not  require  any  very  great  force  to 
effect  the  alteration;  for  in  a  chain,  say  of 
carbon  atoms,  once  the  key  atom  has  its 
polarity  determined,  the  remainder  easily 
alter  their  polarities  in  alternation  with  the 
first,  each  succeeding  atom  bringing  about 
this  effect  in  its  neighbour!  This  cannot  be 
due  to  the  number  of  electrons  in  the  octet. 


since  this  is  a  more  or  less  constant  quan- 
tity, and  is  altered  only  where  large  forces 
are  brought  into  play,  which  may  remove 
an  electron  from  the  octet  of  an  atom  as  in 
an  electro- valence,  such  forces  being  much 
greater  than  those  required  for  an  altera- 
tion in  altern^ate  polarity.  The  octets  of 
the  atoms  in  the  fluorine^  molecule  may  be 
represented  as  in  Fig.  I.      The  two  atoms 


Fig.  I. 

may  share  two  electrons  as  a  co- valence, 
but  there  is  no  reason  why  one  should  be 
more  pcsitive  than  the  other,  if  the  mere 
numbers  of  electrons  in  the  outer  layers  is 
considered.  On  the  other  hand,  the  author 
is  in  agreement  with  Kermack  and  Robin- 
son in  the  view  that  alternate  polarity  is 
not  altogether  due  to  the  supposed  arrange- 
ment of  the  electrons  in  space.  By  this 
process  of  elimination  there  remains  the 
nucleus,  which,  according  to  Lewis  and 
Langmuir,  may  be  viewed  as  a  di-polar 
sphere  having  both  poles  positive  and  at- 
tended by  the  inner  layer  or  layers  of  elec- 
tron®, most  of  which  are  situated  at  or  near 
the  poles.  If  the  nucleus,  therefore,  with 
its  attendant  layers  of  electrons  and  their 
position  with  respect  to  the  octet  be  talen 


'  This  element  was  chosen  because  its  in- 
ternal construction  of  nucleus  and  two 
electrons  is  fairly  simple,  and  its  octet  has 
only  one  vacant  corner,  perm,itting  of  hut  a 
single  normal  primary  valence  bond. 


into  account,  a  reason  for  the  opposite 
polarities  may  be  found.  It  is  possible  for 
the  nucleus  to  rotate  within  the  atom  or 
for  the  octet  to  rotate  around  the  nucleus, 
but  when  an  atom  exists  in  a  compound  its 
octet  is  more  or  le&s  fixed,  so  that  if  there 
were  any  rotation  it  must  necessarily  be 
that  of  the  nucleus,  which  would  presum- 
ably carry  the  inner  electrons  with  it.  If 
this  rotation'  be  stopped  after  passing 
through  each  angle  of  90°  there  would  be 
two  opposmg  positions  for  the  nuclear 
poles  with  respect  to  the  outer  layer  of 
electrons :  the  fluorine  atom,  discussed 
above,  might  be  positive  or  negative  accord- 
ing as  to  whether  the  nuclear  poles  and 
their  accompanying  electrons  pointed  in  a 
perpendicular  direction.  A,  or  in  a  horizon- 


^  The  atom  m-ay  he  normally  in  a  static 
conditivn  as  assumed  by  Langmuir,  hut  the 
dynamic  condition  considered  by  Bohr  may 
he  caused  by  outside  influences,  whieh  ro- 
tate the  nucleus. 


i 


MARCH  2,  1923. 


THE  CHEMICAL  NEWS. 


131 


tal  direction,  B  (see  Fig.  II.)  with  respect 
to  the  face  a.b.c.d.  containing  the  line  a  b 
which  forms  the  edge  where  a  co-valenee 
bond  exists.  Naming  the  two  nuclear  poles, 
in  both  A  and  B,  x  and  y,  then  if  in  A  t-he 
distances  between  ay  and  by  be  called 
unity,  those  between  ax  and  bx  will  be  in 
the  ratio 


ax 
ay 


to  the  former;  where  R  =  radius  of  sphere 
occupying  the  atomic  volume  and  r  r= 
radius  of  sphere  occupying  the  nuclear 
volume.  On  the  contrary,  in  atom  B  the 
ratio  will  be  ax  :  by  :  :  1  :  1.  Thus  the 
ipole  y,  in  A,  is  at  unity  distance  from  b, 
but  the  pole  x  is  at  a  distance  greater  than 
unity  from  (a),  whereas  in  B  both  these  dis- 
tances are  unity.  But  since  the  nucleus  is 
by  no  means  saturated  or  counter-balanced 
by  the  inner  electrons,  the  valence  bond 
(a  b)  in  A  will  have  a  less  quantity  of  posi- 


Fio.  II. 


tive  electricity  opposed  to  it  than  will  (ob) 
in  B,  and  will  in  consequence  attach  itself 
to  B,  or  to  any  atom  constituted  like  B. 
the  edges  Ca  b)  in  each  making  the  union. 
The  direction  of  the  nuclear  poles  in  B  is 
such  that  it  will  tend  to  attract  electrons  to 
the  edge  (a  b)  and  to  fill  up  the  octet,  thus 
making  a  stable  arrangement  which  will 
constitute  B  a  negative  atom,  and  neces- 
sarily A  will  be  a  positive  one. 

The  rigidity  of  this  scheme  and  of  its 
further  applications  here  sot  forth,  is  not  in- 
sisted uipon :  it  has  been  used  more  as  a 
graphic  medium  for  conveying  the  author's 
meaning  than  as  an  exact  picture  of  whof 
takes  place. 


It  can  be  stated,  therefore,  that  a  strong 
outside  influence  may  rotate  the  nucleus  of 
an  atom  in  a  chain  and  so  determine  its 
polarity  and  the  atoms  directly  attached  to 
it  will  have  opposite  polarities  induced  by 
the  rotation  of  their  nuclei,  caused  by  the 
nucleus  of  the  first  atom,  which  may  be 
looked  upon  as  forces  acting  at  a  distance, 
as  assumed  bv  Lapworth  (Mem.  Manches- 
ter PhQ.  Soc'.,  1020,  LXIV..  1-17;  Trans., 
1022,  CXXI.,  416). 

Such  an  alternate  polar  effect  might  be 
shown  by  considering  the  nuclei  of  the 
atoms  withoiit  their  electrons,  somewhat  as 
ff>llows :  — 


132 


THE    CHEMICAL    NEWS. 


MARCH  2,  1923. 


System  I. 


If  the  polarity  of  the  key  atom  were 
altered  we  should  then  have  the  opposite 
effect,  viz. :  — 


+ 


(t)  -e  (D  o-  (b  o 


ke\/  Atom. 


System  II. 


where  the    poles  of    the  nuclei    have    been 
rotated  through  an  angle  of  90°. 

Particular  attention  should  be  given  to 
the  fact  that  there  is  a  fundamental  dif- 
ference between  the  older  conceptions  of 
polarity,  as  applied  to  an  electro  positive  or 
electro  negative  element  in  the  electro 
chemical  sense,  or  as  applied  to  ions,  and 
the  newer  conception  of  induced  polarity. 
The  term  polarity,  as  at  present  in  use,  in- 
cludes two  kinds :  (1)  what  might  be 
termed"  Permanent-Periodic  Polaritv  "  or 
simpl^permanent  polarity,  or  that  which  is 
due  to  the  greater  or  less  numbers  of  elec- 
trons in  the  octet,  combined  with  the 
greater  or  less  strength  of  the  nucleus : 
this  is  a  permanent  periodic  function  .>f 
the  elements,  running  from  the  single 
electron  and  seven  vacant  Sipaces  in  the 
octets  of  the  strongly  electro  positive  alkali 
metals  to  the  seven  electrons  and  one 
vacant  space  of  those  of  the  strongly  electro 
negative  halogens,  in  the  usual  periods  of 
the  periodic  table.  The  formation  of  ions 
also  may  be  put  down  in  the  same  categor^y . 
for  although  the  ion  contains  one  more  or 
less  electron  than  the  atom,  nevertheless 
the  formation  is  confined  to  the  octet,  tnis 
type  of  polarity  being  merely  enhanced  on 
possage  from  atom  to  ion.  The  foregoing 
description  is  that  of  the  older  ideas  of 
ipoiarity.  (2)  What  Lapworth  has  called 
"  Latent  Induced  Alternate  Polarity,"  or 
that  which  is  due  to  the  position  of  the 
nucleus  with  respect  to  the  outer  layer  of 
electrons,  as  has  been  demonstrated  above ; 
this  is  a  variable  and  transitory  condition  of 
an  atom  depending  upon  its  environment, 
and  it  is  the  immediate  cause  of  the  deter- 


mination of  orientation.  The  strength  of 
this  kind  of  polarity  will,  however,  be  much 
less  than  that  exerted  by  the  outer  elec- 
trons, which  will  determine  the  electro  posi- 
tive or  negative  nature  of  one  element  to 
another  and  not  as  in  this  case  the  polarity 
of  the  atoms  of  the  molecule  of  an 
element  to  one  another  or  the  alter- 
nate polarities  of  the  atoms  of  a 
chain.  Induced  polarity  is  not  a  periodic 
function  of  the  elements;  it  is  overbalanced 
in  the  more  strongly  positive  or  negative 
elements  in  the  permanent-periodic  sense ; 
such  elements  as  the  alkali  metals  or  the 
halogens  scarcely  show  alternate  polarity, 
which  becomes  apparent  only  in  the  more 
neutral  elements,  such  as  carbon.  Lap- 
worth's  use  of  the  word  "  latent,"  in  this 
connection,  is  very  apposite  since  either 
positive  or  negative  alternate  polarity  may 
be  called  into  being  in  an  atom,  the  possi- 
bility being  inherent  in  its  constitution. 

The  two  types  of  polarity  may  perhaps  be 
more  clearly  seen  if  considered  with  respect 
to  a  single  element.  Chlorine  is  extremely 
electro  negative  in  permanent  periodic 
polarity,  but  in  its  molecule  one  atom  may 
be  weakly  positive,  the  other  negative  con- 
sistently with  induced  polarity ;  positive 
chlorine  may  therefore  exist  in  a  compound. 
If  this  assumption  of  the  rotation  of  the 
nucleus  be  extended  to  the  other  elements 
the  same  simple  relationship  will  be  found. 
Hydrogen  has  no  inner  electrons,  and  is 
always  positive  in  "  permanent  perio<lio 
polarity  "  :  the  union  of  two  of  its  atoms  to 
form  a  molecule  being  brought  about  by  the 
rotation  of  the  nucleus  alone,  one  atom  oe- 
ing  positive  in  both  kinds  of  polarity  vdll 
rotate  the  nucleus  of  the  second  atom,  mak- 
ing it  negative  in  alternate  polarity,  but 
still  remaining  positive  in  permanent  polar- 
ity. We  can  therefore  have  negative  hy- 
drogen without  any  very  great  boulever.^e- 
nient  of  our  older  ideas  concerning  this 
element.  The  inert  gases,  having  no  pri- 
mary valence  bonds,  cannot  exhibit  any 
kind  of  polarity;  they  might  conceivably 
display  weak  alternate  polarity,  if,  as  some 
chemists  opine,  they  can  form  compounds 
by  means  of  partial  valencies. 

Should  such  compounds  be  proved  to 
exist,  then  the  inert  gases  would  be  capable 
of  exhibiting  polar  properties  which  could 
not  be  accounted  for  by  means  of  the  older 
idea  of  polarity.  The  remainder  of  the  ele- 
ments in  the  series,  sodium  to  fluorine, 
each  having  two  inner  electrons,  will  act  in 
a  fashion  similar  to  that  already  described 


i 


MAKCH  2,  1923. 


THE   CHEMICAL   NEWS. 


133 


for  fluorine,  but  since  thej  have  less  num- 
bers of  electrons,  in  their  octets  thej  will 
have  a  larger  number  of  co-valence  bonds, 
each  of  which  will  be  positive  or  negative 
according  to  the  quantity  of  positive  elec- 
tricity, which  the  rotation  of  the  nucleus 
opposes  to  it  in  any  given  condition  of  the 
molecule  in  which  atoms  of  these  elements 
may  exist.  Carbon,  having  four  electrons 
symmetrically  situated  in  its  octet,  will 
more  easily  cnange  its  induced  polarity  than 
will  those  elements  on  either  side  of  it;  for 
in  any  atom  the  nucleus  will  tend  to  set  it- 


J 

\ 

^^^ 

^^ 

\ 

-  ^      ^r 

y^ 

\ 

\ 

X 

/           / 

X 

V 

/            X 

~"~~v- 

X     1 

\J 

>'  ''■ 

\          -^^ 

^\ 

~  i^_ 

/ 

\ 

/ 

/     / 

\ 
\ 

/ 

^r           ,* 

\ 

/ 

X        "^^ 

\ 

\ 

/ 

^r    ^^ 

X 

X 

f 

B 


self  as  symmetrically  as  possible  with  re- 
spect to  the  electrons  in  the  octet,  and  will 
continually  tend  to  return  to  such  a  posi- 
tion when  not  influenced  by  outside  forces 
which  restrain  it;  the  symmetry  of  the  un- 
combined  carbon  octet  permits  the  nucleus 
to  remain  in  almost  any  position  withovit 
strain.  Elements  of  higher  atomic  weight 
than  those  of  this  series  will  not  change 
their  induced  polarity  so  easily  as  the  latter, 
since  they  have  a  larger  number  of  elec- 
trons in  their  inner  layers  which  will  act  as 
a  retarding  influence. 


a 

Fio.  Ill, 


Before  leaving  the  subject  of  alternate 
polarity  it  may  be  well  to  note  that  the 
whole  idea  of  the  rotation  of  the  nucleus  is 
bound  up  with  that  of  action  at  a  distance. 
Actuated  by  repulsive  fields  or  Faraday 
tubes  of  force  emanating  from  the  nucleus 
of  a  key  atom,  the  nuclei  of  adjoining  atoms 
are  repelled  and  alter  their  positions  by  re- 
volution round  their  own  centres,  thus  alter- 
ing the  direction  of  their  positive  tubes  of 
force  (P'ig.  III.)  which  is  the  immediate 
cause  of  the  alteration  in  polarity  of  such 
atoms.  This  change  in  the  directions  of 
the  tubes  of  force  reacts  upon  the  electr>as 
and  vacant  corners  of  the  octet  with  a  con- 
secpient  fluctuation  in  the  powers  of  attrnc- 
tion  nt  its  various  parts,  which  may  vary 
the  orientation  in  the  molecule  of  which  the 
atom  is  a  part,  or  may  even  influence  the 
valence  of  the  atom  concerned.  Fw  tubes 
of  force,  see  Lapworth  (Trans.,  loc.  cit.) 


Tbb  Effect  of  the  Nucleus  upon  Valence. 

If  this  suggestion  be  applied  to  valence, 
it  will  be  seen  that  it  corroborates,  in  a  re. 
markable  manner,  Lewis'  and  Langmuir's 
representations. 

(1)  Electro  valence  is  determined  chiefly 
by  permanent  polarity.  Where  a  perma- 
nently polar,  electro  negative  element,  as 
for  example  chlorine,  which  has  its  octet 
nearly  complete,  and  tending  to  final  com- 
pletion by  the  actual  passage  of  an  electron 
from  another  atom  of  a  permanently  polar 
electro  positive  element,  say  sodium,  unites 
with  the  latter  with  formation  of  an  elec- 
tro valence  bond  between  the  two,  the  nega- 
tive permanent  polarity  is  so  strengthened 
by  the  alternate  polarity,  both  acting  in  the 
same  way,  that  the  united  force  exerted  is 
suflRcient  to  tear  an  electron  from  the  octet 
of  the  positive  so^lium,  in  which  both  kinds 
of  positive  polarity  are  operating  in  the 
same  direction  (but  in  nn  opposite  one  to 
that  in  the  negative  chlorine),     tending  to 


134 


THE   CHEAiiCAL   KEWS. 


MAKCil  2,  1923. 


give  up  an  electron.  The  action  might  be 
comipared  with  the  united  pull  exerted  upon 
the  earth  by  the  sun  and  moon  when  both 
are  on  the  same  side  of  the  earth.  The 
actual  passage  of  an  electron  from  octet  to 
octet  is  effected  only  by  the  considerable 
force  here  exerted,  and  occurs  chiefly  be- 
tween elements  strong  in  permanent  polar- 
ity, i.e.,  those  near  either  end  of  each  series 
or  period  of  the  periodic  table. 

(2)  Co-valence  is  determined  by  a  similar 
group  of  forces,  but  the  permanent  polari'oy 
and  alternate  polarity  combined  are  not 
sufficiently  powerful  to  remove  an  electron 
from  one  atom  to  another,  hence  a  shari.ig 
of  electrons.  The  elements,  which  exhibit 
co-valence  in  a  supreme  degree  and  rarely 
display  electro  valence,  are  those  in  which 
the  permanent  polarity  is  weak,  and  are 
represented  by  the  ones  towards  the  middle 
of  each  period  of  the  periodic  table.  From 
the  foregoing  it  is  therefore  apparent  that 
the  only  difference  between  electro  valence 
and  CO- valence  is  one  of  degree,  which  view 
is  practically  identical  with  that  expressed 
by  Briggs  (Tram.,  1921,  CXIX.,  1876),  and 
also  by  Kermack  and  Robinson  (loo.  cit.) 


J. 

^r 

^^                     ,-'''  x\ 

^r 

'      \                                        .'^'          X     / 

^ 

'.     \                y      /  I 

^^ 

1            ^                           ^'                  X          / 

X 

>             "l                   X                     X             ' 

y^ 

*                      \                /                                 ^                           f 

X 

*               V        '                     X                     ' 

— -^^ 

V     i  /  .^'^'   J 

/ 

-->.\,«^/ 

/ 
J 

/ 

y 

^  ^''^ /V\        '^ 

• 

/           (    \    )          / 

y 

/ 

1          V  \y   j^ 

f              vV^"^~"^ 

/ 
/ 
/ 
/ 

-^    1  >       ^ 

-^ 

^                        /                          '      »             \ 

/ 

/                           /       \             ^ 

X 

X                   /        ^         \ 

X 

/    /        y     \   \ 

/ 

I         X                      -'                      ^ 

X 

/ 

'  /       ^''                          \ 

X 

Z-^'" 

/ 

Fig.  IV. 

The  partial  valencies  discussed  by  Lap- 
worth  and  by  Kermack  and  Robinson  might 
be  explained  on  the  assumption  that  the 
nucleus  may  be  partially  rotated  through 
an  angle  of  90°,  i.e.,  through  a  fraction  of 
that  angle,  in  some  such  way  as  that  con- 
templated in  Fig.  IV.,   where  the  tubes  of 


force  emanating  from  the  nuclear  poles  will 
reach  the  corners  of  the  octet  in  a  different 
set  of  directions  from,  and  with  forces  vary- 
ing from,  those  depicted  in  Fig.  III.  for 
primary  valence :  thus  some  of  the  octet 
corners  might  be  opposed  to  both  nuclear 
poles,  others  to  but  a  single  one,  which 
would  strengthen  or  weaken  their  power  of 
attracting  electrons,  and  where  such 
strengthening  occurred  partial  valencies 
might  be  possible;  each  of  the  corners 
might  or  might  not  be  occupied  by  an  elec- 
tron, and  thus  a  considerable  number  and 
variety  of  possibilities  for  partial  valencies 
would  occur.  When  a  corner  of  the  ocCet 
of  an  atom  is  unoccupied  by  an  electron  and 
the  nucleus  is  partially  rotated  so  that  the 
tubes  of  force  from  both  nuclear  poles  can 
bear  upon  this  point,  a  negative  partial 
valence  will  re&ult,  but  where  the  corner  is 
occupied  a  positive  one  will  occur.  This  is 
in  agreement  with  the  statement  of  Briggs 
{Urans.,  1919.  CXV.,  278)  concerning  posi- 
tive and  negative  afi&nity. 

The  Effect  of  the  Nucleus  upon 
Orientation. 
The  idea  of  the  rotation  or  oscillation  of 
the  nucleus  is  not  inconsistent  with  (on  a 
larger  scale)  the  known  phenomena  of 
astronomy,  and  it  is  more  than  probable, 
as  has  been  already  assumed  by  other.^, 
that  the  electrons  of  the  octet,  as  well  as 
those  of  the  inner  layers,  oscillate  about 
fixed  positions  in  the  atom.  Such  rotation 
or  oscillation  of  the  nucleus  is  chiefly  de- 
pendent upon  the  strength  of  forces  acting 
from  without  the  atom,  any  alteration  in 
these  forces  would  tend  to  rotate  the 
nucleus  wholly  so  as  to  alter  the  polarity  of 
the  atom  to  opposite  sign,  or  partially  so 
as  to  weaken  the  existing  polar  sign.  In 
the  case  of  one  atom  of  a  chain  of  carbon 
atoms,  this  would  firstly  alter  the  power 
and  direction  of  the  tubes  of  force  operat- 
ing upon  the  bonds  with  side  atoms  or 
chains,  and  might  rearrange  such  bonds, 
their  direction  and  the  consequent  orien- 
tation on  that  particular  atom  also  depend- 
ing to  some  extent  upon  the  atoms  or 
groups  already  attached  to  it ;  secondly,  it 
would  react  upon  the  nuclei  of  the  succc-^d- 
ing  atoms  with  possibly  similar  results, 
and  so  orientation  in  the  molecule  wouid 
be  directly  dependent  upon  the  amount  of 
rotation  of  the  various  nuclei,  the  whole  re- 
sulting from  the  action  of  the  nucleus  of 
the  key  atom  or  atoms,  together  with  the 
secondary  influence  of  the  side  chain  atoms 
or  groups.       For  descriptions  of  the  action 


d 


MARCH  2.  1923. 


THE  CHEMICAL  NEWS. 


135 


.  -« 
of  these  latter,  see  papers  by  Lapworth, 
Kermack  and  Robinson,  Flureoheim,  etc. 
It  should  be  noted,  therefore,  that  the 
nucleus  does  not  necessarily  remain  rigidly 
in  the  positions  indicated  in  Fig.  II.,  but 
may  oscillate  about  these  ipositions,  so  that 
when  a  strong  key  atom  influences  a  chain 
of  atoms,  this  oscillation  may  be  thereby 
considerably  retarded,  or  even  stopped, 
when  the  nuclear  poles  would  face  the 
various  edges  or  corners  of  the  octets,  where 
valence  unions  are  possible,  in  a  more  pei- 
manent  fashion,  and  so  strengthen  those 
positions  that  such  unions  would  be  en- 
couraged. This  permanency  of  position 
would  render  the  various  atomic  bonds 
more  positive  or  negative,  and  thus  more 
or  less  reactive,  as  tne  case  might  be,  de- 
pending upon  the  polarity  of  any  other  re- 
acting atom  or  group. 

The  polarity  of  a  group  depends  to  a  con- 
siderable extent  upon  the  iposition  of  the 
nucleus  of  that  atom,  which  will  affect  the 
union  with  another  group,  and  since  this 
position  is  referable  to  the  strength  of  the 
key  atom  or  atoms,  this  is  one  of  the  chief 
agents,  which  regulates  the  affinity  of 
groups  and  in  the  end  their  orientation  in 
the  molecules  they  may  enter.  As  an  ex- 
ample, the  amido  and  acetyl  groups  given 
by  Lapworth,  will  illustrate  this.  In  the 
amido  group  the  nitrogen  is  negative  in 
alternate  polarity,  and  similarly  in  the 
acetyl  group  the  carbon  atom  attached  to 
oxygen  is  positive,  consequently  the  two 
unite  to  form  aoetamide.  Again  in  the  NO, 
group  the  nitrogen  is  positive,  hence  NO, 
does  not  unite  with  CHjCO.  Here,  then, 
we  have  nitrogen  in  two  groups,  negative  in 
one  and  positive  in  the  other,  a  phenomenon 
which  is  not  readily  explainable  under  the 
older  idea  of  perm.inent  polarity,  nor  even 
by  a  rearrangement  of  tho  electrons  of  the 
octets  of  the  atoms  concenu'd,  but  of  which 
a  simple  solution  is  afforded  by  the  idea  of 
the  rotation  of  the  nucleus  underlying  al- 
ternate polarity  as  described  in  the  preced- 
ing pages.  The  effect  of  those  two  nitrogen- 
containing  groups  upon  orientation  in  eni- 
line  and  nitro-benzene  has  been  shown  by 
Vorlander  (B»r.,  1919,  LU.,  263). 

The  explanations  of  orientation  given  by 
Gough  and  Thorpe  (Trani,.,  1919,  CXV.. 
1155),  and  also  those  bv  Lapworth  and 
Shoosmith  {Trans.,  1922.  CXXI.,  1391)  rre 
interesting  as  demonstrating  the  case  with 
whToh  the  polarity  of  the  atoms  is  alter-^d, 
not  merely  along  a  simple  chain  of  carbon 
atoms,  but  even  through  a  part  of  tho  brn- 
zene  ring,  which  goes  to  show  that  some 
easily    alterable  function    of  the  atoms    is 


brought  into  operation,  such  as  might  be 
attributed  to  nuclear  rotation,  where  little 
force  is  needed  to  affect  its  alteration. 

The  author  wishes  to  express  his  grati- 
tude to  Prof.  A.  Laipworth,  for  his  kind- 
ness in  criticising  this  communication, 
and  also  for  much  valuable  advice  in  con- 
nection with  it. 

Chemical  Research  Laboratory, 
Sch6pl  Gardens, 

Shrewsbury. 


[Contribution  from  the  Department  of 
Chemistry,  Cornell  University.] 

GERMANIUM.      IV.— GERMANIUM 
TETRA-IODIDE.^ 

By  L.  M.  Dennis  and  F.  E.  Hance. 

(From  the  "  Journal  of  the  American 
Chemical  Society,"  December,  1922.) 

{Continued  from  Page  118.) 
From  these  experiments  it  would  appear 
that  the  result  of  the  vapour-density  deter- 
mination at  440°  made  by  Nilson  and  Pet- 
tersson  showed  agreement  with  the  theo- 
retical va(pour  density  not  because  ger- 
manium tetra-iodide  does  not  dissociate  at 
that  temperature,  but  rather  because  the 
vapour  consists  of  a  mixture  of  undis- 
sociated  tetra-iodide  and  of  vapour  of 
ifxiine  which  results  from  the  dissociation 
of  the  tetra-iodide  and  which  at  440"  is  di- 
atomic.'   Gel 4  '''^=^-GeIj  +  I,. 

Before  leaving  the  point,  however,  two 
determinations  were  made  of  the  vapour 
density  of  germanium  tetra-iodide  with  a 
modified  Victor  Meyer  apparatus.'  The 
tube  was  heated  in  an  electric  resistance 
furnace  which  made  possible  the  regulation 
of  the  temperature  within  narrow  limits, 
442-446°.  Taking  the  temperature  as  445", 
0.2827  and  0.0209  g.  of  substance  gave 
10.5  and  24.5  cc.  of  displaced  gas  at  0°  and 
760  mm.,  equivalent  to  vapour  density  of 
20.87  and  19.67  respectively. 

These  result.s  show  the  same  agreement 
with  the  calculated  vapour  density,    20.01 


'  The  investigation  upon  which  this 
article  is  based  was  supported  by  a  grant 
from  the  Hecksrher  Foundntion  for  the 
.Advancement  of  Research,  established  by 
.Auquat  Heckschcr  at  Cornell  University. 

»■  Meifer,  Ber.,  1880,  XIII.,  394,  401. 

»  Weiser,  J.  Phys.  Chem.,  1916,  XX., 
582. 


136 


tHE    CHEMICAL    NEWS. 


MABCH  2,  1923. 


as  was  obtained  by  Nilson  and  Pettersson, 
but  crystals  of  free  iodine  were  found  in 
the  inner  tube  at  the  close  of  each  deter- 
mination which  proves  that  germanium 
tetra-iodide  undergoes  partial  dissociation 
under  these  exiperimental  conditions. 

Chemical  Properties. — Winkler^  stated 
that  germanivim  tetra-iodide  is  highly  hy- 
grosoopio  and  that  it  deliquesces  when  ex- 
posed to  the  air.  He  found  that  it  first 
gained  in  weight  (50  per  cent,  in  1  day), 
and  then  lost  weight  during  the  next  18 
days,  the  residue  then  weighing  only  about 
•J  as  much  as  the  original  sample. 

Several  different  samples  of  the  sub- 
stance that  we  have  prepared  have  shown 
identical  properties  which  are  widely  dif- 
ferent from  those  that  Winkler  has  de- 
scribed. Germanium  tetra-iodide  neither 
gained  nor  lost  appreciably  in  weight  when 
exposed  to  the  air  for  2  days.  A  sample 
that  weighed  0.5622  g.  was  allowed  to  lie 
on  a  watch  glass  exposed  to  the  air  of  the 
laboratory  for  5  months.  At  the  end  of 
that  period  its  weight  had  decreased  6.5 
mg.,  and  a  slight,  white  incrustation  had 
formed  around  the  sample  on  the  watch 
glass,  but  the  appearance  of  the  sample 
was  unchanged. 

When  germanium  tetra-iodide  is  im- 
mersed in  a  small  amount  of  water,  it  is 
slowly  decomposed  with  the  separation  of 
geranium  dioxide,  which  dissolves  when 
more  water  is  added  and  forms  a  clear, 
colourless  solution  of  acid  reaction. 

A  ©ample  of  the  compound,  placed  under 
cone,  sulphuric  acid  of  room  temperature, 
ajpparently  suffered  no  change  in  24  hours, 
for  at  the  end  of  that  period  the  acid  gave 
no  test  for  either  germanium,  or  iodine,  or 
for  hydriodio  acid.  When  the  acid  was 
warmed  to  80°,  iodine  was  slowly  liberated. 

When  placed  in  a  1:4  solution  of  potas- 
sium hydroxide,  germanium  tetra-iodide  is 
slowly  dissolved.  Under  cone,  nitric  acul 
it  turns  black  and  nitrogen  dioxide  is 
evolved.  After  standing  under  the  acid  for 
4  months,  the  residue  still  retained  its 
black  colour. 

Cone,  hydrochloric  acid  of  room  tem- 
perature slowly  dissolves  germanium  tetra- 
iodide,  solution  being  complete  after  some 
weeks.  When  dropped  into  cone,  ammo- 
nium hydroxide,  the  compound  is  at  once 
decomposed  and  decolorised,  a  white  solid 
being  formed.  When  exposed  to  dry  am- 
monia gas,  the  substance  is  slowly  con- 
verted into  a  white  powder  that  is  soluble 
in  water. 

Solubility. — Germanium   t^tra-iodide    dis- 


solves without  apparent  decomposition  in 
the  Hquids  listed  below,  the  solution  in 
each  case  undergoing  no  visible  change  for 
4  months. 


Solvent. 

Benzene 

Carbon  di&ulphide 
Methyl  alcohol 
Ethylene  chloride 
Monoch  lor  obenzene 
Carbon  tetrachloride 
Ethylene  glycol 
Ethylene  chlorohydrin 


Colour  of  solution. 

lied-orange 
Red -orange 
Deep  orange 
Light  orange 
Red-orange 
Light  orange 
Very  light  yellow 
Very  light  yellow 


The  following  solvents  dissolved  the  sub- 
stance at  once,  but  decomposition  slowly 
took  place. 


Solvent. 

Hexane 

Amyl  alcohol 

Chloroform 

Nitrobenzene 

Petroleum  ether 

Butanol 

Glacial  acetic  acid 


Colour  of  solution. 

Orange-red 
Deep  orange 
Pale  yellow 
Red- orange 
Pink 
Orange 
Pale  yellow 


After  standing  for  4  months. 
Pink  (free  iodine) 
Yellow  ppt.,    brown  solution 
Reddish  yellow  solution 
White  ppt.,   dark  brown  solution 
Decomposition,   black  ppt. 
Dark  brown  solution 
Dark  brown  solution 

The   following    liquids    decomposed    the 
substance  at  once. 

Acetone  Light  brown  ppt. 

Ether  Ruby-red  solution,  yellow 

ppt. 
Turpentine  2  liquid    layers  formed, 

the  upper    one   a     light 
red,  the  lower  a  deep 
orange;  solidresidue,  dark 
brown  in   colour 
Oil  of  lavender      Light  yellow  ppt. 

changing  to  black 
Absolute  alcohol  Yellow  solution,  white  ppt. 
7so-propyl  alcoholOrange  solution,   white  ppt. 
Pyridine  Light  yellow  solution 

white  ppt. 
Amyl  alcohol         Brown  solution,   white  ppt. 

Summary. 

This  article  deals  with  the  preparation  of 
germanium  tetra-iodide,     its   analysis,     the 


MABCH  2.  1923. 


TAB   CHEMICAL   NEWS. 


determination  of  its  melting  point,  crystaJ 
form  and  etpecific  gravity,  its  colour  at 
various  temperatures,  the*^  sublimation  and 
dissociation  of  the  compound,  and  some  of 
its  chemical   properties. 

Ithaca,  New  York. 


Ig? 


ARABIAN  ALCHEMY  AND 
CHEMISTKY. 

On  Tuesday,  February  13,  an  important 
lecture  on  the  above-mentioned  subject  vias 
delivered,  under  the  ausj)ice8  of  the  Royal 
Asiatic  Society,  by  Mr.  E.  J.  Holmyard, 
the  Rt.  Hon.  Lord  aialmors,  G.C.B.,  pre- 
siding. 

After  exipressing  his    appreciation  of    the 
greater  interest  now  shown  in  the  history  of 
science,  and  emphasising  the  importance  of 
its  study,  Mr.  Holmyard  pointed  out  that 
there  was  a  serious  gap  in  our  kilowledge  of 
the  hifttOTy  of  alchemy  and  chemistry.  Dur- 
ing the  period  600-1000  ad.  chemistry  was 
monopolised     by    Islam.      The     alchemical 
MSS.  of  this  period  had  received    but   scant 
attention  owing  to  the  difficulties  of  Arabic. 
Berthelot  had  had  about  thirteen  of  them 
translated,  but  at  least  three  hundred  wore 
known  and,  no  doubt,  many  more  existed. 
Dealing  with  the  Arabian  alchemists  indi- 
dividually,  on  the  basis  of  a  first-hand  stu'ly 
of  the  original  MSS.,     Mr.   Holmyard  dis- 
missed Khalid  as  incomprehensible.    Geber, 
however,  was  a  man  of  a  very  different  t^po, 
and  Mr.  Holmyard  controverted    the  views 
of  Berthelot  regarding  the  Latin  works  as- 
cribed to  Geber,   and  gave    reasons  for  re- 
garding   these    as  genuine    translations    of 
works  by  the  Arabian  alchemist.    Berthelot 
was  acquainted    with  only    a  very  few    of 
Geber's    works,    and    Mr.  Holmyard    sug- 
gested that  these  were  not.    strictly  speak- 
ing, his  chemical  works,  but  mystical  writ- 
ings   in  which — as    a  chemist — Geber    had 
employed  chemical    symbolism    to  oxpr.^ss 
his  religious   ideas.        The  originals  of  the 
Latin  works  ascribed  to  Geber  had  not  been 
discovered,  but  there  was  an  Arabic  MS  in 
the  British  Museum  by  Geber,  entitled  the 
"  Book    of  Properties."    which    resembled 
these    books    in  character.      The    sulphur- 
mercury  theory    of  the    metals  was    clearly 
stated  in  Geber's    Arabic    works,    and    the 
"  Book    of    Properties  "    contained    many 
practical    recipes,  such    as  recipes    for  the 
preparation  of  basic  lead  carbonate,  metal- 
li«  lead,  mercuric  sulphide,  etc. 


The  later  Arabian  alchemists,  such  as 
Rhazes,  were  also  briefly  dealt  with  by  Mr. 
Holmyard,  who  pointed  out  that,  in  general, 
they  were  men  of  a  practical  turn  of  mind, 
and  illustrations  from  an  Arabic  MS  in  the 
British  Museum,  showing  the  various 
forms  of  apparatus  used  by  them,  were 
shown  by  means  of  the  lantern. 

In  the  discussion  which  followed, 
amongst  other  speakers.  Prof.  Browne,  Dr. 
and  Mrs,  Singer,  Mr.  R.  Steele,  and  Mr.  H. 
S.Redgrove  took  part.  Mr.  Redgrove  re- 
ferred to  the  work  that  the  Alchemical 
Society,  which  existed  prior  to  the  war,  had 
done  to  stimulate  interest  in  the  history  of 
chemistry.  He  warmly  congratulated  Mr. 
Holmyard  on  his  achievement  in  substan- 
tiating the  genuineness  of  the  Latin  works 
of  Geoer,  and  raised  the  question  as  to 
the  (M'igin  of  the  sulphur-mercury  theory, 
an  important  factor,  in  his  opinion,  being 
the  tendency  of  the  old-time  thinkers  to 
base  their  theories  on  analogies,  not 
infrequently  of  an  unwarranted  character. 


NEW  BRITISH  CHEMICAL 
STANDARD. 

Basic  Slag  "  A." 

The  British  Chemical  Standards  Move- 
ment announces  the  iesue  of  a  Basic  Slag 
Standard. 

The  8f>ecial  uses  of  this  are  twofold:  — 
Primarily  as  an  analytical  standard  for  total 
phoephorip  acid  and  phosphates;  and  as  a 
standard  mainly  for  basic  steel  mskkers, 
but  also  for  acid  steel  makers,  iron  and 
steel  founders  and  others,  to  enable  them  to 
check  their  methods  tor  silica,  iron,  lime 
and  magnesia,  etc.,  in  slag. 

The  analysis  is  as  follows: — Phosphoric 
Anhydride  (P,<)i),  12.93  per  cent.,  equal  to 
Phosphates  (CajP^O,)  28.24  per  cent.,  iron 
8.97  per  cent.,  silica  16.15  per  cent. 

During  the  standardisation  of  this  slag 
the  need  for  such  a  standard  has  been  made 
abundantly  evident  to  the  organisers,  for  it 
has  been  found  that  even  in  the  determina- 
tioa  of  such  elements  as  iron,  silica,  lime 
and  magnesia,  which,  it  may  be  thought, 
present  little  or  no  difficulty,  improvements 
in  methods  have  been  essential  in  order  to 
get  agreement  between  experienced 
chemists. 

The  standard  has  been  tested  by  a  selec- 
tion of  16  prominent  chemists  representing 


138 


THE   CHEMICAL   NEWS. 


MARCH  2,  1923. 


Independent  analysts,  both  metallurgical 

and  agricultural ; 
The  U.S.  Bureau  of  Standards, 
English     and     French     Iron    and     Steel 
Works'  Chemists  (manufacturers),  and 
English    Basic    Slag   Grinders    and    Mer- 

cnants. 
It  is  hoped  that    chemists  will  take    full 
advantage  of  this  standard,  which  has  been 
prepared    with    the      object    of    promoting 
unification  of  analysis. 


GENERAL    NOTES. 


BRITISH    INDUSTRIES    FAIR. 

The  vast  mass  of  exhibits  to  be  displayed 
at  the  1923  British  Industries  Fair  at  Lon- 
don and  Birmingham,  between  February  19 
and  March  2,  possesses  two  angles  of  in- 
terest to  both  home  and  overseas  buyers. 
The  first  is  covered  by  the  numerous  com- 
modities which  have  only  in  recent  years 
been  produced  in  Great  Britain ;  the  second 
will  be  found  in  the  still  larger  number  of 
exhibits  of  goods  which,  while  always  noted 
for  British  quality,  will  show  notable  im- 
provements at  the  Fair,  where  novelty  will 
be  found  allied  with  quality. 

In  giving  the  overseas  buyer  the  oppor- 
tunity to  inspect  Sipecimens  of  products  and 
commodities  which  have  only  been  estab- 
lished in  Great  Britain  during  comparative- 
ly recent  years,  the  Fair  fulfils  the  first 
essential  of  its  existence.  One  of  the  most 
interesting  sections  falling  under  this  class 
will  be  that  devoted  to  dyes  and  fine  chemi- 
cals. The  exhibits  in  this  representative 
and  comprehensive  section  will  range  from 
the  rarest  of  fine  chemicals  for  medicinal 
and  research  purposes  to  those  known  as 
"heavies"  and  sold  by  the  truck  load. 


DYESTUFFS    (IMPORT   REGULATION) 
ACT,  1920. 
Board  of  Trade  Announcement. 
The  total  number  of  applications  received 
during  January  was  562,  of  which  473  were 
from  merchants  and  agents.       These  wore 
dealt  with   as  follows:    Granted,     359;    re- 
fused,   aipplicants  being  referred  to  British 
makers    (British    equivalents    being    avail- 
able), 94;    referred  to  Reparation    supplies, 
53;  outstanding  on  January  31,  56. 


MOROCCO.— PHOSPHATE  BEDS. 

Mr.  C.  E.  Heathcote-Smith,  O.B.E., 
H.M.  Consul  at  Casablanca,  has  forwarded 
to  the  Department  of  Overseas  Trade  the 
following  interesting  report  on  phosphates 
in  Morocco:  — 

Extent  of  Moroccan  Phosphates. — By  the 
discovery  of  rich  and  vast  phosphate  beds, 
Morocco  has  become  a  potential  factor  of 
economic  importance. 

It  is  credited  with  the  possession  of  de- 
posits rivalling  in  extent  those  of  Florida, 
and  in  content  those  of  any  other  country 
in  the  Eastern  Hemisphere. 

Thus  the  Oiied  Zem-El  Bouroudj  beds 
(160  km.  south  of  Casablanca)  cover  a  dis 
trict  of  some  75  km.  in  length  and  from  5 
to  35  km.  in  breadth.  They  consist  of  hori- 
zontal layers  several  metres  deep,  lying 
practically  on  the  surface,  covering  an  area 
of  some  400,000  acres,  and  composed  f  a 
fine  sand  which  is  nothing  other  than  i]^)hos- 
phate  of  lime  of  so  high  a  percentage  (73 
to  78  per  cent.)  that  Florida  alone  can 
show  similarly  rich  deposits.  Even  the 
bed  other  than  at  El  Bouroudj  also  contain 
a  high  percentage  of  phosphates  varying 
from  68  per  cent,  to  72  per  cent.  As  for 
their  quantity,  estimates  vary  from  "many 
milHons  of  tons"  to  "  hundreds  of  mil- 
lions." 

It  has  been  calculated  that  even  if  the 
beds  were  exploited  at  the  rate  of  several 
millions  of  tons  annually,  centuries  v  ill 
elapse  before  their  exhaustion. 


The  American  rubber-growing  proposals 
are  dealt  with  by  a  London  correspondent 
of  the  Manchester  Guardian  Commercial  in 
the  last  issue.  "  Quite  a  number  of  Ameri- 
cans interested  in  the  rubber  trade  have 
been  in  London  lately,"  he  says,  "and  they 
are  all  prophesying  a  considerable  shortage 
in  the  visible  supplies  of  rubber  before  the 
end  of  the  year.  At  the  same  time  they  are 
visibly  upset  at  the  present  price  of  the 
commodity,  and  profess  to  anticipate  higher 
prices  still.  It  appears  to  have  been  sud- 
denly realised  that  the  American  is  practi- 
cally dependent  upon  Britishers  for  the 
whole  of  her  rubber  needs  ,and  it  is  being 
suggested  both  here  and  New  York  that 
rubber  estates  on  the  British  plan  shall  be 
established  in  the  Philippine  Islands  by 
American  interests  to  supply  America's 
needs  in  the  far  future.  Experts  in  rubber 
here  ridicule  this  suggestion.  It  is  pointed 
out  that  the  Philippines  are  parcelled  out  in 
small  tracts  for  the  benefit    of  the  nation, 


MARCH  2.  1923. 


THE   CHEMICAL   NEWS. 


139 


and  that  legislation  would  be  needed  to 
alter  this  system,  A^ain,  an  American 
buyer  has  assured  me  that  the  climate  is 
entirely  unsuitable,  and  that  the  only 
favourable  factor  is  that  Chinese  labour  lor 
tapping  is  easily  procurable.  The  same 
buyer  (who  is  well  known  in  Singaipore) 
admitted  that  but  for  British  enterprise 
American  rubber  users  might  be  paying  ten 
times  the  price  of  rubber  per  pound  that 
they  have  to  do  now ;  he  ridiculed  the  whole 
idea  of  Philippine  rubber,  and  hinted  that 
some  of  his  countrymen  would  do  better  to 
pay  the  market  price  quietly,  as  do  the  cot- 
ton buyers  in  Manchester  and  Liverpool,  in- 
steaul  of  getting  publicity  for  themselves 
over  here  and  incidentally  contributing  to 
the  tendency  for  rilS^ber  quotations  to  go 
still  more  against  their  own  market." 


CHEMICAL  TRADE  WELFARE. 

In  the  House  of  Commons  recently,  Mr. 
Wignall  asked  the  Home  Secretary  if  a  wel- 
fare order  htid  been  issued  to  the  chemical 
trade,  as  promised  in  March,  1922;  and,  if 
not,  would  he  say  when  such  an  order 
would  be  issued  to  this  industry? 

Mr.  Bridgeman  replied  that  the  draft  re- 
gulations which  were  referred  to  in  the 
answer  to  the  question  asked  by  the  honour- 
able member  on  March  27,  1922,  were  finally 
made  and  presented  to  Parliament  in  July 
last,  and  the  great  majority  of  them  took 
effect  on  October  1.  In  the  case  of  a  few  of 
the  regulation®,  however,  strong  objection 
was  taken  to  their  immediate  enforcement 
on  the  ground  of  the  structural  alterations 
involvea,  and  it  was  agreed,  and  was  pro- 
vided in  the  regulations,  that  the  require- 
ments in  question  should  not  come  into 
force  till  April  1  next,  or  such  later  date  or 
dates  as  the  Home  Secretary  might  aippoint. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE    ROYAL    SOCIETY. 
Thursday,  February  22.  1923,  at  4.30  p.m. 

The  Bakerian  Lecture  was  delivered  by 
G.  I.  Taylor,  F.R.S..  and  C.  F.  Elam,  on 
The  Distortion  of  an  Ahiminium  Cry$tal 
d urinal  a  Tensile  Test. 

The  object  of  the  tost  described  wa<^  to 
determine    the    nature     of    the     distortion 


which  occurs  when  a  crystal  of  aluminium 
is  extended  by  a  direct  pull,  and  to  find  out 
the  relations  between  the  orientation  of  the 
crystal  axes  and  the  direction  of  pull. 

A  rectangular  specimen  1  x  1  x  20  cm. 
was  cut  from  a  round  bar  of  aluminium 
which  had  been  treated  by  the  method  of 
Carpenter  and  Elam,  so  that  it  consisted  of 
one  single  crystal.  This  was  stretched 
through  successive  extensions  of  0,  10,  20, 
30,  40,  60  and  78  per  cent,  of  the  original 
length,  and  at  each  stage  of  the  test  the  dis- 
tortion was  determined  by  measurements  of 
scratches  ruled  on  the  surface.  At  the  same 
lime  the  directions  of  the  crystal  axes  were 
determined  in  each  case  by  X-ray  analysis. 

The  method  developed  for  determining 
the  nature  of  the  distortion,  by  which  any 
configuration  of  the  specimen  was  strained 
into  any  other,  was  to  find  lines  of  particles 
which  were  unextended  by  the  strain.  The 
directions  of  these  lines  lie  on  a  quadric 
cone,  which  evidentlv  has  two  positions 
corresponding  with  tne  two  configurations 
from  which  it  was  derived. 

On  applying  this  method  to  the  specimen 
under  consideration,  it  was  found  that  for 
all  stages  of  the  extension  up  to  40  per 
cent,  elongation  the  "unextended  cone" 
was  of  a  degenerate  form  consisting  of  two 
planes,  one  of  which  contained  in  all  cases 
the  same  particles,  while  the  other  con- 
tained different  particles  for  different 
strains.  The  former  plane  was  evidently 
undistorted  during  the  whole  strain  up  to 
40  per  cent,  elongation,  and  the  distortion 
was  due  to  slipping  or  shearing  over  this 
plane. 

The  orientation  of  the  crystal  axes  was 
determined  by  X-ray  measurements,  and  it 
was  found  that  the  slip  plane  was  identical 
with  an  octahedral  (III)  plane  of  the  crystal. 
The  direction  of  the  shear  was  also  deter- 
mined and  found  to  be  along  one  of  the 
three  principal  lines  of  atoms  in  the  octa- 
hedral plane. 

When  the  specimen  was  extended  beyond 
40  per  cent,  elongation,  it  was  found  that 
the  distortion  was  no  longer  due  to  slipping 
on  one  plane.  This  was  explained  by 
showing  that  the  effect  of  the  shear  was  to 
rotate  the  axis  of  the  specimen  relative  to 
the  crystal  axes  in  such  a  way  that  another 
(III)  plane  came  into  a  position  where  its  in- 
clination to  the  axis  was  the  same  as  that 
of  the  slip  plane.  Under  those  circum- 
stances slipping  might  occur  on  both  planes 
simultaneously,  and  it  wa»  verified  that  this 
was  the  case. 


140 


THE   CHEMICAL   NEWS. 


MARCH  2,  1923. 


Thursday,  March  1,  1923,  at  4.30  p.m. 

Papers  read :  — 

A.  Mallock,  F.R.S.  The  Effect  of  Tem- 
perature on  »ome  of  the  Properties  of  Steel. 

Prof.  C.  H.  Lees,  F.E.S.  Inductively 
Coupled  Low  Resistance  Circuits. 

Lord  Rayleigh,  F.R.S.  Studies  of  Iri- 
descent Colour,  and  the  Structure  produc- 
ing it.  I. — The  Colours  of  Potassium 
Chlorate  Crystals. 

Lord  Rayleigh,  F.R.S.  Studies  of  Iri- 
descent Colour,  and  the  Structure  produc- 
ing it.     II. — Mother  of  Pearl. 

Lord  Rayleigh,  F.R.S.  Studies  of  Iri- 
descent Colour,  and  the  Structure  produc- 
ing it.  III. — The  Colours  of  Labrador  Fel- 
spar. 

Paper  read  in  title  only: — 

L.  V.  King,  D.Sc.  On  the  Complex 
Anisotropic  MoUcule  in  Relation  to  the  Dis- 
persion and  Scattering  of  Light.  Commu- 
nicated by  Prof.  A.  S.  Eve,  F.R.S. 


ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

The.  Friday  evening  discourse  on  March 
2,  at  9  o'clock,  v^^ill  be  delivered  by  George 
C.  Simpson,  C.B.E.,  D.Sc,  F.R.S.,  Direc- 
tor, Meteorological  Office.  The  subject  is 
The  Water  in  the  Atmosphere. 

On  Saturday,  March  3,  Sir  Ernest 
Rutherford,  LL.D.,  D.Sc,  F.R.S., 
M.R.I. ,  Prof,  of  Natural  Philosophy,  will 
deliver  his  third  lecture  on  Atomic  Projec- 
tiles and  their  Properties. 

ROYAL  SOCIETY  OF  ARTS. 

On  Monday,  February  19,  Dr.  H.  P.  Ste- 
vens, F.I.C.,  dehvered  his  third  Cantor  lec- 
ture on  The  Vulcamsatio>n  of  Rubber. 

At  the  Ordinary  Meeting  on  Wednesday, 
February  21,  C.  A.  Mitchfj^l,  M.A.,  F.I.C., 
gave  a  paper  on  Handwriting  a(nd  its  Value 
as  Evidence. 

On  Wednesday,  February  28,  1923,  Prof. 
W.  E.  S.  Turner,  O.B.E.,  D.Sc, 
F.Inst. P.,  Head  of  the  Department  of 
Glass  Technology,  University  of  Sheffield, 
delivered  his  lecture,  entitled  Heat  Resist- 
ing Glasses.  The  Hon.  Sir  Charles  Alger- 
non Parsons,  K.C.B.,  LL.D.  D.Sc,  F.R.S., 
presided. 

THE   FARADAY  SOCIETY. 

At  the  meeting  held  on  Monday,  Feb- 
ruary 19,  the  following  papers  were  com« 
municated : —  .   .  a      j 

Electrolysis  icith  an  Aluminium  Anode 
the  Anohfte  being:  I.  Solutions  of  Sodium. 
Nitrite;  11.  Solutions  of  Potassium  Oxalate. 
By  F.  H.  Jeffery,  M.A. 


Summary : 

With  solutions  of  sodium  nitrite  prob- 
ably the  primary  product  of  reaction  at  the 
anode  is  aluminium  nitrite,  which  is  hydro- 
lysed  rapidly  to  hydrated  aluminium  oxide 
and  nitrous  acid,  this  latter  giving  rise  to 
nitric  oxide  and  nitric  acid. 

There  is  no  evidence  of  the  formation  of 
a  complex  anion  of  aluminium  from  these 
experiments. 

With  solutions  of  potassium  oxalate  the 
product  of  reaction  at  the  anode  is  a  com- 
plex anion  derived  from  aluminium. 

The  salt  KgLAKC^OJg]  .  3H,0  can  be  de- 
rived from  the  anolyte©  after  electrolysis. 

From  this  mode  of  derivation  it  seems 
very  probable  that  the  sale  is  a  true  com- 
plex .salt  comparable  with  potassium  chromi- 
oxalate. 

If  this  be  true,  the  alumini- oxalate  com- 
plex can  be  represented  in  three  dimensions 
just  as  Werner  represented  the  chromi oxa- 
late. Jaeger  resolved  the  racemic  potas- 
sium chromioxalate  by  mean®  of  the  potas- 
sium distrychnine  salts.  It  may  be  that 
conditions  can  be  found  for  the  resolution 
of  the  alumini-oxalate. 

The  isolation  of  a  complex  salt  from  an 
anolyte  does  not  imply  necessarily  that  the 
constitution  of  the  anionic  part  of  this  salt 
is  identical  with  that  of  the  complex  anion 
present  in  the  anolyte  after  electrolysis. 

An  attempt  was  made  to  examine  the 
complex  anion  in  solution  by  the  electro- 
metric  method  developed  for  the  investiga- 
tion of  the  plumbo-nitrite  complex 
[Pb(N02)J  which  was  described  in  a  pre- 
vious paper  to  the  Society.  Solutions  of 
potassium  oxalate  containing  a  known  con- 
centration of  the  potassium  alumini-oxalate 
were  prepared,  but  an  aluminium  electrode 
immersed  in  such  a  one  had  a  potential  so 
variable  as  to  be  useless  for  trustworthy  de- 
terminations ;  nor  were  any  conditions  found 
to  nullify  this  disabihty. 

The  Law  of  Distribution  of  Particles  m 
Colloidal  Suspensions,  with  Special  Refer- 
ence to  Perrin's  Investigations.  Part  IL,  by 
Alfred  W.  Porter,  D.Sc,  F.R.S., 
F.Inst. P.,  and  J.  J.  Hedges,  B.Sc 

On  a  ReUtion  between  Surface  Tension 
and  Density,  by    D.    B.    Macleod,    M.A., 

D.Sc.  ,,.        .^       , 

On  a  Relation  between  the  Yncosity  of  a 

D.  B.  Macleod,  M.A.,  D.Sc 

On  the     Viscosity     of    Liquid    Mixtures 

showing    Maxima,     by    D.     B.    Macleod, 

M.A.,  D.Sc 

General  Cdncluswns. 
1.  The  viscosity    of  liquid  mixtures    is  a 


MAECH  2.  1923. 


THE   CHEMICAL   NEWS. 


141 


function  of  the  free  space  of  the  constitu- 
ents and  of  the  mixture. 

2.  In  the  case  of  liquid  mixtures  show- 
ing a  maximum,  the  increase  of  viscosity  is 
due,  mainly,  to  the  increase  of  density, 
which  in  turn  is  due  to  the  (Aemical  affin- 
ity between  the  constituents. 

3.  It  is  probable  that,  comiplexes  which 
are  formed,  further  reduce  the  free  space 
and  consequently  increase   the  visoosity. 

Electric  Potential  of  Antimony-Lead  Al- 
loys, by  S.  D.  MuzAFFAu. 
Summary. 

Measurements  of  the  (  lectric  potential 
of  the  antimony-lead- alloys  are  made  by 
means  of  a  quadrant  electrometer  against 
a  calomel  electrode  in  normal  ipotassium 
hydrate  solution,  normal  lead  nitrate,  and 
tartar  emetic  with  tartaric  acid  solu- 
tions. The  results  reveal  an  identity  of 
potential  up  to  98  per  c<^nt.  Sb  with  that 
of  lead,  which  show  the  formation  of  no 
solid  solution  and  no  chemical  compound 
between  the  two  metals.  This  work  is  in 
agreement  with  the  observations  of  Charpy, 
Gautier,  Gontormann  atid  Sa{)oschnikoff, 
and  Kanewsky. 


THE    CHEMICAL    SOCIETY. 

Ordinary   Scientific   Meeting,   Thursday, 

March  1,  1928.  at  8  p.m. 

The  following  papers  wore  read:  — 

Co-ordinntion  dompoutuh  and  the  Bohr 
Atom,  by  N.  V.  Sidowick. 

Silver  Salvarsan,  by  W.  H.  Gray. 

On  the  Propagation  of  the  Explnsion- 
wave  through  Gaseous  Mixtures,  by  H.  B. 
Dixon. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 
Faraday    Medal. 
The  Council  of  the  Institution  of  Electri- 
cal Engineers  have  made  the  second  award 
of  the  Faraday    Modal  to  the  Honourable 
Sir    Charles     Algernon     Parsons,     K.C.B., 
F.R.S.,  Honorary  Member    of  the  Institu- 
tion. 

The  medal  is  awarded  for  "  notable 
scientific  or  industrial  achievement  in 
electrical  engineering,  or  for  conspicuous 
service  rendered  to  the  nrlvnnooment  of 
electrical  science." 


THE  GEOLOGICAL   SOCIETY. 
At    the    Ordinary    General    Meeting   on 
Wednesday,    February    28,    1923,     at  r^.SO 
p.m.,     the   following  communications   were 
read : — 


The  Late  Glacial  Stage  of  the  Lea  Vai- 
ley  {Third  Report),  by  Samuel  Hazzledine 
Warren,  F.G.S.  With  a  Be,port  on  the 
Arctic  Flora,  bv  Mrs.  Eleanor  Mary  Reid, 
B.Sc,  F.L.S.,"^ F.G.S. ,  and  Miss  M.^rjorie 
Elizabeth  Jane  Chandler. 

The  Elephas-antiquus  Bed  of  Clacton- 
on-Sea  (Essex),  and  its  Flora  and  Fauna, 
by  Samuel  Hazzledine  Warren,  F.G.S. 
With  Appendices  by  Dr.  Charles  William 
Andrews,  B.A.,  F.R.S.,  Mrs.  E.  M.  Reid, 
and  Miss  M.  E.  J.  Chandler,  Alfred  Santer 
Kcnnard,  F.G.S.  and  Bernard  Barham 
Woodward,  F.L.S.,  F.G.S.,  and  Martin  A. 
C.  Hinton. 


ROYAL  MICROSCOPICAL  SOCIETY. 
The  section  of  the  Society  formed  to 
deal  with  the  Industrial  Applications  of 
the  Microscope,  and  to  assist  in  the  de- 
velopment of  Industrial  Research,  met  on 
Wednesday,  February  2«,  1923,  at  7  p.m. 
The  following  demonstrations  and  ex- 
hibits were  made:  — 

Messrs.  Charles  Baker  showed  their 
R.M.S.  Microscope  (new  model). 

Mr.  Conrad  Bock,  C.B.E.,  F.R.M.S., 
showed  Mercury  Globules  under  Polarised 
Fiight,  with  special  reference  to  Dr.  Owen's 
communication  road  at  the  last  meeting. 

Messrs.  A.  Gallenkamp  &  Co.  demon- 
strated the  use  of  the  Gallenkamp  Electro- 
motric  Titration  Apiparatns.  an  "end 
point"  indicator  for  all  Acid  Alkali  and 
Oxidation  Titrations. 

Messrs.  Adam  Hilger  demonstrated  an 
Interference  .Accessory  for  testing  the 
Stands  and  Fine  Adjustments  of  Micro- 
scopes, and  also  i  Vertical  Illuminator  for 
the  Microscopienl  Examination  of  Opaque 
Objects. 

Messrs.  Ogilw  k  Co.  exhibited  a  Silver- 
man Uhmiinator  for  Opaque  Objects  and 
Standard  Illuminator,  both  showing  simi- 
lar specimens  for  comparison  of  image. 

Messrs.  W.  Watson  <t  Sons,  Ltd., 
showed  a  Potrological  Binocular  Micro- 
scope for  Glass  Exaination.  illustrated  by 
lantern  slides. 

Com  w  unications. 
Dr.  James  A.  Murray,  F.R.M.S..  in  the 
chair. 

Mr.  Humphry  J.  Dknham.  M..\., 
F.R.M.S.  (British  Cotton  Industry  Re- 
search Association),  read  a  paper.  On  Some 
Mounting  Media  for  Microscopic  Objects, 
especially  for  Cotton  and  other  Hairs  and 
Fibres,  a-nd  for  general  Microscopical 
Work. 


142 


THE   CHEMICAL    NEWS. 


MARCH  2,  1923. 


Mr.  Thomas  Terrell,  Junr.,  read  a 
paper  on.  The  Use  of  the  Microscope  in  the 
Gas  Mantle  Industry. 

CORRESPONDENCE. 
PERUVIAN    PETROLEUM. 

To  ihd  Editor  of  The  Chemical  News. 

Sir, — Referring  to  your  issue  of  January 
26,  the  article  upon  "  Peru:  A  Land  of 
Mystery  "  has  interested  me  greatly. 

Mention  was  made  of  the  petroleum  de- 
posits around  Callas.  Although  these  are 
really  quite  productive,  and  the  crude  oil 
of  sufficient  calorific  value  to  be  commer- 
cially Uisable,  nothing  was  mentioned  of 
the  vast  subterranean  fields  from  one  hun- 
dred to  two  hundred  and  thirty  miles  north 
of  Iniquitos.  It  has  been  the  general 
opinion  that  these  fields  do  not  yield  oil  of 
a  sufficiently  high  standard  to  cover  the 
cost  of  transiport  to  the  coast.  The  opinion 
is  erroneous.  On  small  holdings,  where 
timber  is  cut  by  machinery,  most  of  the 
well-known  make®  of  internal  combustion 
engines  are  supplied  with  the  oil  in  its 
natural  state,  the  only  processes  of  purifi- 
cation being  the  passing  of  the  liquid 
through  filters  to  remove  suspended  im- 
purities. 

The  real  difficulty  lies  mainly  in  the 
transport  of  the  oil.  From  the  Pestonal 
Region  to  the  commencement  of  the  coas- 
tal region  there  exists  foreist-land  of  almost 
impenetrable  denseness.  To  convey  the  oil 
south  to  the  Amazon  would  mean  long  and 
tedious  journeys  by  river  to,  let  us  say, 
Pemambuco,  where  it  would  have  to  be  re- 
shipped. 

In  my  opinion,  however,  the  fields  are 
sufficiently  extensive  to  warrant  the  ex- 
pense of  a  duct  from  Pestonal  to  Tnma  or 
Callas,  where  it  could  be  linked  up  with 
the  coastal  fields.  The  construction  of  the 
necessary  plant  would  pay  for  itself  in 
time,  although  the  initial  cost  would  be 
heavy,  and  the  construction  period  about 
18  months.— I  am,  Sir,  Yours,  etc., 
Lowestoft,   Februarv  2.  C.    Melrose. 


THE  RUHR  AND  BRITISH  DYES. 
From  N.  Grattan   Doyle,  M.P. 

To  the  Editor  of  The  Chemical  News. 

SiR^ — Whether  the  commercial  com- 
munity a^pproves  or  disapproves  of  the 
occupation  of  the  Ruhr,  that  action  has 
had  one  consequence  which  must  interest 
not  only  most  men  of  business  as  such,  but 
in  general  the  taxpayers  of  this  country.  I 
mean  the  ban  upon  German  dyes.  An  em- 
bargo has  been  placed  upon  the  despatch 
of  tar,  benzol    and  the  other  raw  materials 


of  Germany's  dyestuffs  industry;  lignite, 
the  coal  substitute,  has  been  confiscated; 
transport,  whether  by  rail  or  Rhine,  has 
been  dislocated;  and,  finally,  there  comes 
the  announcement  that  France  begins  to 
occupy  German  dyestuffs  factories. 

What  is  haippening  is  not  only  the  isola- 
tion of  the  Ruhr  from  Germany,  but  the 
isolation  of  Great  Britain  from  German 
dyestuffs.  Is  is  not  fortimate,  then,  that 
we  have  already  had  the  experience  of 
being  cut  off  from  German  dyes,  first  dur- 
ing the  war,  afterwards  in  the  period  of 
disorganisation  that  followed  it?  We  know 
where  we  are;  for,  if  the  British  textile 
trades  were  able,  with  the  help  of  British 
dyes,  to  take  the  fullest  advantage  of  that 
post-Armistice  boom  which  was  one  of  the 
most  extraordinary  in  their  history,  they 
will  be  not  less  independent  to-day,  when 
tthe  range  of  our  dyestuffs  is  much  bigger 
than  it  was  then.  Yet  where  would  we 
have  been  now  without  the  Dyestuffs  Act, 
that  has  made  possible  an  industry  on 
which  £200,000,000  worth  of  our  country's 
trade  depends?  The  enemies  of  our  dyes 
policy  will  do  well  to  greet  in  tactful 
silence,  if  not  with  tardy  penitence,  this 
crisis  in  the  Ruhr  which,  had  they  been 
given  their  way,  would  certainly  have 
meant  a  crisis  in  British  factories. — 
Yours,  &c.,  N.  Grattan  Doyle. 

House  of  Commons,   S.W.I.   February  14, 


NOTICES  OF  BOOKS. 
Questions  and  Prohlems  in  Chemistry , 
by  Floyd  L.  Darrow.     Pp.  VII.  +  177. 
London:   G.  Bell  &  Sons,  Ltd.,  Portugal 
Street,  W.C.     1925.     Price  3s.  6d.  net. 
In  the  preface  to  this  collection    of  over 
1,200  questions,  the  author  states  that  the 
book    is    not  intended    for  the    use  of    the 
teacher,  but  primarily  for  the  student,  as  a 
guide  to  the  every-day    preparation  of  his 
lessons. 

It  is  certainly  true,  as  is  here  stated, 
that  many  students  neglect  to  prepare 
their  work  adequately,  but  it  is  very  doubt- 
ful whether  such  pupils  would  remedy  this 
by  attempting  unaided  these  questions. 

In  the  main,  the  questions  are  instruc- 
tive, and  would  stimulate  interest.  Some 
of  them  are  beyond  the  reviewer's  ability 
to  answer,  and  the  object  of  others,  also,  is 

not  apparent.         

Preliwinary  Experiments  in  Qualita- 
tive Analysis,  ivith  Special  Procedures 
for  the  Systematic  Detection  of  the 
Acids,  by  Louis  J.  Curtman,  Associate 
Professor    of    Chemistry,     Chief    of    the 


MARCH  2.  1923. 


THE  CHEMICAL  NEWS. 


143 


Division  of  Qualitative  Analysis,  College 
of  the  City  of  New  York.  Second  Edi- 
tion. Pp.  63.  New  York :  The  Elsworth 
Press.     1922.  --" 

The  object  of  this  littk'  canvas-covered 
book  is  to  stimulate  the  students'  interest 
in  qualitative  analysis  by  giving  him  a  pre- 
liminary training  in  the  various  reactions 
subsequently  utilised  in  the  systematic 
procedures  of  qualitative  analysis.  The 
student  is  informed  as  to  the  object  of  the 
experiments  he  is  to  perform,  and  has  to 
carry  out  the  teofcs  in  such  a  way  that  the 
quantitative  significance  of  a  reaction  is 
impressed  upon  him. 

The  author  apparently  considers  that  the 
systematic  iprocedures  for  the  detection  of 
thtc  metals  are  beyond  the  scope  of  the 
work,  as  he  does  not  give  them,  although 
he  includes,  in  the  appendix,  a  very  satis- 
factory nKKlification  of  the  analysis  of  the 
filtrate  aft<?r  the  separation  of  the  metal<% 
of  the  silver  group.  However,  contrary  to 
custom,  systematic  procedures  for  the  de- 
tection of  the  acid  radicals  are  included. 
These  tables  have  been  compiled  largely  as 
the  result  of  investigations  carried  out  in 
the  author's  laboratory,  and  are,  certainly, 
the  most  outstanding  feature  of  the  book. 

As  a  whole,  the  bfK>k  can  hardly  claim  to 
be  self-suipportin^,  and  the  author  recom- 
mends that  it  should  be  used  in  connection 
with  Baskerville  and  Curtman's  QiuilUa- 
tivc  AnalyHis,  to  which  numerous  refer- 
ences are  made.  This  is  a  distinct  disad- 
vantage, but  nevertheless  we  think  that 
any  student  would  derive  great  advantage 
if  he  worked  through  this  book  and  did  not 
rest  satisfiifl  until  he  was  able  to  supply  a 
satisfactory  answer  to  all  the  queries  odi- 
tained  within  its  sixty  odd  pages.  Further, 
we  should  like  to  suggest  that  many 
teachers  might  find  this  little  book  very 
useful  as  the  basis  of  a  catechism  for  ele- 
mentary and  moderately  advanced  stu- 
dents of  Qualitative  Analysis.         F.L.S. 

The  Bureau  of  Mines  and  the  State  of 
Colorado  have  jointly  issued  a  Bulletin, 
entitled  OU-Shalc,  a  hisforioai,  technical 
and   economic     Siudy,     by     Martin     J. 

G^AVIN. 

It  is  pointed  out  the  State  of  Colorado 
considers  its  vast  oil-shale  deposits  of  par- 
ticular value,  and  in  co-operation  with  the 
U.S.  Bureau  of  Mines,  a  research  labora- 
tory has  been  equipped  at  Boulder,  with 
the  object  of  determining  the  best  condi- 
tions of  shale  distillation. 


The  bulletin  outlines  the  present  status 
of  the  petroleum  industry,  and  gives  the 
causes  of  increased  consumption  with  the 
possible  new  sources  of  supply. 

There  are  sections  dealing  with  the  liis- 
tory  and  nature  and  oi'igin  of  oil-shale,  the 
chemistry  of  its  distillation.  A  good 
account  of  the  Scotch  industry  is  included, 
and  the  whole  is  well  illustrated  with 
numerous  figures,  graphs,  and  eighteen 
plates. 

We  have  received  from  the  British 
Science  Guild  a  cQpy  of  their  pamphlet, 
Science  in  National  Life. 

It  is  pointed  out  that  every  ounce  of 
scientific  knowledge  and  effort  needs  to  be 
combined  with  industrial  enterprise  if  we 
are  to  maintain  not  only  our  position  in  the 
world  markets,  but  also  if  we  are  to  meet 
the  heavy  expenditure  incurred  by  the 
war. 

The  breadth,  variety  and  value  of  the 
activities  carried  on  in  the  name  of  science 
are  seldom  realised  to  the  full — if  they 
were,  the  whole  commercial  and  industrial 
world  would  co-operate  to  encourage  the 
development  of  scientific  investigation  and 
research  in  all  its  manifold  ramifications. 
On  this  foundation  we  must  build,  and  the 
foundation  must  be  sound,  substantial,  and 
well  laid  if  the  superstructure  is  to  com- 
pete in  strength,  beauty,  and  efficiency 
with  that  of  other  nations. 

There  m  also  a  plate  with  the  photo- 
graphs of  eight  distinguished  pioneers  of 
science. 


The  U.S.   Department  of  the  Interior 
has  issued  a  bulletin  (No.  728).  entitled 
The  Occurrence  and  Usen  of  Peat  in  the 
U.S.,  by  E.  K.  SoPER  and  C.  C.  Osbon. 
The  subject  is  treated    in  a  very  compre- 
hensive  manner   from   both    the   geological 
and  economic  standpf>int.  and  is  well  illus- 
trated   with    photographs  of    typical    ipeat 
bogs  and  format icms  in  variini©  States. 

It  is  pointed  out  that  peat  is  partly  de- 
caved  and  disintegrated  plant  debris.  The 
salient  features  of  the  conversion  of  cellu- 
lose to  peat  are  the  elimination  of  hydrogen 
and  oxygen  as  water,  and  of  carbon  and 
oxygen  as  carbon  diaxide  and  the  genera- 
tion of  methane. 

The  authors  assign  the  formula  CgaH^Oj^ 
to  ,peat,    and    C,,H. ,„()„„  to  cellulose,    but 
give  no  evidence  or  authority  for  this. 
Peat  has  been  used  in  agriculture  a#i  a  ni- 
trogenous fertiliser,     and   as   an   absorbent 


144 


THE  CHEMICAL  NEWS. 


MARCH  2,  1928. 


and  disinfectant.  It  was  used,  especially 
during  the  war,  as  an  antiseptic  dressing, 
and  in  Bohemia  has  found  application  in 
curative  "  mud  baths."  Other  us°s, 
apart  from  the  extensive  use  as  inferior 
fuel,  include  that  as  packing  material  and 
paper  making. 


Chemical  Enghteering  Catalog^  1922 : 
Seventh  Annual  Edition.  Pp.  1183.  New 
York:  The  Chemical  Catalog  Co.  Inc., 
19,  East  24th  Street.     Price  $10. 

To  all  categories  of  chemists,  not  only  in 
America,  but  in  Great  Britain  as  well,  this 
vast  catalogue  is  invaluable.  It  is  very 
obvious  that  it  has  not  been  compiled 
solely  for  individual  enterprise,  but  more 
as  a  work  of  reference.  Practically  every 
requirement  in  chemistry  is  contained 
therein,  from  an  8  cc.  platinum  crucible  to 
a  complete  factory ;  while  sections  have 
been  added  indexing  a  wide  selection  of 
scientific  and  technical  books,  and  indicat- 
ing the  firms  producing  fine  chemicals. 

In  the  preparation  of  this  enormous  work 
the  publishers  have  been  fully  alive  to  its 
value,  and  this  has  greatly  guided  them. 
According  to  the  statement  made  by  the 
compiling  Committee,  firms  are  availing 
themselves  of  the  facilities  for  using  more 
space,  some  reserving  over  60  pages. 

The  Committee  has  been  wise  in  advising 
advertisers  to  standardise  their  respective 
catalogues,  so  that  anyone  using  the 
volume  knows  precisely  where  to  find  what 
he  desires  with  a  minimum  of  expenditure 
of  time.  The  copious  illustrations  and 
cross-sectional  diagrams  also  fall  under 
this  arrangement,  tending  to  eliminate  all 
superfluous  data;  at  the  same  time,  each 
reproduction  is  amply  ticketed. 

The  work  is  certainly  very  fine;  and  it  is 
to  be  hoped  that  those  ooncemed  in  the 
future  will  do  all  in  their  power  to  main- 
tain the  high  level  reached  by  the  com- 
pilers of  the  seventh  edition.  J.M. 


BOOKS  RECEIVED. 

Paracelsus :  His  Personality  and  In- 
fiience  as  Physician,  and  Chemical  Re- 
foTntier,  by  John  Maxson  Stillman.  F^p. 
X.  +  183.  1920.  The  Open  Court  Pub- 
lishing Co.,  149,  Strand,  W.C.2.     10s.  net. 


A  correspondent  is  desirous  of  informa- 
tion concerning  present  prices  for: — Hy- 
drochloric acid  (pure),  sodium  oxy  chloride, 
sulphuric  acid,  and  nitric  acid,  in  ton  lots. 


This  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest   Patent  Applications. 
2685 — Alvord,  E.  B. — Process  of  making  metal  sul- 
phides.   Jan.  29. 
2597 — Michel  1   &  Co.,  J.— Manufacture    of  barium- 

hvdroxide.    Jan    29. 
2944— Naef,   E.   E. — Production     of  compounds     of 
sulphur  with   alkaline  earth  metals.  Jan.  31. 
3198 — Thermal   Industrial     &   Chemical     Research 
Co. — Removal  of  matter  from   surface    of  a 
liquid  in     heat-treatment  by  molten     metal, 
etc.    Feb.  2. 
Specifications  Ptiblishcd  this  Week. 
191793— Mai,   Dr.   A. — Process  of  making  arsenical 
solutions  and   suspensions  for   insecticidal, 
fungicidal,   preservative   and   like  purposes. 
191854— Imray,     O.     Y.     (Chemical     Industry     in 
Basle).— Manufacture    of    dyestufls     of  the 
triarylmethane  series. 
174599 — Soc.   L'Azote    Francais.— Process     for     the 
production  of  granules  of  cyanamide  with 
a  high  nitrogen  content. 
191797— Holliday  &  Co.,   Ltd.,    L.  B.— Manufacture 
of  a  series  of  substituted  alpha-naphthyl- 
amines  and  of  the   dyestuffs   derived   from 
them. 

Abstract  Published  this   Week. 
190688— Cblor ides.— Jacobson,  B.  H.,  of  1324,  Quar- 
riers    Street,    Charleston,     West  Virginia, 
U.S.A. 

Aluminium,  antimony,  arsenic,  iron,  tin,  zinc, 
and  other  chlorides:  double  chlorides  .—In  the 
production  of  anhydrous  chlorides  by  the  reactfon 
of  chlorine  on  a  metal  in  the  presence  of  bromine, 
as  described  in  the  parent  Specification,  a  salt 
such  as  sodium  or  potassium  chloride  or  bromide 
is  added  so  as  to  maintain  the  product  liquid 
without  necessitating  a  high  temperature  or 
pressure.  When  a  bromide  is  used  it  is  not  neces- 
sary to  add  free  bromine.  The  invention  is  de- 
scribed with  reference  to  aluminium  chloride.  In 
an  example,  aluminium  chloride  and  sodium 
chloride  are  melted  in  a  covered  iron  pot  or  ro- 
tating ball  mill  and  aluminium  and  bromine  are 
then  added,  the  temperature  being  suitably  12.'i- 
1.50°  C.  From  time  to  time  portions  of  thfe  melt 
are  drawn  off,  and  more  aluminium  and  salt  arc 
added  and,  when  necessary,  some  additional  bro- 
mine. The  product  withdrawn  may  contain  5  to 
30  per  cent,  of  sodium  chloride,  but  is  suitable 
for  use  in  the  Friedel-Crafts  reaction.  If  the 
temperature  is  maintained  at  200°  C,  aluminium 
chloride  alone  is  volatilized  and  is  recovered  in  a 
condenser. 

Messrs.  Rayner  &  Co.  will  obtain  print«d 
copies  of  the  publisned  specifications,  and  forward 
on  post  free  for  the  official  price  of  Is.  each. 


MARCH  9,  1923. 


THE   CHEMICAL   NEWS. 


145 


THE  CHEMICAL  NEWS, 

VOL.   CXXVI.     No.   3282. 


NOVEL  RESEARCH  NARRATIVES. 

The .  British  Non-Ferrous  Metalfi  Re- 
search Association  has  hit  upon  a  rathor 
ingenious  way  of  communicating  the  re- 
sults of  its  research  investigations  to  its 
members.  Lectures  are  arranged  at  one  or 
more  centre©,  to  which  as  a  rule  only  the 
members  of  the  Association  itself  are  ad- 
mitted. Two  objects  are  served  in  this 
manner,  firstly  early  confidential  commu- 
nication of  the  results  of  the  research  is 
assured  to  those  who  have  given  it  finan- 
cial support,  and  secondly  the  investigator 
gets  into  close  and  immeaiate  contact  with 
that  section  of  the  industry  chiefly  in- 
terested in  his  work. 

In  this  manner  the  future  direction  of 
work  and  the  relative  practical  importance 
of  its  varied  issues  is  subjected  to  the 
mutual  consideration  of  researcher  and  the 
industry. 

The  Non-Ferrous  Metals  Research  Asso- 
ciation is  at  present  engaged  on  some  ten 
investigations,  all  of  which  are  closely  con- 
nected with  different  branches  of  the 
metals  and  engineering  trades. 

So  far  the  private  lecture  system  has 
been  applied  to  two  subjects.  Dr.  W. 
Rospnhain,  F.R.S.,  has  reported  on  the  m- 
vestigation  on  Cqpper  and  the  influence 
upon  its  properties  of  small  quantities  of 
impurities,  which  is  being  carried  out  for 
the  Association  by  Dr.  D.  Hanson  and 
others  at  the  National  Physical  Labora- 
tory. This  research  promises  to  be  of  fun- 
damental importance  to  the  copper  ard 
brass  industry,  and  most  of  the  leading 
firms  are  supporting  the  work  and  eagerly 
take  advantage  of  opportunities,  such  as 
this  lecture  afforded,  of  hearing  the  results 
achieved. 

AijjOther  large  attendance  of  members 
w'&R  occasioned  by  the  lecture  on  "  The 
cause  and  prevention  of  Red  Stains  on 
Brass,"  by  Mr.  E.  A.  Bolton,  M.Sc.  de- 
scribing work  on  this  troublesome  difficulty 
which  he  is  carrying  out  at  the  Birming- 
ham University — another  subject  of  great 
practical  interest. 

The  Association  arranged  a  third  lecture, 
given  both  in  Birmingham  and  Sheffield, 
by  Mr.  Dnrtroy  Lewis,  M.Met.,  on  his  work 
on  "  Material's  used  for  the  Abrasion  and 


Polishing  of  Metals."  In  view  of  the  wide 
interests  covered,  a  limited  number  of 
tickets  was  issued  to  non-members.  The 
Birmingham  lecture  was  held  on  Monday 
evening,  February  26th,  at  7.30  p.m.,  and 
the  Sheffield  lecture  on  Friday  afternoon, 
February  23rd,  at  2.30  p.m. 


NETHERLANDS  INTERNATIONAL 
GAS  EXHIBITION. 

In  connection  with  the  International 
Gas  Exhibition  which  the  Municipal 
Authorities  of  Amsterdam  are  organising, 
and  which  is  to  bo  held  in  that  city  from 
October  13  to  November  11,  1923,  H.M^ 
Consul-General  at  Amsterdam  has  for- 
warded to  the  Department  of  Overseas 
Trade  copies  of  the  rules  and  regulations 
of  the  exhibition,  together  with  forms  of 
applicati<m  for  space. 

It  is  the  intention  to  collect  exhibits 
demonstrating  the  use  of  gas  for  industrial 
purposes  in  large  and  small  concerns,  e.g., 
metal  works,  chemical  works,  food  preserv- 
ing factories,  restaurants,  cycle  factories, 
vulcanising  plants,  central  heating  systems, 
for  the  practical  use  of  doctors,  dentists, 
bakers,  etc.  Household  and  scientific 
appliances  employing  gas  as  fuel  will  also 
be  welccMoaed. 

British  firms  interested  may  inspect  the 
rules,  etc.,  on  application  to  the  Depart- 
ment of  Overseas  Trade  (Enquiry  Room), 
8.5.  Old  Queen  Street,  Westminster,  Lon- 
don. S.W.I.  A  few  copies  are  available 
for  loan  to  firms  imable  to  arrange  for  an 
inspection  in  London.  Ref.,  7808/FB/GP). 


REPORT    OF    THE     INTERNATIONAL 
COMMITTEE  ON  CHEMICAL 

ELEMENTS  (1923). 
Constitution  op  the  Committee. 

The  Intematiomd  Committee  on  Atomic 
Weights  takes  its  instructions  from  the 
International  Association  of  Chemical 
Societies  which  was  dissolved  during  the 
great  war  and  replaced  by  the  International 
lJM\m  of  pure  and  applied  Chemistry. 

During  the  second  Conference,  held  at 
Brussels  on  June  30,  1921,  the  Inter- 
twtional  Union  of  pure  and  applied  Chem- 
istry decided  to  replace  the  International 
Committee  on  Atomio  Weights  by  an  In- 
ternational  Committee     on   Chemical    Ele- 


146 


THE    CHEMICAL    NEWS. 


MARCH  9,  1923. 


nients.  The  scqpe  of  the  new  Committee 
is  more  extended  than  that  of  the  old 
Committee.  The  discovery  of  Isotopj 
first  in  the  domain  of  radioactive  Elements, 
later  in  that  of  non-radioactive  Elements, 
produced  new  problems  not  only  concern- 
ing Atomic  Weights,  but  also  affecting  the 
conception  of  a  chemical  Element. 

In  consequence,  the  International  Union 
has  decided  that  it  should  be  the  duty  of 
the  new  Committee  to  keep  chemists  in- 
formed of  the  various  advances  made  each 
year  in  this  field  already  rich  and  so  full  of 
promise  for  the  future. 

The  Committee  will  therefore  prepare 
three  tables  :  one  Table  of  radioactive  Ele- 
ments containing  their  principal  constants ; 
one  Table  of  Isotopes ;  one  Table  of  Atomic 
Weights. 

The  International  Unio{n  has  decided 
that  the  Committee  should  consist  of  at 
the  most  12  members,  and  it  has  itseff 
elected  7  of  these :  MM.  Aston  (Great 
Britain),  Brauner  (Czeoho- Slovakia),  Dfe- 
bierne  (France),  Ph.  A.  Guye  (Switzer- 
land), RichardiS  (United  States  of  America), 
Soddy  (Great  Britain),  Urbain  (France). 

It  has  appointed  as  experts  for  the  year 
1922  MM.  Baxter  (United  States  of 
America)  and  Moles  (Spain).  MM.  Clarke 
and  Thorpe  are  honorary  presidents. 

The  Committee,  to  complete  itself,  has, 
in  consequence  of  the  regrettable  death  of 
Ph.  A.  Guye,  elected  MM.  Baxter  (United 
States  of  America)  and  Leduc  (France). 
In  accordance  with  its  statutes  the  Coin- 
mittee  has  invited  all  the  national 
branches  of  the  International  Union  to 
create  in  their  countries  national  Commit- 
tees from  which  it  may  receive  notice  on 
any  question  connected  with  its  activities. 

Three  of  these  national  Committees  are 
actually  working,  in  Spain,  France  and 
Switzerland. 

Work  of  the  Committee  During  the 
Year  1921-1922. 

The  Committee  has  prepared  the  two 
tables,  of  which  the  need  was  particularly 
felt :  a  Table  of  radioactive  Elements,  and 
a  Table  of  Isotopes. 

The  work  of  the  Committee  is  not  com- 
plete as  regards  the  Table  of  Atomic 
Weights,  which  will  be  published  later  on. 
As  a  result  the  Table  for  1922  drawn  up  by 
the  old  International  Committee  for 
Atomic  Weights  is  acceipted  for  1923.  It 
is  on  this  a-ccount  that  the  values  which 
appear  in  the  Table  of  Isotopes  under  the 


title  Atomic  Weights  are  these  given  in  the 
International  Table  for  1922. 

In  the  case  of  the  radioactive  Elements 
the  figures  appearing  under  the  title 
Ato-mic  Mass  are  the  values,  rounded  to  the 
nearest  whole  number,  from  the  Atomic 
Weights  of  Uranium  (Uranium  I),  Thorium 
and  Radon  (Radium  Emanation).- 

The  Committee  has  found  it  necessary  to 
modify  the  nomenclature  of  several  radio- 
active Elements. 

Each  of  the  Tables  is  accompanied  by 
notes  which  explain  the  signs,  symbols  and 
new  names  adopted  by  the  Committee. 

The  Committee  consider  that,  as  regards 
the  radioactive  Elements  and  Isotqpes,  its 
work  is  only  provisional.  It  recognised 
that  the  definitions  and  nomenclatures 
which  have  been  adopted  do  not  form  a 
homogeneous  whole.  Until  a  general  re- 
form of  the  nomenclature  of  the  radio- 
active Elements  is  imder  consideration  it 
has  respected  as  far  as  possible  the  names 
given  by  the  discoverers.  On  this  aoooimt, 
before  adopting  for  the  three  emanations 
the  names  Radon,  Actinon  and  TTioron, 
the  approval  of  Mme.  Curie  and  Sir  E. 
Rutherford  was  obtained. 

The  Committee  hopes  that  the  new  In- 
ternational Tables  will  be  favourably  re- 
ceived by  the  scientific  world,  and  that  the 
values  adqpted  will  be  generally  approved. 

F.  W.  Aston. 
Gregory  P.  Baxter. 
BoHUSLAv  Brauner. 
A.  Debierne. 

A.  Leduc. 

T.  W.  Richards. 

Frederick  Soddy. 

G.  Urbain. 

International  Table  of  Isotopes   (1923). 

Atomic  Number. — A  chemical  element  is 
defined  by  its  atowic  number.  This  num- 
ber represents  the  excess  of  positive  over 
negative  charges  in  the  constitution  of  the 
atomic  nucleus;  theoretically  the  atomic 
number  represents  alsorthe  number  of  elec- 
trons which  rotate  round  the  central  posi- 
tive nucleus  of  the  atom.  Each  atomic 
number  also  represents  the  place  occupied 
by  the  element  in  the  Mendeleef  Table. 

Various  methods  have  been  suggested  to 
determine  the  atomic  numbers.  The  most 
important  of  these  consists  in  deducing 
them  from  the  wave-lengths  of  the  high 
frequency  spectra  by  applying  Moseley's 
law. 


MARCH  9,  1923. 


THE  CHEMICAL  NEWS. 


1.47 


Elements  (simple  and  c>fymplex).  Iso- 
topes.— If  the  above  definition  is  accepted, 
each  chemioal  element  may  be  simple  or 
com-plex,  according  as  its  atoms  are  all  of 
equal  mass  or  not. 

In  the  latter  case,  the  element  consists 
of  as  many  isotopes  as  its  atoms  have  dif- 
ferent masses.  A  complex  element  is  a 
m,ixture  of  isotopes.  Three  methods  (J.  J. 
Thomson,  Aston,  Dempster)  have  been  de- 
vised to  determine  isotopes.  The  most 
important  i«  that  of  Aston. 

Notation.  —  The     elements,     simple    or 
complex,  are    represented  by  the    ordinary 
symbols.     To  indicate     any  particular  iso- 
tope its  atomic  mass*  i«  written  as  an  index        j        brackets 
to  the  right  of  the  symbol  representing  the  only, 

mixture.     Thus,  CP*  indicate?  the  isotope  of 

Table  of  Isotopes. 


chlorine  having  an  atomic  mass  35.  This 
number  represents  the  relative  mass  of  its 
atom,  the  atom  of  oxygen  (a  simple  ele- 
ment) being  taken  as  16. 

Elements  included  in  the  Table.  —  The 
isotopes  of  lead  which  are  the  ultimate  re- 
sult of  disintegration  of  radioactive  Ele- 
ments, and  the  radioactive  isotopes  will 
only  appear  in  the  International  Table  of 
the  radioactive  Elements.  Only  those  ele- 
ments appear  in.  the  Table  of  Isotopes 
which  are  recognised  as  simple,  or  are  com- 
plex elements  whose  isotopes  have  been 
determined  with  sufficient  certainty. 

Provisional       Values.    —   Numbers       in 


arc    to    be    taken    as   provisional 


a 

S 

3  a 

<  a 

Minimum 
Number 
of 

o     , , 

%  Accu 

■  Obser- 

■S    .Ma«RP8  of  Isotopes 

racy 

ver 

H 

1 

1.008 

1 

1.008 

0.2 

r  A 

He 

2 

4.00 

1 

4 

**• 

A. 
L.  T    D 

Li 

3 

6.94 

2 

7   :  6 

/ 

Ql 

4 

9.1 

1 

9 

T. 
A. 

B 

f) 

10.9 

2 

11    ;  10 

0.1 

C 

6 

12.005 

1 

12 

A. 
A. 
A. 

A 

N 

7 

14.008 

1 

14 

0.2 

0 

8 

16.000 

1 

16 

F 

9 

19.0 

1 

19 

0.1 

Ne 

10 

20.2 

2 

20  ;  22 

0.1 

A 

Na 

11 

23.00 

1 

23 

A. 
D. 
A. 
A. 

Mg 

12 

24.32 

8 

24   ;  25   ;  26 

Al 

13 

27.0 

1 

27 

Si 

14 

28.1 

2 

28  ;  29  ;  (80) 

•0.1 

P 

15 

31.04 

1 

81 

0.2 

A. 

A. 
A 

S 

16 

32.06 

1 

82 

0.2 

CI 

17 

35.46 

2 

35    ;   37 

0.1 

A 

18 

39.9 

2 

40    ;  86 

0.1 

A. 

K 

19 

39.10 

2 

39    :  41 

A.' 
D. 

Cft 

20 

40.07 

(2) 

40    ;   (44) 

Fe 

26 

55.84 

(1) 

56  :    (54)    ?  • 

A 

Ni 

28 

58.68 

2 

58   ;  60 

0  1 

A 

Zn 

30 

65.37 

4 

64  :  66  ;  68  ;  70 

1). 

As 

33 

74.96 

1 

75 

0  1 

a! 

A 

Se 

34 

79.2 

6 

80;  78;  76;  82;  77;  74 

0.1 

Br 

35 

79.92 

2 

79  :    81 

0.1 

a1  ■ 

A 

Kr 

36 

82.92 

6 

84:  86:  82:  83;  80;  78 

0.1 

A. 

Rl) 

37 

85.45 

2 

85  ;    87 

A 

Sn 

50 

118.7 

7  (8) 

120  ;  118  ;  116  ;  124 
119  ;    117  :    122  ;    (121) 

A. 

I 

63 

126.92 

1 

127 

0.2 

A 

Xe 

54 

130.2 

7  (9) 

129;  1.32:  1.31;   134;  136; 

A*  . 

Cs 

55 

132.81 

1 

128;    130;    (126);    (124) 
133 

0.1 

'■  A. 
A 

Hg 

80 

200.6 

1,  D  = 

(197-200)  ;  202  :  204 

0  1 

A. 

Observers :  A 

=  Astoi 

=  Dempster,    T  =  Thompson  (G.V.) 

148 


THE    CHEMICAL   NEWS. 


MARCH  9,   1923. 


International 

Table  of  the  Radioactive  Elements 

AND  Their 

Constants. 

Atomic 

T 

Name             Symbol 

Radiation 

Wt. 

No. 

Isotope 

Series  of  Uraniu 

M  AND  Radium. 

4.67    X    10«  years 

Uranium  I             UI 

238 

92 

U 

a 

24.6   days 

Uranium  X^          UX^ 

234 

90 

Th 

^ 

1.15  minutes 

Uranium  X^           UXj 

234 

91 

Pa 

^  (y) 

2    X    10^  years 

Uranium  II            UII 

234 

92 

U 

a 

6.9    X    10*  years 

Ionium                    lo 

230 

90 

Th 

a 

1690  years 

Radium                  Ra 

226 

88 

Ra 

a  (fi+y) 

3.85   days 

Eadoji                     Rn 

222 

86 

Bn 

a 

3.0   minutes 

Radium  A              RaA 

218 

84 

Po 

a 

26.8  minutes 

Radium  B             RaB 

214 

82 

Pb 

/5  (y) 

19.5    minutes 

Radium  0  — 

RaC 

214 

83 

Bi 

99  97%  ^  &  v 

10-®   second 

Radium  C 

RaC 

214 

84 

Po 

a 

16.5  years 

Radium  D 

RaD 

210 

82 

Pb 

{f3  and  y) 

5.0  days 

Radium  E 

RaE 

210 

83 

Bi 

P 

136  days 

Radium  F 
(Polonium) 

RaF 

(Po) 

210 

84 

Po 

-  (y) 

Radium  Cl' 
(Lead  ] 

RaQ' 

Pb206 

206 

82 

Pb 

Radium  0  — 

RaC 

214 
210 

83 
81 

Bi 

Tl 

0.03%    a 

1.4  minutes 

Radium  C"            RaC" 

y8 

Radium  Vt"            llaO" 

210 

82 

Pb 

Si 

5RIES  OF  Actinium. 

Uranium   ? 
Uranium.  Y           UY 

92 
90 

U 
Th 

a 

1.04  days 

iS 

1.2     X     10*    years 

Protoactinium       Pa 

91 

Pa 

a 

20    years 

Actinium,                Ac 

89 

Ac 

— 

19.5  days 

Radioactinium       RdAc 

90 

Th 

a    (/3) 

11.4  days 

Actinium  X           AoX 

88 

Ra 

a 

3.9   seconds 

Actinon                   An 

86 

Rn 

a 

2.0    X    10-3   second 

Actinium   A           Ac  A 

84 

Po 

a 

36.1    minutes 

Actinium   B          AcB 

82 

Pb 

{ft   and   y) 

2.15  minutes 

Actinium,  C           AoC 

83 

Bi 

a 

4.71    minutes 

Actinium  C"         AcC" 

81 

Tl 

(3  and  y 

Actinium,  O"          AcQ" 

82 

Pb 

Se 

ribs  of  Thorium. 

1.31    X    10'°  years 

Thorium                  Th 

232 

90 

Th 

a 

6.7  years 

Mesothorium.  1   M«Thl 

228 

88 

Ra 

— 

6.2  hours 

Mesothorixtm  2  MsTh2 

228 

89 

Ac 

ft  and  y 

2.02  years 

Radiothorium      RdTh 

228 

90 

Th 

a    (ft) 

3.64  days 

Thorium  X          ThX 

224 

88 

Ra 

a 

54  seconds 

Thoron                 Tn 

220 

86 

Rn 

a 

0.14  second 

Thorium  A          ThA 

216 

84 

Po 

a 

10.6  hours 

Thorium    B          ThB 

212 

82 

Pb 

ft  and  y 

60  minutes 

Thorium,  C     _  ThC 

212 

83 

Bi 

Q5%  ft 

10-'^   second 

Thorium  C 

ThC 

212 

84 

Po 

a 

Thorium  Q' 

ThQ' 

208 

82 

Pb 

(Lead) 

pb208 

U^ 

Thorium,  C    — 

_  Thn 

212 

83 

Bi 

35%    a 

3.1  minutes 

Thorium  C"      '  TbC" 

208 

81 

Tl 

ft  and  y 

Thorium  0,"         ThQ" 

208 

82 

Pb 

(Lead)               Pb^"* 

19 
37 

K 

39.1 

B 

Rubidium 

Rb 

ss.'e 

Rb 

P 

I 


MARCH  9,  1923. 


THE   CHEMICAL   NEWS. 


U9 


liEMARKS   ON  THE  INTERNATIONAL  TABLE   OF  THE  RADIOACTIVE 
ELEMENTS  AND  THEIR  CONSTANTS. 

It  is  desirable  that  the  nomenclature  adopted  by  the  International  Commission 
should  be  universally  accepted,  but  that  now  put  forward  is  provisional,  serving  as  a 
basis  for  discussion  before  the  ultimate  Adoption  of  a  standard  nomenclature. 

T  stands  for  the  time  in  which  the  quantity  of  radio-element  is  diminished  to 
one-half.  Under  Radiation,  the  brackets  (  )  indicate  that  the  radiation  is  relatively 
feeble. 


'  The  expression  "atomic  mass'  is  re- 
served for  isotopes  or  simple  elements  con- 
sidered from  the  isotopic  point  of  view 
The  expression  atomic  weight    retains  its 


usual  meaning,  and  is  applied  to  elements 
without  consideration  of  their  isoiopie  con- 
stitutwn. 


CATALYST    POISONING. 

At  the  Chemical  Society  of  the  Univer- 
sity of  Birmingham,  on  February  19 — Pro- 
fessor Morgan  presiding — Dr.  Edward  B. 
Maxt^d,  chairman  of  the  Birmingham  and 
Midland  Section  of  the  Society  of  Chemi- 
cal Industry,  read  a  paper  on  "  Catalyst 
Poisoning," 

Poisoning  may  be  Sipecific  rather  than 
general,  the  author  pointed  out,  for  what  is 
a  poison  for  a  given  reaction  with  a  given 
catalyst  may  be  harmless  for  a  second  re- 
action with  even  the  same  catalyst  or  even 
for  the  same  reaction  with  a  different  cata- 
lyst. 

The  following  is  a  summary  of  Dr. 
Maxted's  remarks:  — 

1.  Catalyst  poisoning  oonsista  of  the 
preferential  adsorption  of  the  poison  by 
the  catalyst,  in  such  a  way  that  the  second- 
ary valencies  of  the  catalyst,  in  place  of 
being  free  for  transitory  association  with 
the  normal  reacting  system — the  probable 
mechanism  of  ordinary  catalysis — are  ob- 
structively saturated  by  the  poison.  By 
obstructively  saturated  is  meant  that  the 
free  evaporation  of  the  adsorbed  poison 
from  the  surface  of  the  catalyst  and  its  re- 
placement by  the  normal  roacting[  system 
does  not  take  place — or,  at  nil  events,  not 
readily. 

2.  From  the  above,  it  follows  that  if  a 
given  inhibitant  poisons  a  given  catalyst, 
then  tho  catalyst  will  adsorb  the  poison. 
The  adsoription  of  a  poison  by  a  prelimin- 
ary charge    of  catalyst   may   in    some    in- 


etenoes  be  used  to  purify  a  reacting  sys- 
tem; but  in  most  cases  the  amount  actu- 
ally removed  by  a  given  weight  of  catalyst 
is  too  small  for  the  method  to  be  used 
practically. 

8.  The  activity  of  a  catalyst  during  the 
first  stages  of  poisoning  is  a  linear  function 
of  the  poisMi  content,  and  the  form  of  the 
poisoning  curve  is  intimately  connected 
with  that  of  the  a<i sorption  curve, 

4.  The  general  type  of  the  reaction 
curve  is  not  affected  by  the  prejwjnce  or 
absence  of  a  poison  insufficient  in  quantity 
or  the  oomiplet-e  suppression  of  activity, 
provided  that  tho  concentration  of  the 
poison  on  the  surface  of  the  catalyst  does 
not  change  during  the  reaction,  and  pro- 
vided also  that  the  fMin  of  the  catalyst 
does  not  change. 


DECOMPOSITION    OF    FORMIC    ACID 
BY  SULPHURIC  ACID. 

By  E,  R.  Schierz. 

Sulphuric  acid  deoooiposes  formic  acid 
with  the  evolution  of  carbon  monoxide,  and 
the  velocity  of  the  reaction  decreases  with 
addition  of  water.  The  reaction  is  con- 
sidered to  be  one  of  dehjidration,  an  ex- 
planation of  which  is  suggested  in  the 
equation:  — 
n  H-C(0)-OH  +  m  H^SO,  ->► 

N  CO  +  m  H^SO^-nHjO. 
The  effects  of  other   substances  on  the    re- 


156 


TfiE   CHEMICAL   NEWS. 


MABCH  9,  1923. 


aotion  have  been  studied,  and  whereas  both 
acetone  and  acetic  acid  aot  as  diluents,  not 
actually  decreasing  the  dehydrating  power 
of  sulphuric  acid,  if  the  volume  of  acetic 
acid  is  great,  i.e.,  1  vol.  HjSO^  to  10  vols. 
CH3COOH,  the  formic  acid  is  not  decom- 
posed. On  the  other  hand,  hydrogen 
chloride  increases  the  velocity  of  the  re- 
action. Again,  cQpper,  silver,  and  othe}' 
sulphates  decrease  slightly  the  velocity  of 
reaction. — {Jour.  Amer.  Chem.  80c. ,  1928. 
p.  447.) 


STABILITY     OF     SODIUM     OXALATE 
SOLUTION. 

By  E.  S.  Hopkins. 

In  laboratories  where  oxygen  absorption 
estimations  are  made,  it  is  frequently  the 
custom  to  titrate  back  the  excess  of  per- 
manganate with    N_  sodium  oxalate    solu- 

°  100 

tion.  It  has  been  found  that  this  latter  is 
not  at  all  stable,  but  can  be  rendered  so  bv 
the  addition  of  100  cc.s  of    1:4  H^SO^    to 

the  litre  of  M—     oxalate  when  beina;  made 

100  7^ 

up.     Such  solution  will  not  deteriorate  for 

two  months,    even  when    exposed  to    day- 

hght  in  an  ordinary  colourle^ss  glass  bottle. 

—{Jour.  Ind.  Eng.  Chem.,  1923,  ':    149.) 


In  his  annual  report  for  1922,  Georige  M. 
Cassatt,  President  of  the  American  Cham- 
ber of  Commerce,  stated  that  during  1922 
the  Chamber  continued  to  use  every  pos- 
sible means  at  its  disiposal  to  increase  the 
sale  of  British  products  in  the  United 
States  as  well  as  American  goods  over  here, 
and  in  spite  of  adverse  circumstances  the 
results  of  its  efforts  demonstrate  its  im- 
portance a®  a  factor  in  Anglo-American 
business. 


NOTICES  AND  PROCEEDINGS   OF 
SOCIETIES. 


THE    EOYAL    SOCIETY. 

Papers  read  on  Thursday,  March  1,  1923, 
at  4.30  p.m.  :  — 
A.    Mallock,     F.E.S.       The     Effect     of 


Temperature  on  some  of  the  Properties  of 
Steel. 

In  this  paper  exiperiments  are  described 
in  which  the  period  of  torsional  vibration 
and  the  length  of  a  steel  wire  were  auto- 
matically and  continuously  recorded  in 
terms  of  time,  while  the  temperature  was 
varied  between  15°  and  1,000°  C,  the  tem- 
perature also  being  recorded. 

From  the  experiment  the  variation  of 
rigidity  and  the  coefficient  of  temperature 
expansion  between  these  limits  can  be 
deduced. 

The  results  show  (1)  that  the  variation 
of  the  rigidity  of  steel  between  ordinary 
temperature  and  a  dull  red  heat  is  small 
(less  than  1  per  cent.);  (2)  that  above  the 
critical  temperature  (about  800°  C.)  the 
rigidity  decreases  rapidly;  (3)  that  the  tem- 
perature coefficient  of  expansion  does  not 
show  any  marked  change  as  the  metal 
passes  through  the  critical  temperature ; 
but  (4)  that  a  comparison  with  the  cooling 
curves  of  iron  and  steel  (alluded  to  in  the 
paper)  proves  that  the  specific  heat  of  the 
high  temperature  form  of  the  metal  is 
much  less  than  it  is  at  temperatures  below 
the  critical  point. 

Prof.  C.  H.  Lees,  F.E.S.  Inductively 
Coupled  Low-Resistance  Circuits. 

It  is  shown  that  the  oscillations  in  each 
of  two  circuits  of  low  resistance  coupled  by 
their  mutual  inductance  can  be  simply  ex- 
pressed in  terms  of  a  certain  iproduct  of 
capacitance  and  inductance.  The  expres- 
sions for  the  currents  lead  to  a  simple 
graphical  solution  of  the  problem. 

Lord  Eayleigh,  F.E.S.  Studies  of 
Iridescent  Colour,  and.  the  Structure  pro- 
ducing it.  I. — The  Colours  of  Potassium 
Chlorate  Crystals. 

The  structure  of  the  iridescent  potassium 
chlorate  crystals  investigated  by  Stokes 
and  the  late  Lord  Eayleigh  is  examined 
microscopically. 

The  periodic  twinned  structure  inferred 
by  the  latter  is  clearly  shown  in  the  photo- 
graphs taken  under  the  microscope  with 
polarised  light. 

Some  crystals  have  exceedingly  complex 
structure,  showing  many  groups  of  evenly 
spaced  twin  planes  and  a  very  complex  re- 
flection sipectrum.  It  is  shown  that  this 
results  from  high  interference  from  twinned 
layers  situated  a  considerable  distance 
apart. 

Chlorate  crystals,  giving  a  silvery  reflec- 
tion, were  obtained  by  Madan,  who  heated 
the  ordinary    colourless    crystals  to    about 


MAKCH  9,  1923. 


THE  CHEMICMi  NEWS. 


151 


250°  C.  The  complex  twinned  structure 
induced  by  this  treatment  is  investigated, 
and  photographs  of  the  structure  of  the 
crystal  and  of  the  reflection  spectrum  are 
reproduced.  There  are  corresponding  irre- 
gularities in  each,  resulting  from  want  of 
flatness  in  the  twin  planes. 

Lord  Rayleigh,  F.K.S.  Studies  of 
Iridescent  Colour,  and  the  Structure  pro- 
ducing it.     II. — Mother-of -Pearl. 

The  structure  giving  rise  to  the  colour  of 
mother-of-pearl  was  investigated.  The  re- 
sults generally  are  confirmatory  of  those 
given  by  Brewster  and  A.  H.  Pfund. 
Micro-photographs  were  reproduced  show- 
ing the  grating  structure  of  a  ipearl  oyster 
shell  and  the  structure  of  parallel  layers  of 
an  "ear"«hell.  The  absorption  spectrum  of 
the  latter  was  also  repro<^luced.  In  agree- 
ment with  the  observed  sipacing  of  the 
layers  under  the  microscope,  it  shows  the 
reflection  to  be  of  the  second  order. 

Lord  Rayleigh,  F.R.S.  Studies  of 
Iridescent  Colour,  and  the  Structure  pro- 
ducing it.  III. — The  Colours  of  Labrador 
Felspar. 

The  colours  shown  by  Labradorite  fel- 
spar were  examined  experimentally.  The 
colours  seen  by  reflection  arise  from  two 
distinct  origins:  — 

(1)  Specular  reflection  from  tabular 
inclusions,  which  show  the  colours  of 
thin  plates  and  are  often  as  much  as  0.2 
mm.  in  dimensions.  These  are  distri- 
buted parallel  to  one  of  the  clonvagos. 

(2)  Diffuse  reflection  from  a  piano  15" 
away  from  the  cleavage  mentioned.  This 
is  the  source  of  the  striking  colours 
which  ordinarily  excite  attention. 

When  the  diffuse  reflecting  plane  is 
examined  microscopically  under  conditions 
which  ensure  that  the  light  only  comes 
from  a  very  thin  stratum,  it  is  found  that 
the  plane  of  reflection  is  discontinuous  or 
patchy.  The  patches  are  of  irregular  out- 
line. 

The  diffuse  character  of  the  reflection  is 
accounted  for  by  the  small  diameter  of 
these  reflecting  surfaces,  regarded  as  inde- 
pendent optical  apertures.  Their  size 
(0.005  mm.)  accounts  a,pproximately  for 
the  angular  diameter  of  the  diffuse  image 
of  a  point  source  seen  by  reflection,  if  we 
regard  this  as  a  diffraction  disc.  This  ex- 
planation recjuires  that  the  reflecting 
patehi's,  though  parallel,  should  not  bo 
stnctly  co-planar,  but  rlistributed  at  ran- 
dom depth. 


The  colour  of  the  reflection  is  not 
shai-ply  limited  to  special  regions  of  the 
spectrum,  and  it  appears  that  the  colour 
can  be  explained  by  the  interference  of 
streams  of  light  from  the  two  surfaces  of 
each  patch.  The  patches  may  be  fissures 
in  the  material,  and  there  is  evidence  that 
their  thickness  is  not  absolut.ely  uniform. 

The  brightness  of  the  colour  is  explicable 
by  the  large  number  of  reflecting  patches 
adding  their  effects,  without  definite  phase 
relation  such  as  would  give  rise  to  regular 
interference. 

Micro-photographs  of  the  structure  giv- 
ing rise  to  the  two  reflections  are  reipro- 
duced. 

Paper  read  in  title  only :  — 

L.  V.  King,  D.So.  On  the  Complex 
Anisotropic  Molecule  in  Relation  to  the 
Dispersion  and  Scattering  of  Light.  Com- 
municated by  Frof.  A.  S.  Eve,  F.R.S. 


Thursday,  March  8,  at  4.30  p.m. 

Papers  read :  — 

A.  B.  Wood,  H.  E.  Browne,  and  C. 
Cochrane.  Determination  of  Velocity  of 
Explosion  Waves  in  Sea  Water.  Variation 
of  Velocity  tviih  Temperature.  Communi- 
cated by  F.  E.  Smith,  F.R.S. 

P.  M.  S.  Blackktt.  The  Study  of  Forked 
Alpha  Ray  Tracks.  Communicated  by  Sir 
Ernest  Rutherford,  F.R.S. 

E.  Hatsciiek  and  P.  C.  L.  Thorne. 
Metal  Sols  in  nou-dissocinting  Liquids.  I. 
— Nickel  in  Toluene  and  Benzene.  Com- 
municated by  Prof.  A.  W.  Porter,  F.R.S. 

Paipers  read  in  title  only:  — 

H.  HiRATA.  Constitution  of  the  X-Ray 
Spectra  belonging  to  the  L  Series  of  the 
Elements.  Conununioated  by  Sir  William 
Bragg,   F.R.S. 

A.  Egerton.  On  the  Vapour  Pressure 
of  Lead.  I.  Communicated  by  Prof.  F. 
A.  Lindemann,  F.R.S. 

A.  C.  EoERToN  and  W.  B.  Lee.  Some 
Density  Determinations.  Communicated 
by  Prof.  F.  A.  Lindemann.  F.R.S. 

A.  C.  EoERTON  and  W.  B.  Lee.  Separa- 
tion of  Isotopes  of  Zinc.  Communicated 
by  Prof.  F.  A.  Lindemann,  F.R.S. 


THE    SOCIETY    OF    GLASS 
TECHNOLOGY. 
Prof.  W.  E.  S.  Turnor.  IXSc.    presided 
at  tho  meeting  held  in  Armstrong  CollCi;", 
Newcastle-on-Tyne,   on   February    21. 


152 


THE   CHEMICAL   !tEWS. 


MAECH  9,  1923. 


The  first  paper  was :  Organising  for  Pro- 
duction from  Pot  Furnaces,  by  W.  W. 
Warren,  A.M.I.C.E.,  A.M.I.E.E.  (Mana- 
ger of  Messrs.  Lemington  Glass  Works, 
Ltd.).  The  subject  was  apiproached  from 
experience  gained  at  Lemington,  where 
methods  for  producing  electric  lamp  bulbs 
from  pot  furnaces  were  modelled  on  those 
in  German  and  Dutch  glass  works., 

Comparing  present  practice  at  Leming- 
ton with  that  of  1918,  when  the  output  of 
hand-made  pulbs  was  similar  in  number 
and  weight,  there  were  now  only  20  pots 
in  commission,  as  against  70  pots  in  1918. 
This  intensifying  of  production  had  effected 
an  enormous  saving  of  coal.  Fuel  costs 
were  less  then  than  in  pre-war  times. 

During  the  forenoon,  a  party  of  members 
of  the  Society  visited  the  glass  works  at 
Lemington,  and  saw  in  actual  operation 
the  scheme  outlined  by  Mr.   Warren. 

Two  other  papers  were  communicated : 
The  Effect  of  Boric  Oxide  on  the  Melting 
and  Working  of  Glass,  by  F.  W.  Hodkin, 
B.Sc,  and  Prof.  W.  E.  S.  Turner,  D.Sc, 
and  Some  Physical  Properties  of  Bone 
Oxide-containing  Glasses,  by  Violet  Dim- 
BLEBY,  B.Sc,  S.English,  M.Sc,  and 
Prof.  Turner. 

Boric  oxide  glasses  were  of  great  impor- 
tance. Although  boric  oxide  had  been  used 
as  a  constituent  of  glass  for  at  least  a  cen- 
tury, it  assumed  greater  importance  from 
the  German  researches  at  Jena  forty  years 
ago.  Lately,  borosilicate  glasses  had  been 
more  in  use.  The  new  British  chemical 
glass,  American  Pyrex  glass  for  chemical 
and  cooking  ware,  and  various  illuminating 
glasses,  all  contained  it.  Investigations, 
designed  to  lay  down  a  foundation  of  facts 
concerning  such  glasses,  were  outlined. 

Addition  of  boric  oxide  to  silicate  glass 
increased  the  durability,  but  this  beneficial 
effect  only  held  up  to  a  certain  point,  the 
maximum  benefit  for  the  glass  with  20  per 
cent,  of  soda  being  obtained  at  11  to  12  per 
cent,  of  boric  oxide.  Glass  then  became 
less  durable,  until  when  35  to  40  per  cent, 
was  present  it  dissolved  in  water.  Again, 
reduction  in  thermal  expansion  reached  a 
maximum  effect  at  about  20  per  cent,  of 
boric  oxide  in  both  series  of  glasses.  The 
usefulness  of  boric  oxide  was  limited,  and 
further  exiperiments  of  the  heat-resisting 
glasses  must  lie  in  other  directions  than 
the  employment  of  boric  oxide,  Inversio.is 
in  annealing  temperature,  the  density,  and 


refractive  index,  had  also  been  found  at 
the  Department  of  Glass  Technology  of 
Sheffield  University. 


ROYAL  INSTITUTION   OF    GREAT 
BRITAIN. 

At  3  p.m.,  on  Saturday,  March  10,  Sir 
Ernest  Rutherford,  LL.D.,  D.So., 
F.R.S.,  M.R.I. ,  Prof,  of  Natural  Philoso- 
phy, will  deliver  his  fourth  lecture  on 
Atomic  Projectiles  and  their  Properties. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 

OTHER  ANALYTICAL  CHEMISTS. 

The  next  meeting  of  the  Society  wdll  be 
held  on  Wednesday,  March  7,  at  the 
Chemical  Society's  Rooms,  Burlington 
House,  Piccadilly,   W.,   at  8  p.m. 

The  following  papers  will  be  read. 

The  Examination  of  Firearms  and  Pro- 
jectiles, by  A.  Lucas,  O.B.E.,  F.I.C. 

The  Interpretation'  of  the  Results  ob- 
tained in  the  Analysis  of  Potable  Waters, 
by  R.  C.  Frederick. 

Determination  of  the  Purity  of  Vanillin, 
by  Sydney  B.  Phillips,  A.I.C. 


THE  INSTITUTION    OF  ELECTRICAL 
ENGINEERS. 

Wireless   Section   Meeting. 

Mr.  H.  Morris-Airey,  C.B.E.,  gave  a 
lecture  entitled  The  Development  of  Naval 
High  Power  Valves  on  March  7. 


THE  OPTICAL  SOCIETY. 

At  the  meeting  held  on  Thursday,  8th 
March,  the  following  papers  were  read:  — 

Optical  designing  as  an  Art,  by  H.  Den- 
nis Taylor. 

The  distribution  of  correction  duties  in 
Optical  Instruments,  by  T.  Smith,  M.A., 
F.Inst. P. 


INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

The  tenth  annual  general  meeting  of  the 
Institution    of      Petroleum      Technologists 


MAKCH  9,  1923. 


THB  CHEMICAL  NEWS. 


153 


will  be  held  at  the  house  of  the  Eoyal 
Society  of  Arts  oa  Tuesday,  March  13th. 
at  5.30  ip.m.,  and  will  be  followed  at  about 
6  p.m.  by  a  Presidential  Address  by  Pro- 
fessor J.  S.  S.  Brame,  F.I.C.,  F.C.S.,  the 
retiring  President. 

The  President-elect  for  the  ensuing  sea- 
sion  is  Mr.  Herbert  Barringer,  M.Inst.- 
C.E.,  M.I.Mech.E.,  M.I.N. A.,  and  the 
Vice-Presidents  are  Mr.  Alfred  C.  Adams, 
Sir  Geatge  Beilby,  Sir  John  Cargill,  Vis- 
count Cowdray  of  Cowdray,  Mr.  Arthur  W. 
Eastlako,  and  Sir  Thomas  H.  Holland. 


INSTITUTE  OF  CHEMISTRY. 

At  the  45th  Annual  General  Meeting  of 
the  Institute  of  Chemistry,  held  at  30, 
Russell  Square  on  March  1,  the  President, 
Mr.  A.  Chaston  Chapman,  F.Il.S.,  in  pre- 
senting the  Report  of  the  Council,  re- 
marked on  the  progress  of  the  organisation 
of  the  profession  of  chemistry  under  the 
Institute.  The  roll  oi  Fellows  and  Asso- 
ciates had  increased  during  the  past  twelve 
months  by  421,  to  a  total  of  4,062,  and  the 
regster  of  students  by  72,  to  a  total  of  955. 

The  Institute  was  taking  an  increasing 
(part  in  the  affairs  of  the  country,  and  was 
frequently  appealed  to  by  Government  De- 
partments and  other  authorities  for  advice 
and  help.  Natural  Science — and  in  this 
connection  chemistry  must  be  given  a  posi- 
tion of  prominence — was  by  far  the  most 
important  dynamic  factor  in  humstn  pro- 
gress. Notwithstanding  its  liability  to 
abuse,  its  discoveries  had  made  enormously 
for  the  greater  good  and  happiness  of  the 
human  race.  Science  was  coming  into  its 
own,  and  scientific  men  would  be  given 
their  proper  status  and  rightful  place  in  the 
affairs  of  the  country.  The  Institute,  in 
common  with  other  societies  and  associa- 
tions, was  actively  promoting  a  spirit  of 
solidarity  among  all  concerned  with  chem- 
istry. 

The  direct  utilisation  by  the  State  of  the 
services  of  the  professional  chemist  was  a 
matter  not  only  of  immediate  concern  to 
chemists  themselves,  but  was  of  high  im- 
portance to  the  community,  and  in  the 
country's  interests  no  less  than  in  those  of 
its  members,  the  Institute  was  bound  to  do 
all  it  could  to  ensure  that  the  relations  be- 
tween the  appointing  authorities  and  those 
who  held  official  chemical  positions  were 
satisfactory.     Unfortunately,     some    public 


bodies  did  not  appear  to  be  aware  of  the 
lengthy  and  expensive  nature  of  the  chem- 
ist's training,  or  of  the  difficulties  and  re- 
sponsibilities connected  with  his  work,  and 
consequently  the  Institute  sometimes 
found  the  advertised  conditions  of  certam 
public  bodies  were  not  commensurate  with 
the  importance  of  the  services  demanded. 
The  mere  saving  of  money  was  not  always 
identical  with  true  economy,  and  it  was 
clearly  of  public  importance  that  men  of 
good  general  education,  of  high  profes- 
sional attsdnmentfi,  and  of  high  moral 
character  should  be  chosen  to  fill  these 
positions,  while  it  was  obvious  that  ap- 
pointing authorities  would  seriously  limit* 
the  field  for  selection,  unless  the  conditions 
offered  were  such  that  men  of  the  right 
class  would  be  willing  to  accept.  For  the 
appointment  of  public  analyst  the  remuner- 
ati<»i  (^ered  was  often  entirely  inadequate 
and,  in  some  case*,  even  below  that  paid 
before  the  war. 

The  Institute  had  also  l>een  obliged  to 
complain  of  the  competition  of  state-aided 
institutions  with  private  practitioners,  and 
it  was  a  source  of  gratification  that  the 
Ministry  of  Agriculture  and  Fisheries  had 
recognised  the  legitimate  grievance  of  the 
private  practitioner,  and  had  taken  steps 
towards  limiting  the  agricultural  work  done 
in  the  institutions  receiving  its  grants  to 
that  required  for  strictly  educati<Mial  pur- 
poses or  necessary'  to  the  advisory  work  of 
the  institutions. 

The  disinterested  zeal  of  the  scientific 
worker  was  something  without  parallel  in 
the  whole  world,  but  it  was  not  wise  for 
any  ooimtry  to  presume  too  much  on  this 
disinterestedness.  Science  was  one  of  the 
greatest  and  freest  of  all  givers,  but  it  had 
a  right  to  demand  that  it  should  receive 
that  recognition  and  that  proper  position  in 
the  councils  of  the  country  to  which  it  was 
entitled. 

A  leading  German  industrial  chemist  had 
said  lately  that,  notwithstanding  Ger- 
many's position  of  virtual  bankruptcy,  the 
State  had  come  to  the  help  of  the  great 
chemical  and  physical  societies,  like  the 
Kaiser  Wilhelm  Institute,  and  if  the  State 
could  not  continue  financial  aid  the  Ger- 
man pec^ple  themselves  must  give  their  last 
mark  to  maintain  science. 

Referring  to  the  prospects  of  the  profes- 
sion, the  President  said  chemistry  had 
great  attractions  for  most  boys,  and  there 
were  many  induced  by  a  liking  begotten  in 


154 


THE    CHEMICAL    NEWS. 


MARCH  9,  1923. 


the  school  laboratory  to  embaxk  upon  a 
profession,  for  which  they  had  perhaps  no 
real  aptitude,  A  chemical  career  was  not 
a  succession  of  fascinating  exiperiments, 
but  it  involved  a  good  deal  of  hard  work  of 
a  comparatively  unattractive  character, 
made  very  great  demands  on  its  devotees, 
and  called  for  much  self-sacrifice  on  the 
part  of  those  who  adopted  it  as  a  profes- 
sion. The  profession  had  attracted  a  larger 
number  of  young  men  during  the  last  four 
years  than  in  any  previous  corresponding 
period,  but  he  was  optimistic  in  regard  to 
the  future.  It  was  a  remarkable  fact  that, 
notwithstanding  industrial  depression,  the 
new  members  of  the  profession  were  being 
steadily  absorbed.  This  absorption  might 
be  taken  as  an  indication  that  chemistry 
was  more  highly  valued  by  manufacturers 
than  formerly.  Leaders  of  industry  were 
turning  more  to  science  to  ass^ist  them  in 
solving  their  problems. 

The  Eeport  of  the  Council  and  Financial 
Statements  were  received  and  adopted, 
and  the  officers.  Council,  and  censors  for 
the  ensuing  year  were  elected. 

The  Meldola  Medal  was  awarded,  for  the 
second  time,  to  Dr.  Christopher  Keik 
Ingold. 


SOCIETY  OF    CHEMICAL  INDUSTRY. 
Birmingham  and  Midland   Section. 

At  the  meeting  on  February  20,  the  fol- 
lowing papers  were  delivered:  — 

Interaction  of  Formaldehyde  and  the 
Nitronarphthyla mines,  by  Professor  Gil- 
bert T.  Morgan  (Head  of  the  Chemical 
Department  of  the  University),  and  F.  R. 
Jones. 

The  authors  state  that  the  seven  known 
nitronaphthylamines  have  been  condensed 
with  formaldehyde  under  varying  condi- 
tions: —  4-nitro-a-naphthylanine  and  2- 
nitro-a-naphthyl  amine  give  dinaphthyl- 
methane  bases ;  l-nitro-;S-naphthylamine 
furnishes  the  hydrolysable  methylenebis — 
1-nitro-^-naphthylamine,  which  exists  in 
two  differently  coloured  modifications;  5- 
nitro-/3-naphthylamine  gives  rise  to  two 
products,  a  dinaphthylmethane  base  an^  a 
dinaphthacridine ;  8-nitro-/3-naphthylamine 
gives  methylenebis-8-nitro-/3-naphthylam- 
ine,  which  becomes  transformed  into  a  di- 
naphthylmethane base ;  5-nitro-a-naphthyl- 
amine  resembles  a-naphthylamine  in  yield- 


ing ill-defined  products,  whereas  8-nitro-a- 
naphthylamine  furnishes  methylenebis-B- 
nitro-a-naphthylamine  and  a  dinaphthyl- 
methane base  which  has  the  noteworthy 
prqperty  of  separating  in  yellowish  white 
tabular  crystals  containing  three  molecular 
proportions  of  formaldehyde. 

These  results  show  that  the  nearer  the 
nitro-group  is  to  the  amino-radicle  in  the 
nitron aphthyl amine  the  more  marked  is  the 
retarding  effect  of  this  nitro-group  on  the 
condensation  with  formaldehyde. 

Note  on  the  Preparation  of  ^-NaphfhoL- 
4:-sulphonic  Acid,  by  Professor  Morgan 
and  Eveline  Jones. 

An  attemjpt  has  been  made  to  obtain  13- 
naphthol-4-sulphonic  acid  from  the  com- 
mercially available  naphthalene-l-diazo-2- 
oxide-4-sulphonic  acid  by  boiling  this  diazo- 
compound  with  alcohol,  when  elimination 
of  the  diazo-group  occurs,  the  resulting  fj- 
naphthol-sulphonic  acid  being  characterised 
by  means  of  its  azo-derivatives  with  the  di- 
azonium  salts  of  p-toluidine,  p-nitroaniline 
and  j8-naphthyl amine. 

S.  R.  Carter,  M.Sc,  Chemistry  Depart 
ment  of  the  University,  read  a  paper  on 
the  Concentration  of  Hydrogen  Ion.  The 
advantages  of  reducing  all  degrees  of  acid- 
ity and  alkalinity  to  one  common  scale 
were  demonstrated,  and  the  basis  of  Soren- 
sen's  Hydrogen  Ion  experiment  (P^)  was 
explained.  The  constitution  of  indicators 
was  discussed  and  their  application  to  the 
detei'mination  of  Ph  values  was  illustrated 
by  experiments.  The  latter  portion  O'f  tlie 
lecture  was  devoted  to  the  electro  metric 
methods  employed  for  hydrogen  ion  mea- 
surements, and  to  electro  metric  titrations 
and  the  principles  involved  were  illustrated 
by  reference  to  potentiometers  and  elec- 
trodes lent  by  the  Cambridge  and  Paul  In- 
strument Co. 


GENERAL    NOTES. 


VERTICAL  RETORTS  AND  CHEMICAL 
PROBLEMS. 
Mr.  Joseph  Poulson,  F.C.S.  (Stafford 
Corporation  Gas  Works)  read  a  paper  on 
"  Experiences  of  Vertical  Retorts,"  before 
the  members  of  the  Midland  (Junior)  Gas 
Engineers,  at  the  Birmingham  Council 
House,  on  Thursday,  January  14.  He  gave 


I 


MARCH  9,  1923. 


THE   CHEMICAL   NEWS. 


155 


the    following    particulars  of    the  tar    pro- 
duced :  — 

Per  ton  of  coal  carbonised  ...  17.3  gallons. 

Sipecific  gravity  of  tar  1.095 

Water  content  of  tar  3.5  per  cent. 

Free  carbon  in  tar  3.1  per  cent. 

Sulphate  of  Ammunia.  —  Twenty-three 
lbs.  of  neutral  dry  quality,  testing  25^  per 
cent,  of  ammonia  are  obtained  per  ton  of 
ooal  carbonised.  Ammonia  is  at  present 
allowed  to  go  forward  to  the  purifiers  to 
assist  in  purification. 

Since  the  commencement  of  operation 
of  the  vertical  retorts,  the  district  has  been 
remarkably  free  from  naphthalene,  and 
there  has  not  been  recorded  one  single 
complaint  from  this  cause  ior  over  3^  years. 
The  naphthalene  content  of  the  gas  is  0.85 
grain  per  100  cubic  feet.  The  freedom 
from  such  deposit  has  permitted  the  instal- 
lation of  a  station  meter  of  the  Rotary  type, 
but  further  information  regarding  this  is 
not  yet  available,  the  motor  having  been  in 
operation  only  a  few  months. 

No  pitching  troubles  have  been  experi- 
enced. The  collecting  mains  are  run  off 
daily,  and  before  opening  the  valve  to 
effect  this,  any  accumulation  of  thickened 
matter  that  has  drained  to  the  exit  end  of 
the  main  is  scooped  out.  The  amount  of 
thick  tarry  matter  obtained  from  each  main 
daily  averages  14  to  16  lbs.  The  period  of 
draining    of    each    main     is    about    three- 

auarters  of  a  minute.  After  closing  the 
raining  valve,  the  collecting  main  is  then 
filled  to  the  level  of  the  weir  overflow  with 
warm  and  weak  liquor  siippUed  from  an 
overhead  tank.  The  temperature  of  the 
gas  from  the  retorts  is  185°  C,  and  of  the 
gas,  near  the  outlet  of  the  collecting  main, 
US'*  C. 

As  to  the  refractory  materials  used  in 
the  settings,  he  stated  that  examination  of 
the  materials  proved  them  to  be  remark- 
ably true  to  size  and  shape.  The  surfaces 
were  smooth,  and  edges  well  defined.  The 
fracture  of  portions  of  the  various  segments 
revealed  a  uniformity  of  texture.  Small 
nodules  of  unconverted  quartz  were  evenly 
disseminated  throughout  the  mass.  The 
materials  used  in  the  construction  of  the 
floors  of  the  combustion  chambers  were  of 
close  texture,  and  the  strength  of  the 
materials  was  good,  when  taking  into  con- 
sideration their  composition.  The  follow- 
ing are  analyses  of  the  various  portions 
used :  — 


Silica  Retort  Segments. 


per  cent. 

89.27 

0.77 

8.53 

0.84 


Silica       

Titanic    Oxide    

Alumina       

Ferric  Oxide    

Manganese  Oxide    — 

Magnesia       0.23 

Lime        — 

Potash        0.20 

Soda 0.30 

Loss       0.05 


Combustion  Chambers. 


per  cent, 

91.60 

0.46 

6.32 

0.30 


Silica        

Titanic   Oxidi     

Alumina       

Ferric   Oxide   

Manganese  Oxide   — 

Magnesia       0.21 

Lime        0.26 

Potash 0.85 

Scxla       ..  0.18 

Loss  0.09 

Ordinary   Silica   Brickwork. 

per  cent. 

Silica       87.23 

Titanic    Oxide    1.85 

Alumina       8.55    ^ 

Fejrio   Oxide    1.26 

Manganese    Oxide    — 

Magnesia       0.10 

Lime       0.28 

Potash        0.54 

Soda        4^ 0.36 

Loss 0.25 


H.M.  Commercial  Secretary  at  Cqpen 
hagen  (Mr.  Richard  Turner,  O.B.E.)  re 
p<»^s  that  a  well  established  local  firm  is 
desirous  of  setting  up  a  permanent  exhibi- 
tion on  behalf  of  ten  or  twelve  United 
Kingdom  firms  manufacturing : 

Scientific  instruments. 

Surgical  instruments. 

Cinematograph  apparatus. 

Laboratory  articles. 

X-Ray  apparatus  and  tubes. 

Dentists'  requisites. 

Surveying  instruments. 

Drawing  instruments. 

Polariscopes. 

Pyrometer'^    mid    measuring    instruments. 

Micrf>80opes. 

Telescopes. 


156 


THE   CHEMICAL   NEWS. 


MARCS  9,  1923. 


Further  particulars  regarding  this  ipro- 
position  can  be  obtained  by  interested 
firms  on  application  to  the  Department  of 
Overseas  Trade,  35,  Old  Queen  Street, 
Westminster,  S.W  1. 


SAFEGUARDING  OF  INDUSTRIES 
ACT— PART  I. 

Arbitrations  Under  Section   1,    Sub- 
Section  (5). 

The  Board  of  Trade  have  received  formal 
notices  of  complaint  under  the  above  sub- 
section, that: 

"Rochelle  Salts"  and 
Formaldehyde 

have  been  improperly  included  in  the  lists 
of  articles  chargeable  with  duty  under 
Part  I.  of  this  Act. 

These  comiplaints  will  be  submitted  in 
due  course  to  the  Referee  appointed  by  the 
Lord  Chancellor  for  the  purposes  of  the 
sub-section,  and  any  person  interested 
should  communicate  immediately  with  the 
Assistant  Secretary,  Board  of  Trade  (In- 
dustries and  Manufactures  Department), 
Great  George  Street,  S.W.I. 


NORWAY'S  FOREIGN  TRADE. 

The  Commercial  Secretary  at  Christiania 
has  informed  the    Department  of  Overseas 
Trade    that    the    statistics    of    Norwegian 
foreign  trade,   published   by  the   Statistical 
Central  Bureau,  for  the  month  of  Decem- 
ber, 1922,  show  the  total  of  Norwegian  ex- 
ports    during     the      past     year     to     have 
amounted  to  729.4  million  kroner,   and  the 
re-export  of    foreign   goods  to  24.4  million 
kroner.     Of  Norwegian  goods,  paper  to  the 
value  of  250  million    kroner  was  exported, 
animal   fQodstuffs  167  millions,     fertilisers, 
chemical   products,    etc.    76  millions,     fats, 
oils,    etc.  46  millions,    and  timber  76  mil- 
lions. 

During  December,  1922,  exports  of  Nor- 
wegian goods  amounted  to  57.5  million 
kroner,  as  compared  with  about  71  and  68 
million  kroner  in  November  and  October 
respectively. 


CHEMICAL  TRADE  IN  BRITISH 
MALAYA. 

In  common  with  other  parts  of  the  world, 
there  has  been  a  decided  improvement  in 
trade  generally  in  the  Malay  Peninsula, 
the  improvement  being  most  marked  in  the 
latter  half  of  last  year.  The  following 
statistics  dealing  with  supplies  of  chemi- 
cals, drugs,  dyes,  etc.,  for  the  Malay  region 
clearly  indicate  this,  and  should  be  of  in- 
terest" to  manufacturers  and  export  mer- 
chants in  this  country. 

The  exports  go  mainly  to  Siam  and  the 
Siamese  Malay  States,  Borneo,  French 
Indo-China,  and  the  Dutch  Islands  in  the 
Archipelago.  Acetic  acid  is  extensively 
used  for  the  coagulation  of  latex  on  the 
rubber  estates  of  Malaya.  In  1921,  when 
the  output  of  rubber  was  lower  and  other 
chemicals  were  being  used,  the  total  im- 
port of  acetic  acid  amounted  to  48,660 
gallons,  with  an  export  of  24,699  gallons. 
Last  year  the  import  rose  to  387,594  gal- 
lons, while  only  30,964  gallons  were 
exported. 


IMPORTATION  OF  DYE  STUFFS. 

Dr.  Attlee  asked  the  President  of  the 
Board  of  Trade  whether  there  was  a  scale 
for  licences  on  the  importation  of  dyestuffs 
under  the  Dyestuffs  Act;  and,  if  so,  was 
the  licence  per  pound  based  upon  the  colour 
or  its  quality,  or  was  it  purely  arbitrary? 

Viscount  Wolmer  replied :  Section  2  (7) 
of  the  Dyestuffs  (Import  Regulation)  Act, 
1920,  empowers  the  Board  of  Trade  to 
charge  in  respect  of  each  licence  a  fee  not 
exceeding  five  pounds,  to  provide  for  the 
expenses  of  administration.  The  fees 
actually  charged  are  on  a  sliding  scale, 
based  on  the  value  of  the  consignment  to 
which  each  licence  relates,  and  range  from 
2s.  6d.  on  consignments  of  a  value  up  to 
£100,  to  £5  on  consignments  exceeding 
£3,000  in  value. 


MORPHINE     FACTORIES. 

Cr.  Bridgeman,  the  Home  Secretary,  in- 
formed Lord  Robert  Cecil  that  morphine 
factories  were  subject  to  inspection  by  the 
Home  Office  Inspectors  under  the  Dan- 
gerous Drugs  Act.  Manufacturers  were 
also  required  to  keep  detailed  records,  and 
make  periodical  returns,  of  their  purchases 


I 


MARCH  >  9,  1923. 


THE    CHEMICAL    NEWS. 


157 


of  the  raw  material,  their  production  of  the 
drug,  and  their  sales,  and  a  licence  had  to 
be  obtained  for  each  consignment  of  the 
drugs  which  was  exported  from  this  coun- 
try. The  Government  were  doing  all  that 
was  in  their  power  to  check  the  abuses  of 
the  drug  traffic,  but  until  full  international 
co-operation  had  been  secured  it  would  be 
imipossible  to  prevent  them  altogether. 


BIRMINGHAM   SECTION  OF  THE 
INSTITUTE  OF  CHEMISTRY. 

It  has  been  decided  to  revive  the  Bir- 
mingham and  Midlands  Sootion  of  the  In- 
stitute of  Chemistry,  whic-h  lapsed  during 
the  war.  A  provisional  committee  has 
been  appointed,  rules  approved  and  sub- 
fitted  to  the  Council  of  the  Institute  for 
confirmation,  and  the  following  officers 
elected  : — Chairman,  Professor  G.  T.  Mor- 
gan, Professor  of  Chemistry  at  the  Univer- 
sity; hon.  treasurer,  Dr.  .1.  N.  Friend,  of 
the  Birmingham  Technical  School ;  and 
hon.  secretary,  Mr.  C.  A.  F.  Hastilow. 

It  is  intended  to  hold  meetings  of  both  a 
social  and  professional  character,  and  to 
endeavour  to  promote  cD-operatiMi  and 
friendly  intercourse  between  members  of 
th,""  chemist's  profession. 

Mr.  R.  B.  Pilcher  (Registrar  of  the  In- 
stitute) addressed  a  meeting  recently  of 
Fellows  and  Associates  of  the  Institute  of 
Chemistry  in  Birmingham. 


CORRESPONDENCE. 


THE  AUTHENTICITY  OF  THE  LATIN 

WORKS  OF  GEBER. 

To  the  Editor  of  The  Chemical  News. 

Sir. — I  wa»  very  interested  in  the  ac- 
count given  in  The  Chrinirnl  NewH  of  Mr. 
Holmvard's  lecture  on  "  .Arabian  Alchemy 
and  Chemistry." 

It  seems  to  be  a  matter  of  importance 
that  as  many  of  the  Arabian  alchemical 
MSS.  as  possible  should  be  translated. 
These  may  add  to  our  knowledge  concern- 
ing the  early  history  of  ehemistry,  and 
settle  the  question  as  to  whether  the  works 
attributed  to  Geber  are  to  be  regarded  as 
thofie  of  Dsohabir  or  not. 


An  English  authority,  Mr.  H.  S.  Red- 
grove,  in  his  Alchemy,  p.  42  (second  edi- 
tion), inclines  to  Berthelot's  view,  as  does 
also  a  German  authority,  Prof.  E.  O.  von 
Lippmann,  and  recently,  Dr.  E.  Darm- 
staedten  has  published  a  volume,  entitled 
Die  Alchemie  des  Geber  ubersetzt  und 
erkldrt  (Berlin :  J.  Springer,  1922),  in 
which  he  also  distinguishes  between  Geber 
and  Dschabir. 

Among  other  points,  he  adduces  that  the 
Latin  works  are  written  in  an  obscure 
style,  which  would  not  have  been  the  case 
if  they  were  translations. 

I  regret  I  was  unable  to  attend  Mr. 
Holmyard's  lecture,  since  it  would  be  in- 
teresting to  know  upon  what  evidence  he 
bases  his  conclusions  that  Berthelot  was 
wrong  in  supposing  these  publications  of 
Geber 's  to  be  spurious. — I  am,  yours  etc.. 

E.  E.  Whale,  B.Sc,  F.C.S. 
London,  S.W.17. 


NOTICES  OF  BOOKS. 


Handbook  on  Petroleum,  by  Captain 
J.  H.  Thomson  and  Sir  Boverton  Red- 
wood. Fourth  edition,  revised  and 
added  to  by  Major  A.  Cooper-Key,  C.B. 
Pp.  XIX.  +  342.  London:  Charles 
Griffin  &  Co.,  Ltd.,  Exeter  Street, 
W.C.2.     1922.     128.  6d.  net. 

The  ever-increasing  demand  for  petro- 
leum and  its  products,  and  the  consequent 
progress  in  all  branches  of  the  industry  has 
necessitated  the  publication  of  this  fourth 
revist'd  edition  of  Thomson  and  Redwood's 
standard  and  comprehensive  treatise  on  the 
subject. 

Since  the  publication  of  the  previous 
edition,  technical  science  is  the  poorer  by 
the  death  of  Sir  Boverton  Redwood,  and 
the  present  one  has  been  revised  and 
brought  up-to-date  by  Major  Cooper-Key. 
His  special  knowledge  relating  to  such 
matters  as  transport,  storage,  questions  of 
averting  risks  and  dangers,  and  the  official 
Actn,  Orders  and  Regulations,  is  now  made 
available  for  all  in  a  form  suitable  for 
immediate  reference. 

The  chapters  originally  compiled  by  Sir 
Boverton   have   undergone   little   alteration. 

As  the  old  sources  of  ipetroleum  oils  will 


158 


THE   CHEMICAL    NEWS. 


MARCH^,   1923. 


gradually  become  inadequate  to  meet 
modern  requirements,  considerable  skill 
and  enterprise  will  be  required  to  develop 
and  exploit  new  fields. 

This  indispensable  volume  will  continue 
to  render  most  useful  service  to  those  en- 
gaged in  any  phase  of  the  industry  with 
which  it  deals. 


A  Method  for  the  Identification  of 
Pure  Organic  Compounds,  by  Samuel 
P.  MuLLiKEN,  Ph.D.  Vol.  "IV.  Pp. 
VII.  +  238.  London:  Chapman  &  Hail, 
11,  Henrietta  Street,  W.C.2.  New  Yorlc : 
John  Wiley  &  Sons,  Inc.  1922.  30s. 
•    net. 

The  chief  portion  of  Prof.  Mulliken's 
compendium  is  completed  by  the  appear- 
ance of  Vol.  IV. 

This  haiS  added  fourteen  "Orders"  to 
'the  "  Method,"  and  has  involved  the  tabu- 
lation of  3,900  additional  specific  charac- 
terisations to  enable  the  identification  of 
the  more  important  organic  compounds  of 
these  Orders  when  encountered  in  practi- 
cal work. 

Vol.  I.  of  the  Method  provided  for  com- 
ipounds  of  carbon,  hydrogen  and  oxygon 
only;  Vol.  II.  covered  compounds  contain- 
ing nitrogen  as  well.  Vol.  III.  was  special, 
and  contained  descriptions  of  pre-war  com- 
mercial dyes.  Vol.  IV.  deals  with  the  re- 
maining classes  of  organic  compounds,  in- 
cluding halogen  and  sulphur  derivatives, 
alone  and  with  nitrogen  bodies. 

The  sub-divisions  are  here  extensive 
since  all  these  elements  are  able  to  form 
wide  series  of  Orders. 

The  rapid  multiplication  of  known  and 
applied  organic  substances  and  the  intro- 
duction of  better  methods  of  classification 
necessitates  careful  revision  from  time  to 
time,  and  it  is  anticipated  that  a  supple- 
mentary volume  will  appear*  at  an  early 
date. 


Dyes  and  their  application  to  Textile 
Fabrics,  by  A.  J.  Hall,  B.Sc.  (Lond.), 
F.I.C.,  F'C.S.  Pp.  118.  London:  Sir 
Isaac  Pitman  &  Sons,  Ltd.  1922.  3s. 
net. 

The  subject  of  this  little  monograph  has 


received  the  attention  of  numerous  writers 
during  the  past  few  years,  but  it  is  ques- 
tionable whether  the  non-technical  reader 
can  obtain  satisfaction  from  the  extensive 
literature  which  already  exists.  The  author 
has,  therefore,  made  an  attempt  to  interest 
general  readers  in  this  important  industry, 
and  we  think  he  has  succeeded.  He  has 
certainly  written  an  excellent  little  book, 
in  which  he  gives  a  delightful  bird's-eye 
view  of  the  whole  of  the  industry  devoted 
to  the  manufacture  of  dyestuffs  and  their 
apphcation  to  various  textile  materials. 

The  first  chapter  gives  an  account  of  the 
development  of  the  dye  industry  as  it  is  to- 
day, and  shows  how  it  originated  in  the 
successful  manufacture  of  coal  gas  from  the 
work  of  William  Murdoch  at  the  com- 
mencement of  the  nineteenth  century.  It 
was  not  until  fifty  years  after  this  event 
that  Perkin  produced  the  first  synthetic 
dyestuff — Mauverne — by  the  use  of  the  de- 
rivatives of  products  obtained  from  the  tar 
productd  in  the  manufacture  of  coal  gas — a 
bye-product  previously  considered  as  prac- 
tically valueless  and  always  as  a  nuisance. 
Perkin's  discovery  had  the  immediate 
effect  of  directing  the  energy  of  chemists  in 
ths  direction,  so  that  to-day  we  have  about 
a  thousand  differently  constituted  dyestuffs 
which  are  capable  of  serving  the  dyes  in 
one  way  or  another. 

Chapters  two  and  three  are  devoted  to 
the  nature  of  dyestuffs  and  their  manufac- 
ture. To  illustrate  the  kind  of  operations 
which  go  on  inside  a  factory  manufactur- 
ing synthetic  dyestuffs,  the  manufacture  of 
methylene  blue  is  described.  At  the  con- 
clusion of  this  description  the-  author  draws 
the  attention  of  the  reader  to  the  fact  that, 
from  his  description  of  the  difficulties  which 
have  to  be  solved  before  a  single  dyestuff 
can  be  manufactured,  there  is  no  cause  for 
complaint  against  those  who  are  endeavour- 
ing to  establish  a  dye  industry  in  this  coun- 
try when  it  is  realised  that  over  a  thousand 
dyes  have  to  be  manufactured  before  dyers 
consider  that  they  have  an  adequate  range 
of  colours. 

Chapters  four  to  ten  are  devoted  to  a 
description  of  the  properties  of  the  various 
textile  fibres  and  the  treatments  to  which 
they  have  to  be  submitted  in  order  that 
they  may  acquire  the  pleasing  effects  which 
we  have  become  accustomed  to  expect  in 
the  present-day  manufactured  text'le 
fabrics. 

In  conclusion,  this  book  contains  numer- 


MARCH  9.  192&. 


THE  CHEMICAL  NEWS. 


159 


OU8  excellent  illustrations  of  the  type  of 
plant  used  in  the  industry.  It  is  also  pr(»- 
vided  with  an  index 


The  "Rapid"  Decimal  Calculator  and 
Universal  Reckoner,  by  J.  Gall  Inglis, 
F.R.S.E.  London:  Gall  &  Inglis,  31, 
Henrietta  St.,  W.C.2.  1923.  Is.  6d.  net. 

Since  a  system  of  decimal  cmnage  does 
not  yet  exist,  it  may  be  thought  rather 
premature  to  publish  a  Rapid  Decimal  Cal- 
culator. But  the  publishers  seem  to  view 
the  matter  with  equanimity,  and  iplunge 
into  issuing  a  book  of  80,000  calculationfl. 

A  glance  at  the  leaflet  accompanying  the 
book  indicates  that  it  is  neither  more  nor 
less  than  a  gigantic  multiplication  table, 
with  every  unit  up  to  100  times  160;  and 
the  largest  figure  504  times  1,06(X  The 
publishers  also  point  out  that  fweign 
money  exchanges,  percentages,  and  even 
petrol  consumption  in  miles  iper  gallon  can 
be  easily  found ;  while  the  multiplication 
table  in  itself  will  save  calcula€ing  in 
square  or  cubic  measures.  This  is  the  77th 
reckoner  issued  by  this  firm. 


Cements  and  Artificial  Stones,  by  the 
late  John  Watson,  Hon.  ^LA.,  F.G.S. 
Edited  by  R.  H.  Ra  stall,  Sc.D.. 
M.Inst.M.M.  Pp.  XII.  +  181.  Cam- 
bridge, W.  Heffer  &  Sons,  Ltd.  1922. 
6s.  net. 

The  MSS.  dealing  with  the  specimens  in 
the  Sedgwick  Museum,  Cambridge,  illus- 
trating the  economic  geology  of  building 
materials,  left  by  the  late  Mr.  Watson, 
have  now  been  published  imder  the  above 
title. 

The  volume  is,  however,  more  than  a 
museum  catalogue,  but  is  not  a  textbook, 
since  the  author  does  not  go  deeply  into 
the  chemistry  and  physics  of  cement- 
making. 

The  historical  develoipment  of  this  pro- 
cess is  most  interesting,  and  valuable  in- 
formation has  been  included  by  this 
method  of  treatment. 

In  the  descriptive  sections,  specimens  to 


illustrate  the  raw  materials,  intermediate 
substances  and  finished  cements  and  arti- 
ficial stone.  The  specimens  in  the  collec- 
tion represent  exclusively  cements  made  in 
the  British  Isles.  Acknowledgment  is 
m£uie  to  those  firms  who  have  contributed 
to  the  collection. 

It  is  noticeable  that  most  attention  is 
now  given  to  Portland  cements,  which  are 
here  described  in  greater  detail.  Others, 
including  Roman  and  Sirapite  cements, 
and  Plaster  of  Paris,  9te  also  briefly  de- 
scribed. 

The  bibliography  at  th<'  (iiij.  aiid  index, 
leave  little  to  be  desired. 

The  book  certainly  deserves  the  attention 
of  economic  Geologists,  Architects,  Chemi- 
cal and  other  Engineers,  and  others  con- 
cerned with  the  manufacture  and  uses  of 
cement. 


H.M.  Department  of  Scientific  and 
Industrial  Research  has  just  issued  a 
Second  Report  u,pon  investigations  con- 
duck'd  at  the  British  Museum,  entitled 
The  Cleaning  and  Restoration  of  yfnseum 
Exhibits.     Price  2s. 

The  continuation  of  Dr.  Scott's  re- 
searches has  shown  the  urgent  need  for  in- 
vestigations of  this  kind.  It  is  stated  that 
the  first  report,  issued  in  1921,  has  led  to 
numerous  enquiries  and  requests  for  advice 
from  museums,  collectors,  and  iven  inter- 
ested Continental  firms.  The  latter,  of 
course,  fall  outside  the  9rr'p<>  of  theso  m- 
quiries. 

Especial  importance  will  now  be  .at- 
tached to  these  investigations  in  view  of 
the  recent  discoveries  in  the  tomb  of  King 
Tutankhamen. 

It  is  a  serious  duty  to  succeeding  genera- 
tions to  take  adequate  steps  to  preserve  all 
collections  of  the  tangible  evidence  of  past 
phases  in  the  life  of  mankind,  and  the  ap- 
pearance of  this  report  should  be  widely 
welcomed. 

The  methods  and  reagents  described 
must  necessarily  be  used  with  care  and 
discretion.  Variations  should  only  be  in- 
troduced    by     experts     possessing     sound 


160 


THE  CHEMICAL  NEWS. 


MARCH  0,   1923. 


scientific  knowledge,  and  only  after  prior 
experiments  have  been  made  upon  value- 
less objects. 

Bulletin  No.  8  (January,  1923)  of  the 
Bureau  of  Bio-Technology,  has  just  been 
issiued  by  Messrs.  Murphy  &  Son,  Ltd., 
thus  comipleting  the  first  volume,  in  which 
a  number  of  practical  contributions  to  tech- 
nical biological  science  have  appeared. 

The  first  number  of  Vol.  II.  will  appear 
in  March,  and  will  contain  articles  on  the 
destruction  of  timber  in  mills,  breweries, 
and  other  buildings,  and  its  prevention; 
the  suppression  of  insect  pests  and  fungus 
diseases  in  relation  to  agriculture,  malt- 
ing, &c.,  micro-organisms  in  leather  indus- 
tries; and  other  matters  of  industrial  im- 
portance. 


BOOKS  RECEIVED. 

Vat  Colours,  by  Jocelyn  Field  Thorpe, 
C.B.E.,  D.Sc,  &c.,  and  Christopher 
Kelk  Ingold,  D.Sc.  Pp.  XV.  +  491.  1923. 
Messrs.  Longmans,  Green  &  Co.,  39,  Pater- 
noster Row,   E.C.4.     16s.  net. 


The  Rapid  Decimal  Calculator  and  Uni- 
versal Reckoner,  by  J.  Gall  Inglts, 
F.R.S.E.  1923.  Messrs.  Gall  and  Inglis, 
20,  Bernard  Terrace,  Edinburgh.  Is.  6d. 
net. 


This  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 


Latest   Patent   Applications. 

3348— Coley,   H.   E.— Manufacture     of     iron     from 
iron  oree.    Feb.  5. 


3727— Jackson,  W.  J.— Treatment  of  copper  ores. 
Feb.   7. 

3538 — Koppers  Co.  —  Treatment  of  ammonia- 
charged  gas.    Feb.  6. 

3488 — Plauson  Parent  Co. — Manufacture  of  emul- 
sions of  oleic  acid,  etc.    Feb.  6. 

3697— Soc.  Chimique  de  la  Grande-Paroisse.- Pro- 
duction of  a  nitrogen-hydrogen  mixture  for 
synthetic   manufacture  of   ammonia.  Feb.   7. 

3476— Sundstrom,  C. — Manufacture  of  a  sodium 
compound.    Feb.  6. 


Specifications   Published   this   Week. 

192106— Marks,  E.  C.  R.  (Hoever  Co.).— Process 
of  recovering  aluminium  chloride  used  in 
the  conversion  of  high  boiling  point  hy- 
drocarbons into  loAv  boiling  point  hydro- 
carbons. 

192298— Boehringer  Sohn,  C.  H.— Process  for  the 
preparation  of   papaverine   nitrite. 

192385— Pocock,  L.   D.— Fertilisers. 

181719— Dessmond,  A.,  and  Another. — Process  for 
making  Prussian  blue  starting  from  coal 
gas. 


Abstract  Published  this  Week. 

190286 — Barbituric    acid      comiwunds. — Jones,     H., 
of  285,  High  Holborn,   London. 

The  water-soluble  calcium  and  magnesium  salts 
of  C-C-diethyl  and  C-C-phenylethylbarbituric 
acids  are  obtained  by  digesting  a  hot  saturated 
solution  of  tlie  acid  with  the  theoretical  quan- 
tity of  freshly  precipitated  magnesium  carbon- 
ate, which  has  not  yet  assumed  the  crystalline 
state,  or  of  calcium  or  magnesium  hydroxide, 
filtering  the  solution  obtained  and  concentrating 
and  drying  in  vacuo  at  as  low  a  temperature  as 
possible.  An  example  shows  the  treatment  with 
fr;^shly  precipitated  magnesium  hydroxide.  It  is 
po-t  free  for  the  official  price  of  Is.  each, 
stated  that  the  salts  thus  obtained  are  easily 
absorbable,  and  give  permanent  mixtures  witji 
the  earth-alkali  salts  of  acetylsalicylic  acfd. 


Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  piiblished  Si>ecifications.  and  forward  oti 
en  post  free  for  the  official  price  of  Is.  each 


SITUATION    WANTED. 


4 


ANALYTICAL  CHEMISTS  (metallurgi- 
cal preferred). — Gentleman  with  uni- 
versity training,  desirous  of  experience  and 
specialising,  is  willing  to  give  his  services 
as  Junior  Assistant  Chemist  for  nominal 
consideration.  Midlands  preferred. — Ad- 
dress, A.  L.  Hues,  1,  Castle  Lane, 
Warwick. 


MARCH  16,  1923. 


THE   CHEMICAL   NEWS. 


161 


THE  CHEMICAL  NEWS, 

VOL.  CXXVL      No.  3283. 


THE    PROBLEM    OF    SUBSTITUTION 

IN    THE    BENZENE    NUCLEUS    AND 

THE    THOMSON-LEWIS-LANOMUIR 

THEORY    OF    CO- VALENCE. 

By  Ronald  Fbaser  and  James  Ernest 
Humphries. 

The  work  of  the  organic  chemists  who  ' 
have  directed  their  atUntion  to  the  prob- 
lem of  substitution  in  the  benzene  nucleus 
falls  naturally  under  two  heads:  8f)ecula- 
tion  on  the  mechanism  of  substitution  and 
the  study  of  the  directive  influence  of  sub- 
stituents  already  present  in  the  nucleus. 
The  present  paper  deals  only  with  the 
second  part  of  the  problem,  though  it  is 
realised  that  the  two  are  probably  inter- 
dependent, and  the  pofisihle  effect  of  addi- 
tion preceding  substitution  has  been  kept 
constantly  in  view. 

Modem  theories,  as  exemplified  by  the 
ideas  of  Lapworth,  Fry,  Vorlander,  Prins, 
anfl  Flurscheim,*  agret'  in  regarding  orien- 
tation as  occasioned  by  a  differentiated 
condition — polarity  or  state  of  strain — of 
alternate  carbon  atoms.  These  theories 
inevitably  hear  among  themselves  a  certain 
formal  analogy,  and  the  ideas  here  de- 
veloped are  no  exception.  They  agree 
more  particularly  with  those  of  Lapworth 
and  Fry  in  possessing  an  electrical  basis. 
Nothing  is  postulated,  however,  as  to  the 
constitution  of  the  beny-<'ne  nucleus,  ex- 
cept that  it  is,  of  course,  regarded  as  a 
six-memhercd  ring;  and  we  consider  that 
the  state  of  the  molecule  after  the  entry  of 
a  substituent  and  resulting  from  its  pre- 
sence is  the  important  factor  in  orienta- 
tion (c/..  Mills,  .7.  Soc.  Chem.  Ind.,  1021, 
XL.,  417,  R.,  in  his  review  of  Fry's  mono- 
graph). 


*  The  folloiijing  references  may  be  given 
to  the  fiapern  of  thrnc  nuthorft:  Lapworth, 
Mew.  Man.  Phil.  .Soc.  1920.  LXIV.,  ii., 
1;  T.,  1022,  CXXI.,  410;  Fry,  The  Elec- 
tronic Conception  of  VaJcnce  and  the  Con- 
stitution of  Benzene,  1921;  Voridnder, 
Ber.,  1010,  LII.  (B),  268;  Prins.  Chem. 
WecUhlad,  1918,  XV.,  571;  b'liirscheim,  ./. 
pr.  Chem.,  1002,  LXVT.,  321;  ihul.,  100.",. 
LXXL.  497. 


We  have  taken  as  our  basis  the  Thom- 
son-I.iewis-Lan^iuir  theory  of  co- valence, 
and  on  this  foundation  have  built  uip  an 
ele<jtrMiic  int<^rpre.tation  of  Lapworth 's 
Principle  of  Induced  Alternate  Polarities, 
as  already  elaborated  by  Kermack  and 
Robinson  (T.,  1022,  CXXI.,  427).  We  are 
not  prepared  at  the  present  stage  to  differ- 
entiate between  the  relative  sizes  of  the 
octets  surrounding  positive  and  negative 
centres,  and  for  our  present  puripose  tiiis 
appears  to  be  of  secondary  importance. 
The  development  of  the  theory  is  based  on 
the  following  three  postulates.  In  order 
to  avoid  the  introduction  of  \mnecessary 
synonyms,  we  shall  adopt  in  the  sequel  the 
terminology  used  by  Kermack  and  Robin- 
son (loc.  cit.). 

Postulate  1 :  The  tendency  of  a  disin- 
tegrated octet  is  tow^ards  further  disrup- 
tion; and  of  a  nearly  comipleted  octet  to- 
wards completioo. 

Postulate  2 :  The  tendency  towards 
f>otet  stability  of  an  atom  with  nearly 
completed  octet  is  greater  than  the  ten- 
dency to  octet  instability  of  an  atom 
with   disruption  only   incipient. 

Postulate  3:  The  more  nearly  a  group 
approaches  octet  stability,  the  greater 
the  ease  of  replacement  at  that  point. 
It  will  be  observed  that  Postulate  2  is 
simjily  a  stat«'ment  in  terms  of  octets  of 
the  conclusion  arrived  at  by  Briggs  (7., 
1908.  XCIIL.  1564;  ibid..  1917,  CXI., 
258;  ibid.,  1910,  CXV..  278),  viz.,  that 
negative  fields  are  id  general  stronger  than 
positive  gelds.  Further,  the  relation  of 
the  carbon  at^m  to  Postulate  2  is  of  im- 
portance. It  is  generally  recognised  that 
carbon  is  unicjue  in  that  it  occupies  the 
middle  position  in  the  first  series  of  the 
periodic  system,  and  is  the  first  member  of 
its  group,  containing  the  fewest  number  of 
electrons.  It  follows,  then,  that  in  a  chain 
of  carbmi  atoms  of  alternately  positive  and 
negative  character,  the  positive  centres 
tend  to  incrcaaing  negative  character. 
Some  interesting  consequences  of  this  ele- 
ment's electrical  individuality  will  appear 
in  the  sequel. 

Postulate  3  requires  further  discussion. 
We  are  of  opinion  that  the  distinction  be- 
tween polar  and  non-polar  compounds  is 
merely  one  of  de^ee,  and  our  views  in  this 
re»peot  are  those  of  Briggs  (T.,  1021. 
CXIX.,  1879),  and  of  Kermack  and  Robin- 
son (loo.  cit).  The  extreme  case  of  octet 
stability  is  evinced  in  compounds  which 
have  come  to  be  known  as  polar,  where  an 


162 


THE    CHEMICAL    NEWS. 


MAECH  16,  1923. 


atom  surrounded  by  a  completed  octet  can 
actuiilly  exist  free  as  an  ion  {e.g.,  sodium 
chloride).  There  are  evidently  all  grada- 
tions of  octet  stability  from  such  extreme 
cases  to  those  of  typically  non-polar  com- 
pounds such  as  carbon  dioxide,,  where  octet 
sitability  is  apparently  only  possible  so 
long  as  there  is  electron-sharing  among  the 
octets.  It  is  practically  a  universal  rule 
that  the  reactivity  of  compounds,  as 
measm-ed  by  the  velocity  of  reaction,  is 
greater  in  the  case  of  ionised  than  of  non- 
ionised  bodies,  although  some  doubt  is 
thrown  on  the  complete  generality  of  this 
statement  by  the  work  of  Kahlenberg  (J. 
Phys.  Ghem.,  1902,  VI.,  1;  and  subse- 
quent papers.  Compare,  however,  Stieg- 
litz's  discussion  oi  Kahlenburg's  results, 
Qualitative  Chemical  Analysis,  Part  1., 
1912,  pp.  84-87).  Thus,  although  we  do 
not  anticipate  ionisation  as  a  cause  of  the 
reactivity  of  a  substituent  possessing  a 
stable  octet,  we  do,  as  a  result  of  the  con- 
sideration of  the  above  gradation  in  re- 
activity, regard  increasing  octet  stability 
as  parallel  with  increasing  likelihood  of 
lability. 

TSe  Brown  and  Gibson  Rule. 
Of  the  many  empirical  rules  which  have 
been  from  time  to  time  proposed  to  .sum- 
marise the  directive  influence  of  substitu- 
ents  on  an  entering  group,  undoubtedly  the 
best  known  is  that  of  Brown  and  Gibson 
(T.,  1892,  LXI.,  367).  It  was,  unfortunate 
that  Brown  and  Gibson  based  at  least  part 
of  their  rule  on  the  lack  of  knowledge  of 
certain  reactions  (c/.,  Hollemann,  Bull. 
8oc.  Chim.,  1911,  IV.,  series  9,  1-14). 
Brown  and  Gibson  based  their  rule  on  the 
oxidisability  or  otherwise  of  the  compound 
HX,  where  X  is  the  substituent,  whereas 
the  real  basis  of  the  rule  is  rather  the  ten- 
dency to  oxidation  or  reduction  of  the  sub- 
stituent itself.  On  the  electronic  theory  of 
oxidation  and  reduction,  oxidation  means 
loss  of  electrons,  reduction  gain  of  elec- 
trons. The  ortho-para  directive  substi- 
tuents  listed  by  Brown  and  Gibson  have  in 
each  case  the  atom  which  is  linked  to  the 
nucleus  in  a  state  approaching  octet  sta- 
bility, hence  loss  of  electrons  (i.e.,  oxida- 
tion) is  resisted  (Postulate  1);  while  in  the 
case  of  the  meta- directive  substituents, 
viz.,  NO2.  COOH,  SO3H,  COCH3,  the 
octets  of  N,  C,  S,  C,  are  in  a  state  of  in- 
cipient diisrutption    due  to  the  effect  of  the 

negative  (octet  stable)  O,    /.^  ,   O3,  OCH3 


respectively  (c/.,  Kermack  and  Robinson, 
loc.  cit.):  hence  loss  of  electrons  (i.e.,  oxi- 
dation) is  favoured  (Postulate  1).* 

In  short,  negative  (octet  stable)  substi- 
tuents direct  ortho-para;  positive  (octet  un- 
stable) substituents  7neta.\ 

From  the  above  argument  the  state  of 
polarity  of  the  carbon  atoms  in  a  mono- 
substituted  benzene  oo^mpound  containmg 
(1)  an  ortho-para  directive  substituent  X 
(Fig.  I.,  a),  and  (2)  a  meta  directive  sub- 
stituent Y  (Fig.  I.,  b)  readily  follows.     In 


*  CCI3  is  listed  by  Brown  and  Gibson 
among  the  ortho-para  directive  substitu- 
ents, by  Vorldnder  (loc.  cit.)  among  the 
meta-directive  substituents.  Spreckels 
(Ber.,  1919,  LIL,  B,  315)  has  obtained  the 
meta  nitra  compound  under  conditions 
which  preclude  hydrolysis.  This  is  in  com- 
plete agreement  with  the  octet  view,  for 
the  carbon  atom  in  CCI3,  being  attached  to 
thi^e  negative  (octet-stable)  chlorines,  is  a 
positive  centre,  and  hence  falls  into  the 
meta-directive  class.     Cf-,  also  below. 

It  is  convenient  to  note  here  the  meta- 
directive  nature  of  the  ammonium  salt 
group,  as  investigated  by  Vorldnder  and 
SiebeH  (Ber.,  1919,  LIL  [B] ,  233).  On 
nitratmg  C6H,N(CH3)3N03,  for  instance, 
the  meta  compound  is  obtained.  It  is  evi- 
dent that  the  condition  of  octet  stability  in 

+  -  +- 
CgH5N(CH3)3N03  is  as,  shown;  the  signs  + 
and  -  indicating  polarity  as  resulting  from 
octet  instability  and  octet  stability  respec- 
tively; the  N  atom,  attached  to  the  nucleus 
being  a  positive  centre,  the  whole  group 
would  be  expected  to  direct  meta. 

We  might  mxntion  here  that  some  of  the 
ortho-para  directive  substituents,  com- 
prised of  a  side  chain  (Vorldnder,  loc.  cit.), 
present  a  difficulty  inasmuch  as  the  in- 
duced pohuty  of  the  nucleus  woidd  appear 
to  differ  from  case  to  case,  as,  for  example, 
in  -CH^COOH,  -CH,  -CH^  -COOH,  -OH. 
CH'COOH,  all  these  groups,  however,  be- 
ing ortho-para  directive. 


MARCH  16,  1923. 


THE  CHEMICAL  NEWS. 


Fig    I     a,  the  octet  of  X  tends  to  comple- 
tion    hence  the  electrons    shared  with    C 
are  drawn  into  X,  making  C,  positive^    c' 
can  now  appropriate  electron^  shared  with 
the  unstable  system  C„  acquiring  negative 
polarity;  C,  assumes  positive  polaritv.  and 
so  on.      In  Fig.    I.,  b.     containing  Y  in   a 
Rtate  of  mcipiont  disruption,  the  polarit-'os 
are  obviously     as  shown     (cf.      Lanworth 
Mem.  Man.  Phil.  Hex-..,  1020,  TAIV     H    1  ' 
A  consideration  of  the  fijrures  will  sh.m" 
that  whatever    is  the  cause    of  ortho-para 
sub«t,tutK>n  m  Fg.  I.,  a.    will  cause  meta 
substitution  m  Fig.  I.,  b.     The  elucidation 
of  these  causes  involves  a  special  considr-r- 
ation  of  the  position  of  hvdrogen  with  re- 
gard   to   rKjtet    stability.    ^  We    regard  the 
condition  corresponding    to  octet    stability 
of  hydrogen  as  represented  by  the  nucleus 
with    no  electrons.*       On    this    view,    the 
hydrogen  atom  should   l>e   almost    entire! v 
lacking  m  a  tendency  to  acquire    an  elec- 
tron,    and   become   the  negative    hydrogen 
posttilated  by  Fry    {op,  rit.,  ,pp.  20127.     p. 
.)0).  Our  views  receive  strong  support  fiv>m 
the  arguments  of  Stieglitz  (,/.  Amer.  Chcm 
Soc,  1022,  XLIV.,  1293)  against  the  exist- 
ence of  negative  hydrogen  in  benzene  com- 
pounds. 

The    main    consideration     seems    to    be 
rather  tli,.   state    of  the    carbon    atom     to 
which  the  hydrogen  is  attached.     In  a  car- 
bon atom  of  negative  polaritv,  the  octet  is 
comparatively  firmly  held;    hence  the   hy- 
drogen attached    to  it  is  to    a  great  ext^-nt 
dc^prived  of  its  electron;  the  converse  hold- 
mg  with  a  carbon  atom  of  positive  polaritv 
Bearing   m   mind     the  unicjue     position  of 
f  Attention    nhmild  be    direcied  at    thifi 
point  to  the  use  of  the  tenrnt  positive    and 
negative  applied   to   the   (froups  mentioned, 
in  view  of  the  fact  that'  in  discussions  on 
orientation  the  terms  arc  used,     arhitrardij 
and  in  general,  with  the  opposite  meaning. 
This  has  already    been  n/)tirrd   by     Dairies 
(T.,  1922,  CXXT.,  footnote  to  p.  78G).  The 
same   writer   (T.,    1922,   CXXI.,    809)    dis- 
proves the    statement  made  by  one    of  us 
(Frascr,  T.,   1922.  CXXI.,     195)     that     the 
d'rertive     influence      of     substituents     was 
P'lrtlg    dependent    on   their   volume.        The 
statement  above  is  nmv  preferred. 

*  These  remarhs  bring  hydrogen  (and 
the  metals)  into  line  with  Postulate  2. 
which  iras  stated  in  such  a  form  as  to  make 
more  obvhus  its  application  to  the  com- 
mon organic  elements,  which  lie  to  the 
right  of  the  Periodic  Table. 
liydro^^on  with  regard  to  oclet  stability,  it 
is  evident  that  the  hydrogen  nuclei  at- 
tached to  negative  carbon  atoms  are  in   a 


163 


rX'^S)""    ^'''"  '^^^^    substitution     (Postu- 

artWn  '^  J^^^'^Je^t    (Fig.     I.)    that    the 
ortho-para  hydrogens  in  Fig.  I.,  a,  are  in  a 
condition   for   ready   substitution,    while   in 
(b)   it  IS   the   meta    hydrogens     which    are 
the  more  easily  replaced.     It  is  seen  that 
the  e.ssential    difference  between    the    two 
types   of  substitution   is  brought   out   with 
exceptional  clearness     on  this   view;     and 
lurther,     the  ortho-para  directive  influence 
ot    A    on    the    one    hand,    and    the    meta- 
direotive  influence  of  Y  on  the  other,  is  as 
It  should  be,  independent  of  the  nature  of 
the  entering  grou,p. 

.  The  special  reactivity  of  the  hydrogen 
in  the  para-position  to  an  ortho-para  direc- 
tive substituent  follows  immediately  from 
the  above  considerations,  inasmuch  as 
(tig.  I.,  a),  there  is  a  reinforcing  negative 
mfluenc<>  on  the  polarity  of  the  4-carbon 
atom. 

Entry  of  Positive  Groups. 
It  IS  well  known  that  most  of  the  radicles 
which    can    be    introduced    directly     (i  e 
without  the  action  of  catalysts),    into    the 
benzene   nucleus    are    positive    (octet    un- 
stable).     This  follows  at  once  from  the  pre- 
ceding considerations.     We  have  computed 
the    number    of    electrons    present    in    the 
typical    positive    radicles,    COOH,    SO  H 
and   NO,,     with   the  following  results:   '(1) 
COOH.  charge   +   1,    has  sixteen    electrons 
available  for  the  formation  of  octet^s ;  adopt- 
ing thi'     Hantzsch-Lapworth  structure     for 
carboxyl.  it  is  found  that  the  carbon  atom 
contains  only    six  electrons  in  the    sheath 

thus:  C    .-^yH.       If  the    group    replace    a 

hydrogen  nucleus,  the  carboxyl  carbon  can 
readily  complete  its  octet  by  sharing  with 
the  negative  (octet  .stable)  carbon  atom  in 
the  nucleus,  the  octet  of  this  atom  being 
left  cr>mplet«  by  the  removal  of  the  hvdro- 
gen  nucleus.  (2)  SO^H.  In  sulphonation 
H.,SO,  reacts  as  OH-  and  SO,H+ ;  on  this 
basis,  the  SO,H  radicle  contains  twenty- 
four  electrons  available  for  octet  formation. 


This  leads  to  the  stnicture  H:6:S 


q: 
•  o: 


in  which  the  suliphur  atom  contains  only 
SIX  electrons  in  the  sheath.  (3)  NO  In 
nitration.  HNO,  reacts  as  OH-  and^NO^; 
on  this  basis  the  number  of  electrons  in  the 
^Oj  radicle  available  for  octet  formation  is 

eighteen;  this  learls  to  the  structure  N  *'  ?' 
in  which  the  unstable  centre,  N.  ncnm  nnn. 


tains  six  electroas  in  the  sheath.       Similar 
tains  SIX  «  n-         the    replacement    ot 

arguments    regaramg  r  ,^ 

hydrogen  apply  to  cases  (2)  and  (3)  as  nom 

:renr:b^letUe  th^-l  attainment  o, 

h:  "S^Tt  p^^i^^vrsSitnent 
and  hence  we  should 'not  expect  the  nega- 
Uve  c  a  "  to  be  so  readily  suscep  ible  to 
direct  int^-oduction  into  the  nucleus. 

T?t  Possible  that  we  have  here  an  under- 
WinV  ^ason  for    the  greater    stabU.ty     ot 
Smiounds  of  the  type  (b)    («^e  ^ig;^/ 
last  week's  issue)    than  those    of  type 
(Cf    Vorlander,  loc.  cit.). 

The  Hollemann  Series. 
The  relation  between  octet  stability  and 
directive  influence  can  now  be  discussed^ 
Comder  a  typical  case  of  a  di- substituted 
V^  o+!.rP  OH  XY  where  the  octet  stabil- 
denvative,  ^6^4"^^',  "  .1,  4.  ^^  v 
ity  of  X  is  greater  than  that  of  X. 


m 
^a) 


It  follows  from  the' relative  stabilities  of 
the  octets  of  X  and  Y  that  the  Pf  a-tie^^^^^ 
the  carbon  atoms  should  be  as  lUustratea 
in  F^R  iT  (a)  rather  than  that  sl^^wn  m 
11.  (b)".  Generalising,  it  can  be  stated  tl.a 
iie  relative  directive  power  of  ^tf^^l^^^] 

s^rt:^t;^u^-^?i^^ 

T  .  ^  /  i-up  f.r>TYimoner  substituents  tol- 
dencies  of  the  commonex 

Sncy  to'«tet  stability  ^-J'^t.^c*"  (rf 
the  'descending  ord^:  0>N>C  (^^ 
Brigt"S,  Phil.   Mat,..  1921,    "'..fV'^^^;  ?//, 

xro-  TTT  it  beins  remembered  that  tne 
^e^^d'^^tets  are  atta'ched  to  Positive  hydro- 
gen nuclei.  The  greater  volumes  f  ^1^  ^i, 
T  affree  with  their  comparatively  low  place 
in  tfe  series,  increase  in  electropositiveness 
'^th  increase  in  volume  being  a  well  estab- 


r  \.nA  tPndencY  which  is  readily  interpreted 

J^.^Xt'ln'^SUparr  d?;etu:e  sub- 
'?i^  Lc  meoede  the  meta  follows  trom 
pSulate  •^^      Considenng   the   rneta-d.rec- 

^d^atn'fr  m  tht  labile  carbon  ato,„  tban 
tZ  the  m«e  f-'Xr  aTcX-ed  wi^b 
l„ger  ™l"««^°*";?[P-"  high  position,  the 

will  now  be  con&idered. 


in  the  disub^tituted  ^"^l^^X^^Z 
sented  above,  X.^d^.j^.  y, 
ST\ri  »eta  dSL    (octet  unntable) 

't±- V  ^^V•  s'u%fshrw?tot) 

tipc;  of  the  carbon  atoms  is  as  shown  i  v  y 
rS    b),  according  a,s  the  -Av^e-e^of  X^^^^^^ 

X,  predominates^  there  willbe  an  equili- 
effects  are  opposed  tbere  J  ^^^  ^^  .^^. 
brium  between  the  two  eiei. 

dicated  above.  areater    con- 

The  electronjer    present  J  „rea^^^^.^^^ 

centration-a  factor  eviaem  y 
«l,n*t^th'  5    3tg-- 


i„e  and  brom,neoff"sa  J-  ^^■^^^^g 

Owing  to  ihc  *f  f  ^^;'  l°!,t  „/  acoironn 

'iZ:  Z\!::'nofiu^^^tea  U   amount 
for  it. 


MARCH  16,  1923. 


THE   CHEMICAL   NEWS. 


165 


the  final  products.  If  Xj  has  the  greater 
octet  stability,  further  substitution  will 
take  place  at  the  4  and  6  positions;  if  Xj, 
at  the  3  and  5  positions;  i.e.,  considered 
from  the  standpoint  of  Xj  alone,  ortho- 
para  if  Xj  is  negative  and  meta  if  Xj  is 
positive.  If  the  octet  stabilities  of  Xj  and 
Xj  are  widely  different,  one  electromer  may 
he  present  in  such  small  concentration  that 
its  resultant  will  not  be  capable  of  detec- 
tion in  the  final  products.  On  the  other 
hand,  if  the  octet  stabilities  of  X,  and  X, 
are  of  the  same  order,  the  number  of  pro- 
ducts will  be  greater.  The  two  possibilities 
may  be  illustrated  by  the  iodination  of 
o-toluidine  (Wheeler  and  Liddle,  Amcr. 
Chem.  J.,  1909,  XLII.,  501),  and  the  nitra- 
tion of  o-chlortoluene  (Wibaut,  Rec.  Trav. 
Chim.,  1913,  XXXII.,  244). 

Similar  reasoning  applies  to  disubstituted 
derivatives  of  the  type  CgH^  X,(,)  X,(  J 
Case  2,  Fig.  III.,  ii.  In  this  case  the  octet 
tendencies  of  X,  and  X^  reinforce  each 
other,  and  a  single  electromer  exists.  Sub- 
stitution would  be  exipected  to  occur  at  the 
4  and  6  positions,  which  is  in  agreement 
with  the  facts. 

Case  3.  This  is  similar  to  Case  1.  If 
the  octt't  instability  of  Y,  is  greater  than 
that  of  Yj,  electromer  (a)  will  predominate, 
and  if  conversely,  electromer  (b).  Further 
substitution  will  proceed  aco<M'dingly. 
The  type  C,H,  Y,(,)  Y,(,)  is  similar. 
Case  4.  A  single  electromer.  Further 
substitution  at  5. 

Case  5.  A  single  electromer.  The 
groups  X  and  Y  reinforce  each  other's 
natural  octet  tendency.  The  smooth  ni- 
tration of  the  nitrophenols  is  all  in  agree- 
ment with  this  statement.  The  type 
C.H,  X(,)  Y(J  falls  imder  this  case. 
Case  6.  Equilibrium  between  electro- 
mers  holds  in  this  case ;  reference  to  Postu- 
late 2  indicates  that  the  direction  of 
equilibrium  will  be  that  shown  (Fig.  III., 
vi.),  and  hence  ortho-para  directive  sub- 
stituents  will  exert  the  greater  influence  in 
orientation. 

The  Effect  of  Conditions. 

One  of  the  main  difficulties  to  the  form- 
ulation of  definite  rules  summarising  the 
facts  of  orientation  is  the  effect  of  condi- 
tions in  altering  the  relative  amounts  of 
the  final  products  of  a  reaction.  On  the 
octet  view,  this  means  that  the  equilibrium 
pictured  above  in  the  oleotromoric  cqu.T- 
tions,  or,  in  the  cases  where    a  single  elec- 


tromer exists,  the  relative  octet  stabilities 
of  the  substituents,  is  altered.  In  either 
instance,  this  would  indicate  that  the  effect 
of  conditions  is  largely  one  of  electron 
transference. 

^The  work  of  Biltz  (Z.  Elek.,  1911,  XVII., 
676)  has  shown  that  carbon  possesses  a 
very  high  characteristic  vibration  fre- 
quency; and,  as  stated  by  W.  C.  McC. 
Lewis  (System  of  Physical  Chemistry,  vol. 
III.,  62),  "  an  atom  possessing  high  fre- 
quency is  no  doubt  the  most  likely  type  of 
atom  to  allow  of  the  transference  of  elec- 
trons to  and  from  itself."  That  electron 
energy  increases  with  rise  of  temiperature 
has  been  indicated  by  Koenigsberger  (Z. 
Elch.,  1911,  XVII.,  289),  and  electron 
lability  must  also  be  affected  by  the  nature 
of  the  solvent  medium  (dielectric  constant, 
etc.).  It  is  along  these  lines  that  we  hope 
to  approach  the  problem  of  conditions. 

Replacements  and  Octet  Stability. 

The  term  "Replacement"  is  used  to  de- 
note the  exchange  of  one  substituent  for 
another;  "SubstitutiMi"  refers  to  the  ex- 
change of  hydrogen  for  an  entering  group. 
It  seems  to  us  that  no  essential  distinction 
can  l?e  drawn  between  the  two  processes; 
and  we  regard  substitution  merely  as  a 
special  case  of  reiplaoement.  No  rule  of  re- 
placement corresponding  to  a  rule  of  sub- 
stitution has,  so  far  as  we  can  find,  been 
formulated;  but  consideration  of  our  re- 
marks on  the  special  case  of  the  '*  octet 
stabilitv  "  of  hydrogen  appears  to  lead  to 
some  dc^ee  of  uniformity  in  this  respect. 
It  was  pointed  out  that  the  lability  of  hy- 
drogen was  conditioned  by  its  tendency  to 
give  U)p  its  electrons ;  whereas  octet  com- 
pletion is  the  determining  factor  in  the 
lability  of  all  other  elements  attached  to 
the  nucleus.  In  other  words,  a  labile  hy- 
drogen is  attached  to  a  negative  carbon 
atom,  while  a  labile  radicle  other  than 
hydrogen  is  attached  to  a  positive  carbon 

Thus,  any  rule  which  expresses  the  facts 
of  substitution  will  be  reversed  in  the  case 
of  replacement;  by  "reversed"  we  mean 
that  a  group  which  causes  substitution  in 
the  meta  position  will  favour  replacem.ent 
in  the  ortho-para  ipositions,  and  conversely. 
For  example,  the  nitro  group  causes  substi- 
tution in  the  meta  position ;  but  in 
the  hydrolysis  of  the  nitrani  lines,  re- 
placement of  NHj,  by  OH  occurs 
at  the  ortho-para  positions  to  the 
nitro  group,  and  not  at  the  meta 
iposition.       R^'asoning  on  the  same  lines  as 


166 


THE    CHEMICAL    NEWS. 


MARCH  16,  1923. 


those  employed  in  the  discussion  of  substi- 
tution, it  will  be  seen    (Fig.  IV.,  a  and  b). 


that  the  octet  stability  of  NHj  is  reinforced 
by  the  polarity  effects  of  the  nitro  group  : 
whereas  in  Fig.  IV.  (c),  the  polar  tenden- 
cies of  NHg  and  NOj  are  opposed,  and  the 
lability  of  NH2  consequently  diminished. f 
We  have  found  the  above  rule  (which  is,  of 
course,  the  obverse  of  the  Brown  and  Gib- 
son rule)  to  be  of  general  application  to  the 
simpler  cases. 

Another  interesting  rule  follows  from  the 
unique  electrical  character  of  the  carbon 
atom  discussed  above,  if  we  enquire 
how  the  tendency  there  mentioned  to- 
wards increasing  differentiation  of 
polarity        in        a       chain        of        carbon 

*  A  ringed  group,  thus  vjy  >  is  used  here 
to  demote  lability  following  on  octet  stabil- 
ity. 

t  Reference  to  Case  VI.  shows  that  m- 
nitraniline  exists  as  two  electromers,  the 
NH,  group  exerting  the  greater  directive  in- 
fluence. It  would  appear  that  the  lability 
of  a  group  is  more  easily  influenced  by  one 
of  opposite  polar  tendency  than  is  its  direc- 
tive influence;  and  this  is  in  general  agree- 
ment with  our  views  on  reactivity.  In  this 
connection  it  should  be  noted  that  the  NH, 
group  in  aniline  itself,  while  exerting  full 
directive  power,  requires,  the  reinforcement 
of  ortho  or  para  nitro  groups  to  render  it 
labile  in  hydrolysis;  and  m,any  other  simi- 
lar instances  could  be  cited. 


atoms  can  be  satisfied.  §  The  inductive 
effect  of  a  substituent  on  the  carbon  atoms 
of  the  nucleus  is  greater  the  greater  its  octet 
stability  (c/.  discussion  of  the  Hollemann 
Series);  hence  the  differentiation  of  pohur- 
ity  of  the  carbon  atoms  will  be  increased 
by  the  replacement  of  the  given  substituent 
by  a  group  of  greater  octet  stability.  The 
rule  may  therefore  be  stated  thus;  in  re- 
placements, the  entering  group  is  one  of 
greater  octet  stability  than  the  group  re- 
placed. The  hydrolysis  of  the  nitranilines 
is  a  case  in  point,  and  many  others  have 
been  examined,  and  the  rule  found  to  hold.'^ 

A  striking  example  of  the  application  of 
the  rule  is  seen  in  the  recent  work  of 
Swarts  [Bull.  Acad.  roy.  Bclg.,  1920,  389) 
on  the  nature  of  the  CFg  group.  CF3  is,  as 
one  would  expect,  meta  directive. 
Unlike  CeHsCClg,  CeHsCFg  can  be 
nitrated  under  ordinary  conditions  withoiit 
hydrolysis  of  the  CF3  group.  This  is  pre- 
be  looked  for,  replacement  of  F  by  OH  is, 
according  to  the  rule,  difficult  or  impossible. 

Hitherto  the  application  of  the  rule  has 
been  confined  to  the  entry  of  groups  of  an 
essentially  electronegative  character;  but 
wo  have  found  that  the  important  class  of 
reduction  reactions,  where  a  groaip  is  re- 
placed by  hydrogen,  falls  equally  under  the 
rule.     In  a  recent    series  of  papers,     Mao- 


§  Thf  rules  of  Michael  and  Markoivni- 
Icoff  may  be  :i  consequence  of  this  property 
of  a  chain  of  carbon  atoms,  the  inductive 
effects  being  more  pronounced  ivhen  the 
chain  is  unsaturated  (Kermack  and  Robin- 
son, loc.  cit.,  pp.  430-432).  In  the  ex- 
amples CH.,CH:COOH  +  HBr  =  BrCH^. 
CH^.COOH;  and  CHj.CBriCH^  +  HBr  = 
CH3.CBr2.CH3,  the  reaction  has  taken 
place  which  increases  the  polarity  (positive 
or  negative)  of  the  carbon  atoms. 

*  An  apparent  exception  to  the  rule  is  the 
action  of  rCl,  on  phenols,  where  OH  is  re- 
placed by  CI.  The  chlorines  in  PClg,  how- 
ever, may  be  in  an  exceptional  state  of  octet 
stability  (cf.  Thomson,  Phil.  Mag.,  1921, 
[vi.],  XLI.,  521).  It  is  in  agreement  with 
the  deductions  on  p.  16  that  the  reaction 
takes  place  more  readily  with  p-nitrophenol 
than  with  phenol  itself. 
cisely  what  we  should  expect  on  the  octet 
view.  It  was  pointed  out  (see  last  week's 
issue)  that  fluorine  was  in  all  probability 
more  octet  stable  than  any  other  atom  or 
group ;  therefore,  while  the  replacement  of 
CI  by  the  more  octet  stable  OH  group  is  to 


MARCH  16,  1923. 


THE  CHEMICAL  NEWS. 


167 


beth  and  his  co-workers  (Henderson,  and 
Macbeth,  T.,  1922,  CXXI.  892;  Hirst  and 
Macbeth,  ibid.,  p.  904;  Macbeth,  ibid.,  p. 
1116)  have  pointed  out  that,  different  as 
are  the  structures  of  compounds  with  halo- 
gens labile  towards  reducing  agents,  they 
have  in  common  the  possession  of  halogen 
with  a  strong  induced  positive  polarity — 
that  is,  on  our  view,  octet  unstable.  The 
octet  instability  in  the  cases  cited  by  these 
authors  appears  to  be  unusually  4)ro- 
nounced,  and  hence  their  ready  replace- 
ment by  negative  (octet  stable)  groups  is 
not  to  be  expected.  Their  replacement  l.y 
hydrogen,  however,  which  tends  to  become 
electropositive  and  "octet  stable"  at  thp 
same  time  (vide  supra),  is  in  agreement 
with  the  rule  and  with  its  underlying  foun- 
dation, viz.,  the  tendemy  towards  increas- 
ing differentiation  of  polarity  of  the  carbon 
atoms.     The  replacement  of  the  halogen  by 

It  is  important  to  note  here  the  finding 
of  Burton  and  Kenner  (T.,  1922,  CXXI.. 
675),  that  in  the  removal  of  halogen  in  the 
reduction  of  halogenated  nitro-com pounds, 
the  reduction  of  the  nitro  groups  to  amino 
groups  in  all  probability  pn'cedes  the  re- 
moval of  the  halogen  (cf.  the  examp!e*< 
cited  by  Burton  and  Kenner,  loc.  cii.,  and 
the  papers  of  Macbeth  and  his  co-workers- 
mentioned  above).  The  present  theory 
would  predict  that  such  is  the  course  of 
these  reactions. 

Effect  of  Groups  on  Each  Others 
Reactivity. 

We  can  now  refer  more  particularly  to 
the  loosening  or  tightening  offecte  on  suh- 
stituents  caused  by  other  groups  present  in 
the  nucleus,  as  has  been  referred  to  already 
in  the  simpler  cases  (Fig.  IV.).  Among  the 
numerous  examples  examined,  may  be 
cited  the  following:  the  loosening  effect  of 
meta  directive  grou})s  on  substituents  in 
the  orthopara  positions  (Schopf  and  his 
collaborators,  Ber.,  1880,  XXII.,  900.  ei 
seq.;  Kenner,  loc.  cit.);  the  loosening  of 
ortho-ipara  directive  groups  on  substituents 
in  the  meta  position  (Kenner  and  Parkin. 
T.,  1920,  CXVII.,  855;  Hollemann  and 
metals  in  this  class  of  compound  (Hender- 
son and  Macbeth,  loc.  cii.  p.  896)  is  a  simi- 
lar example  of  the  rule.* 


*  The  activity  or  inert nesH  of  halogen  in 
thr  compounds  cited  by  Kenner  (T.,  1914, 
CV..  2710)  and  explained  by  him  on 
FliirHchcini's  formulation,  can  be  equally 
well  interpreted ,  along  the  above  lines,  on 
our  views. 


Hollander,  Rec.  trav.  chim.,  1920, 
XXXIX.,  435;  Guia,  Gazzetta,  1921,  LI., 
i.,  307;  Burton  and  Kenner,  T.,  1922, 
CXXI.,  489);  the  tightening  effect  of  ortho- 
para directive  groups  on  bromine  in  the 
para  pociition  (Meyer,  Ber.,  1921,  LIV., 
[B] ,  2265).  An  examination  of  these  will 
show  that  our  views,  and  in  particular  Pos- 
tulate 3,  are  capable  of  predicting  the 
observed  facts. 

The  Directing  Group  in  Polysubstituted 
.  Compounds. 
In  a  large  number  of  cases  examined  by 
Robinson  (Perkiu  and  Robinson,  T.,  1914, 
CV.,  2379;  Jones  and  Robinson,  T.,  1917, 
CXI.,  906;  Gibson,  Simonsen,  and  Rau, 
T.,  1917,  CXI.,  73),  ft  is  found  that  when 
a  negative  group  is  in  the  wtho-para  posi- 
tion to  a  positive  group,  they  neutralise 
each  other,  and  the  orientating  effect  is  ex- 
ercised by  the  second  positive  grouip.  The 
wOTk  of  Davies  on  the  cumulative  effect  of 
the  chlorine  atom  and  the  methyl  and  sul- 
phonyl chloride  groups  on  substitution 
(Davies,  T..  1921,  CXIX.,  858-876;  ibid., 
1922.  CXXI.,  785)  affords  interesting  ex- 
amples of  the  applicability  and  otherwise 
of  the  Robinson  rule. 

In  attempting  to  determine  the  position 
taken  up  by  a  fourth  substitucnt  in  a  tri- 
substituted  derivative,  two  main  considera- 
tiMiR  are  of  importance,  viz.,  the  relative 
octet  stabilities  of  substituents  already  pre- 
sent, and  the  persistence  of  their  inductive 
effects  through  a  chain  of  carbon  atoms. 


Vc/ 


^2 


Percentage    yield     of    corresponding     nitro 
compounds    (substitution    at    asterisk). 
The  substances  on  which  Davies  worked 


168 


THE    CHEMICAL   NEWS. 


MAECH  16,  1923. 


(Fig.  V.)  contain  in  each  case  CHg  and  CI 
in  the  ortho  relation,  the  SOgCl  occuipjing 
various  positions  relative  to  them.  The 
octet  stability  of  CI  being  greater  than  that 
of  CHg,  the  predominating  polar  state  of 
the  molecule,  in  the  absence  of  the  SOgCl 
group  would  be  as  indicated  in  Fig.  V.,  ia, 
iia,  iiia.  Consider  now  the  question  of  the 
persistence  of  induction.  In  Fig.  5  i.,  the 
inductive  tendency  of  CI  in  reversing  the 
natural  polarity  of  SOjCl  is  greater  than 
that  of  CHg,  which  has  the  opposite  ten- 
dency, owing  to  the  difference  in  the  num- 
ber of  carbon  atoms  through  which  induc- 
tion has  to  be  effected.  On  the  other  hand, 
in  Fig.  5  ii.,  the  greater  inductive  power  of 
CI  as  compared  with  CHg  is  balanced  by 
the  weakening  effect  of  the  carbon  atoms 
intervening  between  CI  and  SO2CI.*  In 
Fig.  5  iii.,  the  SOjCl  and  CI  have  the  same 
polar  effects  on  the  nuclear  atoms.  The 
electromerio  equilibria  in  the  three  cases 
will  therefore  be  as  shown  in  that  figure, 
and  the  yields  of  the  nitration  products  are 
in  agreement.  Thus  it  will  be  seen  that 
the  present  theory  is  borne  out  by  the 
above  experiments;  whereas  the  Robinson 
rule  fails  in  the  third  example  (v.,  Davies, 
T.,  1922,  CXXL,  786;  but  ccn\i)are  foot- 
note to  same  page). 

The  results  of  Gibson,  Simonsen,  and 
Rau  (T.,  1917.  CXI.,  69)  on  the  nitration 
of  2-acetylamino-3-4-dimethoxy  benzoic 

acid  and  of  3-acetylamino-veratrole,  and  of 
Simonsen  and  Rau  (T.,  1917  CXI..  220)  on 
the  nitration  of  isomeric  acetylamino  meth- 
oxybenzoic  acids,  are  difficult  of  interpreta- 
tion on  the  octet  view,  partly  owing  to  the 
large  number  of  substituents,  and  hence 
the  difficulty  of  determining  their  mutual 
interdeipendence ;  and  partly  to  the  diffi- 
culty at  the  present  stage  of  dogmatising 
with  regard  to  the  relative  octet  stabilities 
of  NHAc  and  OMe. 

In  the  above,  we  have  attempted,  on  the 
basis  of  the  Thomson-Lewis-Langmuir 
theory    of    00- valence,    to  connect    various 


*  Morgan  and  Jones  (T.,  1921,  CXIX., 
187)  on  nitrating  2-chloro  6-nitrot&luene , 
obtained  90  per  cent,  of  the  compound  cor- 
responding to  iia  above,  and  5-10  per  cent, 
of  iib.  Reference  to  remarks  on  the  order 
of  the  meta  directive  substituents  indicates 
that  electromer  (7)  can  exist  in  greater  con- 
centration when  an  NO2  group  is  in  place 
of  SO2CI. 


theories  and  rules  which  at  first  sight  may 
seem  wide  apart;  to  give  as  consistent  a 
basis  as  we  could  to  certain  observed  regu- 
larities; and  further,  to  formulate  general- 
isations which  may  be  of  use  in  classifying, 
and  perhaps  in  predicting  the  course  of, 
substitution  reactions. 

Chemistry  Department, 

University  of  Aberdeen. 


GENERAL   MEETING   OF  THE  CO- 
OPERATORS  IN  THE  BRITISH 
CHEMICAL  STANDARD  S ' 
MOVEMENT. 

(Standard  Analysed  Samples  of  Iron, 
Steel,  Etc.) 

On  February  9,  at  York,  a  "  Report  on 
the  Second  Three  Years'  Working  "  (end- 
ing Sept.  30th,  1922)  was  read,  and  de- 
tails of  the  work  during  this  period  were 
given.  A  fist  was  given  of  53  analysts  who 
had  taken  part  in  the  standardisation, 
and  20  firms,  who  had  provided  material. 
Ten  new  samples  comprising  46  actual 
standards  were  described.  Reference  was 
made  to  the  outstanding  events  since  the 
commencement,  and  a  chronological  fist  of 
standards — including  the  total  weights 
standardised — was  shown;  and  copies  of 
the  32  certificates  issued  (from  the  earliest 
onwards).  British,  French,  and  Itafian 
price  lists,  and  diagrams  illustrating  tfie 
preparation  of  the  standards,  were  ex- 
hibited. The  extreme  precautions  taken 
to  ensure  perfect  homogeneity  were  ae- 
scribed.  No  allegation  as  to,  or  eviden;e 
of,  lack  of  homogeneity  of  the  standards 
was  elicited.  In  view  of  their  wide  adop- 
tion, every  means  was  used  to  meet  even 
theoretical  difficulties,  to  warrant  the  con- 
fidence of  users.' 

A  sample  of  shavings  of  the  latest  stan- 
dard, "C,"  was  shown,  illustrating  their 
extreme  thinness  and  suitability  for  direct 
combustion  carbon  determination.  A  sin- 
gle portion  of  usual  weigit  averaged  1,700 
pieces  with  90  sq.  ins.  superficial  area. 

Within  six  years  the  movement  had 
steadily  developed  and  become  consoli- 
dated, maintaining  its  progress,  in  sipite  of 
the  many  adverse  conditions  of  recent 
years.  Commencing  with  a  few  co-opera- 
tors in  a  few  localities,  their  number  and 
range    of    interests    had    multiplied    many 


MARCH  16,  1923. 


TBS   CHEMICAL   NEWS. 


169 


times,  and  now  included  members  from 
several  countries,  some  15  to  20  co-opera- 
Ws  taking  part  in  each  standardisation. 
The  23  samples  produced,  comprising  83 
standardised  results,  had  covered  practic- 
ally the  whole  range  of  plain  carbon  stcc-ls 
in  regular  use,  and  included  four  alloy 
steels  as  well  as  two  cast  irons  and  a  basic 
elag.  The  weight  per  standard  had  risen 
to  twenty  or  twenty-five  times,  and  the 
available  duration,  permanency,  and  value 
for  reference,  had  increased  proportion- 
ately; yet  the  quality,  homogeneity,  and 
fine  state  of  turnings,  etc.,  had  not  merely 
been  maintained,  but  improved.  Many 
large  works'  laboratories  used  these  stan- 
dards, and  their  use  had  so  spread  that 
sole  agents  had  been  appointed  in  Italy 
and  France.  The  450  British  and  foreign 
users  included  10  Government  Depart- 
ments, 30  universities  and  technical 
schools,   and  5  railways. 

This  progress  had  fully  justified  the 
policy  adopted;  the  organisers,  whilst  hav- 
ing had  the  advice  and  general  guidance  of 
the  oo-operators,  had  also  freedom  of 
action  in  detail. 

The  organisation  was  not  restricted  to 
any  one  society  or  industry,  and  was  not 
dependent  on  the  same  group  for  standards 
for  which  it  might  not  be  fitted.  For 
each  type,  oo-operators  recognised  as  ex- 
perienced specialists  in  that  class  of  analy- 
sis were  selected. 

Their  work  had  demonstrated  that  in 
analysis  divergencies  occurred  to  an  un- 
realiHcd  degree  on  every  sample  tested, 
even  under  the  most  favourable  conditions 
of  homogeneity   and  careful  working. 

Jointly  standardised  samples  were  n 
necessity  to  reveal  these  divergencies  and 
clear  them  up. 

The  rapid  devclopmcnf  of  their  move- 
ment and  consequent  creation  of  such  stan- 
dardised samples  for  certain  types  of 
material  was  the  surest  nay  to  analytical 
co-ordination — which  desideratum  not  only 
vitally  affected  the  value  and  status  of 
chemists,  but  gave  the  maker  a  depnite 
gauge  by  which  to  attune  his  manufacture, 
secure  for  the  engineer  or  user  closer  adher- 
ence to  specification,  and  save  m^ny  delays 
in  delivery,  and  disputes  which  now  oc- 
curred. 

Their  organisation  provided  practwil 
working  machinery  for  the  production  and 
distribution  of  standards,  and  they  wre 
justified  in  believing  that  the  same  methods 
used  for  iron  and  steel  standards  could  be 


applied     with     equal     efficiency     to     other 
materials. 

A  thorough  and  interesting  discussion 
followed. 

A  series  of  iron  and  steel  standards  now 
existed,  which  covered  the  needs  of  en- 
gineers, users,  and  makers  fairly  com- 
pletely, and  it  was  now  for  these  to  make 
full  use  of  them,  so  that  the  movement's 
objects  could  be  achieved.  Co-operators 
had  offered  to  arrange  meetings  to  expi.iin 
the  objects  of  the  movement  and  uses  of 
the  standards.  Anyone  interested  could 
be  invited. 

Resolutions  were  passed :  (1)  Approving 
of  the  general  conduct  of  affairs  by  the 
organisers  and  adopting  their  report;  (2) 
thanking  the  Committee  for  their  assist- 
ance in  the  past  and  reappointing  them 
with  two  others,  to  act  in  all  matters 
where  it  might  not  be  considered  necessary 
to  consult  the  whole  body. 

(Q)  "  That  we,  as  co-operators  in  the 
Bntish  Chemical  Standards'  Movement, 
recommend  that  the  fullest  use  should  be 
made  of  standard  analysed  samples  of 
steel,  iron,  and  other  substances,  particu- 
larly in  the  following  ways:  — 

(j^l  By  engineers,  in  their  chemical 
specifications.  referring  regularly  to 
eome  specific  standard  sample  of  similar 
type,  and  requiring  that  in  cases  of  dis- 
pute, a  check  analysis  of  it  shall  be 
made  concurrently  by  the  reference 
chemist,  as  a  gauge  of  the  values  found. 
(b)  By  chemists  (a)  using  them  period- 
ically for  checking  and  co-ordinatinf, 
their  routine  tests,  and  (b)  invariably  as 
an  aid  to  settling  disputes,  (c)  stating  on 
their  reports  that  such  standards  have 
been  used." 

"  We  would  recommend  any  suitable 
standards,  prepared  on  a  sufficiently  tride 
basis,  for  acceptance  by  those  between 
ivhom  disputes  may  arise,  and  obtainable 
by  all  parties  (for  example) — so  far  asi  any 
or  all  of  them  conform  to  this — those  pre- 
pared bv  the  United  States  Bureau  of 
Standards,  those  prepared  jointly  by  the 
Iron  and  Steel  Institute  and  National 
Physical  TiJiboratory,  or  our  own  series  of 
British  Chemieal  Standards  which  are  al- 
ready in  use  in  about  450  laboratories  in 
Great  Britain,  the  Colonies,  and  other 
countries ; 

"  And  further,  we  recommend  that  a 
oop3'  of  this  resolution  be  .sent  to  engineer- 
ing and  chemical  societies,  and  that  they 
be  earnestly  requested  to  consider  the  im- 


170 


THE   CHEMICAL    NEWS. 


MARCH  16.  1923. 


portance  of  bringing  before  their  members 
the  scientific  and  practical  value  of  chemi- 
cal standards." 

The  fourth  resolution  bore  on  the  limits 
of  accuracy  of  analytical  methods. 

It  was  resolved,  in  view  of  the  import- 
ance of  figures  with  which  it  should  be 
coupled,  that  the  Committee  should  obtain 
supplementary  data  and  submit  this  with 
the  resolution  to  the  whole  body  of  co- 
operators  and  to  such  other  persons  as  they 
might  think  desirable. 

The  fifth  resolution  appointed  a  Com- 
mittee to  consider  the  question  of  forming 
on  a  financial  basis  a  more  formal  organi- 
sation, with  separate  official  headquarters, 
and  to  report  to  the  co-operators. 


GENERAL    NOTES. 


AUSTRIA'S  FOREIGN  TRADE  IN  1922. 

The  Commercial  Secretary  at  Vienna 
(Mr.  O.  S.  Phillpotts)  has  forwarded  a  re- 
port on  the  foreign  trade  of  Austria  for 
1922. 

In  1922  there  was  a  large  reduction  in 
the  value  of  the  imiports,  and  a  still  larger 
increase  in  that  of  the  exports.  Conse- 
quently, there  is  an  important  diminution 
in  the  excessive  adverse  balance  of  trade 
from  which  this  country  has  suffered  since 
the  war. 

Exports  of  wood,  magnesite,  and  manu- 
factured goods  generally,  showed  a  lai^ge 
increase.  The  value  amounted  to  900  mil- 
Hon  gold  crowns  (£35.4  millions),  or  86  per 
cent,  of  all  the  exports.  There  were  also 
important  increases  in  cotton  goods,  made 
up  clothing,  pafper  and  paper  goods,  rub- 
ber goods,  wooden  goods,  cement,  and  iron 
and  metal  goods.  The  export  of  machinery 
declined,  and  although  the  quantity  of 
leather  and  leather  goods  was  greater.  Of 
the  imports  into  Austria,  Germany  sent 
37.7  per  cent.,  Czecho- Slovakia  37.1  per 
cent.,  Hungary  6.3  per  cent.,  Poland  5.5 
per  cent.  No  other  country  sent  more  than 
2  per  cent.  The  share  of  the  United  King- 
dom was  only  0.6  per  cent.,  but  it  does  not 
send  to  Austria  much  of  the  bulky  and 
heavy  articles  such  as  fuel  and  foodstulTs. 
According  to  British  nfficial  statistics,  the 
value  of  the  produce  and  manufactures 
from  the  United  Kingdom  was  £1,308,288. 


This  is  considerably  less  than  the  figure  for 
1921,  £1,734,000,  but  is  much  larger  than 
the  British  imports  into  the  Succession 
States,  Czecho- Slovakia,  Hungary,  and 
Yugoslavia,  where  the  import  of  Britisli 
goods  declined  during  the  year  in  about  the 
same   proportion. 


CALCIUM  ARSENATE  AND  WHITE 
ARSENIC  FOR  THE  UNITED  STATES. 

The  Commercial  Counsellor  at  Washing- 
ton reports  that  certain  firms  in  Savannah 
are  desirous  of  receiving  quotations  from 
United  Kingdom  firms  for  the  supply  of 
calcium  arsenate  and  white   arsenic. 

The  names  and  addresses  of  the  firms  in 
question,  together  with  further  particu- 
lars on  the  subject,  may  be  obtained  by 
U.K.  firms  interested  upon  application  to 
the  Department  of  Overseas  Trade,  35, 
Old  Queen   Street,    S.W. 


BARIMAR  MOVE  TO  LARGER 
PREMISES. 
To  keeip  pace  with  the  enormous  growth 
of  their  scientific  welding  business,  Bari- 
mar,  Ltd.,  have  moved  to  larger  and  more 
commodious  London  premises  at  14/18, 
Lamb's  Conduit  Street,  Theobalds  Road, 
London,  W.C.I.  While  Barimar,  Ltd., 
make  this  move  from  their  old  premises 
with  considerable  reluctance,  they  feel 
that  they  will  be  serving  the  interests  of 
their  customers  best  by  operating  a  larger 
factory  with  the  offices  on  the  spot,  and 
so  speed  up  delivery  of  repaired  parts  and 
be  free  to  handle  a  greater  volume  of  work 
under  the  best  conditions.  The  Barimar 
Service  Depots  at  Birmingham,  Manches- 
ter, Tweeds,  Newcastle-on-Tyne,  Cardiff  and 
Glasgow  will  continue  to  repair  scored  cy- 
linders by  their  metallurgical  (patented) 
process,  and  to  deal  with  welding  and  re- 
pair work  as  hitherto. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  March  8,   1923. 
Papers  read  :  — 

A.  B.  Wood,  H.  E.  Browne  and  C. 
Cochrane.  Determination  of  Velocity  of 
Explosion- Waves  in  Sea  Water.     Variation 


MARCH  16,  1923. 


PHE   CHEMICAL   NEWS. 


171 


of  Velocity  with  Temperature.  Communi- 
oated  by  F.  E.   Smith,  F.R.S. 

P.  M.  S.  Blackett.  The  Study  of 
Forked  Alpha-ray  Tracks.  Communicated 
by  Sir  Ernest  Rutherford,   F.R.S. 

The  methods  described  in  a  former 
paper  were  applied  to  the  study  of  the 
forked  alpha-ray  tracks  obtained  by  the 
Wilson  condensation  method. 

Measurements  of  the  lengths  of  the 
tracks  of  the  recoil  atoms  yielded  informa- 
tion concerning  the  relative  ionieation  due 
to  different  kinds  of  ionising  particles,  and 
of  the  average  charge  carried  by  them. 

Special  methods  were  developed  for  ob- 
taining accurate  measurements  of  the 
anglee  between  different  parts  of  the  tracks. 
Ajpplication  of  this  was  made  to  the  deter- 
mination of  the  masses  of  the  recoil  atoms 
in  three  particularly  favourable  cases. 
These  measurements  gave  values,  within 
the  limits  of  the  probabhi  error,  in  agree- 
ment with  thoee  to  be  expected  from  the 
composition  of  the  gas. 

A.  EoKRTON.  On  the  Vapour  Preasure 
of  Lead.  I.  Communicated  by  Prof.  F. 
A.  Lindemann,  F.R.S. 

The  vapour  pressure  of  lead  is  measured 
by  effusion  of  vapour  at  low  preeeuro 
through  a  hole  of  measured  area.  Tem- 
perature is  maintained  constant  by  a 
selenium  cell  relay  arrangement  within 
1/3°  C.  for  many  hours  at  tempi-rature 
about  800°  C.  Pressures  have  been 
measured  to  10-*  mm.  The  vapour  pres- 
sure of  ordinary  lead  between  1.200-600' 
absolute  is  expressed  by  the  equation 

9982 

log  p  =  7.908 . 

T 

An  attempt  has  been  madfi  to  determine 
the  different  of  vapour  pressure  of  lead 
and  the  uranium-lead  isotope;  the  exjperi-^ 
meats  lead  to  a  diffcrenco  of  2  per  cent., 
but  the  result  is  rendered  uncertain  by  an 
unexplained  lowering  of  vapour  pressure 
which  lead  undergoes  on  prolonged  heating 
in  vacuo. 

A.  C.  Egerton  and  W.  B.  Lee.  .Swhc 
Density  Determinations.  Communicated 
by  Prof.  F.  A.  Lindemann,  F.R.S. 

The  Archimedes  method  of  determining 
densities  is  rendered  more  accurate  by  uti- 
lising certain  mobile  nnrl  heavy  organic 
liquids  which  avoid  air  hubbies  and  damp- 
ing difficulties,  and  incn^ase  the  weight  of 
V\(\\nd  displaced.  The  suspension  difficulty 
is  also  overcome. 


The  density  and  boiling  points  of  the 
hquids  employed — ethylene  dibromide  and 
carbon  tetrachloride — have  been  detei- 
mined  with  accuracy.  Density  determina- 
tions are  discussed  and  a  differential 
method  suggested. 

The  preparation  of  a  sati.siactory  sample 
of  metal  for  density  determination  is  ren- 
dered possible  by  filtering,  casting  and 
heating  in  vacuo. 

The  density  of  lead  is  determined,  viz., 
11.3437  at  20°  C.  The  probable  error  of 
the  nine  determinations  on  three  different 
samples  of  metal  is  1  part  in  100,000.  The 
maximum  departure  from  the  mean  value 
for  any  single  determination  is  less  than  1 
part  in  12,000. 

The  density  of  a  sample  of  uranium- lead 
is  checked,  and  would  have  an  atomic 
weight  ol  206.20  from  the  density  obtained. 

Determinations  of  the  density  of  a  small 
sample  of  cadmium  of  1.5  grams  weight 
agree  to  1  part  in  20,000. 

A.  C.  Eoerton  and  W.  B.  Lee.  Separa- 
tion of  Isotopen  of  Zinc.  Communicated 
by  Prof.  F,  A.  Lindemann,  F.R.S. 

Two  sets  of  distillations  of  pure  zinc 
have  been  carried  out  in  high  vacuum, 
under  conditions  to  obtain  a  slightly  differ- 
ent oMioentration  of  the  isotopes  in  the 
final  residue  of  the  final  distillate.  The 
conditicms  undir  which  the  samples  are 
preipared  for  density  determinations  are 
described.  The  samples  are  cast  in  vacuo 
and  seeded  with  a  particular  kind  of  zinc. 

The  measurements  of  density  are  carried 
out  by  the  method  described  in  the  preced- 
ing paper,  with  improvements  to  the 
apparatus. 

The  fifst  set  of  distillations  gave  a  resi- 
due of  slightly  increased  density,  but  the 
distillate  (}ossessed  the  same  density  as  the 
original  zinc.  The  second  set  of  dbtilla- 
timis  gave  a  nsidue  of  increased  density 
f about  1  part  in  3,700)  and  a  distillate  of 
aecreased  density  (about  1  part  in  3,000). 
Determinations  on  seven  samples  of  ordi- 
nary zinc  agree  in  giving  the  density  of 
zinc  (prepared  in  the  described  way)  as 
7.1400  (the  probable  error  being  less  than 
1  part  in  100,000). 

Flaws,  allotropes,  different  physical  con- 
ditions, and  imipurities  as  explanations  of 
the  result  are  shown  to  be  improbable. 
The  result  lies  outside  the  experimental 
errw. 

The  amount  of  the  separation  agrees 
with  Dempster's  observations  of  isotopes 
of  weights  extending  over  six   units    (viz., 


172 


THE    CHEMICAL    NEWS. 


MAECH  16,  1923. 


34-70),  but  is  not  as  great  as  might  be 
found  for  equal  parts  of  64  and  of  atoms  of 
weights  66,  68  and  70. 

E.  Hatschek  and  P.  C.  L.  Thorne. 
Metal  Sols  in  Nan-dissociating  Liquids. 
L — Nickel  in  Toluene  and  Benzene.  Com- 
municat-efl  by  Prof.  A.  W.  Porter,  F.R.S. 

The  results  obtained  so  far  may  be  sum- 
marised   as   follows  :  — 

Very  stable  sols  of  nickel  in  a  medium 
free  from  ions  can  be  prrxluced  by  decom- 
posing nickel  carbonyl  dissolved  in  mix- 
tures o  toluene  and  benzene,  containing  a 
small  amount  of  rubber,  at  100°  C. 

In  the  electric  field  the  particles  of  dis- 
perse phase  move  to,  and  deposit  on,  both 
electrodes. 

Electrophoresis  in  fields  of  different 
strengths,  all  other  factors  being  equal, 
sihows  that  the  amounts  deposited  are  pro- 
portional to  the  first,  or  a  lower,  power  ^f 
the  potential  gradient.  The  charges, 
therefore,  are  not  induced  ones,  but  posi- 
tively and  negatively  charged  particles  are 
originally  present  in   the  sol. 

The  sol  resembles  typical  protected 
aqueous  sols,  inasmuch  as  it  is  coagulated 
by  liquids  which  are  not  solvents  for  the 
protective  colloid,  i.e.,  rubber.  The  co- 
agulum  is  only  very  imperfectly  peptized 
again  by  rubber  solvents,  such  as  toluene 
or  benzene. 

Paper  read  in  title  only:  — 

H.  HiRATA.  Constitutiorn  of  the  X-rny 
Spectra  belonging  to  the  L  Series  of  the 
Elements.  Communicated  by  Sir  William 
Bragg,   F.R.S.  ^ 

Thursday,  March  15,  1923. 

Papers  read :  — 

G.  C.  Steward.  Aberration  Diffraction 
Effects.  Communicated  by  Prof.  A.  S. 
Eddington,  F.R.S. 

Papers  read  in  title  only:  — 

Lord  RAYLEiOfi,  F.R.S.  Further  Ob- 
servations on  the  Spectrum  of  the  Niqht 
Sky. 

Lord  Rayleigh,  F.R.S.  Studies  of 
ridescent  Colour,  and  the  Structure  pro- 
ducing it.     IV. — Iridescent  Beetles. 

Prof.  J.  W'.  Nicholson,  F.R.S.  Ob- 
late Spheroidal  Harmonies  and  their  Ap- 
plications. 

Prof.  J.  W.  Nicholson,  F.R.S.,  and 
Prof.  F.  J.  Cheshire.  On  the  Theory  and 
Testi^ig  of  Right-angled  Prisms. 

Prof.  J.  C.  McLennan,  F.R.S.,  and  D. 


S.  AiNSLiE.  On  the  Fluorescence  and 
Channeled  Absorption  Spectra  of  Caesium 
and  other  Alkali  Elements. 

W.  Stiles,  Sc.D.  The  Indicator 
Method  for  the  Determination  of  Coeffi- 
cients of  Diffusion  in  Gels,  with  special  re- 
ference to  the  Diffusion  of  Chlorides.  Com- 
municated by  W.  B.  Hardy,   Sec.  R.S. 

H.  T.  Flint.  A  Generalised  Voctor  An- 
alysis of  Four  Dimensions.  Communi- 
cated by  Prof.  0.   W.   Richardson,   F.R.S. 


ROYAL   INSTITUTION  OF   GREAT 
BRITAIN. 

On  Saturday,  March  17,  Sir  Ernest 
Rutherford,  LL.D.,  D.Sc,  F.R.S.,  will 
give  his  fifth  lecture  on  Atomic  Projectiles 
and  their  Properties,  dealing  with  the  life 
history  of  an  a-particle  from  radium. 

On  March  13,  Prof.  C.  G.  Seligman  de- 
livered the  first  of  two  lectures  at  the 
Royal  Institution,  on  Rainmakers  and 
Divine  Kings  of  the  Nile  Valley;  and  on 
March  15,  Colonel  E.  F.  Strange  began 
a  course  of  two  lectures  on  Japanese  and 
Chinese  Lacquer. 


THE    CHEMICAL   SOCIETY. 

Ordinary    Scientific  Meeting,    Thursday, 

March  15,    1923. 

The  following  papers  were  read. — 

The  oxime  of  mesoxamide  ii&onitro- 
somalonamide)  and  som,e  allied  compounds. 
Part  III. — Ring  formation  in  the  tetra- 
substituted  series.  E.  H.  Usherwood  and 
M.  A.  Whitley. 

The  preparation  and  stability  of  cuprous 
nitrate  and  other  cuprous  salts  in  the  pre- 
sence of  nitrites.    H.  H.  Morgan. 

The  interaction  of  hydrogen  sulphide, 
thiocyanogen  arid  thiocyani  cacid  with  un- 
saturated compop,nds\.  F.  Challenger, 
A.  L.   Smith,  and  F.  J.  Paton. 

The  polarity    of  double    bonds.       T.    M. 

LOWRY. 


INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 
The  Tenth  Annual  General  Meeting  was 
held  at  the  House  of  The  Royal  Society  of 
Arts,  John  Street,  Adelphi,  on  March  13. 
Prof.  J.  S.  S.  Brame,  F.I.C.  F.C.S.,  the 
retiring  President,  gave  an  address. 


MARCH  16,  1923. 


THE    CHEMICAL    NEWS. 


173 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

At  the  Ordinary  Meeting,  held  at  the 
Chemical  Society's  Rooms  on  March  7, 
Mr.  P.  A.  Ellis  Richards,  President,  in  the 
chair,  certificates  were  read  for  the  first 
time  in  favour  of:  Mr.  Jf>lm  Myers,  F.I.C., 
and  John  Loudon  Buchanan,  F.I.C. 

Certificates  were  read  for  the  second 
time  in  favour  of:  Messrs.  Joseph  John  V. 
Baikes,  A.R.C.Sc,  A.I.C.,  D.I.C.,  Samuel 
Gordon  Stevenson,  A.I.C.,  Laurence  Bar- 
nett  Timmis,  M.Sc.Tech.  (Manch.), 
A.I.C.,  Richard  William  Sutton,  B.Sc- 
Tech.  (Manch.),  A.I.C.,  Alfred  Edward 
Johnson,         B.Sc,         (Lond.),  F.I.C, 

A.R.C.S.I.,  Ernest  Victor  Jones.  F.I.C, 
Francis  Kenelm  Donovan,  S.  Gordon 
Liversedge,  F.I.C. 

The  following  were  elected  members  of 
the  Society :  Messrs.  George  Henry  Ap^le- 
yard,  F.I.C,  Arthur  William  Starev, 
A.R.CS.,  B.Sc.  (Lond.),  A.I.C,  John 
Matthew  Wilkie,  B.Sc.  i  rx»d.),  F.I.C. 

The  following  are  abstracts  of  the 
papers  communicated:  — 

The  Examination  of  Firearmt  and  Pro- 
jectiles, by  A.  Lucas,  O.B.E.,  F.I.C. 

The  scientific  methods  used  fw  the  iden- 
tification of  firearms  and  projectiles  in 
cases  of  wounds  or  deaths  from  shooting 
were  discussed.  It  was  shown  that  a  pju-ti- 
oular  weapon  may  somel lines  be  recognised 
by  the  rifling  marks  imprinted  on  a  bullet, 
and  that  the  nature  of  the  fouling  left  in 
the  barrel  after  the  weapon  has  been  firfid 
may  also  afford  valuable  information  both 
as  to  the  nature  of  the  orifpnal  powder  and 
also,  in  some  case<?.  the  perio(l  that  has 
elapsed  since  the  Inst  discharge.  The 
composition,  dimensions,  and  markings  on 
bullets,  slug.s.  etc.,  were  described,  and 
directions  were  given  for  the  reproduction  of 
rifling  marks  on  bullets,  and  for  the  chemi- 
cal analysis  of  projectiles  of  all  kinds. 

The  Interpretation  of  the  Results  ob- 
tained in  the  Analysis  of  Potable  Waters, 
by  RoBKRT  C  Frederick. 

This  is  an  account  of  an  extended  inves- 
tigation into  the  chemical  changes  which 
occur  in  samples  of  exoretally  polluted 
water.  The  findings  are  considered  in  con- 
junction with  the  results  obtained  by  the 
author  in  the  analysis  of  a  very  large  num- 
b(>r  of  samples  from  tnery  kind  of  supply 
throughout  the  British  Isles.  The  ortho- 
dox idoa«  in  regard  to  the  interpretation  of 
the  analytical  results  of  such  examinations 


are  criticised    and  the  author's  own  views 
detailed. 
~     Determination  of  the  Purity  of  Vanillin, 
by  Sydney  B.  Phillips,  A.I.C. 

After  reviewing  the  various  methods  pro- 
posed from  time  to  time,  the  author  de- 
scribed two  processes  for  estimating  vanil- 
lin. The  first  was  a  volumetric  one,  where 
1  gram  of  vanillin  is  dissolved  in  20  cc.  of 
neutral  alcohol,  and  acid  impurities  are 
neutralised.  1.2  grams  of  p-toludine  are 
then  added^  and  20  cc.  of  semi-normal 
sodium  hydroxide  solution  are  measured 
in,  followed  by  100  cc.  of  cold  water.  The 
solution  at  15°  C.  is  titrated  with  semi- 
normal  sulphuric  acid  until  the  permanent 
precipitate  of  the  condensation  product  of 
vanillin  and  p-toluidine  is  formed.  The 
difference  between  the  volumes  of  alkali 
and  acid  represents  the  volume  of  alkali  re- 
quired to  combine  with  the  vanillin. 

A  summary  of  the  gravimetric  method  is 
as  follows : — One  gram  of  vanillin  is  dis- 
solved in  13.6  cc.  of  semi-normal  sodium 
hydroxide.  To  this  is  added  a  solution  of 
2.4  grams  semi-carbazide  hydrochloride 
and  3  grams  of  anhydrous  sodium  acetate, 
(H*  5  grams  of  the  crystalline  salt  in  30  cc. 
of  water.  The  mixture  is  heated  on  a  boil- 
ing water  bath  for  10  minutes,  allowed  to 
stand  in  the  cold  for  four  hours,  and  the 
semi-carbazone  filtered  off,  washed,  dried, 
and  weigherl.  It  is  treated  with  ammonium 
hydroxide  solution,  and  the  insoluble  por- 
tion filtered  off,  washed,  dried.  and 
weighed.  This  weight  is  deducted  from 
the  original  weight  of  semi-carbazone,  and 
the   remaind<'r  calculated   to  vanillin. 


MINER.\LOGICAL    SOCIETY. 

The  following  papers  were  communi- 
cated on  March  13:  — 

A.  Hutchinson.  A  Graphical  Method 
of  Correct iny  Specific  Gravity  Determina- 
tions. 

C  E.  TiLLEV,  Qeness  of  Rhombic  Pp- 
Toxene  in  Thermal  Metamorphism.  Mine- 
ral Associations  and  the  Phase  Rule. 

C.  S.  Garnrtt.  On  a  Peculiar  Chlorite- 
rock  from  Ilile,  Derbyshire.  The  Dissocia- 
tion of  Dolomite. 

A^  Brammall  and  H.  F.  Harwood.  The 
Dartmoor  Granite :  (c)  Porphyritic  Fel- 
spars ami  Biotite,  (h)  Andalusite,  Siili- 
manite,   Cordierite,   and  Spinellids. 

J.  G.  C  Leech.  Some  occurrences  of 
Titanium  Minerals  on  St.  Austell  Moor. 


174 


THE   CHEMICAL    NEWS. 


MARCH  16,  1923. 


ROYAL   SOCIETY  OF  ARTS. 

Arrangements  for   Meetings   During 
March,    1923. 

• 

Monday,  March  5,  8  p.m.  (Canton  Lec- 
ture). —  J.  E.  Sears,  C.B.E.,  M.A., 
M.I.Mech.E.,  Superintendent  of  Metrol- 
ogy, National  Physical  Laboratory,  ynd 
Deputy  Warden  of  the  Standards,  Lengili 
Measurement.      (Lecture   1.) 

Tuesday,  March  6,  4.30  p.m.  (Do- 
minions and  Colonies  Section). — Major  E. 
A.  Belcher,  C.B.E.,  Assistant  General 
Manager,  British  Empire  Exhibition,  The 
Domimon  and  Colonial  Sections  of  the 
Bfithh  Empire  Exhibition.,  1924.  The 
Rt.  Hon.  L.  S.  Amery.  M.P.,  will  preside. 

Wednesday,  March  7,  8  p.m.  (Ordinary 
Meeting). — Prof.  E.  P.  Stebbing,  M.A., 
F.L.S.,  Professor  of  Forestry,  University 
of  Edinburgh,  The  Forests  of  North  Russia 
and  their  Economic  Importance.  The  Rt. 
Hon.  Lord  Clinton,  Forestry  Commis- 
sioner, will  preside. 

Monday,  March  12,  8  p.m.  (Cantor  Lec- 
ture).—L  E.  Sears,  Jun., -C.B.E.,  _  M.A., 
M.I.Mech.E.,  Superintendent  of  Metrol- 
ogy, National  Physical  Laboratory,  and 
"Deputy  Warden  of  the  Standards,  Accur- 
ate Length  Measurement.     (Lecture  2.) 

Wednesday,  March  14.  8  p.m.  (Ordinary 
Meeting). — Sir  William  Warrender  Mac- 
kenzie, K.B.E.,  K.C.,  President  of  the  In- 
dustrial Court,  Industrial  Arbitration. 
Lord  Askwith,  K.C.B.,  K.C.,  D.C.L., 
Vice-Pesident  of  the  Society  and  Chair- 
man of  the  Council,  will  preside. 

Friday,  March  16,  4.30  p.m.  (Dominions 
and  Colonies  and  Indian  Sections). — Lt.- 
CoL.  Sir  Leonard  Rogers,  CLE.,  F.R.S., 
F.R.C.P.,  F.R.C.S..  Physician  and  Lec- 
turer, London  School  of  Tropical  Medicine, 
Recent  Advances  towards  the  Solution  of 
the  Leprosy  Problem. 

Monday  March  19,  8  p.m.  (Cantor  Jx^c- 
ture).— J.  E.  Sears,  Jun.,  C.B.E..  M.A., 
M.I.Mech.E.,  Superintendent  of  Metrol- 
ogy, National  Physical  Laboratory,  and 
Deputy  Warden  of  Standards,  Accurate 
Length   Measurement.     (Lecture  3.) 

Wednesday,  March  21,  8  p.m.  (Ordinary 
Meeting).  —  F.  W.  Edridge-Oreen, 
C.B.E.,  M.D.,  F.R.C.S.,  Some  Curious 
Phenomena  of  Vision  and  their  Practical 
Importance.  Prof.  E.  H.  Starling,  C.M.G., 
F.R.S..   will  preside. 

On  Monday,  March  12,  J.  E.  Sears, 
Jun.,  C.B.E.'.  M.A.,  M.I.M.E.,  Assoc. M.- 
Inst. C.E.,      Superintendent    of     Metrology 


Dept,,  National  Physical  Laboratory,  gave 
his  second  Cantor  Lecture,  entitled  Accur- 
ate  Length  Measurement. 


THE  INSTITUTE  OF  METALS. 

At  the  Annual  General  Meeting  of  the 
Institute  of  Metals,  held  in  London,  on 
Wednesday,  March  7,  the  following  officers 
were  elected  to  serve  for  the  year  1923-24  : 

President:  Leonard  Sumner,  O.B.FJ., 
M.Sc. 

Past-Presidents:  Sir  Gerard  A.  Muntz, 
Bart.,  Engineer  Vice-Admiral  Sir  Henry 
J.  Oram,  K.C.B.,  F.R.S.,  Sir  George 
Heilby,  Kt.,  F.R.S.,  LL.D.,  Professor  H. 
C.  H.  Carpenter,  M.A.,  Ph.D.,  A.R.S.M., 
F.R.S.,  Engineer  Vice-Admiral  Sir  George 
Goodwin,    K.C.B.,    LL.D. 

Honorary  Treasurer:  A.  E.  Seaton, 
London. 

Sixty  new  members  were  elected,  bring- 
ing the  membership  total  to  1,458.  The 
next  election  is  due  to  take  plsice  on  April 
19.  Particulars  can  be  obtained  frorh  the 
Secretary,  Mr.  G.  Shaw  Scott,  M.Sc,  36, 
Victoria  Street,   London,    S.W.I. 


NOTICES  OF  BOOKS. 


Theophrastus  Bombastus  von  Hohen- 
heim  called  Paracelsus,  by  John  Max- 
son  Stillman.  Pp.  X.  +  183.  London : 
The  Open  Court  Publishing  Co.,  149, 
Strand,  W.C.2.     Price  10s. 

For  almost  four  centuries  the  name  and 
fame  of  Paracelsus  have  come  down  to  us 
with  something  oi  the  legendary  haze  of 
fables.  Not  all  that  is  associated  with  his 
name  can  truly  be  ascribed  to  him.  Re- 
cent investigatons  have  indicated  how 
greatly  his  teachings  and  practices  revivjd 
a  spirit  of  scientific  enquiry  in  medicine 
and   chemistry. 

It  is  interesting  to  note  that,  in  con- 
formity with  the  custom  of  the  times, 
Hohenheim  adopted  the  Latin  name  Para- 
celsus, yet  he  delivered  his  discourses  at 
Basel  and  elsewhere   in  German. 

He  was  a  very  zealous,  original  writer, 
and  distinguished  himself  by  being  very 
critical  of  the  time-honoured  ideas  and 
methods  of  his  age.  The  accusation  that 
he  was    intolerant  is  probably  true,     since 


MAKCH  16.  1923. 


THE  CHEMICAL  NEWS. 


175 


he  violently  opposed  all  the  works  and 
methods  of  Galen,  although  these  oontaintd 
much  that  was  true. 

It  appears  that  Paracelsus  wrote  no  de- 
finitely chemical  or  alchemical  treatises, 
but  in  many  of  his  medical  and  iphilosophi- 
cal  writings  he  contributed  much  to  early 
chemical  knowledge.  He  developed  the 
theory  of  the  three  elements — sulphur, 
mercury,  and  salt — but  his  theoretical 
views  were  naturally  fanciful,  and  might 
even  be  styled  unscientific. 

However,  he  made  one  thing  clear, 
namely,  that  the  transmutation  of  metals 
wiis  not  the  sole  aim  of  alchemy,  and  that 
attention  could  be  more  profitably  directed 
to  the  discovery  of  curative  medicaments. 

The  present  biography  of  Paracelsus  is 
probably  the  best  in  existence,  dealing  as 
it  does  in  a  fair  and  scientific  manner  with 
his  stormy  and  nomadic  career,  and  his  in- 
fluence upon  contemporary  and  later 
science  and  medicine.  The  volume  will 
undoubtedly  be  widely  read  by  chemists 
and  students  interested  in  the  history  iif 
their  science.  J.G.F.D. 


Discaverieft     and     Invrniions    of      the 

Tuenticth  Century,  by  Edward  Cressy. 

Second    edition.       Pp.     XXIII.     +    453. 

London  :  George  Routled^'f  .t  Sons.  T^td. 

1922.     Price  128.  6d.  net 

The  first  edition  of  this  excellent  hook 
appeared  in  1914,  and  the  general  scope  of 
the  work  remains  very  nuich  the  same  as 
previously.  As  the  result  of  the  war  we 
•have  passed  through  a  period  of  inteii<!0 
activity  in  discovery  and  invention,  and 
therefore  considerable  altorntions  have 
been  made  to  bring  all  the  subjects  dealt 
iwith  previously  up  to  date.  In  only  one 
instance  has  no  attempt  been  made  to 
carry  out  the  nece.s«ary  revision,  and  in 
this  cas<'  Ships  of  War  and  their  Weapons 
— the  information  available  was  not  suffi- 
ciently reliai)le  to  render  such  revision  pos- 
sible, and  so  the  chapter  has  been 
omitt^'d  altogether.  In  its  place  a  new 
chapt^T  appears,  which  endeavours  to  give 
an  elementary  account  of  some  of  the 
achievements  of  modem  chemistry,  espe- 
cially in  relation  to  physics  and  biology, 
under  the  title,  "  The  Borderland  of 
Chemistry." 

Thi-;  chapter  is  divided  into  sections, 
and  the  subjects    dealt  with  are    oofloids, 


the  utility  of  .fioth,  catalysis,  fermentation 
and  vitamines.  The  treatment  apipears 
nulequate  in  each  case.  In  the  section 
dealing  with  colloids  we  find  the  following 
statement :  ' '  Many  sols  are  only  sta"ble  in 
the  presence  of  an  electrolyte."  Of  course 
it  should  read  that  the  absence  of  electro- 
lytes favours  the  stability  of  certain  so's. 
This  is  an  unfortunate  error,  but  readers 
should  easily  detect  it.  Again,  when 
speaking  of  oleum  in  the  section  on  cata- 
lysis, oleum  is  given  the  formula  H^SjO^, 
which  is  incorrect.  Actually,  oleum  is 
aimply  a  solution  of  sulphur  tri oxide  in 
sulphuric  acid,  and  has  no  fixed  composi- 
tion. In  industry,  certain  more  or  less 
standard  strengths  of  oleum  are  met  with, 
such  as  20  per  cent,  and  60  per  cent. — 
this  percentage  figure  simply  referring  to 
the  content  of  sulphur  trioxide  in  the 
oleum. 

Generally  siK'aking,  the  book  is  well  pub- 
lished, and  the  illustrations  are  good,  tut 
we  have  noticed  a  few  minor  errors,  such 
as  "sodium  chlorine"  for  "sodium  chlor- 
ide" (p.  433),  and  the  spelling  of  radio- 
activity on  ipage  442.  Such  errors  are  per> 
haps  fiardonablo,  and  accordingly  we  have 
nf>  hesitation  in  recommending  this  book 
to  all  those  who  desire  to  have  a  non- 
technical account  of  the  chief  scientific 
and  material  triumphs  which  man  has 
iiehieved   anri     is   iwhieving  at    the    present 

tlllH'. 


BOOKS  RECEIVED. 


Skinner'a  Cotton  Trade  Directory,  by 
Thomas  Skinner  k  Co.  Pp.  CCLVI.  + 
1,504.  1923.  Messrs.  Thomas  Skinner  k 
Co..  Gresham  House,  E.C.2.  12s.  6d.  nol. 

Baok  to  Prosperity :  A  New  Aspect  of 
Practical  Life.  In  Henry  TiOWKNFELD  and 
his  Daughter,  Margaret  Lowenfeld.  Pp. 
268  +  XI.  1923.  Effingham  Wilson,  16, 
Copthall  Avenue,  E.C.2.     5s.  net. 

The  ^fathe^natical  Theory  of  Helativitji. 
by  A.  S.  EnnixoTON.  Pp.  IX.  +  247. 
1923.  The  Cambridge  University  Press, 
Fetter  Lane,   E.C.4.     208.   net. 

The  U.S.  Deipt.  of  the  Interior  has  is- 
sued  the   following  bulletins:  — 

The  Inorganic  Constituents  of  Marine 
Invertebrates,  by  Frank  Wioolesworih 
Clarke  and   Walter  Colboi'rn   Wheelkr. 


176 


THE  CHEMICAL  NEWS. 


MARCH  16,  1923. 


Prelim'nianj  Report  on  Fossil  Verte- 
brates of  the  ScDi  Pedro  Valley,  Arizona, 
by  James  W.  Gidley. 

The  Shapes  of  Beach  Pebbles,  by  Ches- 
ter K.  Wentworth. 

Forty-third  Annual  Report  of  the  Direc- 
tor of  the  United  States  Geological  Survey 
to  the  Secretary  of  the  Interior. 

Gold,  Silver,  Copper  and  Lead  in  South 
Kahota  and  Wyoming  hi  1921,  by  C.  VV. 
Henderson. 

Gold,  Silver,  Copper,  Lead  and  Zinc  in 
Utah  in  1921,  by  V.  C.  Heikes. 

Manufactured  Gas  and  By-products  in 
1920,   by  R.   S.  McBride. 

Slectric  Brass  Furnace  Practice,  by  H. 
W.  GiLLETT  and  E.  L.  Mack. 

Preparation  of  Light  Aluntinium  Copper 
Casting  Alloys,  by  R.  J.  Anderson. 

Surface  Water  Supply  of  the  United 
States,  1918,  Part  IIL—Ohio  River  Basin. 

Surface  Water  Supply  of  the  United 
States,  1919-1920.  PaH  VIL— Lower  Mis- 
sissippi River  Basin. 

High-Grade  Clays  of  the  Eastern  United 
States,  by  H.  Ries,  W.  S.  Bayley,  and 
others. 

Phytrographic  Provinces  and  Sections 
in  Western  Oklahoma  and  Adjacent  parts 
of  Texas,  by  Nevin  M.  Fenneman. 

General  Features  of  the  Magnetite  Ores 
of  Western  North  Carolina  and  Eastern 
Tennessee,  by  W.   S.  Bayley. 

Peridotite  Dikes  in  Scott  County,  Arkan- 
sas, by  Hugh  D.  Unker  and  Clarence  S. 
Ross. 

Geology  of  the  Ranger  Oil  Field,  Texas, 
by  Frank  Reeves. 

The  Brooks,  Steen  and  Grand  Saline 
Salt  Domes,  Smith  and  Van  Zandt  Coun- 
ties, Texas,  by  Sydney  Powers  and  Oliver 
B.  Hopkins. 

Chromite  of  Kenar  Peninsula,  Alaska,  by 
A.  C.  Gill. 


Geology  of  the  York  Tin  Deposits,  Alas- 
ka, by  E.   Steidtmann  and    S.    H.    Cath- 

CART. 

Natural  Gas  Manual  for  the  Home. 


This  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chanoery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 


Latest    Patent   Applications. 

4503 — Basset,  L.  P.— Process  for  direct  reduction 
of  iron,  etc.,  ores.    Feb.   16. 

4140-Berlin,  D.  W.— Method  of  reducing  metal- 
lic oxiaes.    Feb.    12. 

4fl64— Dutt,  E.— Extraction  of  radio-active  con- 
stituents from  titaniferous  materials. 
Feb.  12. 

4065— Dutt,  E.— Separation  of  hafnium  from  ti- 
taniferous   materials.    Feb.    12. 

4619— Jques,      A.— Manufacture        of      ammonium 

4619-Jaques,  A.— Manufacture  of  ammonium 
compounds.    Feb.    16. 

4509— Maydegger,  O.— Process  of  manufacturing 
sulp&ate  of  chrome.    Feb.   15. 

4619— West,  J.  H.— Manufacture  of  ammonijim 
compounds.    Feb.    16. 

Specifications   Published   this    Week. 

192426— Reid,  J.  H.^Reduction  of  ore  and  the 
production  of   gas. 

192438— Akt-Ges  Fur  Anilon-Pabrikation.— Manu- 
facture  of   new-ortho-oxyazo   dyestuffs. 


Abstract  Published  this   Week. 

191?15— Barium     Oxide.— Dietrich,    W.    v 
wig,   Anhalt,   Germany. 


Cos- 


The  manufacture  of  barium  oxide  by  the  action 
of  heat  on  a  mixture  of  barium  carbonate  and  a 
reducing  agent  such  as  carbon,  pitch,  tar,  or  the 
like,  is  carried  out  under  reduced  pressure  in  a 
rotary  furnace  or  a  furnace  provided  with 
means  for  agitating  the  reaction  mixture.  Phe 
furnace  is  preferably  heated  internally  by  elec- 
trical means,  but  heat  may  be  applied  instead, 
or  in  addition,  from  the  outside.  Tn  an  example 
a  mixture  of  100  kgs.  of  barium  carbonate  and  7 
kgs.  of  carbon  is  heated  to  1,000-1,100°  C,  under 
a   pressure  of  65-70  cms.   of   mercury. 

Meii=rs.  Rayner  &  Co.  wiM  obtain  printed  copies 
of  the  published  Sppcifications,  and  forward  on 
post  free  for  the  official  price  of  Is.  each. 


MARCH  23,  1923, 


THE   CHEMICAL    NEWS. 


177 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.      No.   3284. 

VALENCY. 

By  William  R.  Fielding,   M.A.,  M.Sc. 
(Vict.). 

Senior  Science  Master,   King  Edward  VII. 
School,   Lythn}!!. 

(1)  Drfixition  of  Valf.ncy. 
Valency  is  tlio  capacity  which  one  atom 
of  a  substance  has  of  holdinj,'.  or  combining 
with,  one  or  more  atoms  of  itsolf  or  another 
element.  It  is  the  means  whioh  holds  to- 
gether the  bricks  out  of  wiiich  chemical 
compounds  are  built  up. 

(2)  Hydrogf.n  as  xnK  Standarp. 
The  capacity    of  hydrogen     to    combine 

with  other  elements  is  taken  as  the  stand- 
ard.    Thus,   in  ■ 

HCl,  hydrogen  and  chlorine  are  monads; 

HjO,   oxygen  is  a  dyad  ; 

H,N,  nitrogen  is  a  triad  ; 

TT,C.  carbon  is  a  tetrad. 

This  i.^  the  highest  valeney  shown  by  any 
element  towards  hydrogen.  In  their  com- 
pounds with  hydrogen  the  halogens  are 
monads  (exceipt  \vhere  assfniiition  or  poly- 
merisation takes  place),  sf>  lliat  the  valency 
of  elements  is  often  deihiced  from  the 
halides, 

e.g.,      NaCl,      B;iC"l„.      PCI,. 

(3)  Method  of  Ftvoino  Valency. 
The    valencv   of   anj'   particular     element 

differs  according  to  the  stnndard-elenient 
with  which  it  is  compared  (hydrogen  or 
halogen),  e.g.,  phosphorus  is  triad  in  PH, 
and  pentavalent  in  PCI., ;  iwline  is  monad 
in  in  and  KT,  but  appears  to  he  triad  in 
ICl, :  nitrogen  is  a  tria<l  in  NH,.  but  pentad 
in  the  easily  dissociable  compound  NH^CI; 
sulphur  is  dyad  in  S,C1.,,  tetrad  in  SO,  and 
SCI      and  hexad  in  SO,"  and  SF,. 

Tne  simplest  method  (but  it  is  not  al- 
ways applicable  )of  finding  the  valency  is 
to  find  both  the  atomic  weight  and  the 
equivalent  of  the  element  in  question,  when 
it  is  found  that  the  following  relationship 
holds  : 

Atomic  Weight 

=     Valency. 

Equivalent  Weight 
If    the    composition    of     the    compnunl 
gives    the    empirical    formula    A,  By.    the 


valencies  are  as  v  :  x.  unless  the  problem 
is  rendered  more"  difficult  by  the  existence 
of  complex  linkages  which  are  sometimes 
diflficult  to  recognise. 

(4)  Repuesentation  of  Valency. 
Owing    to    the  custom    of  the  last    half- 
centurA-,       valencies     are     represented     by 
straight  lines  or  dots,  thus:  — 
"  H— CI  H.  O. 


H 


\ 


H 


The  length  and  direction  of  the  lines  re- 
presenting valencies,  links,  bonds,  etc.,  are 
matters  of  no  importance;  the  valencies  of 
the  elements  fwming  a  compound  do  not 
necessarily  act  in  the  same  plane.  \  fre- 
quent source  of  error  in  reckoning  the 
valency  of  an  element  is  the  overlooking  of 
some  of  its  linkages,  which  may  be  unused 
(as  in  unsaturated  compounds),  or  even 
doubled  or  trebled. 

Carbon  is  tetrad  in  CH,  and  C  Cl^ ;  also 
in  =C  =  0;  but  two  valencies  are  reposing 
in  the  latter  molecule  until  they  have  an 
opportunity  of  combining  with  chlorine  or 
sulphur,  to  form  C'OClj  or  COS  respectively. 
In  CjH,  one  of  the  valencies  of  carbon  ap- 
pears to  be  absent  until  we  write  the  form- 
ula graphically,  when  the  position  of  the 
fourth  valeney  i*:  discovered. 

(5)  Law  ok  the  Indestructihility  of 

Valencies. 
What  may    be  termed  the    law  of  inde- 
structibility of  valencies    at  any  tempera- 
ture may  ne  seen  from    the  folh 
amples  (Fig.  L):  — 


lowing  ex- 


(a) 


H' 


-f    0 


"Rrcki  v>o  of     ^ 

H' 


3    ox^ge-r^     <x» 


H' 
H' 

H' 

Toto-l     T>0      of 


-f    o 


12. 


12. 


(Fiq       1.) 


178 


THE    CHEMICAL    NEWS. 


MARCH  23,  192S. 


If  the  whole  of  the  valencies  were  used 
up  in  forming  a  compound,  there  would  be 
no  association  or  polymerisation  (Fig.  2):  — 


N 

Yo.1, 


CO 


Hg 


H^ 


-t. 


V 


O 

Va.l»»e.««s:- 


O—H 


I — K 


It. 


<A)       —  C--IL        Br' 
—  C — B.Z      :&*-' 


it. 


McU 


(Tig    2.) 


(e)  As  long  as  the  temperature  at  the 
beginning  and  end  of  the  action  is  the  same 
the  law  holds.  E.g.,  the  "combining"  of 
hydrogen  and  oxygen  at,  say,  8,000°  C. 


0 


H 

Valencies 


H 
H 


O 


0 


0  (no  water  farmed) 


(■f) 


«. 


H 
H~C— r 


Ycxl 


ericies  -.— 


18. 


<3^ 


2?1)=0   -fC""   =  2Pb"+C<^ 

CSm  also  §  II.) 

CPig  4?.) 

(6)  Variability  of  Valencies. 

A  most  perplexing  question  is  the  vari- 
ability of  valency 

(1)  for  any  particular  element, 

(2)  according  to  the  position  of  the  ele- 
ment in  the  periodic  table  (this  will  be  re- 
erred  to  later).  E.g.,  oxygen  is  dyad  in 
H„0:    is     it  tetrad    in  carbon     monoxide? 


Chlorine  is  a  monad  in  KCl ;    what  is  it  in 
KCIO3  andKClO^? 

K O — O O O — ex        ('Movia.d.?) 


K— O- 


■ci^o 


(H«J>^<vxl.?) 


CT;q    S) 


The  monovalent  element,  iodine,  be- 
comes ipentavalent  in  IF5.  In  hydrofluoric 
acid  fluorine  is  monad  at  100°  C.  (Gore); 

XT "p 

divalent  at  30°  C.   (Mallet); 
H— F 

I 
H— F 

and  poly-valent  (H^  F,)  at  lower  tempera- 
tures. A  oryoscopic  determination  of  the 
mo'lecular  weight  gives  Hg  Fj.    (Abegg). 

Even  the  valency  of  the  standard  ele- 
ment appears  to  alter  in  triatomic  hydro- 
gen! 

H    — H 

\h 


O"      = 


Ci^^3  3.) 


H 


\ 


H 


H 


l§, 


It  is  as  difficult  to  explain  why  phos- 
phorus is  only  trivalent  towards  hydrogen 
but  pentavalent  towards  oxygen  and  chlor- 
ine as  it  is  to  exiplain  why  a  person's  appe- 
tite for  one  food  is  so  different  for  another. 

(7)  Variation  of  Valency  with 
Temperaeure  and  Pressure. 
Then  valency  may  vary  according  to 
changes  in  temperature  and  pressure,  etc. 
Phosphorus  is  trivalent  in  PH.,,  but  if  a 
mixture  of  equal  volumes  of  Pllg  and  HCl 
is  subjected  to  pressure,  the  two  combine 
to    form  phosphonium    chloride,     in   which 


f 

I 


MARCH  23,  1923. 


THE  CHEMICAL  NEWS. 


170 


phosphorus  is  pentavalent.  When  the 
pressure  is  reduced  the  valency  is  reduced, 
also,  from  5  to  3.  The  same  thing  happens 
in  the  case  of  NH3  and  HCI,  except  that 
the  reaction  takes  place  at  (our  presents 
"  ordinary  temperature  and  pressure." 

The  changes  in  valency  with  changes  of 
temperature  are  very  significant  Repre- 
senting an  atom  by  a  circle,  and  showing 
only  the  interchanged  electrons  (by  dots), 
we  can  reipresent  a  molecule  of,  say,  NaC! 
thus  (Fig.  VI):  — 


O    O 


Na 


CI 


Fig.  VI. 


the  chlorine  drawing  an  electron  from  the 
sodium  atom  towards  it.  It  may  either  be 
included  in  the  outer  ring  of  electrons  in 
the  chlorine  atom  or  oscillating  between 
the  two  atoms.  Both  the  sodium  and 
chlorine  atoms  become  ionic,  and  within 
each  atom  there  is  a  readjustment  in  the 
orbits  of  the  electrons  to  meet  the  now 
situation.  As  temperature  rises,  the  NaCI 
is  decomposed,  the  oloctronio  "  link" 
snapping  or  ceasing  to  function.  From 
the  practical  point  of  view  of  formation  of 
compounds,  all  elements  are  n<Mi-valont 
towards  each  other  above  a  certain  tem- 
perature, as  they  are  below  a  certain  tem- 
perature. Even  sodium  and  chlorine  whii^h 
unite  with  such  vigoiir  at  OTdinarv  tem- 
peratures, will  not  combine  below 
as  the  temperature  falls,  polymeriention  or 
association  is  often  increased  so  that  the 
valency  which  causes  polymerisation  is  less 
strong  than  that  required  for  combination 
between  unlike  atoms.  We  might  tabulate 
the   results  as  follows:  — 

(1)  At  very  hiqh  temperatures,  say,  the 
frwpernfnrc  of  the  snn.  Sodium  and  chlor- 
ine are  non-valont  towards  each  other. 

(2)  At  ordinary  temperature,  Sodium  anrl 
chlorine  are  approximately  monovalent  to- 
wards each  other,  uniting  to  form  NaCl. 

(3)  At  very  low  temperatures,  Sodium 
and  chlorine   are   non-valent  towards   each 


other;  but  molecules  of  sodium  associate 
with  other  molecules  of  sodium  and  moie- 
cules  of  chlorine  with  other  molecules  of 
chlorine.  Sodium  must  be  at  least  di- 
valent, making  no  distinction  at  present 
between  primary  and  secondary  valencies. 
These  facts  have  more  than  a  passing  in- 
terest for  us  because  throughout  the  whole 
range  of  temperature  through  which  the 
universe  has  passed,  or  will  pass,  say,  from 
20,000°  C.  to  the  absolute  zero,  it  is  only 
through  a  relatively  small  range  of  temp, 
that  life  in  any  form  is  possible.  On  val- 
ency depends  the  formation  of  compounds 
— organic  compounds  for  food,  organic 
compounds  present  in  the  make-up  of  a  liv- 
ing organism — all  of  which  are  destroyed 
when  heated  over  a  small  range  of  tem- 
perature. Whatever  the  genesis  of  life  (as 
we  know  it  in  the  material  world),  imless  it 
gets  a  foothold  during  this  vital  range  of 
temperature,  life.'  either  on  the  earth,  or 
Mars,  or  other  celestial  bodies,  is  impos- 
sible. 

Many  chemical  compounds  might  be 
mentioned  to  show  that  the  valency  of  one 
element  for  another  element  frequently 
varies  even  within  the  valency- limits  just 
referred  to;  e.g.,  the  chlorides  of  sulphur. 

Sulphur  Monochloride   (SjCl,). 


B.ip. 
M.P. 


i3apc. 

—SCfC. 


(41  r  A) 

(193"  A) 


This  liquid  saturated  at  251"  A  with 
chlorine  is  transformed  into  SCl^  M.P. 
242°  A.  On  removing  it  from  the  freezing 
mixture  the  valency  is  reduced  and  S.^  CU 
and  Clj  are  again  formed.  These  changes 
are  sho\vn  in  the  diagram   (Fig.  VII.) 

The  valency  bf^tween  sulphur  and  chlor- 
ine is  shown  in  steps.  At  2.51"  A.  thirty- 
two  parts  by  weight  of  sulphur  can  "hold" 
142  parts  of  chlorine;  at  a  higher  temp, 
only  35.5  parts  of  chlorine.  There  may  be 
an  intermediate  point  where  32  parts  of 
sulphur  are  satisfied  by  60  or  RO  parts  of 
chlorine  if  there  existed  a  standard  sub- 
stance with  whieli  thev  could  be  compared  ; 
only  as  union  between  sulphur  and  chlorine 
takes  place  in  atoms  and  not  in  fractions 
of  an  atom,  the  r-ompound"  of  sulphur  and 
chlorine  must  bo 

e     CI  ,     S2  CI,  ,     etc. 


180 


THE    CIIEMICAI.    NEWS. 


MAi:CH  23.  1923. 


3 


(A 


1. 


■|o.rion:—   Sjj.,Clvj,  (^03^C1^J.2l- 


scit,^. 


SxCla.  ^ 


i  ^N. 


200*  •♦oo*  boo" 

(T.g     r.) 


«oo* 


looo' 


The  dotted  line  shows  the  possible  value 
of  the  valency  of  sulphur  for  chlorine  and 
accounts  for  the  "residual"  valency  which 
is  used  to  account  for  the  formation  of  poly- 
mers, complex  atoms,  etc. 

Water  might  be  quoted  as  another  ex- 
ample. At  high  temperatures  it  is  disso- 
ciated into    hydrogen     and    oxygen     (when 


they  become  non-valent  towards  each 
other);  between  0°  and  100°  C.  not  only  is 
HjO  present,  but  varying  amounts  of 
(H^0)2,  and  (H^O),.  The  formation  of  the 
latlci  postulate  a  higher  valency  for  either 
hydrogen  or  oxygen,  or  both. 

(To  be  Continued.) 


ON  THE  USE  OF  POTASSIUM  OR 

SODIUM  BROMIDE  AS  A  SOURCE 

OF  BROMINE  FOR  UREA 

ESTIMATIONS. 

By  C    H.  Colling  s. 

In  urine  analysis  the  estimation  of  urea 
is  usually  carried  out  by  means  of  the  in- 
teraction of  sodium  hypobromite  and  the 
urine  to  be  analysed.  Sodium  hj'pobro- 
mite,  as  such,  cannot  be  kept  in  stock,  and 
has  therefore  to  be  made  shortly  before 
use,  by  the  addition  of  bromine  to  sodium 
hydrate  solution.  Bromine  in  its  native 
form  needs  extreme  care  in  handling  if  un- 
pleasant consequences  are  to  be  avoided,  it 


is  expensive,  and  its  carriage  is  costly  and 
subject  to  delay,  and  in  some  cases  (such 
as  India)  is  prohibited  altogether.  It  fol- 
lows, therefore,  that  a  method  of  obtaining 
and  handling  bromine  that  is  at  once  safe 
in  even  unskilled  hands,  is  economical,  and 
is  unaffected  by  such  prohibition,  may  be 
regarded  as  of  some  practical  utility.  I  am 
not  disregarding  the  usual  laboratory 
methods  for  the  evolution  of  bromine  from 
its  compounds,  but  the  advantage  in  prac- 
tice of  the  method  here  described  is  evi- 
dent. 

The  apparatus  previously  described  and 
figured  respectively  in  The  Chemical  News 
(this  vol.,  pp.  55  and  95,  Jan.  26  and  Feb. 
9)  is  used. 


MAECH  23.  1923. 


THE   CHEMICAL   NEWS. 


181 


Tt  i«  connected  up  with  an  aspirator  or 
puinp,  Mild  air  is  drawn  steadily  through  it 
during  the  whole  operation.  The  role  of 
the  air  is  rather  important.  It  not  only 
exercises  an  obviously  useful  mechanical 
function,  but  directly  contributes  to  the 
separation  and  removal  of  the  Br  from  the 
mixed  fluids  in  which  it  first  finds  iteejf  on 
disengagement  from  its  chemical  tie  with 
potassium  or  sodium,  the  air  pawsing 
through  the  mixed  fluids  from  bottom  to 
top. 

The  method  is  as  follows:  Make  a  stock 
solution  of  potassium  or  sfxlium  bromide, 
in  the  ipr()portions  of  10  griiiii.s  of  pota^^siiim 
bromide  to  2^}  cc.  of  distilled  wat^^r  -or 
NaBr  8  gr.  to  2r)  cc.  wat^^).  Twenty-five 
oc.  of  sodium  hydrate  solution  of  the  usual 
hypobromite  formula  are  introduced  into 
HJ  via  the  cup  H.  and  its  tap  turned  off. 
Fifteen  cc.  of  nitric  an-  pi  need  in  A,  and 
at  once  run  into  MC  and  the  tap  turned 
off.  Twentv  cc.  of  KBr  <>r  NaBr  solution 
arc  placed  m  W.*  The  aspirator  is  now 
started,  and  the  tap  of  W  turned  on,  about 
40  droj)s  only  admitted,  and  the  tap  closed 
again.  The  aspirator  must  be  kept  going 
during  this  and  the  whole  of  the  subse- 
quent operations.  (Should  a  break  be 
necessary  for  later  readjustment,  the  tap 
W  must  \ye  tumrd  off  meantime.) 

.\  curious  feature  nf>w  arises.  The 
mixed  bromide  solution     and  the  acid    de- 


velop a  strong  reddish  colour,  which  is 
transparent.  This  persists  for  about  three 
minutes;  then,  with  remarkable  sudden- 
ness, an  opacity  develops  in  the  mixture 
and  becomes  absolute.  This,  of  course,  is 
the  sign  of  bromine  evolution ;  the  air  cur- 
rent picks  it  up.  tmd  the  sodium  hydrate 
solution  in  HJ  begins  to  show  a  yellow 
tinge  (hypobromite  formation);  and  the 
tap  of  W  should  at  once  be  turned  on  to 
give  60  drops  a  minute  or  faster,  provided 
that  no  bromine  is  observed  to  condense 
on  the  walls  of  MC,  or  sediment  just  over 
its  discharge  tap  at  the  bottom.  Brown 
fumes  of  nitrous  acid  may  also  be  ob- 
served in  the  air  in  MC;  these  are  also  car- 
ried over  and  neutralised  by  the  sodium 
hydrate,  of  which  the  fornmla  provides  an 
ample   margin   for  spare   alkalinity. 

The  air  should  he  kept  passing  after  all 
the  bromide  solution  is  in  and  until  the 
mixed  acid  and  bromide  loses  its  opacity 
and  regains  its  fcwrmer  deep  orange-red 
transparency.  The  hypobromite  will  now 
be  ready  for  use  and  may  be  drawn  off  by 
the  delivery  taip  HD. 

The  obvious  equations  for  the  reaction 
are:  — 

KBr  +  HNO,  =  KNO,  +  HBr. 
2HBr  +  HNO3  =  Br  J  +  H,0  +  HNO^. 

Should  any  crystals  (KNO,)  be  precipi- 
tated at  the  bottom  of  MC.  they  are  readily 
soluble  in  a   littK'  water,   subsequently. 

As  regards  cost,  that  of  a  2.2  cc.  tube  of 
bromine  is  about  7d. ;  of  potassium  bro- 
mide to  produc<^  an  equivalent  amount, 
somewhere  between  a  halfpenny  and  a 
penny.  To  this  must  be  added  the  vaiue 
of  15  cc.  of  nitric  aoid. 

The  details  of  the  apparatus  not  already 
described  are  as  follows :  I  is  the  air  inlet 
to  valve  V- — this  is  nearly  filled  as  shown 
with  sodium  hydrati'  solution  to  trap  any 
back  pressure  of  bromine.  BD  is  the  tube 
that  delivers  the  free  bromine  into  HJ 
containing  the  waiting  sodium  hydrate 
solution,  which  (H.J)  is  supported  on  VVS. 
The  aspirator  or  pump  is  connected  up  at 
P.  The  large  jar,  RJ,  takes  the  residual 
fluid  from  the  operation  at  its  conclusion, 
via  the  tap  below  MC,  and  is  periodically 
syphoned  empty  via  the  tube  RD,  dis- 
charging at  O. 

*  The  full  anionnt  to  corrcHpond  to  2.2 
cc.  Br  shouhl  hr  about  27.5  cc,  but  this 
really  represents  an  excess  over  usual 
needs. 


182 


THE    CHEMICAL    NiHWS. 


MARCH  23,  1923. 


SCIENTIFIC  INVESTIGATIONS  ON 
METAL  POLISHING  AND   GRINDING. 

A  lecture  was  given  recently  at  the 
Chamber  of  Commerce,  Birmingham,  b;y 
Mr.  Dartrey  Lewis,  M.Met.,  describing  an 
investigation  on  the  materials  used  in 
metal  polishing,  which  he  has  undertaken 
for  the  British  Non-Ferrous  Metals  Re- 
search Association. 

This  work  has  been  carried  out  at  the 
Sheffield  University,  under  the  supervision 
of  Professor  Desch,  F,R.S.,  Dean  of  the 
Faculty  o  Metallurgy. 

In  introducing  the  lecturer.  Dr.  R.  S. 
Hutton,  Director  of  the  British  Non- 
Ferrous  Metals  Research  Association,  ex- 
plained that  the  lecture  would  describe  the 
first  fruits  of  one  of  a  series  of  researches, 
undertaken  by  this  Association,  on  prob- 
lems of  direct  practical  importance  to  the 
Metal  Industries.  The  polishing  process 
played  a  very  important  part  in  the  pro- 
duction of  every  variety  of  metal  articles, 
an  din  general,  accounted  for  a  high  frac- 
tion o  fthe  cost  of  production.  In  Shef- 
field and  Birmingham,  buffers  and  metal 
polishers  totalled  many  thousands,  their 
work  was  laborious  and  frequently  highly 
skilled,  but  little  had  been  done  to  explore 
possibilities  of  imiprovement.  A  previous 
investigation  with  which  he  had  been  con- 
nected had  been  devoted  to  the  more 
human  side  of  the  process,  and  in  connec- 
tion with  this,  he  had  visited  a  French  fac- 
tory, where  an  output  in  spoon  and  fork 
buffing  of  two  to  three  times  that  usual  in 
this  country  had  been  achieved.  Such  cases 
should  serve  as  an  incentive  to  industrial 
research. 

Mr.  Dartrey  Lewis  explained  that  he  had 
devoted  his  attention  to  investigating  the 
fundamental  properties  of  the  materials 
used  in  metal  polishing,  sand,  pumice, 
emery,  etc.  Methods  had  been  devised  for 
measuring  the  abrading  or  cutting  power  of 
these  materials  on  brass  and  other  metals 
in  the  loose  powdered  form  in  which  they 
are  generally  used.  The  relative  durability 
of  the  materials,  or  the  useful  life  of  their 
grains  before  they  broke  down  into  too  fine 
a  state  of  division  to  effect  any  more  useful 
grinding,  had  also  been  measured. 

Information  of  this  nature  appeared  to 
be  completely  lacking,  although,  of  course, 
the  experts  in  the  trade  possessed  a  vast 
amount  of  accumulated  experience.  The 
necessity  for  quantitative  comparative 
measurements  was  all  the  greater,  because 
in  recent    years    new    abrasive    materials. 


such  as  artificial  corundum  and  carborun- 
dum had  been  discovered  of  much  better 
grinding  power,  and  of  greater  durability. 
This  experimental  work  supplied  certain 
basic  information,  but  it  was  for  the  indus- 
try to  consider  how  far  and  in  what  direc- 
tions one  material  was  superior  to  another 
for  any  given  works  process.  It  was,  how- 
ever, suggested  that  advantage  might  be 
taken  of  some  of  the  superior  materials  to 
remove  the  rougher  and  thicker  layers  of 
metal,  whilst  still  using  sand  and  pumice 
for  smoothing  off  preparatory  to  the  real 
polishing. 

Mr.  Lewis  also  briefly  described  his  ex- 
periments in  comparing  chromic  oxide  and 
rouge  for  polishing  steel  and  silver. 

The  British  Non-Ferrous  Metals  Re- 
search Association  is  extending  the  investi- 
gation to  "glazing"  and  other  abrasive  pro- 
cesses, in  which  the  abrasives  are  fixed  to 
wheels  by  glue. 

In  view  of  the  widespread  use  of  polish- 
ing processes  it  is  hoped  that  this  work  will 
attract  to  the  Association  the  support  of 
many  firms  in  branches  of  the  metal  indus- 
try hitherto  unrepresented  in  its  member- 
ship. 


NOTE  ON  p-NITROBENZYL- 
PYRIDINIUM  SALTS. 

By  H.  H.  Grainger,  B.Sc,  A.I.C. 

In  the  course  of  some  exiperiraents  on 
the  tinctorial  properties  of  azo-dyes  con- 
taining the  pyridinium  group  it  became 
necessary  to  prepare  dyes  from  aminoben- 
zylpyridinium  salts.  Lellmann  and  Pek- 
run  (Annalen,  1890,  CCLIX.,  52)  found 
that  p-nitrobenzylchloride  reacts  easily 
with  pyridine  to  give  a  quaternary  salt,  al- 
though they  did  not  analyse  the  product, 
which  they  describe  as  forming  yellow 
prisms  which  sinter  at  90°  and  melt  at  103". 
They,  however,  were  ohviously  dealing 
with  a  very  impure  product,  and  it  has  now 
been  found  that  if  the  chloride  is  purified 
by  recrystallisation  from  a  mixture  of  alco- 
hol and  ether,  it  forms  a  snow-white  crys- 
talline powder  which  melts  and  decomposes 
sharply  at  208°.  (Found:  CI  =  13.9. 
CigHijOgNaCl  requires  CI  =  14.2  per  cent.) 
The  corresponding  bromide  is  readily 
obtained  by  the  action  of  pyridine  on  p- 
nitrobenzyl bromide,  and  is  best  purified  by 
recrystallisation  from  alcohol  and  ether. 
It  melts  at  222°.     (Found :   C  =  48.6,    Br 


MARCH  23,  1923. 


THE  CHEMICAL  NEWS. 


183 


=  27.0.  Cj^H^O^N^  Br  requires  C  =  48.8, 
Br  =   27.1  per  cent.) 

The  addition  of  picric  acid  to  a  solution 
of  the  chloride  or  the  bromide  gives  an  im- 
mediate precipitate  of  the  very  sparingly 
soluble  picrate  which  can  be  recrystallised 
from  boiling  water  and  then  forms  beauti- 
ful glistening  yellow  needles  which  melt  at 
172°.  (Found:  N  =  15.8,  C.gH^O.N,  re- 
quires N  =  15.8  per  cent.) 

By  reducing  aqueous  solutions  of  the 
chloride  by  means  of  tin  and  hydrochloric 
acid,  solutions  of  the  aminobenzylpyri- 
dinium  salt  can  be  obtained.  These  were 
sulphuretted  hydrogen  ,  and  the  result- 
freed  from  tin  in  the  usual  way  by 
ing  solution  then  diazotised  and  coupled 
with  /8-na)phthol,  dimethylaniline  and  R- 
salt.  By  this  means  very  soluble,  red, 
basic  dyes  were  obtained,  but  these  proved 
to  be  far  too  unstable  to  be  of  any  techni- 
cal value. 

Sir  John  Cast  Technical  Institute, 

Jewry  St.,  Aldgatc,  London,  E.C.3. 


THE    SPEED    OF   CHEMICAL 

REACTION  THROUGH  A  SOLID. 

By  C.  D.  Niven. 

Much  work  has  been  done  cm  Chemical 
Reaction  in  Solution,  but  the  reactions  of 
a  solid  with  a  solution  seem  to  have  fallen 
into  the  background.  There  are,  however, 
many  reactions   of  this   kind. 

Thi'  object  now  in  view  is  to  determine 
the  thiH>retical  time  for  a  reaction  to  go 
throu<.'li  a  solid  of  definite  shape  and  size, 
the  solvent  being  semipermeable  to  the 
solid. 

Two  cases  arise.  First,  when  the  solute, 
i.e.,  the  reactive  part  of  the  solution,  ren- 
ders the  solid  more  impermeable  to  the 
solvent,  and  secondly,  less  impermeable; 
but  as  it  is  the  permeability  after  reaction 
is  complete  that  determines  the  stpeed  of 
reaction,  the  fonner  of  these  cases  is  the 
important  one.  It  is  very  important  in 
such  a  case  to  know  when  the  reaction  ha« 
reached  the  centre  of  the  body.  Obviously 
the  shape  of  the  body  would  determine  to 
some  extent  the  time  required  to  reach  the 
most  distant  point  from  the  surface,  and  a 
small  increase  in  thickness  in  certain 
bodies  might  cause  enormous  increase  m 
the  time  required  to  complete  the  reaction. 


if  the  material  of  which  the  body  was  com- 
posed became  very  impermeable  after  the 
reaction. 

In  the  case  of  a  sohd  body  in  a  solution 
which  reacts  with  the  solid  body 
semipermeable  to  the  body  before  and 
after  reaction,  it  is  seen  that  each 
point  on  the  surface  of  the  body  is  a  start- 
ing point  for  reaction. 


Taking  a  point  A  on  the  surface,  the 
ohemioal  can  be  supposed  to  find  its  way 
into  the  solid  like  a  ray  of  light  shining 
through  a  pin-hole  on  a  surface  and  spread- 
ing in  concentric  spherical  shells.  If  a 
point  B  be  taken  near  the  point  A,  similar 
currents  start  in  all  directions,  but  the 
currents  from  B  resolved  along  BA,  and 
which  act  in  that  direction,  are  counter- 
balanced by  the  currents  emanating  from 
A  resolved  along  AB  in  direction  AB. 
Therefore  the  main  reaction  travels  perpen- 
dicular to  the  line  AB;  that  is  to  say  the 
reaction  travels  into  the  body  in  the  direc- 
tion of  the  normal  to  the  curve  or  surface. 

As  the  solid  is  semipermeable  to  the  sol- 
vent in  which  the  chemical  is  dissolved,  it 
is  reasonable  to  imagine  that  the  solvent 
really  acts  as  a  carrier.  For  simplicity  it 
is  assumed  that  the  body  is  cylindrical  in 
shape.  This  permits  dealing  with  a  curve 
instead  of  a  surface,  as  the  reaction  would 
clearly  travel  at  the  same  speed  through 
any  cross -section. 

Let  C  D  N  be  a  section,  C  and  D  two 
points  near  on  the  surface,  and  CM  and 
DN  normals  resp<^ctively  at  C  and  D;  and 
let  the  reaction  reach  M  and  N  at  the  same 
time,  say  t,  and  let  it  reach  P  and  Q  in 
time  8t. 

Let  CM  =  X  and  MP  =  8x. 


184 


THE    CHEMICAL    N£WB. 


MARCH  23,  1923. 


Then  as  C  and  D  are  near  CN  =  x  and 
NQ  =  8x.  the  area  acted  on  in  time  8t  is 
MNQP   -   MN8x. 

The  amount  of  chemical  required  to  act 
on  this  area  is  proportional  to  the  area. 

The  distance  the  chemical  has  to  come 
is  CM  =  X. 

But  as  CD  is  greater  than  MN  in  a  con- 
vex curve,  the  chemical  could  travel  much 
more  quickly  near  CD  than  near  MN,  as 
the  molecules  would  pack  up  together  as 
they  travelled  in.  The  solid  material  only 
being  semipermeable  to  the  solvent  will 
have  a  certain  restraining  effect  to  the  re- 
action. This  will  depend  on  the  nature  of 
the  substances  reacting,  and  in  most  cases 
on  the  concentration  of  the  solution. 

In  order  to  visualise  what  has  been  said 
above,  the  reader  may  imagine  an  area 
covered  with  causeway  or  concrete,  which 
has  to  be  covered  to  a  depth  of  a  foot  with 
sand,  beginning  from  the  outside — as  many 
vehicles  of  transport  being  allowed  to  work. 
The  farther  from  the  edge,  the  harder  the 
work  becomes,  as  in  the  first  place  the 
distance  is  greater,  in  the  second  place 
fewer  vehicles  can  work  as  there  is  no  room 
near  the  centre,  and  in  the  third  place  the 
sand  renders  the  ground  .to  be  .covered 
more  difficult.  From  this  analogy,  it  is 
easy  to  see  that  the  number  of  molecules 
that  could  pass  in  at  a  time,  i.e.,  number 
of  vehicles,  is  prqportional  to  the  width  of 
the  passage  or  road,  and  in  a  wedge-shaped 
passage  the  number  would  be  proportional 
to  the  area  of  wedge  divided  by  the  length 
of  distance. 

Turning  again  to  Fig.  I,,  the  time  to 
complete  the  chemical  reaction  on  the 
small  area  MNQP  is  (1)  propoi'tional  to 
distance  chemical  has  to  come,  (2)  in- 
versely proportional  to  average  width  of 
passage,  and  (3)  proportional  to  amount  of 
chemical   required, 

i.e..  Time   =   K  x  x 

X    MN6x 


X 


AMNB 


=   K     a;=^MN8a; 


AMNB 

.•.  Total  time  to  react  from  outside  to  a 
distance  x^  is 

Xi 

/  K  x'-  MN8a; 
j        AMNB 

In  the  case  of  a  body  of  any  shape  in- 
s.tead  of  the  piece  of  curve  MN,  there  is  a 
small     curved  area,     and     instead  of     the 


wedged  area  AMNB  is  a  frustum  of  a  cone. 

Three  important  forms  of  solid  deserve 
special  investigation,  viz.,  the  plane  sur- 
faced plate,  the  cylinder  of  circular  sec- 
tion, and  the  sphere. 

In  the   first  case    when  the    surface     is 
plane  the  normals  are  all  parallel  and  the 
line  of  the  reaction  always  advances  para 
llel  to  the  surface. 


(^~ 


Considering  a  small  area,  A,  on  the  sur- 
face, the  time  to  react  at  a  distance  x  on 
same  size  of  area  is 

K    X    x_^       X      Adx 

Ax 


Total  time         = 


K  X  dx  =  Kcc* 

2~i 


2 

In  the  case  of  a  cylinder  of  circular  sec- 
tion, the  value    of  MN  in  terms  of    x  and 
the  radius    of  the  circle    is  required,     and 
also  a  value    for  the  area    AMNB  in    the 
same  terms.  If  "a"  be  the  radius  of  circle 
and  a  =  angle  AOB  where  0  is  the  centre, 
then  MN  =  a  (a-x)     .     .     .     m 
Area  AMNB_=  AOB-MON 
=   ^a  (a'^-a-x'^) 
=    ia   {2ax-x^)     -     -     -     -  (2) 

Hence,  total  time  to  depth  x, 


I      K  x^  •g.-g-x  dx 
0     r^d'x  {2a- x) 


MARCH  23,  1923. 


TfiB   CHEMICAL   NEWS. 


185 


X, 


K  2  X  (a-x)  dx 
2a -X 


Substituting  z  for  2a-x  and  int^'grating, 
•2a  2a 

Total  time  =  2K  [3aZ-Zv      -4a     logZ 

2a  -  x^  2a  -  x, 

To  complete  the  reaction  to  the  heart 
put  j\=a.  The  total  time  then  becomes 
Kx-227(k/^ 

In  the  third  c:vse,  viz.,  a  sphere  of  ra<liuR 

a,"  it  is  required  to  find  a  value  of  the 
small  area  MX  and  the  volume  of  the  frus- 
tum ABNM. 


Let  the  area  AB  subtend  a  solid  angle  12 
at  the  centre  O.     Then  the  area  MN  is 

il.a-x' (1) 

and  the  volume  of  the  frustum  ABNM   is 

kil[a^  -  tt-x'] (2) 

Substituting      in     the     general     formula 
found  above,  the  total  time  to  a  depth  x^  is 

K:x':ilTa^x^dT      =      '6\\\a-x^    xdx 


ill[a»  -  -i-x'] 


'ar-Sax+'Sa" 


0 


On  integration,  the  total  time  ia 

X,  X, 

=  3Iw^ 
2 

0  o 


(x* - 3ax 


+3a')/ 


SKax        ^   SKa'  lojr 


—  3v/3K  a= 


—  3K  Xj* 
2 


3^3   ta-    l+aii,-\-^  )-+an-\-  j^3)j. 

When  the  reaction  reaches  the  heart  ot 
the  sphere  x,  =  a  and  the  total  time  oe- 
comes 

Iv  a^  X  0.1271. 

The  times  then  for  a  plane  plate  of  thick- 
ness 2'i,  a  circular  cylinder  of  radius  a,  and 
a  sphere  of  radius  a,  ai-e  in  the  j)roportiou 
of  0.5  :  0.227G  :  0.1271,  no  matter  wiiat 
the  reacting  cheuiical  is.  or  its  streugtli, 
prorided,  ol  course,  it  doe«  react  accoramg 
to  the  urigiuul  assumption. 

To  demonstrate,  the  foiiowuig  is  a  prac- 
tical example.  In  a  bath  of  formaldehyde 
varioiLs  pieces  <>t  casein  plates  were  steeped 
from  3  millimetres  upwards,  and  various 
pieces  of  cylinders,  all  circular  in  section 
and  solid. 

These  were  watched  and  the  times  when 
the  reaction  was  compieteti  v\ere  noted. 
Each  piece,  when  ready,  was  dried  and 
measured  in  a  micrometre.  The  values  tor 
plat<.s  were  found  to  be  very  near  the  curve 
y  =  «ttbx^,   where  y  =  time  and  x   thickness. 

A  curve  may  tlien  be  plotted  and  the 
points  found  by  experiment  marked 

The  following    is    a  table    showing     the 
times  got     by    rxperiment     and   the     times 
agri-eing    witli    the     theoretical     curve     for 
4)iat*'s   y  =  0.««Hx-.— 
Thickness   in   iiim.     3.3     4.6     5.b     7.5     I'd 

Expt.,    days    9      19      32      ;50  140 

Theur..    days 9.0  18.8  29.U  49.9   150 

For  the  rods  tiir  curve  is  fixed  assuming 
the  solutiwi  is  the  same  as  for  the  plates, 
viz.,  y  =  0.4O4x^  and  the  following  are  the 
t-vperimental  values  and  the  theoretical 
values  of  the  times  for  certain  thicknesses 
of  rods :  — 
Diameter  in  mm.      5     7.8      10     12.7  17  9 

Expt.,   days    11      25      38        (31     133 

Theor.,  days  ...lO.l  24.6  40.4  05.2  130 
The  values  iwr  suirieiently  near  to  jus- 
tify the  theory  piopofied  above  as  the  diffi- 
culty in  getting  the  exact  end  point  in  a 
very  slow  reaction  is  of  course  great. 


186 


THE    CHEMICAL    NEWS. 


MARCH  23,  1923. 


Owing  to  the  exipense  of  getting  moulds 
made  for  spheres,  it  has  been  impossible  to 
get  a  series  of  readings,  but  one  sphere 
was  taken  and  oompared  under  simiiar 
conditions  with  a  5  mm.  plate  or  sheet — 
more  rapid  conditions  than  those  under 
which  original  pieces  were  tested. 

The  5  mm.  plate  took  14  days  and  the 
Siphere  13  mm.  in  diameter  took  25  days. 
Calculating  what  time  this  sphere  would 
have  taken  if  the  5  mm.  sheet  took  14 
days,  we  get 

0.1275  169  14 

— ' X      X  =   24.05    days. 

0.5  25 

This  supports  the  theory. 


GENERAL  NOTES. 


ACETONE  FOR  THE  UNITED  STATES. 

Mr.  G.  Campbell,  H.M.  Consul-General 
in  San  Francisco,  reports  that  a  local  firm 
of  manufacturers  of  compressed  acetylene 
gas  are  desirous  of  getting  into  touch  with 
United  Kingdom  manufacturers  of  acetone 
for  the  purpose  of  purchasing  supplies  for 
use  in  their  business.  The  acetone  must 
comply  with  the  British  War  Office  specifi- 
cations. The  enquirers  are  understood  to 
enjoy  a  very  good  standing  and  reputation, 
and  they  stipulate  that  quotations  should 
state  price  per  pound  F.A.S.  British  ship- 
ping port  on  quantities  of  approximately 
30,000  pounds.  The  price  must  be  in  com- 
petition with  that  of  21  cents  per  pound  in 
the  United  States. 

An  import  duty  of  25  per  cent,  ad 
valorem  is  levied  on  acetone  imported  into 
the  United  States. 

The  name  and  address  of  the  firm  in 
question  may  be  obtained  by  manufac- 
turers on  application  to  the  Department  of 
Overseas  Trade  (Room  62). 


Sir  Eric  Geddes,  President  of  the  Feder- 
ation of  British  Industries,  delivered  an 
imjportant  speech  on  the  Trade  Future,  at 
Birmingham,  on  Tuesday,  March  13,  on 
the  occasion  of  the  Annual  General  Meet- 
ing of  the  West  Midland  Branch  of  the 
F.B.I. 

The  Department  of  Overseas  Trade  has 
just  issued  a  small  explanatory  handbook, 
indicating  the  aims  and  objects  of  the  De- 
partment, and  the  directions  in  which  it  is 
intended  to  assist  and  develop  commerce. 


CRESYLIC  ACID  FOR  THE  UNITED 
STATES. 

Mr.  D.  H.  M.  Sinclair,  H.M.  Consul- 
treneral  at  Philadelphia,  reports  that  a 
local  firm  of  wholesale  oil  dealers  desire  to 
receive  from  U.K.  manufacturers  quota- 
tions for  cresylic  acid  97  to  99  per  cent, 
pure,  straw  colour,  and  95  to  97  per  cent, 
pure,   dark,  as  well  as  lower  grades. 

The  name  of  the  firm  may  be  obtained 
by  interested  firms  upon  application  to  the 
Departinent  of  Overseas  Trade. 

The  British  Vice-Consul  at  Constantza 
(Mr.  Tottenham  Smith)  reports  that  a 
local  authority  desires  to  be  put  in  touch 
with  United  Kingdom  suppliers  of  medico- 
surgical  instruments  necessary  for  a  com- 
plete polyclinic,  including  X-ray  equip- 
ment, and  to  receive  copies  of  catalogues, 
in  French  if  possible. 

Further  particulars,  together  with  the 
name  and  address  o  the  enquirer,  can  be 
obtained  by  firms  on  application  to  the  De- 
partment of  Overseas  Trade. 

PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  March  15,  at  4.30  p.m. 

Papers  read :  — 

J.  A.  Carroll.  Note  on  the  Series- 
Spectra  of  the  Aluminium  Suh-Group. 
Communicated  by  Prof.  A.  Fowler,  F.R.S. 
(Paper  read   by  communicator.) 

In  contradistinction  to  the  alkali  metals, 
the  highest  terms  in  the  known  series-spec- 
tra of  the  elements  of  the  aluminium  sub- 
group are  the  common  limits  of  the  sharp 
and  diffuse  series,  and  not  the  limits  of  the 
principal  series. 

Measurements  of  the  ionisation  and  re- 
sonance potentials  for  thallium,  however, 
have  suggested  that  there  might  be  a  yet 
undiscovered  principal  series  in  the  far 
ultra-violet,  the  limit  of  which  would  be 
the  greatest  term  and  would  correspond 
with  the  normal  state  of  the  thallium 
atom.  In  the  present  paper  it  is  pointed 
out  that  against  this  is  the  absence  of 
positive  evidence  of  such  a  series,  and  the 
easily  reversible  nature  of  the  lines  of  the 
subordinate  series  in  the  arc  spectra. 

It  seemed  that  valuable  evidence  as  to 
the  normal  state  of  the  atoms  might  be 
afforded  by  an  investigation  of  the  absorp- 


MARCH  23,  1923. 


THE   CHEMICAL  NEWS. 


18? 


tion  spectrum  of  the  oool  vapour  of  one  of 
the  elements  in  question.  Thalhum  was 
chosen  as  an  easily  obtainable  and  repre- 
sentative member  of  the  group,  which  is 
not  too  difficult  to  deal  with  experiment- 
ally. It  was  found  that  the  lines  obtained 
in  absorption  were  members  of  the  subordi- 
nate series,  thus  confirming  the  original 
series  arrangement.  The  results  arc  in 
accordance  with  the  latest  develoipments  of 
Bohr's  theory,  according  to  which  two  of 
the  outermost  electrons  in  the  thallium 
atom  are  in  6^  orbits  and  one  is  in  a  6  orbit. 

W.  E.  CuKTis,  D.Sc.  The  Structure  of 
the  Band  Spectrum  of  Helium. — //.  Com- 
municated by  Prof.  O.  W.  Biohardson, 
F,R.S. 

Seven  of  the  doublet  bands  previously 
examined  by  Fowler  have  been  studied  in 
detail,    with  the   following  results:  — 

1.  Tables  of  wave-lengths,  etc.,  and 
least-square  empirical  formulae  were  given 
for  the  constituent  series  of  each  band. 

2.  The  structure  of  the  bands  was  c<mi- 
sidered.  In  the  main  this  is  in  agreement 
with  the  requirements  of  the  quantum 
theory,  but  some  important  discrepancies 
were  noted  and  discussed  in  connection 
with  Kratzer's  half-quantum  hypothesis. 

3.  Values  for  the  moments  of  inertia  of 
the  molecules  concerned  were  derived  by  a 
graphic  method  and  used  to  verify  certain 
theoretical  conclusions. 

4.  Several  perturbations  were  recorded 
(the  first  examples  in  this  Sipectrum),  and 
their  significance  is  discussed. 

6.  A  new  combination  law  was  tested 
and  found  to  be  obeyed. 

6.  Some  peculiarities  noted  by  Fowler 
were  verified  and  explained. 

G.  C.  Steward.  Aberration  Diffraction 
Effects.  Communicated  by  Prof.  •A.  S. 
Eddington,  F.R.S. 

Diffraction  theory  would  indicate  that 
the  image  of  a  luminous  point,  given  by  a 
symmetrical  optical  system,  .^^ould  be  a 
system  of  luminous  rings,  and  this  was  in- 
vestigated by  Airy  in  1834;  geometrical 
theory,  on  the  other  hand,  leads  to  a  ccm- 
sideration  of  several  types  and  orders  of 
aberration — the  more  common  ones  being 
better  known  as  the  "  Five  Aberrations  of 
Von  Seidel."  They  arc:  Spherical  Aber- 
ration, Coma,  Astigmatism.  Curvature  of 
the  Field,  and  Distortion.  These  are  well 
known  and  have  been  invrstigatod  by  a 
number  of  writers.  In  the  present  paiper  *a 
consideration  is   undertaken  of  the  modifi- 


cation of  the  "ideal"  diffraction  pattern 
produced  by  these  geometrical  aberrations. 

The  method  adopted  depends  upon  the 
Eikonal  Function  of  Bruns,  and  a  sum- 
mary of  the  properties  of  this  function  was 
given,  therefore,  in  Part  I.  of  the  ipaper. 
Part  II.  dealt  with  the  Aberration  Diffrac- 
tion effects. 

Throughout  Parts  I.  and  II.  it  is  as- 
sumed that  the  stops  of  the  optical  system 
are  circular,  with  centres  upon  the  axis  of 
symmetry;  and  this  is  generally  the  case. 
Occasionally,  however,  other  stops  are 
used,  and  in  Part  II.  of  the  paper  is  under- 
taken a  wMisideration  of  the  diffraction 
effects  of  such  in  the  presence  of  the  various 
geometrical     aberrations.  The     precise 

lorms  of  aperture  considered  are  the  follow- 
ing:— 

1.  The  usual  circular  aj>erture,  but  with 
the  central  portion  stopped  out. 

2.  One  (cm-  two  parallel)  narrow  rectan- 
gular aperture. 

3.  A  semi-circular  aperture. 

Papers  read  in  title  (mly :  — 

Lord  Rayleioh,  F.R.S.  Further  Obser- 
vations on  the  Spectrum  of  the  Night  Sky. 

This  psiper  is  a  continuation  of  the 
author's  previous  studies  cm  the  spectrum 
of  the  night  sky. 

Specially  designed  spectrographs  having 
a  working  aperture  of  /  /.9  are  described. 
The  northern  and  southern  horizons  have 
been  photographed  simultaneously  on  the 
same  {)late,  and  the  aurora  line  recorded 
almost  down  to  the  horizontal  direction  in 
each.  It  is  ound,  however,  that  there  is 
no  marked  difference  of  intensity  between 
them. 

The  negative  nitrogen  bands  appear 
fairly  often  in  photographs  of  the  night- 
sky  spectrum  exposed  for  several  nights 
running  in  the  North  of  England.  Similar 
spectra  taken  in  the  South  of  England  do 
not  show  them.  As  previously  shown  they 
are  always  strong  in  the  Northern  Lights  in 
Shetland. 

The  spectrum  of  the  night  sky  shows  two 
bright  lines  or  bands  in  the  blue  a^d  violet, 
the  aipproximate  positions,  as  nearly  as 
they  oould  be  determined  on  the  very  small 
scale  spectra,  were  4200  and  4435.  The 
origin  c>f  these  is  not  known.  In  addition, 
there  is  the  aurora  line  5578,  also  of  rn- 
known  origin,  and  the  dark  Fraunhofer 
lines  H  and  K.  These  various  lines,  bright 
and  dark,  are  shv/wn  oo  a  photograph  sent 


188 


THE   CHEMlCilL   NEWS. 


MARCH  23,  1028. 


to  the  author  by  Dr.  E.  C.  Slipher,  which 
was  taken  about  the  same  time. 

Lord  Rayleigh,  F.R.S.  Studies  of 
Iridescent  Colour,  and  the  Structure  pro- 
ducing it.     IV.— Iridescent  Beetles. 

It  is  shown  that  some  of  the  iridescent 
beetles  which  have  striking  metalJic 
colours  show  band  systems  in  the  spectrum 
of  the  reflected  light.  Two  such  spectra 
are  reproduced. 

The  first,  from  Pelidnota  sumptuos^j 
shows  a  central  maximiim  bordered  on 
either  side  by  subordinate  maxima  in 
exactly  the  way  that  reflection  from  a  quite 
uniformly  spaced  assemblage  of  thin 
plates  would  require.  The  number  of 
planes  calculated  to  be  required  in  this 
case  is  no  less  than  34.  A  Lippmann  film 
shows  a  similar  spectrum. 

The  second  spectrum  is  from  one  of  the 
golden  beetles,  Callodes  parvulus.  The 
bands  are  accounted  for  on  the  supposition 
of  two  assemblages,  each  consisting  of 
several  reflecting  planes,  the  distance  be- 
tween the  assemblages  being  about  B/x. 
This  would  result  in  a  series  of  equally 
spaced  bands  over  a  limited  range  of  the 
spectrum  as  observed. 

The  possibility  of  either  of  these  spectra 
being  produced  on  the  alternative  Ihofiry 
of  surface  reflection  is  discussed,  and  is 
found  to  require  a  number  of  special  sup- 
positions which  seem  very  difficult  of 
acceptance. 

Prof.  J.  W.  Nicholson,  F.R.S.  Ohlnte 
Spheroidal  Harmonics  and  their  Applica- 
tions- 

Prof.  J.  W.  Nicholson,  F.R.S.,  and 
Prof.  F.  J.  Cheshire.  On  the  Theory  and 
Testing  of  Riqht-angled  Prisms. 

Prof.  J.  C'.  McLennan,  F.R.S.,  and  D. 
S.  AiNSLiE.  On  the  Fluorescence  and 
Channelled  Absorption  Spectra  of  CcBsium 
and  other  Alkali  Elements. 

Caesium  has  been  shown  to  exhibit  a 
fluorescence  and  a  channelled  absorption 
spectrum  in  the  neighbourhood  of  A  — 
2O0O  when  the  vapour  of  the  element  is 
traversed  by  white  light.  In  the  absorption 
spectrum  the  bands  were  found  to  be 
separated  by  intervals  that  were  simple 
multiples  of  24  A.  Like  sodium,  potassium 
has  been  shown  to  exhibit  channellings  in 
its  absorption  spectrum  in  the  neighbour- 
hood of  the  second  member  of  its  doublet 
series.  The  fluorescence  spectrum  of  rubi- 
dium has  been  photographed,  and  the  wave- 
length of  its  bands  measured.  Indica- 
tions have  been  obtained  of  channelling  in 


the  absorption    spectrum  of  lithium  in  the 
near  ultra-violet  region. 

W.  Stiles,  Sc.D.  The  Indicator  Method 
for  the  Determination  of  Coefficients  of 
Diffusion  in  Gels,  with  special  reference  to 
the  Diffusion  of  Chlorides.  Communi- 
cated by  W.  B.  Hardy,  Sec.  R.S. 

1.  An  indicator  method  is  described  by 
which  the  coefficients  of  diffusion  of  chlor- 
ides, sulphates  and  other  substances  can  be 
simply  determined. 

2.  The  coefficients  of  diffusion  of  a  num- 
ber of  chlorides  in  0.5  per  cent,  agar-agar 
gels  are  recorded. 

3.  The  effect  of  temperature  on  the  co- 
efficient of  diffusion  of  these  chlorides  has 
been  investigated.  The  coefficient  increases 
at  a  greater  rate  per  degree  rise  in  tempera- 
ture the  higher  the  temperature ;  the  rela- 
tion between  coefficient  of  diffusion  and 
temperature  in  gels  is  thus  not  a  linear  one 
as  is  usually  assumed  to  be  the  case  for 
free  diffusion  in  water. 

4.  The  coefficient  of  diffusion  decreases 
with  increasing  concentration  of  gel.  Em- 
pirical expressions  are  given  to  record  the 
relation  between  coefficient  of  diffusion  and 
concentration  of  gel. 

5.  The  coefficient  of  diffusion  increases 
with  decreasing  concentration  of  the  diffus- 
ing salt.  An  empirical  expression  is  given 
to  exip/ess  approximately  the  relation  be- 
tween coefficient  of  diffusion  and  concentra- 
tion of  diffusing  salt  in  the  case  of  sodium 
chloride. 

H.  T.  Flint.  A  Generalised  Vector  An- 
alysis of  Four  Dimensions.  Communicated 
by  Prof.  0.  W.  Richardson,  F.R.S. 

The  paper  gives  an  account  of  an  in- 
variant Vector  Calculus  in  a  notation  which 
is  the  natural  generalisation  of  that  of 
Gibbs.  Contravariant  and  covariant  vec- 
tors are  related  by  means  of  an  operator — 
the  extended  idem-factor,  and  tensors  Me 
introduced  as  dyadics  and  polyadics.  The 
expressions  familiar  in  the  Tensor  Calculus 
of  Riemann  and  Christoffel  appear  very 
simply  in  the  analysis.  Separated  points 
are  connected  by  the  geodetics  and  a  sim- 
ple definition  of  par^lelism  at  two  points 
leads  at  once  to  the  Weyl  parallel  displace- 
ment relations. 


ROYAL  INSTITUTION  OF  OREAT 
BRITAIN. 

The  Friday  evening  discourse  on  Friday, 
March  23  (at  9  o'clock)  will  bo  delivered"  by 
Sir  Ernest  Rutherford,    IjL.D.,     D.Sc, 


MAECH  23.  1923. 


ttlE    CHEMICAL    NEWS. 


isa 


F.R.S.,  M.R.I.,  Prof,  of  Natural  Philoso- 
phy ;Cavendish  Prof,  of  Experimental  Phy- 
sics, Univ.  of  Cambridge.  The  subject  is 
Life  History  uf  an  Aljiha  Particle  fru}n 
Radiuvi. 

Saturday,  March  24.  —  Sir  Ernest 
UUTHERFOKU,  LI..D.,  D.Sc,  F.K.S., 
M.li.I.,  Prof,  of  Natural  Philosophy,  ou 
Atomic  Projectiles  and  their  Properties. 
(Lecture   VI.) 


ROYAL  AGRICULTURAL  SOCIETY. 
Proceedings  at  Monthly   Council,    Held 
AT  16,   Bedford  Square,   W.C.I,  on 
Wednesday,  March  7. 
Lieut. -Col.   E.   W.   Sianyforth  (President) 
in  the  Chair. 
Among  the  reports  of  the  various  Stand- 
ing Committees  present4?d  and  adopted  was 
the  following:  — 

Chemical  Report. 
Lord  Bledisloe,  in  the  absence  of  Mr. 
Luddington,  reported  that  the  Consulting 
Chemist  had  presented  to  the  Committee  a 
list  of  the  samples  analysed  by  him  for 
members  during  the  past  month. 

The  Chairman  had  reported  that  he,  to- 
gether with  Mr.  J.  W.  PearsMi,  had  had  an 
interview  with  the  Minister  of  AgricuJtun- 
on  the  question  of  the  new  Bill  to  amend 
the  existing  Fertilisers  and  Feeding  Stuffs 
Act.  Sir  Robert  Sanders  had  premised  to 
write  his  decision  in  the  course  of  a  few 
days.  As  this  reply  had  not  yet  been  re- 
ceived, it  was  decided  that  a  nirther  meet- 
ing should  not  be  called  until  the  promised 
repiv  from  tlie  Ministry  was  in  the  hands 
of  tne  Chairman.  Should,  however,  a  con- 
siderable time  elapse,  the  Chairm«n  wouid 
call  anothir  meeting  of  the  representatives. 
Dr.  Voelcker  had  submitted  various  mat- 
ters arising  out  of  his  correspondence, 
which  dealt  chiefly  with  castctf  oil  bean  in 
feeding  cakes,  basic  slag  which  was  in- 
suHiciintly  ground,  fish  meal  with  exces- 
sive oil,  and  the  cost  of  burning  chalk  for 
Hme. 

The  Committee  received  with  regret  the 
report  of  the  death  of  Mr.  F.  J.  Lloyd, 
formerly  senior  assistant  in  the  Society's 
laboratory. 

Lord  Bledisloe,  in  moving  the  adoiption 
of  this  report,  referred  to  the  recent  death 
of  Mr.  IJoyd,  who  at  one  time  had  been 
an  assistant  in  the  Society's  laboratory. 
Mr.  Lloyd  had  done  valuable  work  during 
his  lifetime  as  an  agricultural  chemist. 


THE  GEOLOGICAL  SOCIETY. 

Annual  General  Meeting. 

Fsbruanj  \Q. — Prof.   A.  C.  Seward,   8c. D., 

F.H.8.,   Prtsident,   in  the  Chair. 

The    Reports    of    the    Council     and    the 

Library  Committee  were  read. 

The  completion  of  Vol.  LXXVill.  of  the 
Quai'terly  Journal  was  announced,  as  also 
the  publication  of  the  Lists  of  Geological 
Literature  for  1914  and  1022. 

The  President  presented  the  Wollaston 
Medal  to  William  Whitaker,   F.R.S. 

The  Murchison  Medal  was  presented  to 
Prof.  John  Joly,  F.R.S. ,  the  Lyell  Medal 
to  M.  Gustave  F.  Dollfus,  the  For.Memb.- 
G.S. 

The  Bigsby  Medal  was  awarded  to  Mr. 
Edward  Battersby  Bailey,  M.C.  Mr.  G. 
W.  Lamp  I  ugh,  F.R.S.,  acknowledged  it  for 
the  recipient. 

The  ballot  ft>i-  the    Council    and    Officers 
wae  taken,  and  the  following  were  declared 
duly  elected  for  the  ensuing  year: — Coun- 
cil: Charles  William  Andrews,  B.A.,  D.Sc, 
F.R.S.;   Frederick     Noel  Ashcroft,     M.A., 
F.C.S.;  Prof.  Percy  George  Hanmall.Bos- 
v,e[\,   O.B.E..     D.Sc;    Prof.     William    S. 
BoultcMi,   D.Sc.  Assoc. R. C. Sc  ;  James  Ar- 
chibald   Douglas.    M.A.,    B.Sc;     Gertrude 
Lilian  Elles,  M.H.E.,  D.Sc;  John  WilHam 
Evans.    C.B.E.,    D.Sc,     LL.B.,     F.R.S.; 
John  Smith  Flett,  O.B.E.,  M.A.,    LL.D., 
D.Sc,  M.B.,  F.R.S. ;  Sir  Archibald  Geikie, 
O.M.,     K.C.B.,     D.C.L..     LL.D.,    ScL)., 
F.R.S.;   Frederick   Henry   Hatch,   O.B.E., 
Ph.D.;    Robert    Stanafield   Herries,     M.A.; 
Prof.  Owen  Thomas  Jones,   M.A.,     D.Sc; 
William  Bernard   Robinson  King,   O.B.E., 
M..V.;  William  Dickson  Lang,  M.A.,  ScD. ; 
Richard  Dixon  Oldham.  F.H.S. ;  Prof.  Sid- 
ney Hugh  Reynolds,     M.A.,  ScD.;    Prof. 
Albert     Charles    Soward,     ScD.,     F.R.S., 
F.L.S. :    Walter    Campbell    Smith,     M.C, 
M.A.;  Sir  Aubrev  Strahan,  K.B.E.,  ScD., 
LL.D..  F.R.S.:  Sir  Jethro  J.  Harris  Teall, 
M.A.,     D.Sc.     LL.D.,     F.R.S.;     Herbert 
Henry  Thomas.   M.A.,  ScD.;     Prof.    Wil- 
liam Whit<?head     Watts,     LL.D.,      ScD., 
M.Sc,   F.R.S.;  and  Henry  Woods,   M.A., 
F.R.S. 

Officers :  President,  Prof.  Albert  Charles 
Seward,  ScD.,  P\R.S.,  F.L.S. ;  Vice-Pre- 
sidents, John  William  Evans,  C.B.E., 
D.Sc,  LL.B.,  F.R.S.;  Richard  Dixon 
Oldham,  F.H.S. ;  Herbert  Henry  Thomas, 
M.A.,  ScD. ;  and  Prof.  William  White- 
head Watts.  LL.D.,  ScD..  M.Sc,  F.R  S. 
Secretaries,  Walter  Camipbell  Smith,  M.C, 
M.A.,     and     James     Archibald     Douglas, 


190 


THE   CHEMICAL   NEWS. 


MAECH  23,  1923. 


M  \     B  Sc  ;  Foreign  Secretary,  Sir  Archi- 
bald Geikie,  O.M.,  K.C.B.,  D.C.L.,  LL.D 
Sc.D.,     F.E.S.;     and    Treasurer,      Kobert 
Stansfield  Herries^  M.A. 

The  thanks  of  the  Fellows  were  unani- 
mously voted  to  Prof,  E.  J.  Garwood  and 
Dr  G.  T.  Prior,  retiring  from  the  office  of 
Vice-President,  and  also  from  the  Council ; 
and  to  the  other  retiring  members  of  Coun- 
cil •  Dr.  F.  A.  Bather,  Mr.  T.  C.  Cantrill, 
and  Mr.  J.  F.  N.  Green. 

Fesruary  28,  1923. 
Prof    A    C.   Seward,  Sc.D.,  F.R.S.,  Presi- 
dent, and,  afterwards,  Prof.  W.  W.  Watts, 
8c  D  ,  F.R.S.,  Vice-President,  in  the  Chair. 
The  list  of  donations  to  the  Library  was 

read.  .     ,. 

The     following       communications     were 

^^^hThate  Glacial  Stage  of  the  Lea  Valley 
'(Third    RepoH),    by    Samuel    Hazzledine 

Warren,  F.G.S.  ^   -,    r  r,,    j. 

The  Elephas-antiquus  Bed  of  Clacton-on- 
Sea  (Essex),  and  its  Flora  and  Fauna,  by 
Samuel  Hazzledine  Warren,  F.G.b. 

The  two  papers  were  followed  by  discus- 
sions. 


EOYAL  SOCIETY  OF  ARTS. 
The  Cantor  Lecture  (3),  entitled  Accu- 
rate Length  Measurement,  was  read  on 
Monday,  March  19,  by  J.  E  Sears  Jun., 
CBE.,  M.A.,  M.I.M.E.,  Assoc.M.Inst.- 
C.E.,  Superintendent  of  Metrology  I>ept., 
National  Physical  Laboratory. 

At  the  Ordinary  Meeting  on  Wednesday, 
March  21,  a  paper  entitled  Some  Cunous 
Phenomena  of  Vision,  and  the^r  Practical 
Importance,  was  read  by  F,  W  Edridge- 
Green,  C.B.E.,  M.D.,  F.R.C.S  Specia 
Examiner  and  Adviser  of  the  Board  of 
Trade  on  Colour- Vision  and  Eyesight,  ihe 
paper  was  illustrated  with  lantern  and 
other  demonstrations.  Professor  B.  H. 
Starling,  C.M.G.,  M.D.,  Sc.D.,  F.E.S., 
presided. 


THE    CHEMICAL    SOCIETY. 

The    Annual    General    Meeting     of     the 
Chemical    Society  was    held   on  Thursday, 

March  22. 

Business. 
The  Eeiport  of  the  Council    for  the  year 


ended  December    31,     1922,    was    received 
and  adopted. 

The  President,  Sii-  James  Walker,  D.bc, 
F.E.S.,  delivered  his  Presidential  Address, 
entitled  Symbols  and  Formula. 


THE  OPTICAL  SOCIETY. 
A  meeting  was  held  at  the  Imperial 
College,  Imperial  Institute  Eoad,  South 
Kensington,  at  7.30  p.m.  on  Thursday, 
March  22.  1923,  when  the  fifth  of  the  series 
of  lectures  dealing  with  the  evolution  and 
develoipment  of  optical  instruments  was 
delivered. 

Subject:  Surveying  and  nautical  instru- 
ments from  a  historical  standpoint.  Lec- 
turer :  Dr.  L.  C.  Martin. 

The  lecture  was  illustrated  by  ex- 
hibits from  the  collection  in  the  Science 
Museum,  Kensington  (by  the  kind  permis- 
sion of  the  Director,  Col.  Lyons,  F.E.S.). 

SOCIETY  OF  GLASS  TECHNOLOGY. 

A  meeting  of  the  Society  was  held  in  the 
Latin  Theatre,  The  University,  Edmund 
Street,  Birmingham,  on  Wednesday, 
March  21,   1923. 

The  following  papers  were  read   and  dis- 

CUiSSCU.  *.  — 

A  Rapid  Method  of  Testing  the  Durabil- 
ity of  Glassware,  by  H.  S.  Blackmore, 
Violet  Dimbleby,  B.Sc,  and  Prof.  W.  R. 
S.  Turner,  D.Sc. 

The  Corrosion  of  Fireclay  Refractory 
Material  by  Glass  and  Glass-making 
Materials,  by  Donald  Turner,  B.Sc. Tech. 
(Latelv  Salter's  Eesearch  Fellow),  ar.d 
Prof.  W.  E.  S.  Turner,  D.Sc 

The  Effect  of  Saltcalce  in  Corroding  Fire- 
clay Materials,  by  Edith  M.  Firth,  B.Sc, 
F.  W.  HoDKiN,  B.Sc,  and  Prof.  W.  E.  b. 
Turner,  D.Sc. 

By  the  courtesy  of  the  directors,   a  visit 
was  made  to  the  works  of  Messrs.    Austm 
Motor  Co.,   Ltd.,   No'rthfield,  Birmingham. 
"  Directory  for  the  British  Glass 

Industry." 
This  Directory,  the  publication  of  which 
has  been  unavoidably  delayed,  will  be 
ready  on  March  20.  It  is  bound  in  cloth 
and 'contains  384  pages.  It  may  be  pur- 
chased by  members  at  the  very  low  price  of 
6s.,  post  free.  Members  who  have  not  yet 
ordered  a  copy  should  send  their  ^order, 
with  remittance,  to  the  Secretary,  Society 
of  Glass  Technology,  Damall  Road, 
Sheffield. 


MARCH  23.  1923. 


THE  CHEMICAL  NEWS. 


191 


THE  ESTIMATION  OF  LACTOSE. 

By  Vincent  Edwards,  F.I.C. 
The  determinatiou  of  milk  sugar  in 
various  milk  products  has  for  many  years 
past  been  carried  out  by  Fehling's  well- 
known  method  either  volumetrically  for 
O 'Sullivan '»  weight  method  if  the  amount 
large  percentages,  or  by  modification  of 
was  small.  There  can  be  no  doubt  that 
with  certain  precautions  and  experience  a 
rapid  and  accurate  estimaticai  can  be  made 
volumetrically,  and  as  the  subject  is  of  in- 
creased interest  owing  to  the  proposed  new 
regulations  concerning  "total  solids"  in 
milk,  I  venture  to  put  forward  a  slight 
modification  of  the  method  which  I  have 
found  useful  as  giving  a  much  clearer  indi- 
cation  of  the  end  of  the  reaction,  the  ob- 
scurity of  which  has  always  been  one  of 
the  drawbacks  of  this  historic  procedure. 

I  take  10  cc.  of  milk  or  other  liquid  milk 
product,  or  one  gram  of  milk  powder,  dis- 
solve in  hot  water,  make  up  to  nearly  100 
CO.,  and  boil  with  a  few  cc.  of  10  per  cent, 
acetic  acid;  allow  to  cool,  dilute  to  100  cc, 
filter  off  the  casein;  a  perfectly  clear  fil- 
trate should  result.  Ten  cc.  of  mixed  Feh- 
ling  solution  are  now  run  into  a  small 
porcelain  dish,  and  before  dilution  with  40 
cc.  of  distilled  water,  a  pinch  (about  suffi- 
cient to  go  on  the  point  of  a  knife)  of  mag- 
nesium tartrate  is  mixed  in.  This  valuable 
improvement  is  due  to  the  late  S.  A. 
Vasey.  The  red  precipitate  is  collected  in 
the  centre  of  the  dish,  with  a  ring  of  cle^r 
liquid  round  the  sides,  in  which  the  blue 
colour  is  seen  quite  plainly. 

My  modification  is  in  the  subsequent 
stages.  A  piece  of  pure  paraffin  wax, 
about  the  size  of  a  walnut,  is  put  in  the 
dish,  the  titration  is  then  CMitinued  with 
the  usual  precautions,  and  with  the  addi- 
tions mentioned  a  much  better  end  indica- 
tion can  th\is  be  obtained.  If  a  slight  ex- 
cess, about  0.5  cc.  of  the  test  solution  or 
a  little  more  is  run  in,  and  allowed  for,  the 
clear  yellow  tinge  showing  the  complete 
absence  of  copper  in  the  solution  is  very 
apparent.  As  10  cc.  or  one  gram  of  the 
milk  proruct  is  taken,  the  calculation  of 
the  result  is  quite  simple,  the  factor  0.72 
being  taken  for  milk  sugar.  It  is  to  be 
desired  that  in  place  of  the  term,  "  total 
solids,"  fuller  particulars  were  given  of  the 
ingreditnts  of  milk.  The  public  are  becom- 
ing aware  that  the  fat  is  not  the  only  con- 
stituent worth  consideration,  and  that  pro- 
teins, sugar  and  phosphates  have  their 
own  special  value  for  dietetic  purposes. 


CORRESPONDENCE. 


PROJECTED  COMPENDIUM  ON 
COLLOID  CHEMISTRY. 
To  the  Editor  of  The  Chemical  News. 
Sir, — With    the    assistance   of  prominent 
specialists  the  world  over,  I   am  preparing 
a  comprehensive  book    on  Colloid  Chemis- 
try, Theoretical  and  App'it'd.       The  exten- 
sive and  int<;rnati<Hial  character  of  the  book 
is  evidenced  by  the  list    of  those  who  have 
already    promised    contributions. 

Many  unusual  experimental  facts  and 
practical  applications  of  colloid  chemistry 
principles  are  unpublished,  and  the  object 
of  this  letter  is  to  ask  anyone  in  any  field 
of  science  or  ex^perience,  who  may  have  in- 
formation of  interest,  to  send  me  a  brief 
statement  for  inclusion  in  the  book. 

Contributions  may  consist  of  a  para- 
graph, a  page,  or  several  pages,  and  will 
(unless  contrary  request  is  made)  be  duly 
acknowledged.  If  possible,  they  should  be 
submitted  in  p]nglish,  and  duplicate  copies 
will  be  appreciated.  Authors  should  state 
their  full  names  and  titles. 

The  editors  of  scientific,  technical  and 
cultural  publications  in  all  countries  arc 
asked  to  disseminate  this  appeal. — Yours, 
etc.,  Jerome  Alexander,  M.Sc. 

50,  Kaxt  41«<  Street,  New  York,  U.S.A. 
Fchnuinj  10,   1923. 
[A  long  list  of  distinguished    chemists 
and  scientists  of  all  coimtries,   who  have 
contributed  to  the  knowledge    of  colloid 
chemistry,   is  appended. — Ed.,  C.N.] 


THE  AUTHENTICITY  CF  THE  LATIN 
WORKS  OF  GEBER. 

To  the  Editor  of  The  Chemical  News. 

SiE, — I  was  much  interested  to  read  Mr. 
E.  E.  Whale's  letter  on  the  above  topic,  in 
your  issue  for  March  9,  and  the  excellent 
report  of  Mr.  Holmyard's  IcKjture  on 
"  Arabian  Alchemy  and  Chemistry,' 
which  appeared  in  the  previous  issue.  In 
that  report  yon  were  kind  enough  to  \n- 
clude  my  own  nmarks — to  which  I  would 
draw  Mr.  Whale's  attention— which  per- 
haps sufficiently  define  my  own  position 
towards  the  question  of  Geber  in  the  light 
of  Mr.  Holmyard's  researches;  but  it  may 
possibly  be  of  use  if  I  briefly  expand  these 
here.  Like  Berthelot,  I  know  no  Arabic, 
and  in  common  with  him  and  other  writers 


102 


THE  CHEMICAL  NEWS. 


MARCH  23,  1923. 


on  the  historj'-  of  chemistry,  I  had  to  rely, 
when  writing  Alchemy:  Ancient  and  Mod- 
ern, upon  the  translations  of  Geber's  origi- 
nal works,  which  Bcrthelct  had  had  pre- 
pared for  the  purposes  of  his  own  studies. 
Judging  from  these,  no  other  conclusion 
seemed  possible  than  would  appear  to  be 
that  for  adequate  translations  of  these  Ara- 
bic MSS.,  and  it  is  to  be  hoped  that  Mr. 
Holmyard  might  be  persuaded  to  undertake 
this  important  work.  A  translation  of 
Geber's  Book  of  Properties,  for  example, 
the  MSS.  of  which  is  in  the  British 
Museum,  would  be  especially  welcome. 
Until  such  translations  have  been  made  it 
may  be  as  well  to  retain  an  open  mind  con- 
cerning the  question  of  the  authenticity  of 
til  Latin  works ;  but  certainly  the  evidence 
for  reversing  the  decision,  arrived  at  by 
Berthelot,  which  Mr.  Holmyard  has  al- 
ready put  forward  is,  to  my  mind,  very 
convincing. 

As  to  the  different  spellings,  "  Geber  " 
and  "  Dschabir,"  these  are  merely  differ- 
ent transliterations  of  the  same  Arabic 
name,  and  do  not  refer  to  different  indi- 
viduals.— Yours,  etc., 

H.    Stanley  Eedgrove, 
B.Sc,  A.I.C.,  F.C.S. 

191,  Camden  Eoad.  N.WA. 
March  10.  1923. 


BOOKS  RECEIVED. 

A   Comprehensive  Treatise  on    Inorganic 

and  Theoretical  Chemistry,  by  J.  VV. 
Mellor,  D.Sc.  Pp.  X.  +  927.  Vol.  III., 
1923.*  Messrs.  Longmans,  Green  &  Co., 
39,  Paternoster  Row,  E.C.4.     63s.  net. 

Anorganische  Cheniie,  by  Dr.  Fritz 
Ephraim.  Pp.  VIII.  +  742.  1923.  Ver- 
lag  von  Theodor  Steinkopff,  Dresden  and 
Leipzig.     8s.  6d.,  Bound  10s.  2d. 

Glue  and  Gelatin,  by  Jerome  Alexander. 

Pp.  236.  1923.  The  Chemical  Catalog 
Co.  Inc.,  19,  East  24th  Street,  New  York, 
U.S.A.     3  dollars. 

Chemical  Technology  and  Analysis  of 
Oils,  Fats  and  Waxes,  by  Dr.  J.  Lew- 
KOwiTscH,  M.A.,  F.I.C.  Entirely  revised 
by  George  H.  Warburton.  Pp.  VIII.  + 
508.  Sixth  Edition.  Vol.  III.  1923. 
Messrs.  Macmillan  &  Co.,  Ltd.,  St.  Mar- 
tin's Street,  W.l.     36s.  net. 

Vital  Factors  of  Foods,  Vitamins  and 
Nutrition,  by  Carleton  Ellis,  S.B,, 
F.C.S. ,  and  Annie  Louise  Macleod,  Ph.D. 


Pp.  XIII.  +  391.  1923.  Messrs.  Chapman 
&  Hall,  Ltd.,  11,  Henrietta  Street,  Covent 
Garden,  W.C.2.     25s.  net. 

The  Maihi'inatical  Theory  of  Relativity, 
by  August  Kopff.  Translated  bv  H. 
Levy,  M.A.,  D.Sc,  F.R.S.E.  Pp.  VIII. 
+  214.  1923.  Messrs.  Methuen  k  Co., 
Ltd.,  36,  Essex  Street,  W.C.2.  8s.  6d. 
net. 

Year   Book 

by       L. 

Pp.  1,107. 


The    Choiiists' 
Atack,      assisted 
A.M.C.T..  A. I.e. 
II.       1923.      Messrs.    Sherratt 
34,   Cross  Street,   Manchester. 
(Abroad,  il  2s.). 


by  F.  W. 
Whinyates, 
Vols.  I.  and 
&  Hughes, 
£1   Is.  9d. 


This  list  ii;  .si>ecially  compiled   for     The  Chemical 
News,  by  Messrs.  Rayner  &  Co..  Registered  Patent 
Agents,  of  5.  Chanoery  Lane.  Ixindon.  from  whom 
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Monoazo     dyes,     yielding      fast 
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naphtlialene-4-sulphonic      acid,     or   a    fubstituti^ 
product   thereof,     with  B-resorcylic   acid;     in   ex- 
amples the  diazo  compound  itself  and  the  nitrated 
diazo  compound  are  used. 

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Week. 
Tndustrv 


violet-blue     to 


MAECH  29,  1923. 


THK   CHEMICAL    NEWS. 


193 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3285. 


A  NEW  DISTINCTION   BETWEEN 
SODIUM  AND  POTASSIUM. 

By  C.  W.  L.  Bourlet  and  W.  Thomas. 

The  elements,  sodium  and  potassium, 
are  so  much  alike  chemically  that  any 
ipoint  of  marked  difference  between  them 
seems  worthy  of  note. 

The  following  facts,  which,  so  far  as  wo 
know,  are  brought  forward  for  the  first 
time,  point  to  a  highly  interesting  differ- 
ence in  the  colloidal  constitution  of  the 
aqueous  solutions  of  the  fatty  aoid  salts  of 
potassium  and  sodium. 

It  is  common  knowledge  that  eoluticms 
of  sfxlium  oleate  of  higher  concentration 
than  5  per  cent,  form  a  gel  on  cooling  to 
nortnal  temperatures.  Solutions  of  potas- 
sium oleate,  on  the  other  hand,  may  be 
poured  from  one  vessel  to  another  till  the 
concentration  reaches  approximately  40  per 
cent.  In  the  case  of  the  potassium  soaps 
the  change  of  concentration  gradually  in- 
creases the  viscosity  till  the  mass  becomes 
very  viscous,  and  finally  plastic. 

In  the  case  of  the  sodium  soaps,  how- 
ever, the  change  from  sol  to  f,'el  is  sudden : 
slight  variations  in  concentration  or  tem- 
perature induce  enormous  variations  in  vis- 
cosity. 

The  addition  of  phenol  or  cresol  to  a  po- 
tassium soap  solution  "thiolcons"  it,  i.e., 
the  viscosity  is  increased,  the  effect  being 
most  marked  in  the  case  of  phenol. 

In  the  case  of  the  sodium  soatp.  how- 
ever, the  effect  is  reversed  :  phenols  par- 
tially- destroy  the  power  of  gel  formation 
and  lower  the  viscosity.  Thus,  the  addi- 
tion of  4  per  cent,  phenol  or  2^  per  cent,  cf 
o,  m,  or  p-cresol  to  a  10  per  cent,  solution 
of  sodium  soap  reduces  it  to  a  liquid  com- 
iparabTe  in  viscosity  with  water  at  ordinary 
temperatures.  Super-cooling  causes  it  to 
gel  at  a  lower  temperature,  depending  on 
the  concentration  of  soap  and  phenol.  Oel 
formation,  however,  is  always  svddev; 
there  is  no  gradual  increase  in  viscosity  ns 
in  the  case  of  a  potassium  soap.  The  addi- 
tion of  sodium  hydroxide,  carbonate,  or 
silicate  in  suflficient  quantities  restoree  the 
power  of  gel  formaticm. 

To  distinguish  between  a  potash  and  a 
soda  "soft"  soap,    it  is  only  necessary  to 


prepare  a  15  per  cent,  aqueous  solution, 
measure  the  efflux  time  at  constant  tem- 
perature from  a  pipette;  then  add  (say)  4 
per  cent,  phenol.  In  the  case  of  a  ipota^h 
soap  the  efflux  time  will  be  increased;  in 
the  case  of  a  soda  soap,  decreased. 


VALENCY. 

By  William  B.  Fielding,  M.A.,  M.Sc. 
(Vict.). 

Senior  Science  Master,  King  Edward  VII. 
School,   Lytham. 

(Continued  from  Page  180.) 

(S)  Manifestations  of  Valency. 

Valency  is  manifest  in  different  ways, 
and  it  is  impossible  to  differentiate  between 
the  different  "  kinds,"  if  any  difference 
exists.  It  is  a  force  holding  two  portions 
^>f  mattt>r  together. 

1. — Valency  of  Atomic  Structure,  hold- 
ing the  positive  nucleus  and  the  electrons 
together.  As  an  atom  loses  or  gains  an 
electron  its  valency  is  increased  by  one 
unit. 

2. — There  is  molecular  valency 

(a)  holding  the  atoms  in  an    elemen- 
tary molecule  together; 

(h)  holding  imlike    atoms  together    in 

cht*micjil  combination. 

3. — Polymolecular  valency  holding  two 
or  more  like  molecules  together. 

4. — Valency  of  aggregation,  holding  a 
number  of  molecules  together  in  an  aggi'e- 
gation  (see  The  Chemical  News,  1920, 
rXX..  3136;  CXXII.,  3170). 

5. — Valency  of  Cohesion  (holding  like 
aggregations  together),  and  adhesion  (un- 
like  aggregations). 

fi. — Valency  of  solution.  This  subjectj 
will  be  dealt  with  in  a  subsequent  article. 

Valencies  8.  4.  6  rapidly  change  with 
temperature  (see  The  Chemical  News, 
1921.  ('XXII..  13.  289,  etc.). 

(9)  When  to  Compare  Valencies. 

We  ought,  if  possible,  to  compare  the 
valencies  of  elements  (No.  2  above)  under 
the  same  conditions,  say,  either  at  the 
B.P.  or  just  at  the  moment  of  decomposi- 
tion. 


194 


THE   CHEMICAL    NEWS. 


MARCH  29,  1923. 


Eq!- 


H^O 


H' 


H- 


\. 


'O 


H.^ 


(F.9    8.) 


This  would  lead    us  to  form    a  table    of 
valencies  like  the  f  ol  lowing  :  — 
Elements.  Valency. 

H  1 

O  2  (H,0) 

S  4  (SO,) 

C  4  (CH,  .  CO,) 

P  3  (PCI3) 

Hg  2  (HgO) 

A  complete  table  could  only  be  oomipiled 
from  data  obtained  from  compounds  which 
can  be  vapourised  without  decomposition. 
No  account  would  be  taken  of  "residual" 
or  "supplementary"  valencies  (which 
might  exist),  but  we  should  at  least  be  con- 
sistent. 


(10)  Periodicity  of  Valency. 

Certain  elements   which   are  diatomic  in 
the  gaseous  state  have  come  to  he  regarded 
as  monovalent  or  standard  elements. 
H  —  H,      F  —  F,      CI  —  CI,       H  —  CI. 

Also  certain  radicles  which  exist    in  the 
"paired"  state :  — 


CH, 

I 
CH, 


CjHg 


C2H5 


Also  note      C^SL^ 


^ 


H 

I 
OH 


etc. 


The  highest  valencies  are  shown  by  ele- 
ments in  their  oxides  (as  usually  written  in 
their  graphical  formulae).  From  the  oxide 
XjOy  the  valency   (which   may    be   as  high 

2y 

as  8)  is    — 

X 

The  highest  valencies  obtained  by  dif- 
ferent methods  are  shown  below  for  two 
series  of  the  periodic  table  (Fig.  IX.), 


G-'Rou  T»s:- 

0 

I 

H 

111 

■ 

rv 

2: 

ja. 

VIC 

VI LL 

\/a.le»>c^  -from 

He 

L.L 

IBe 

3 

c 

N 

0 

p 

— 

0  xLdcs.- 

0 

« 

2. 

-3 

'^ 

5 

— 

— 

— 

H^c*.**icle.^    and. 

0 

— 

— 

— 

4- 

3 

2. 

1 

— 

Hs<*-**ox  idLes.- 

0 

1 

2 

3 

-1- 

Ho(nO^ 

— 

— 

-- 

HolI  i  dles:- 

0 

1 

2. 

3 

^ 

3 

2. 

1 

— 

Vo-lencv^    -fvo»-n  B     Nc 

Ncx 

M3 

Al 

SL 

-P 

S 

Cl 

— 

OxidLes-.- 

0 

1 

2. 

3 

^ 

5 

b 

7 

O&Q,^ 

"R  o-ci  teles: — 

0 

1 

2 

3 

-4- 

■3 

2. 

1 

— 

H^  d.  rox  v,d.e,s-.- 

0 

1 

Z 

•3 

< 

3 

a 

1 

— 

Ho.^JcL«s.- 

0 

1 

a 

3 

4- 

5 

4- 

— 

— 

MARCH  29,  1923. 


THE  CHEMICAL  NEWS. 


195 


Frequently  an  element  does  not  reach  as 
high  a  valency  in  one  comipound  as  in  an- 
other, although  it  is  surprising  how  many 
of  these  cases  can  be  explained  away  by 
the  simple  process  of  valency  bonds  (Fig. 
X.):- 


N 

I 
O 

I 
N 


I 
•O 


or 


rsi 


O 


^ 


O 


^< 


o 


o 


("Fi^    lO) 

In  nClO,  HCIO2,  HCIO,,  HCIO,  chlor- 
ine is  gradually  climbing  to  its  maximum 
valency  (7). 

Iron  is  dyad  in  FeO, 

triad  in  FcjOj, 

tetrad  in   Fe,0,   (FeO  .  Fe,Os). 
The   phosphorus    compounds     with     the 
halogens    show     the      following     valencies 
(Fig.  XI.):- 


^C, 


\ 


ci 


k 


c/\i 

(■p.^  n) 

In  the  crystalline  mixed  halide,  PCI,.Br^. 
phosphorus  has  a  still  higher  valency  un- 
less we  write  it 


o^ 


(T\<^  l^) 


the  dotted  lines  showing  the  points  where 
decomposition  readily  occurs  (the  weak 
links). 

Herf     bromine    would    be    dyad.       Also 
note 


H 


O- 


-3v: 


.^ 


o 

o 
o 


(Ti3     13.) 


Iodine  can  be    conveniently    pven    any 
valency  between  1   and  7.     Thus:  — 

1 


K— I 

K l<Zj^ 

i<6 


I — o — o — o — < 


:— o-i^. 


2.3. 

I     ■ 
3.5. 

1 

2. 

3.  T. 


Adding  a  molecule  of  water  we  get 

n O OH 


-OH 


HO- 


or     2H0 


.0-1^ 


(T.3   I?) 


THE   CHEMICAL    NEWS. 


MARCH  29,  1923. 


The  acid    iodates    may    be    regarded    as 
as  derived  from 


(  HO — i^o  )^ 


C^-O 


HO— I 


/ 


■I— HO 


HO     ^^O 
(Tig    It.) 


or  the  valency  of  iodine    mav  be  increased 
to  7. 

MendeMef  pointed  out  that  in  many 
cases  the  sum  of  the  valencies  in  oxides 
and  hydrides  was  8,  and  attempts  have 
been  made  to  give  such  low-valent  ele- 
ments as  sodium  a  valency  of  7.  The  hy- 
drate NaOn  .  3H2O  may  be  written 
Na(0H)4.H3,  and  the  compound  repre- 
sented thus  (Fig.   17) : 


(Tig  n.) 


Valencies  numbers  1,  12,  10,  8,  are  in 
the  first  instance  strong;  the  remainder 
"residual"  or  supplementary.  After  the 
hydrate  has  been  formed  there  is  probably 
a  redistribution  of  valency-strength,  but 
these  four  will  remain  stronger  than  the 
others.  Further  molecules  of  water  could 
be  added  without  altering  the  heptavalent 
character  of  the  sodium,  thus: — 


0H> 


H 


N 


cxr 


.OH 


H 


OM- 


-M 


^OH 


(Tig    l«) 


(iVofe.— There  should  be  a  bond  between  Na  and 
the  lowest  H.) 

The  valency  of  hydrogen  is  more  than 
one,  but  it  can  be  reduced  to  2  by  cancell- 
fhg  bonds  9,  II,  13. 

(11)  Theories  op  Valency. 

It  would  be  impossible  in  the  space  of  a 
short  article  to  refer  to  the  many  different 
and  often  ingenious  theories  put  forward 
to  explain  the  phenomenon  of  valency. 

Probably  Werner's  theory  is  the  one 
most  widely  held  to-day.  Werner  sup- 
posed that  atoms  could  be  connected  to 
each  other  in  two  ways,  directly  and  in- 
directly by  the  existence  of  a  force  which 
is  able  to  penetrate  the  envelope  of  pro- 
tective at5ms  or  groups  which  surround  the 
central  atom.  The  latter  is  directly  united 
with  the  non-ionisable  groups,  such  as 
NH3,  NOj,  which  are  included  in  the  com- 
plex radicle  and  they  are  not  ionised  in 
solution.  The  valencies  so  employed  are 
termed  the  supplementary  valencies  of  tlie 
central  metal.  The  principal  valencies  are 
used  to  link  on  to  ionisable  groups.  These 
ionisable  groups  are  outside  the  complex 
formed  through  the  agency  of  the  supple- 
mentary valencies.  Werner  put  the  ionis 
able  part  of  the  molecule  outside  a  square 
bracket,  thus:  — 


[Co(NH3)JCl3 

[CoCKNHOslCl^  

[PtCl3.(NH3),]Cl3\^^ 


This  chlorine  is. 
ionic,  i.e.,  can  be 
.precipitated  by  a 
solution  of  silver 
nitrate. 


In  chloroplatinic  acid,  HgPtClg,  none  of 
the  chlorine  is  ionic,  i.e.,  can  be  precipi- 
tated by  silver  nitrate. 

The  number  of  groups  or  atoms  directly 
bound  to  the  central  atom  (in  the  above 
eases)  is  6;  this  is  termed  the  "  co-ordina- 


MARCH  29,  1923. 


THE   GHEMlCAl^    NEWS. 


M 


tion  number  " — "  a  fundamental  prqperty 
of  the  elementary  atom."  This  theory  pre- 
dicted and  explained  the  existence  of  iso- 
mers, many  of  which  have  been  since  iso- 
lated. Where  the  co-ordination  number  is. 
6  the  groups  can  be  represented  at  the 
angles  of  a  regular  octahedron,  thus : — 


NH« 


NM« 


NH 


NO  a 
<LonLc) 


must  be 

used    in 

'6Uf>ple- 

'positions 


Cl   (tonic) 

A  recent  writer  hag  said:  '  It 
admitted  that  the  conceptions 
Werner's  theory,  e.g.,  those  of 
tjientary  valencies'  and  of  the 
inside  and  outside  the  nucleus'  are  vague," 
and  the  author  has,  he  believes,  discovered 
an  alternative  method  of  explaining  the 
formation  of  these  complex  molecules. 
Several  compounds  were  examined  with 
the  object  of  finding  out,  whether,  if  p  and 
Pi  are  the  rates  of  polymcri8ati<Mi  of  the 
component  parts  of  a  coinipound  and  A  and 
B   the   percentage  composition, 


pA  +  p,B 
100 


=    Pa 


wTiere  p,  is  the  rate  of  polymerisation  of 
the  compound  (see  The  Chemical  Newt, 
1921,  CXXII.,  3170). 


Lead  Sulphide. 

Temp.  (A°)  p 

Pb                   307  1.47 

S  (rhombic)   304  1.83 

PbS                305  1.62 


Pb 

S 


Percentage. 
86.6 
13.8 


P- 
1.47 
1.83 


Calculated 
from      specific 
heats. 

P    X    % 

127.3 

24.8 


151.6 


Average     p  =  1.516 
Observed  p  =  1.62 


Bad.. 
BaCi; 
2H,0 


2H,0. 


BaCl,.2H,0 


329 
273 


305 


1.59 
3 


2.05 


BaCl^ 
2H^0 


% 

85.2 
14.8 


IP 
1.59 
3 


(Consider- 
ed as 
trihydrol) 

%  X  p 

135.5 

44.4 


Average    p  =  1.8+ 
Observed  p  =  2.05 


CuSO,.  5H,0. 

CuSO^ 
5H,0 


T 
335 
273 


% 
63.8 
36.2 


P 
2+ 
8 


179.9 
At  305° 


P  X  % 

127.6+ 

108.6 


236.2 


Average     p   =  2.36+ 
Observed  p  =  2.61  (335'') 


Mg(OH).. 


MgO 
H,0 

T 

335 

273 

% 

71.4 
28.6 

IP 
2.01 

3 

P    X    % 

143.5 
85.8 

229.3 

Average    p  =  2.29 
Observed  p  =  2.65  (at  308") 

The  value  of  p  for  solid  water  is  reckoned 
as  3  (its  value  at  273"),  and  so  the  average 
value  of  p  would  be  lower  in  every  case, 
and  the  disparity  between  the  "average" 
and  the  "observed"  values  greater. 

{To  be  Continued.) 


THE  LAW  OF  MAGNETIC  ROTATION. 
By  Hawksworth  Collins. 

The  magnetic  rotation  of  an  electro- 
positive element,  when  in  combination,  is 
the  product  of  half  its  atomic  weight  and 
the  reciprocal  of  its  relative  volume. 

The  observation  of  this  law  rests  not 
only  upon  the  data  given  below,  but  also 
upon  a  very  large  number  of  facts  arranged 
in  a  particular  manner,  which  is  called 
"  The  Correlation  of  Physico-Chemical 
Constants." 


198 


THE   CHEMICAL    NEWS. 


MAH^H  29,  1923. 


Earlier  papers  concerning  the  Heat  of 
Formation  of  molecules  were  published  in 
The  Chemical  News  of  August  18  and  25, 
1922.  The  publication  of  the  whole  mat- 
ter concerning  these  constants  was  com- 
menced by  The  Chemical  News  on  January 
7,  February  11  and  18,  and  August  19, 
1921. 


Table  I.  gives  the  relative  volumes  of 
tlie  elements  concerned.  Table  II.  gives  all 
available  experimental  results  by  Perkin 
in  magnetic  rotation;  excluding  com- 
pounds in  whioh  hydrogen  occurs,  for 
these  cannot  be  included  in  a  short  paper. 
Table  III.  demonstrates  the  law. 


lielative  Volume. 

CaCO,  13.25  +  20.55  =  33.8 

CaO  13.25  +  4.45  =   17.7 

CaCl,  13.25  +  2(15.085)  =•  43.42 

CaBr^  12.24  +  2(23.09)  =  58.42 

CaS  12.24  +  15.53  =  27.77 

BaCla  24.0     +  2(15.085)   =  54.17 

BaBr^  24        +  2(23.09)  =  70.18 

CdCla  14.57  +  2(15.085)  =  44.74 

CdBr^  14.57  +  2(23.09)  =  60.75 

Cdl^  14.57  +  2(27.73)  =   70.08 

CdO  15.16  +  2.51  =  17.67 

CdSO^  15.16  +  15.53  +  2(7.53)  +  2(2.51) 

=  50.77 

SrCl^  23.96  +  2(15.085)   =  54.13 

SrCOg  19.56   +   20.55   =  40.11 

Srij  19.56  +  2(27.73)  =  75.02 

SrBr,  19.56  +  2(23.09)   =  65.74 


Table  I. 

Theor.  S.G.        Obs.  S.G.  &,  Observer. 

100 

2.959     2.938—2.995      Breit- 

33.8  haupt 


56 

=   3.164    3.161   Karsten 

17.7  3.18  Filhol 

111 

=  2.56       2.48  Playfair  &  Joule 


43.42 
198 


58.42 
72 


-   =  3.39      3.32  11°   Bodeker 


2.59      2.58  Maskelyne 


27.77 
207 

=  3.82      3.82  Schiff 

54.17 
296 
=  4.22       4.23   Schiff 


70.18 

182 

=  4.07       4.05  25°  Van  Nos- 

44.74  trand 

271 
=  4.46      4.712   14°  Bodeker 


60.75 
365 

70.03 
127 

17.67 
207 


5.21       5.543    Kebler 

4.576  10°  Bodeker 

7.19      8.11  Werther 
6.95   Karsten 

=  4.08      4.447  Schroder 

50.77 

159 

=   2.94      2.960  Filhol 

54.13  2.8033  Karsten 

148 
3.69      3.68—3.714  Dana 


40.11 
342 

75.02 

248 


65.74 


=   4.56       4.55   25°  Van  Nos- 
tra nd 

-   3.77      3.962  12°  Bodeker 


MARCH  29,  1923. 


THE  CHEMICAL  NEWS. 


199 


42.5 


LiCl     6.21  +  15.085  =  21.295 

LijS     2(6.21)  +  15.53  =  27.95 

Li,SO^  2(6.21)  +  15.53  +  2(7.58)  + 

2(2.51)  =  48.03 

NaCI  11.85  +  15.085  =  26.935 

NaBr  11.85  +  23.09  =  34.94 
Na^CO,      2(11.85)  +  20.55  =  44.25 

Nal  11.85  +  27.73  =  39.58 

KCl  22.29  +  15.085  =  87.375 

KBr  22.29  +  28.09  =  46.88 


K,SO^       2(18.05)  +  15.58  +  2(7.58)  + 

2(2.51)  =  71.71 

KjS  2(18.05)  +  15.53  =  61.68 


21.295 
46 


=   1.996     1.998  Kremers 


27.95 
110 

48.03 

58.5 


=   1.646     1.63—1.7  Van  Nos 

trand 

=-   2.29      2.21  15°  Brauner 


=  2.17 


26.935 

108 
=  2.95 


2.17  20°  Kaye  & 

Labjr 


34.94 
106 

44.26 
160 


2.952  Sohiff 
=  2.40      2.407  Favre 
-   ^  8.79      3.654  18"  Favre 
1.994  Filhol 


89.58 
74.6 

=   1.994 

87.876 
119 

=  2.62 

45.88 
174 


71.71 
110 

51.68 


=  2.48 


2.672  P  &  J 
2.505  18°  Spring 

2.4073  Hassenf 
2.572    Buivnet 


=  2.130    2.130  Filhol 


I'ABLE    II. 

ThcM'etical  Magnetic  Rotation. 
CaCI,  1.51    +   2(3.982) 

CaBr,  1.635  +  2(7.96) 

BaCl,  2.833  +  2(3.982) 

BaBr,  2.833  +  2(7.96)  = 

CdCl,  3.81   +  2(3.982) 

CdBr,  3.81   +  2(7.96) 

Cdl,  8.81   +  2(18.82) 

CdSO^  8.66  +  1.03  +  2(0.042)  + 

2(0.202) 
SrCl,  1.886  +  2(3.982) 

RrBr,  2.25  +  2(7.96) 

T.iCl  0.564  +  3.982 

Li.SO^  2(0.564)   +  1.08   +   2(0.042 

+   0.202) 
NaCI  0.97  +  3.932  = 

NaBr  0.97  +  7.95 

\al  0.97  +  18.32 

NaCO^CH,    0.97  +  2.209 
NaCO,C,H,  0.97  +  2.299  +   (1.023) 
NaCO,C,Hr    0-97  +  2.299  +  2(1.023) 
KCl  1.749  +  3.932 

KBr  1.749  +  7.95 

Kl  1.08  +  18.32 

K,SO,  2(1.08)  +  1.03  +  2(0.042  + 

0.202) 
LiNOj  is  the  only  o()her  available  compound, 
higher." 


M.R.  by  Perkin. 

9.374 

9.88 

17.535 

17.6 

10.967 

10.08 

18.733 

18.64 

11.674 

11.78 

19.71 

19.7 

40.45 

40.8 

5.178 

5.17 

9.7 

9.7 

18.15 

18.16 

4.6 

4.61 

2.646 

2.27 

4.fK)2 

6.068 

8.92 

9.19 

19.29 

18.46 

3.269 

3.281 

4.292 

4.308 

5.316 

5.332 

5.681 

5.66 

9.699 

9.36 

19.4 

18.95 

8.678 

3.57 

lie  M.B.  is  given  as  "1.124  and 


200 


tSE   CHEMICAL    NEWS. 


MARCH  29,  1923. 


The  experimeiital  data  for  the  magnetic 
rotation  ire  always  dependent  upon  the 
specific  gravity.  By  employing  a  slightly 
different  value  from  that  which  was  prob- 
ably used,  the  exiperimental  figures  can  in 
nearly  every  case  be  brought  exactly  to  the 
theoretical  figures.  For  instance,  the  fol- 
lowing are  given  as    the  S.G.  of  BaCl, :  — 

3.82     Schiff 
3.860—4.156  Boullay. 

Suppose  4.056  was  employed  as  the  S.(jr. 
If  3.82  had  been  used  instead,  the  result 
would  have  been 


10.08   X  4.056 


=    10.697 


3.82 


Table  III. 
Calcium. 
40 
=   1.51 


2   X    13.25 

Calcium. 
40 

— =   1.635 

2    X    12.24 

Barium. 
136 
=  2.833 


2    X   24 

Cadmium. 

Ill 
=  3.81 


2   X    14.57 

Cadmium. 

Ill 

=  3.66 

2    X   15.16 

Strontium. 

88 
- — =   1.836 


2    X    23.96 

Strontium. 
88 

=  2.25 

2   X    19.56 

Lithium. 
7 

=   0.564 

2   X    6.21 

Sodium. 
23 


=  0.97 


2   X    11.85 

Potassium, 
89 

2   X    18.05 


1.08 


In  addition  to  these    results    concerning 
electro-positive  elements,    the   non-metallic 
element  sulphur  gives — 
Sulphur. 
32 

=  1.03 

2   X   15.53 

and  potassium  gives  another  result,   which 
differs  from  the    others  in    not  having    its 
atomic  weight  halved  :  — 
Potassium. 
39 

=   1.749 

22.29 

If  in  the  futm'e  any  results  similar  to  the 
last  can  be  demonstrated,  it  will  of  course 
be  evident  that  there  is  no  discrepancy  in 
the  matter,  but  that  the  exceptions  only 
lead  to  a  deeiper  truth. 

As  the  atomic  numbers  are  sometimes 
stated  to  be  rather  less  than  half  the 
atomic  weights,  it  seems  possible  that  with 
more  accurate  experimental  data,  the  law 
may  in  the  future  be  stated  as  follows:  — 
"  The  magnetic  rotation  of  an  electro- 
positive element,  when  in  combination,  is 
the  product  of  its  atomic  number  and  the 
reciprocal  of  its  relative  volume." 

The  two  values  4.45  and  2.51  for  oxygen, 
given  in  the  relative  volumes,  are  sup- 
ported exactly  by  the  Heats  of  Formation 
of  the  two  substances  CaO  and  CdO  as  pub- 
lished in  The  Chemical  News,  August  18, 
1922. 


A  NEW  METHOD  OF  DETECTING 

NICKEL  IN  SOLUTION. 

By  C.  G.  Vernon,  B.A.,  B.Sc. 

Concentrated  ammonia  in  excess  was 
added  to  the  solution  containing  nickel, 
and  hydrogen  sulphide  was  passed  through 
for  a  short  time. 

The  solution  was  then  boiled. 

A  bright  mirror  of  metallic  nickel  was 
deposited,  and  its  production  was  accom- 
panied by  a  blackening  of  the  solution. 

This  has  been  shown  to  occur  even  in 
very  dilute  solutions.  If  only  a  small 
trace  of  nickel  was  present  the  mirror  took 
the  form  of  an  iridescent  film. 

Since  the  presence  of  cobalt  does  not 
affect  it,  the  test  is  of  some  use  in  detect- 
ing nickel  when  mixed  with  cobalt.  It 
may  be  introduced  into  the  ordinary 
course  of  qualitative  analysis  by  adding  ex- 
cess of  strong  ammonia  before  passing  in 
hydrogen  sulphide  to  precipitate  the  sul- 
phides of  the  metals  in  the  nickel  group. 


MARCH  29,  1923. 


TMS  CHEMICAL   NEWS. 


201 


GENERAL  NOTES. 


GERMANY'S  TRADE  AND   INDUSTRY 
IN  FEBRUARY. 

The  Commercial  Secretary?  at  Berlin,  Mr. 
J.  W.  F.  Thelwall,  has  forwarded  a  report 
on  the  state  of  trade  and  industry  during 
February. 

The  report  states  that  in  spite  of  the 
cutting  off  of  the  industrial  west  from  the 
remainder  of  Germany,  it  has,  in  general, 
been  possible  to  maintain  industry  in  the 
Ruhr  district  and  on  the  Rhine,  as  also  in 
the  rest  of  Germany.  Ruhr  coal,  »o  far  as 
not  required  within  occupied  territory,  is 
being  accumulated  at  the  pit  dumps  and  in 
the  depots  of  the  large  works.  The  non- 
delivery of  reiparation  coal  to  France  and 
Belgium  practically  makes  good  the  reduc- 
tion of  output  which  has  naturally  taken 
pliiet'  since  the  <xx;upation.  Unoccupied 
Germany  is  helping  itself  by  means  of  in- 
creased production  and  larger  imports, 
above  all,  of  English  coal,  so  that  the  de- 
mand can  be  covered.  It  was  endeavoured 
to  make  up  fof  the  shortage  of  pig  iron, 
firstly,  by  an  increased  pr(Kiuction  of  this 
material  in  Upper  Silesia;  finished  iron 
was  also  delivered  on  a  large  scale  thence, 
while  the  oceupied  territory  had,  to  a  large 
extent,  to  work  on  stock. 

Potash. — In  spite  of  the  oocupati>  u  of 
the  Ruhr,  the  full  maintenance  of  the  pot- 
ash industry  wjw;  possible.  Only  oomipara- 
tively  small  quantities  of  individual  goods 
wore  stored.  The  sale  of  potash  raw  salts 
have,  however,  again  fallen  r^  as  a  result 
of  increased  railway  freights,  the  latter  al- 
ready far  exceeding  the  value  of  the  goods. 
The  call  for  by-products  of  the  potash  in- 
dustry was  only  partially  satisfactory;  con- 
siderable quantities  of  sulphate  of  potash 
were,  however,  exported  to  the  United 
States. 

Aluminium. — In  the  Liidenscheid  alu- 
minium EUid  finished  metal-goods  indus- 
tries, employment  was  bad.  and  the  out- 
look for  the  future  is  not  at  all  favourable. 
The  industries  are  suffering  from 
diminished  foreign  sales,  and  consequently 
the  removal  of  the  exiport  duty  and  of 
foreign  trade  control  is  more  than  ever  ur- 
gently desired. 

Electrical  Industry. — In  the  electrical 
industry  the  inland  purchasing  power  is 
still  weak.       Neither    official    nor    private 


customers  dare  place  orders  for  large  plant 
and  machinery.  Further,  the  partial  fall 
of  prices  is  causing  some  customers  to  hold 
back  in  the  hope  of  further  reductions. 
Foreign  countries  are,  for  the  most  part, 
showing  reserve,  in  so  far  as  the  German 
prices,  which  have  partly  reached  the 
world's  market  level  and  partly  already  ex- 
ceeded it,  admit  of  any  competition.  Ac- 
cordingly a  general  falling  off  in  orders  is 
noticeable  in  high  pressure  current  articles, 
machinery,  apparatus,  calculators,  instal- 
laticm  materials  and  cables.  With  regard  to 
measuring  instruments  and  electro-medical 
apparatus,  the  position  is  no  better,  owing 
to  customers'  loss  of  purchasing  ipower. 
The  outlook  for  railway  safety  appliances 
is  bad.  The  sale  of  electric  lamps  at  home 
and  abroad  shows  no  improvement. 

Chemical  Industry. — No  details  are  avail- 
able with  regard  to  the  chemical  industry 
in  the  occupied  territory.  In  general, 
however,  «t  may  be  said  that  the  chemical 
industry  of  the  south  portion  of  the  oceu- 
pied territory  is  suffering  from  a  scarcity  of 
coal.  In  the  northern  portion  conditions 
are  better.  No  restrictions  of  w<«"k  have 
yet  taken  place.  The  hourly  wage  for  un- 
skilled workers  is  now  1,780  marks. 

Glass  Industry. — In  the  sheet  glass  in- 
dustry very  few  inland  orders  were  re- 
ceivea.  The  general  export  figure  remained 
unaltered.  The  works  which  deliver  to  the 
Russian  border  States  lost  practically  their 
whole  market  as  a  result  of  cheaper  offers 
from  the  CzechfvSlovakian  glass  industry. 
In  the  hollow-glass  industry  the  supply  of 
raw  materials,  with  the  exception  of  soda, 
was  adequate. 

Mining  Industry. — ^The  events  in  the 
Ruhr  district  accentuated  the  importance 
of  Upper  Silesian  pit  coal  for  the  ooal  sup- 
ply of  the  country.  The  Coal  Commis- 
sioner of  the  Reich  drew  larger  supplies  of 
such  coal  for  despatch  to  South  Germany 
and  Saxony,  at  the  same  time  partly  di- 
verting Upper  Silesian  coal  from  the  coast- 
al district,  as  those  are  better  able  to 
obtain  supplies  of  English  coal.  Besides 
English  coal,  the  import  of  coal  from  the 
Ostrau  mines,  which  is  particularly  suit- 
able for  use  in  gasworks,  has  begun. 


MEDICAMENTS  FOR  BULGARIA. 

The  Bulgarian  Government  invites  len- 
ders for  adjudication  on  the  16th  April  for 
the  supply  of  various  medicaments,    a  list 


202 


tflfc   CHEMICAL   NEWS. 


March  29,  192a. 


of  which  is  available  for  inspection  at  the 
Department  of  Overseas  Trade  by  firms  in- 
terested. 

Local  representation  is  essential.  Firms 
desirous  of  tendering,  but  not  locally  repre- 
sented, will  be  furnisHed  upon  application 
to  the  Department  with  the  names  of  suit- 
able firms. 


OILS,  PAINTS  AND  VARNISHES  FOR 
EGYPT. 

The  British  Commercial  Agent  for  Egypt 
reports  that  the  Egyptian  Government  in- 
vite tenders  for  the  supply  of  oils,  paints, 
and  varnishes.  Tenders  close  on  the  17th 
April,  and  local  representation  is  essential. 
The  Department  of  Overseas  Trade  will  be 
pleased  to  supply  firms  desiring  to  tender, 
not  locally  represented,  with  the  names  of 
some  United  Kingdom  houses  with  Egyp- 
tian connections  open  to  handle  tenders  on 
behalf  of  third  parties. 

Copies  of  the  specification  and  condi- 
tions of  tender  are  available  for  instpection 
at  this  Department  (Room  53). 


CZECHO-SLOVAKIA. 
Demand  for  British  Chemicals. 

The  Commercial  Secretary  at  Prague 
(Mr.  W.  F.  Vaughan  Scott)  reports  tTiat  up 
to  the  present  no  falling  off  in  the  imports 
of  chemicals  from  Gemaany  has  been 
noticeable,  but  there  is  no  doubt  that, 
owing  to  the  rapid  increase  in  prices  of  ail 
German  chemicals,  and  to  the  difficulty 
which  importers  anticipate  exiperienoing  in 
obtaining  delivery  of  goods,  an  increased 
demand  is  likely  to  arise  for  the  following 
British  chemicals:  — 

Coal-tar  and  its  derivatives. 

Resin. 

Cresines    and   petroleum  jelly. 

Refined  yellow  and  white  beeswax. 

Oils  for  perfumes,  soapmakers,  and  for 
medicinal  purposes. 

Pharmaceutical  products. 

Photographic  chemicals. 

Raw  materials  for  the  chemical  industry. 

The  Commercial  Secretary  has  also  fur- 
nished (1)  the  names  and  addresses  of 
agents  who  might  suitably  represent  Brit- 
ish firms  of  chemical  manufacturers,  and 
(2)  a  list  of  the  most  important  Czecho- 
slovak importers  of  chemicals.  Copies  of 
these  lists  may  be  obtained  by  interested 
United  Kingdom  firms  upon  application  to 
the  Department  of  Overseas  Trade. 


TRADE  FAIRS. 
Are  Trade  Fairs  and  Exhibitions  Worth 
THE  Outlay? 
Last  week's  Manchester  Guardian  Com- 
mercial states  that  much  energy  and  money 
must  have  been  wasted  on  fair  schemes, 
energy  which,  if  only  directed  by  intelli- 
gence instead  of  imagination,  might  have 
produced  real  results.  Trade  fairs  gener- 
ally fall  under  one  of  two  heads.  Direct 
Business  and  Propaganda.  Under  the  for- 
mer fall,  those  attended  iprincipally  by  "the 
trade,"  and  at  which  actual  orders  from 
trade  buyers  are  expected,  the  attendance 
of  the  general  public  is  neither  invited  nor 
encouraged.  The  remainder  come  under 
the  heading  of  Propaganda.  With  certain 
notable  exceptions,  the  possibility  of  imme- 
diate business  diminishes  in  proportion  to 
the  attendance  of  a  merely  curious  pubHc. 
Many  of  them  undoubtedly  are  good 
value  for  the  money  demanded, 
either  in  publicity,  in  direct  busi- 
ness, or  in  both  combined.  Firms 
taking  part  in  these  may  receive  a 
good  return  on  the  money  paid  for  the 
space  occupied.  Few  firms  have  a  con- 
sidered and  definite  policy  in  regard  to  ex- 
hibitions. Like  any  other  medium  of 
trade,  an  exhibition  should  be  the  subject 
of  a  definite  policy,  and  each  proposal 
should  receive  due  consideration. 


INDIAN  IMPORTS  FROM  APRIL  TO 
DECEMBER,   1922. 

Mr.  T.  M.  Ainscough,  O.B.E.,  H.M. 
Senior  Trade  Commissioner  in  India,  draws 
attention  to  the  followiij^g  features:  — 

The  total  imports  of  rnlrchandise  for  the 
nine  months  declined  somewhat.  Ship- 
ments from  the  United  Kingdom  declined, 
but  the  British  share  of  the  total  rose  from 
56  per  cent,  to  61  per  cent.  The  most 
striking  feature  has  been  the  increase  in 
the  proportion  of  goods  derived  from  Ger- 
many,    from    2.4  per  cent,    to  5  per  cent. 

There  are  good  grounds  for  satisfaction 
that  in  a  time  of  such  depression  the 
United  Kingdom  should  be  maintaining  her 
position  in  the  Indian  import  trade. 

Dyestuffs  obtained  from.  Coal  Tar. — The 
total  trade  fell  from  207  to  189  lakhs.  The 
British  share  was  reduced  from  58  to  15 
lakhs,  and  that  of  America  from  24  to  7 
lakhs,  but  Germany,  who  once  again  con- 
trols this  trade,  increased  her  share  from 
92  to  146  lakhs. 


H 


MARCH  29,  1923. 


THE  CHJSMICAL  NEWS. 


203 


Coal. — Although  the  total  trade  fell  con- 
siderably, the  reduction  has  mainly  been 
in  Natal,  Portuguese  East  African,  and 
Austrahan  coal.  The  imports  from  the 
U.K.  were  reduced  only  slightly. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE    ROYAL    SOCIETY. 
Thursday,  March  22,  1923. 

Papers  read:  — 

L.  T.  HoGBEN  and  F.  K.  Winton.  The 
Pigmentary  Effector  System.  III. — Colour 
Response  in  the  HypophyHectomised  Prog. 
Communicated  by  Prof.  E.  W.  MacBride, 
F.R.S. 

H.  R.  Sewer.  Studies  on  Amphibian 
Colour  Change.  Communicated  by  Prof. 
E.   W.  MaoBridc,  F.R.S. 

J.  Walton.  On  Rhexoxylon,  Bancroft. 
A  Triassic  Genus  of  Plants  exhibiting  a 
Liayie-type  of  Vascular  Organisation.  Com- 
municat<id  by  Prof.  A.  C.  Seward,  F.R.S. 

Papers  read  in  title  only:  — 

G.  Hewett.  The  Dusuns  of  lirilinh 
North  Borneo.  Communicated  by  \A'.  IV 
Hardy,  Sec.  R.S. 

M.  Tribe.  The  Development  of  the 
Hepatic  Venous  System  and  the  Postcaval 
Vein  in  the  Marsupialia.  Communicated 
by  Prof.  J.  P.  Hill,  F.R.S. 

J.  Gray.  The  Mechanism  of  CUiary 
Movement.  III. — The  Effect  of  Tempera- 
ture. Communicated  by  Prof.  J.  S.  Gardi- 
ner, F.R.S. 

E.  Ponder.  The  Inhibitory  Effect  of 
Blood  Serum  on   ■!!  .      Communi- 

cated by  Sir  E.  Shai|    ,        nafer,  F.R.S. 


ROYAL    MICROSCOPICAL   SOCIETY. 

The  section  of  the  Society  which  has 
been  formed  to  deal  with  the  Industrial 
Applications  of  the  Microscope,  and  to  as- 
sist in  the  development  of  Industrial  Re- 
search in  British  Industries,  held  a  mott- 
ing  at  20,  Hanover  Squnn  .  W.l,  on  Wed- 
nesday, March  28. 

Messrs.  J.  W.  Atha  d-  Co.  exhibited  the 
new  Zeiss  Photographic  Eye-piece, 
"  Phoku." 

Mr.  John  H.  Barton  exhibited  a  new  Re- 
search Microscope  of  original  design. 

Messrs.  R.  &  J.  Beck,  Ltd.,  exhibited  a 
microscope   Sipecially  suitable    for  the   ex- 


amination of  large  surfaces  of  paper  and  of 
prints  and  engravings. 

The  Edison  Swan  Electric  Co.,  Ltd.,  de- 
monstrated the  Ediswan  Pointolite  Lamp, 
30,  100,  500  and  1,000  c.p.  in  operation. 
They  also  exhibited  and  explained  the 
working  of  the  alternating  cuiTent  Pointo- 
lite lamp. 

Messrs.  Ogilvy  &  Co.  exhibited  a  new 
stereoscopic  magnifier  giving  large  field  of 
view  and  long  w<wking  distance. 

Mr.  Mansell  P.  Swift  demonstrater  Pro- 
fessor Shand's  recording  micrometer  which 
is  designed  to  facilitate  the  quantitative 
estimation  of  minerals  in  rocks. 

Communications. 
Mr.  J.  Lkunard  Spicer  in  tlie  chair. 
Mr.       James       Strachan,       F.Inst. P., 
F.R.M.S.,   The  Manufacture  of  Containers 
and  Papers  used  for  the  wrapping  of   Food- 
stuffs. 

Mr.  Harold  B.  Wrighton,  B.Met., 
F.R.M.S.,  The  Microscope  in  Metallurgicjl 
Research. 

Mr.  Sydney  R.  Wycherley,  F.R.M.S., 
Microscopy  in  the  Examination  of  Manu- 
factured Paper. 

Future  meetings,  for  which  invitations 
may  be  obtained  on  application  to  the  Sec- 
retary, will  be  he  14  as  follows:  — 

April  18:  Mr.  D.  W\  Cutler  (Rotham- 
sted  Experimental  Station),  The  Protozoa 
of  the  Soil. 

May  16 :  Mr.  Leonard  Taverner, 
A.R.S.M.,  The  Principles  and  Application 
of  Technical   Metallurgical   Microscopy. 

Mr.  W.  M.  Ames,  M.A.,  B.Sc,  A.I.C, 
Applications  of  the  Microscope  in  the 
Manufacture   of  Rubber. 

May  30:  Mr.  H.  B.  Milner,  The  Micro- 
scopical Investigation  of  Sands  for  various 
Industrial  Purposes. 

Enquiry  Bureau. 
Enquiries  have  been  already  received  re- 
lating to  the  following  matters,  and  any  in- 
formation relating  to  them  will  be  greatly 
a(ppreciated :  — 

Examination  of  metals  for  making 
machinery. 

Examination  of  crystal  structure  of  fats. 
Examinaticm  of  powders  of  the  same  re- 
fractive index  as  Canada  Balsam. 

Examination  of  silk  used  in  fine  sieves. 
How  can  thin  oil    deposits  be  examined 
with  transmitter!     light  in  order    to  deter- 
mine shape,  distribution  and  thickness? 

*  How  can  one  ascertain  by  means  of 
the  miooscope  the  suitability  of  moulding 


204 


rfiE   CHEMICAL    NEWS. 


MARCH  29,  1923. 


sand  for  producing  fine  surfaces  on  cast- 
ings? 

Wanted,  a  suitable  method  of  cutting 
sections  of  soap,  and  a  suitable  mounting 
medium  for  the  same. 

What  is  the  best  method  of  testing 
mounting  media  for  refractive  index  by 
means  of  the  Microscope? 

*  This  subject  will  be  dealt  with  at  the 
meeting  on  May  30. 


MINERALOGICAL  SOCIETY. 
March  13,  1923. 

Dr.  A.  Hutchison,  President,  in  the 
Chair. 

Dr.  a.  Hutchison.  A  Graphical  Method 
of  correcting  Specific  Gravity  Determina- 
tions. 

A  diagram  was  given  by  which  the  cor- 
rection for  air  disiplacement  and  reduction 
to  4°  C.  can  be  read  off  directly. 

A.  Brammall  and  H.  F.  Harwood.  The 
Dartmoor  Granite  {Widecombe  Area). 

Field  evidence  and  analyses  support  the 
conclusion  that  the  granite  is  a  composite 
laccolite,  and  that  four  successive  stages 
of  intrusion  are  recorded  by  (1)  dark  anrl  re- 
latively basic  granites  scantily  exposed 
and  by  certain  cognate  xenoliths  resemb- 
ling basic  segregations;  (2)  a  more  acid 
granite  which  caps  many  tors  and  yields 
mineral  evidence  of  having  assimilated 
country  rock;  (3)  a  still  more  acid  granite 
intrusion  into  the  latter;  (4)  minor  acid  in- 
trusions, felspars,  garnet,  cordierite,  etc., 
were  described,  and  evidence  for  differen- 
tiation was  given. 

C.  E.  TiLirEY.  Genesis  of  Rhombic  Py- 
roxene in  Thermal  M etamorphism ;  Mine- 
ral Associations  and  the  Phase  Rule. 

Free-silica    hypersthene-bearing    hornfel- 
ses  of    sedimentary  origin    can  be    divided 
into  a  calcic  and  non-calcic  group,  and  con- 
sidered   as  derived    from    a  normal    shale 
hornfels  by  increments  either  of  CaO,  (MgO 
+  FeO),    or  less  commonly  KjO.        Silica- 
poor  hypersthene  homfelses  can  be  derived 
from  the  free-silica  types  and  the  hypers- 
thene is   then  frecLuently   accompanied     by 
spinel.     The  derivation  of  all  these  homfel- 
ses can  be  graphically  expressed  in  systems 
of  three  or  four  components.     The  hypers- 
thene is  derived    from  the  chlorite    in    the 
original     sedimentary    rocks     subjected     to 
metamorphism.     Hypersthene  arises   when 
enstatite,   augite,   or  amphibole-bearing    ig- 


neous rocks  enter  contact  aureoles,  and  ex- 
amples of  these  are  given.  Reference  is 
made  to  the  production  of  rhombic  pyrox- 
ene by  contamination  of  gabbroic  rocks. 
The  homfelses  are  .considered  from  the 
standpoint  of  the  phase  rule,  a  classitica- 
tion  considered,  and  the  condition  of  equih- 
brium  in  the  inner  zone  of  homfelses  in  con- 
tact aureoles  discussed. 

C.  S.  G-ARNETT.  On  a  peculiar  chiorite- 
rock  at  Ible,  Derbyshire. 

A  band  in  the  dolerite  still  at  Ible  is 
completely  altered  to  a  foliated  mass  of 
chlorite,  with  associated  veins  of  fibrous 
chlorite  (resembling  chrysotile  in  appear- 
ance). The  analyses  and  characters  of  this 
material  are  compared  with  those  of  "  epi- 
chlorite." 

C.  S.  Garnett,  The  Dissociation  of  Do- 
lo'tnite. 

The  statement  in  the  text-books  that 
dolomite  dissociates  in  two  stages,  giving 
when  half-burnt  a  mixture  of  calcium  car- 
bonate and  magnesia,  is  not  confirmed. 
Dissociation  is  inappreciable  up  to  625"", 
and  at  898°  it  is  complete.  The  tempera- 
ture-dissociation curve  is  continuous. 

J.  G.  C.  Leech.  Occurrences  of  Rutile, 
Brookite,  ayid  Anatase  in  the  St.  Austell 
Granite. 

These  minerals  occur  in  the  red  pneuma- 
tolysed  granites  of  the  area,  the  mode  of 
occurrence  being  essentially  the  same  as 
that  recorded  for  Dartmoor  occurrences  of 
those  minerals. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 
The  next  meeting  of  the  Society  will  be 
held  on  Wednesday,  April  4,  at  the  Chemi- 
cal Society's  Rooms,  Burlington  House, 
Piccadilly,  W.,  at  8  p.m.  The  following 
papers  will  be  read:  — 

Physiological  Standardisation,  by  Dr. 
Stanley  White. 

An  Investigation  into  the  Chemistry  of 
the  Reinsch  Test  for  Arsenic  and  Anti- 
m-ony,  and  its  extension  to  Bism,uth,  by  B. 
S.  Evans,  M.B.E.,  M.C.,  B.Sc,  F.I.C. 

The  Estimation  of  Boric  Acid  in  "Liquid 
Eggs"  and  other  Foodstuffs,  by  G.  W. 
Monier- Williams,  M.A.,   Ph.D.,  F.I.C. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 
The  programme  for  the  summer  meeting 
at  North-Westem  Centre,  5 — 8  June,   will 
be  as  follows  :  — 


MARCH  29,  1923. 


THE   CHEMICAL    NEWS. 


205 


Visits. 
Tuesday,  June  5. 

Morning  (a)  The  electrically  driven  roll- 
ing mill  equipment  of  Messrs.  E,  Johnson 
and  Nephew,  Ltd.,  Bradford,  Manchester, 
and  the  engineering  works  of  Messrs. 
Mather  and  Piatt,  Ltd.,  Newton  Heath;  or 
ib)  The  No.  2  Dunlcip  Rubber  Cotton  Mills, 
Ltd.,   Rochdale. 

Lunch  at  the  Manchester  Town  Hall  as 
the  guests  of  the  Corporation  Electricity 
and  Tramways  Committees. 

Afternoon  (c)  Messrs.  Pilkington  Tile  & 
Pottery  Co.,  Ltd.  (makers  of  the  Lancas- 
trian art  pottery);  (rf)  The  Chloride  Elec- 
trical Storage  Co.,  Ltd.;  (c)  The  Ivondon, 
Midland  and  Scottish  Railway  Company's 
power  station,  and,  at  Ringley,  (/)  The 
Lancashire  Electric  Power  Company's  sta- 
tion. 

Wednesday,  June  6. 

Morning. — Proceed  at  the  invitation  of 
the  Manchester  Ship  Canal  Co.,  Ltd..  by 
special  steamer  from  Pomona  Docks,  view- 
ing the  swing  bridges  and  other  engineer- 
ing features  en  route,  to  Barton,  where  the 
party  will  disembark  and  inspect  the  Man- 
chester Corporation's  new  generating 
station. 

Lunch  at  Traflford  Park  as  the  guests  of 
the  Metropolitan- Viokers  Electrical  Co.. 
Ltd. 

Afternoon. — Visit  the  works  of  the  Met- 
ropolitan-Vickers  Electrical  Co.,  Ltd.,  and 
the  Lancashire  Dynamo  and  Motor  Co.. 
Ltd.,  Trafford  Park. 

As  alternatives  to  the  foregoing  visits, 
members  may  visit  the  following  places  at 
any  time  on  'J'uesday  or  \\'ednesday : 

(1)  The  outdoor  33,000-volts  sub-station 
(in  High  Street)  of  the  Manchester  Cor- 
poration; and 

(2)  The  Manchester  Guardian  Offices,  for 
the  Murray  Multiplex  System  of  Tele- 
graphy, and  Rotary  Printing  Presses. 

(3)  On  Wednesday  morning  only,  the 
Laboratories  of  The  University,  Manches- 
ter, will  be  open  for  inspection. 

Thursday.  June  7. 

Alternative  morning  visits:  — 

(a)  The  British  Insulated  and  Helsby 
Cable  Works,  Prescot, 

(h)  (1)  The  Liverpool  Corporation  Tram- 
ways, Lambeth  Road  Works. 

C2)  Automatic   Sub-station,  Walton. 

(8)  liister  Drive  Power  Station. 

(c)  The  Cunard  Company's  s.s.  Scythia, 
or  some  other  big  liner. 


Alternative    afternoon    visits:  — 

(d)  Messrs.   Lever  Bros.,   Port  Sunlight. 

(e)  The  University  Applied  Electricity 
Laboratories,  where  demonstrations  in 
radio  reception  will  be  given,  and  The 
Automatic  Telephone  Manufacturing  Co., 
Ltd. 

(/)  (If  sufficient  applicants) : 

(1)  The  Liverpool  Coriporation  Tram- 
ways, Lambeth  Road  Works. 

(2)  Automatic  Sub-station,   Walton. 

(3)  Lister  Drive  Power  Station. 

Note — As  other  alternatives  to  the  after- 
noon visits,  members  may  also  visit :  [g) 
The  Mersey  Power  Co.,  Runcorn  (the  com- 
pany will  arrange  for  tea  and  transport  at 
Runcorn) ;  (h)  The  United  Alkali  Com- 
pany's Power  Station,  Widnes;  (/)  The 
London.  Midland  and  Scottish  Railway, 
Southi>ort  Electrified  Line. 

Friday,  June  8. 

Morning. — Leave  Liverpool  by  special 
t:ain  for  Llandudno  Junction,  where  the 
party  will  transfer  to  motor  coaches  and 
proceed  by  alternative  routes  as  follows:  — 

(a)  Via  Conway  Valley.  Bettws-y-Coed, 
Capel  Curig,  Llanbcris  or  Nant  Ffranoon 
Pass  to  Carnarvon  and  Bangor,  returning 
along  the  coast  road  to  Llandudno;  a  halt 
will  be  made  at  Dolgarrog  to  inspect  the 
hydro-electric  power  station  an'd  works  of 
the  Aluminium   Corporation,   Ltd. 

(b)  Generally  as  (o)  above,  but  the  halt 
will  be  made  at  Pen-y-Gwryd  to  inspect 
the  North  Wales  Power  Company's  hydro- 
electric station  at  Cwm  Dyli. 

(c)  Generally  as  (a)  above,  but  the  halt 
will  be  made  at  Lord  Penhryn's  Slate 
(Quarries.  Bethesda. 

A  meeting  was  held  on  Thursday,  March 
22,  when  a  discussion  on  papers  by  Mr. 
Francis  Hooper  and  Mr.  J,  W.  Beau- 
champ,  on  the  Co-operation  between  the 
Architect  and  the  Electrical  Engineer,  was 
continued. 


The  January  issue  of  the  Journal  of  the 
Chemical  Society  of  Japan  contains  the 
following  papers  communicated  to  the 
Society. 

The  Detection  and  Separation  of  Iri- 
dium, by  IsABURo  Wada  and  Lunao  Ato. 

Uses  of  Analgams  in  Volumetric  An- 
alyses, Part  VIII.  On  the  Determina- 
tion of  Chromium  and    of  Iron    Accom- 


206 


THE   CHEMICAL   NEWS. 


MARCH  29,  1923. 


panying  with  Chromium,  by  Naotsuna 
Kano. 

Uses  of  Amalgams  in  Volumetric  An- 
alyses, Part  IX.  On  the  Determination 
of  Titaniutn  and  of  Iron  Accompanying 
u-ith  Titanium,  by  Naotsuna  Kano. 

On  the  Nitrogenous  Compounds  in  the 
Flesh  of    Mactra    sulcataria,     Desh,     h\ 

KlYOHISA    YOSHIMURA. 

On  the  Nutritive  Value  of  the  Proteins 
of  Soy  Bean  and  Pea  Nut,  by  Tokitaka 
Shiba  and  Manshi  Koyama. 

On  the  Protein  of  Rice  Em^bryo  and 
its  Nutritive  Value,  by  Matsukichiro 
Hamada. 

Preparation  of  Petroleum,  from  Fatty 
Oils,   Part  II.,  by  Masakazu  Inonye. 


CORRESPONDENCE. 


THE  TITLE,  "  CHEMIST." 

To  the  Editor  of  The  Chemical  News. 

Sir, — The  Retail  Pharmacists'  Union,  in 
their  recent  announcement  with  regard  to 
the  subject  of  the  accurate  dispensing  of 
medicines  have,  I  think  it  will  be  genera) ly 
agreed,  made  a  good  statement  on  behalf 
of  the  profession  of  pharmacy. 

I  would,  however,  venture  to  place  be- 
fore your  readers  a  matter,  arising  from 
the  above,  which  is  one  of  no  small  con- 
cern to  those  chemists  who  are  engaged  in 
the  practice  of  Chemistry  as  distinct  from 
Pharmacy — that  is  to  say,  who  are  con- 
cerned with  the  science  of  chemistry  and 
its  applications  to  the  arts  and  manufac- 
tures, and  have  nothing  to  do  with  the  dis- 
pensing of  medicines. 

The  Retail  Pharma<!ists'  Union  have 
headed  their  announcement  with  the  words 
"  The  Chemist,"  and  I  would  like  to  make, 
in  the  public  Press,  the  suggestion  which 
has  so  often  been  made  in  the  scientific 
Press,  that  the  time  has  come  for  the 
pharmacist  to  relinquish  the  use  of  the 
term  "  chemist  "  in  favour  of  those  who 
definitely  practise  chemistry. 

The  war  was  instrumental  in  directing 
the  attention  of  the  public  more  closely  tf> 
the  existence  of  the  profession  of  chemis- 
try, the  profession  on  which  the  country 
found  it  necessary  to  rely  or  the  production 
of  explosives  and  materials  of  war  gener- 
ally, as  well  as  for  the  means  of  protecting 
our  troops  against  the  methods  of  chemical 
warfare  initiated  by  the  enemy. 


During  the  past  half-century,  the  science 
of  chemistry  has  developed  by  leaps  and 
bounds,  and  its  practice  as  a  profession  has 
become  more  and  more  firmly  established. 
In  this  country  the  science  is  now  taught 
in  1,0(X)  or  more  public  and  secondary 
schools,  and  in  nearly  300  technical 
schools,  while  our  University  Departments 
of  Chemistry  are  renowned  throughout  the 
world. 

The  Institute  of  Chemistry,  as  the  repre- 
sentative Chartered  professional  body  of 
chemists,  numbers  upwards  of  4,000  Fel 
lowis  and  Associates,  whose  qualification 
demands  a  four  years'  University  course, 
or  the  equivalent,  and  the  majority  of 
whom  are  engaged  in  the  many  branches 
of  industry  on  which  the  science  has  a 
bearing. 

In  other  countries,  the  strict  equivalent 
of  the  word  "chemist"  signifies,  as  it 
should,  one  who  professes  chemistry,  and 
not  in  any  case  the  pharmacist,  druggist, 
or  dispenser  of  medicines.  How  the  mis- 
application of  the  word  has  arisen  in  this 
country  is  a  matter  which  I  need  not  here 
pursue.  The  enormous  importance  of 
chemistry  is  becoming  daily  more  widely 
recognised,  and  it  is  highly  desirable  in 
order  to  avoid  confusion,  that  the  word 
"Chemist"  should  be  confined  to  those 
who  practise  chemistry  in  the  full  sense  of 
the  word.  It  is  bad  enough  when  mental 
confusion  is  the  unfortunate  consequence 
of  the  poverty  of  a  language,  but  in  this 
instance  the  correct  and  distinctive  words 
are  ready  to  our  hand. 

I  would  like  to  express  the  hope  which  I 
have  already  expressed  on  a  good  many  oc- 
casions, that  our  friends  the  Pharmacists 
— notwithstanding  the  provision  of  the 
Pharmacy  Act — will  lose  no  opportunity  of 
referring  to  their  ancient  and  important 
calling  by  the  word  which  more  accurately 
defines  and  describes  it.  In  addition,  i 
would  appeal  to  the  Press,  which  is  so  im- 
portant a  factor  in  the  enlightenment  of 
the  general  public,  to  assist  so  far  as  they 
can  by  employing  the  terms  "Chemist" 
and  "Pharmacist"  respectively  in  their 
obviously  correct  significations,  so  that 
those  practising  chemistry  may  be  de- 
scribed as  Chemists,  and  those  practising 
pharmacy  as  Pharmacists. — Yours,  &c., 
A.  Chaston  Chapman,  F.R.S., 
President  of  the  Institute  of  Chemistry 
of  Great  Britain  and  Ireland. 

30,  Russell  Square,  London,  W.C 
March  17,  1923. 


MARCH  29,  1923. 


THE  CHEMICAL  NEWS. 


207 


NOTICES  OF  BOOKS. 

The  Chemist's  Year  Book,  1923. 
Edited  by  F.  \V.  Atack,  M.Sc.  (Tech.), 
D.Sc,  F.I.C.,  assisted  by  L.  Whinyates, 
A.M.C.T.,  A. I.e.  In  two  volumes.  Pp. 
VII.  +  1,108.  Manchester:  Sherratt  & 
Hughes,  34,  Cross  Street.  1923.  21s. 
9d.,  post  free  (abroEul  22s.). 

EngHsh-speaking  chemists  have  for 
several  years  had  the  opportunity  of  pos- 
,  sessing  a  volume  (or  rather  two)  convenient 
for  the  [xxjket  and  containing  an  enormous 
amount  of  information  such  as  is  fre- 
quently needed  in  the  ordinary  course  of 
their  work.  That  this  is  the  8th  edition  is 
sufficient  testimony  to  indicate  how  much 
the  Chemist's  Year  Book  is  appreciated. 

In  this  editi<«i  a  new  section  on  LeMthi-r 
Analysis,  by  W.  Mather,  A.M.S.T.,  A.l.C 
has  been  incorporated.  Various  sections 
have  been  revised  and  corrected  where 
necessary,  in  accordance  with  the  results 
f)f  the  most  recent  researches. 

The  Chemist's  Year  Book  for  1923 
should  thus  prove  as  popular  among  chem- 
ists as  its  predecessors  have  been. 

J.G.F.D. 


Vat  Colours,  by  Jocelyn  Field 
Thorpe,  D.Sc,  Pn.D..  F.I.C.,  F.R.S.. 
and  Christopher  Kelk  Inoold,  D.S<'. 
Pp.  XV.  +  491.  London:  Ivongmans. 
Green  &  Co.,  89,  Pat^moeter  How, 
E.C.4.     1928.     168.  net. 

It  has  long  been  recognised  that  fast 
colours  can  only  be  imparted  to  fabrics  by 
forming  the  coloured  compound  within  the 
fibres  of  the  material  to  be  dyed. 

The  vat  dyes  include  chemically  very 
dissimilar  types  such  as  indigo,  indnn- 
threne  and  indophenol.  The  essential  fea- 
ture is  that  the  substance  must  possess  a 
oarbonyl  group,  capable  of  being  reduced  to 
the  group  COH,  forming  a  lenco-oom- 
pound,  soluble  in  alkalis. 

The  vat  colours  are  usually  insoluble  in 
ordinary  solvents,  and  are  applied  in  the 
form  of  colourless  and  soluble  reduction 
products. 

Ke-oxidation  by  exposure  to  air  develops 
the  original  colour  within  the  fibre. 

Of  the  vat  dyes,  the  "Purple  of  the 
Ancients,"  and  especially  Indigo,  were 
known  to  the  earliest  dyers,  and  the 
authors  have  rightly  devoted  adequate  and 
careful  attention    to  the     history  of    these 


colours.     Indigo  was,  until  the  last  few  de- 
cEuies,  the  only  vat  dye  of  commercial  im- 
portance. 

Baeyer's  extensive  researches,  and  also 
those  of  other  German  chemists  which  led 
to  the  elucidation  of  its  structure,  were  fol- 
lowed by  various  syntheses  of  indigo  itself, 
and  subsequently  by  the  preparation  of 
similar  dyestutis  of  different  shades. 

These  syntheses  also  revealed  the  essen- 
tial structure  of  the  vat  dyes,  and  more  re- 
cently, important  new  types  of  these  com- 
pounds have  been  produced  from  anthra- 
(luinone.  The  authors  give  a  coniiplete  ac- 
count of  these  bodies,  some  of  which  are 
very  complex,  and  whose  molecules  con 
tain  many  condensed  rings. 

The  last  section  of  this  very  complete 
monograph  gives  detailed  instructions  for 
the  preparation  of  the  dyes  themselves, 
and  also  their  intermediate  products. 

An  appendix  gives  a  list  of  British  vat 
dyes  and  their  German  equivalents. 

The  monograph  will  he  of  great  service 
to  chemists  and  others  engaged  in  the  dye 
industry,  since  it  is  the  only  volume  deal- 
ing e.xciusively  and  com,proheusively  with 
this  class  of  dyes.  It  will  also  be  widely 
consulted  by  the  general  scientific  world 


Back  to  Prosperity,  by  Henry  Lowen- 
EELD  and  his  daughter,  Margaret  Low- 
ENFELD.  Pp.  268  +  XII.  London:  Ef- 
fingham Wilson,  16,  Copthall  Avenue, 
E.C.2.     1923.     58. 

This  very  original  volume  on  the  intrica- 
cies of  monetary  systems  and  present  ano- 
malies arising  from  the  chaotic  state  of 
foreign  exchanges,  should  prove  of  interest 
and  importance  to  those  connected  with 
the  financial  side  of  chemical  and  other 
businesses. 


BOOKS  RECEIVED. 


Atoms,  by  Jean  Perrin,  translated  by 
D.  H.  Hammick,  M.A.  P,p.  XIV.  +  231. 
Second  English  Edition.  1923.  Messrs. 
C  nstable  &  Co..  Ltd..  10  A-  12,  Orange  St., 
Leicester  Square,  W.C.2.     8s.  fid.  net. 

Hcadahh  School  Chetnistry  :  A  Book  for 
Beginners,  by  J.  A.  CocriRANE,  B.Sc  Pp. 
IX.  +  84.     1923.     Messrs.  G.  Bell  A  Sons, 


208 


THE  CHEMICAL  NEWS. 


MAECH  29,  1923. 


Ltd.,  York  House,  Portugal  Street,  W.C.2. 
2s. 


The  Generation  and  Utilisation  of  Cold  : 
A  General  Discussion,  bv  The  Faraday 
Society.  Pp.  137,  141  +  273.  1923.  The 
Faradaj  Society,  10,  Essex  Street,  Strand, 
W.C.2.     10s.  6d.  net. 


A  Tested  Method  of  Laboratory  Organi- 
sation, by  Seymore  Pile,  M.A..  and  Regi- 
nald G.  Johnston,  with  an  Introduction 
by  W.  R.  Barclay.  O.B.E.  Pp.  IX.  + 
98.  1923.  Messrs.  H.  F.  &  G.  Witherby, 
326,  High  Holborn.  W.C.     7s.  6d.  net. 


The  Destructive  Distillation  of  Wood. 
bv  H.  M.  Bunbury,  M.Sc.  (Bris.),  B.Sc. 
(Lond.).  Pp.  XIX.  +  328.  1923.  Messrs. 
Benn  Brothers,  Ltd.,  8,  Bouverie  Street, 
E.C.4.    358.  net. 


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ing fused  salts  of  metals  and  recovering 
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5576— Boudett,  A  E.  P.— Reduction  of  calcium 
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5877 — Royston,  G. — Drying  sulphate  of  ammonia. 
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Specifications   Published   this    Week. 

193071— Plauson's  Parent  Co.,  Ltd.  (Plauson,  Dr. 
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176779— Norsk    Hydro-Elektrisk    Kvaelstof-aktiesel- 
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these  gases. 

193304 — Quinan,  K.  B.— Manufacture  of  super- 
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organic  matter,  and  the  destruction  of 
the  offensive  character  of  putrescible  or- 
ganic matter. 

193561 — Chemische  Fabrik  auf  Actien  (vorm  E. 
Svhering). — Process  for  solidifying  formic 
aldehyde. 

193618— British  Dyestuffs  Corporation,  Ltd.,  and 
Perkin,  W.  H.,  and  Clemo,  G.  R.— Manu- 
facture of  a  new  chloroethyl-ester  and  the 
treatment  of  phenols,  alcohols,  and 
amino-compounds  therewith. 

19378(^-Casale,  Dr.  L.,  and  T^prestre,  R.— Ap- 
paratus for  the  catalytic  synthesis  of  am- 
monia. 


Abstract  Published  this  Week. 

191687— Ferrocyanides.-— Silver  Springs  Bleaching 
and  Dyeing  Co.,  Ltd.,  and  Hall,  A.  J., 
Timberbrook,  Congleton,   Cheshire. 

The  waste  liquor  from  aniline  black  dyeing  in 
which  ferrocvanide  is  used,  is  treated  with  fer- 
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as  described  in  the  parent  case,  and  the  blue  pre- 
cipitate is  separated  and  dissolved  by  means  of 
an  alkali,  alkaline  earth,  or  ammonia.  The  iron 
hydrate  rlso  produced  is  separated  from  the 
solution  and  the  ferrocvanide  is  obtained  by  cry- 
stallisation  from  the  filtrate. 

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I 


APBIL  6,  1923. 


THK   CHEMICAL    NEWS. 


209 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3286. 


THE  STYLE  OF  SCIENTIFIC 
LITERATURE. 

What  one  fool  can  do,  another  can." 

This  sweeping  assertion  is  to  be  found  on 
one  of  the  fly-pages  of  the  late  Professor 
Silvanus  P.  Thompson's  book,  Calculux 
Made  Easy-  The  assertion  is  raiuer  signi- 
ficant, and  we  should  hesitate  to  contradict 
it,  but  a  great  moral  lies  in  the  words. 

At  the  time  when  Professor  ThompsfMi 
wrote  the  book  in  question,  he  probably 
held  pronounced  views  upon  how  Science 
should  be  regarded,  and  gives  one  the  im- 
pression that  he  looked  upon  it  as  a  hug>' 
joke,  not  to  be  inconsiderat^^ly  thrust  aside, 
nut  to  give  food  for  deep  reflection. 

What+'ver  may  be  the  attitude  of  the  stu- 
dent of  Science  to  his  subject,  the  writing.' 
of  a  scientific  book  is,  essentially,  a  teach- 
ing process,  whether  it  be  an  elementary 
text-book  or  an  exposition  upon  6om«' 
greatly  obscure  discovery.  Yet  how  often 
has  a  chemist  sat  down  in  the  evening  with 
a  pile  of  laboratory  results  before  him.  al- 
most groaning  with  vexation  because  the 
worke  of  reference  he  must  of  necessity  use 
are  tedious  and  prolix?  They  contain  the 
information  he  requires,  but  he  is  only  able 
to  find  it  by  m\ich  wnding  through  a 
hideous  sequence  of  almost  incomprehen- 
sible words.  Incoherency  of  text  often 
worries  him  still  more. 

One  can  learn  more  in  ten  minutes  from 
a  hook  of  the  typo  Professor  Thompson  has 
written  uhnn  from  three  hundred  (pages  of 
unrelieved  letterpress  in  several  hours,  anH 
this  is  not  nn  hyperholie  n'jsertion  by  any 
means.  One  is  intorestin}]:  in  itself:  the 
other  is  not,  but  only  in  the  matter  it  con- 
tains. We  do  not  maintain  that  every 
book  of  scientific  tendencies  should  be  com- 
piled similarly,  for  it  would  bo  an  impos- 
sible expectation ;  but  if  the  compilation 
was  less  elaborate,  it  would  save  the  re- 
search chemist  much  valuable  time.  The 
exact  difference  is  in  writing  what  one  may 
have  to  write  within  200  pp.  of  large, 
widely-spaced  print,  and  putting  down  pre- 
cisely the  same  information  in  double  the 
page-quantity  of  small  print. 

The  matter  has  been  discussed  widely  be- 
fore now.       Present  conditions  make  fref^h 


comments  desirable.  Formerly,  admission 
to  the  learned  professions  was  made  only 
via  the  Universities;  now,  it  is  purely  a 
question  of  initiative  on  the  part  of  those 
who  have  not  the  means  of  studying  at  the 
higher  educational  centres.  They  must 
gain  their  knowledge  mainly  irom  books, 
and  simplification  is,  to  them,  desirable. 


VALENCY. 

By  William  R.  F^kldino.  M.A. 
(Vict.). 


M.Sc. 


Senior  Science  Master,  King  Edward  VII. 
School,  Lytham. 

(Continued  from  Page  197.) 

All  these  compounds  are  exothermic, 
i.e.,  as  the  energy  of  the  system  is  reduced, 
p  is  increased,  and  we  may  safely  predict 
that  as  heat  is  absorbed  p  is  reduced. 

WTien  an  exothermio  compound  is  heated 
p  is  reduced;  as  a  substance  is  cooled  p  is 
increased  —  again  showing  that  Ets  the 
energy  of  a  system  is  increased  p  is  reduced 
whereas  as  heat' is  taken  out  of  a  system  the 
substance,  either  element  or  compound, 
becomes  more  polymerised.  The  maximum 
of  polymerisation  occurs  at  the  absolute 
zero  (see  The  Chemical  News,  Vol.  CXXIII 
p.  97). 

The  halide  acrids  illiwtr.tto  this  well,  for 
the  jra.seous  state. 


HF 
HCl 
HBr 
HI 


Heat  of  formation. 
+  38,500  cais. 
+  22,000 
+     8,440 
-     6,040 


Hydrofluoric  acid  is  undoubtedly  poly- 
merised at  300°  A.  (H,Fj)  and  is  H,F. 
(where  x  >  2)  at  stilJ  lower  temperatures. 
On  the  other  hand,  HI  is  endothermio,  and 
it  is  not  only  less  disposed  to  polymerise, 
but  it  is  readily  decomposed  into  its  con- 
stituents. There  is  a  kind  of  law  of  direct 
self-preservation — the  more  encrgv  leaving 
the  system  and  the  more  organised  (p)  does 
the  system  become.  There  seems  grounds 
for  believing  that  the  different  valency- 
values  obtained  by  the  different  methods 
may  be  due  in  part  to  ignoring  these 
charges  in  the  enorpy  of  the  system. 

It  is  this  variable  quantity  of  energy 
which  afppears  as  heat-energy  one  moment 
and  polymerisation  another  which  accoimts 


210 


THE    CHEMICAL    NEWS. 


APEIL  6,  1923. 


for  the  many  inexplicable  ex<3eptions  to  our 
preconceived   valency -values. 

Latent  Heat.   p.  Heat  absorbed. 

3 
<2 
1 


Ice 

Water 

Steam 


80 


587 


>^ 


Data  respecting  endothermic  compounds 
are  not  very  abunda»t,  but  for 

T  p 

CS.,    (Liauid)   243  1.88 

273  1.88 

303  l.^H 

(see  The  Chemical  News,  CXXII.,  289). 

An  atom  of  hydrogen  consists  of  a  positive 
nucleus  and  one  (negative)  electron.  As  the 
temperature  is  raised  the  tendency  to  poly- 
merise with  other  hydrogen  atoms  is  re- 
duced; so  is  the  density;  therefore  the 
atomic  volume  is  increased.  This  rnay  be 
due  to  the  electron  increasing  its  distance 
from  the  +  nucleus.  If  in  combination 
with  a  chlorine  atom,  the  hydrogen  atom 
will  tend  to  be  electro-negative  on  the  chlor- 
ine side  and  electro-nositive  on  the  side  re- 
mote from  the  chlorine.  If  the  electron 
enters  the  chlorine  atom,  or  if  it  is  only  sup- 
posed to  come  to  the  "noint  of  contact"  or 
be  the  "point  of  contact"  of  the  two  atoms, 
there  will  be  a  readjustment  of  the  electri- 
cal forces  within  the  two  atoms  (Fig.  XX.) : 

CI      H 


oo 


A. — Owing  to  the  accaptance  of  electron 
from  hydrogen  there  will  be  a  disturbance 
in  the  orbits  of  at  least  some  of  the  elec- 
trons of  the  chlorine  atom.  This  side  of 
the  chlorine  becomes  electro- negative. 

B. — ^This  side  becomes  electro- positive. 

C. — ^The  electron  accepted  by  the  chlor- 
ine from  the  hydrogen. 

Hydrochloric  acid  may  become  polymer- 
ised thus :  — 


H- 


-CI 


■CI 


CI 


•CI 


From  the  st^dy  of  radio-active  sub- 
stances it  is  accepted  that  existing  atoms 
have  a  positive  nucleus  and  negative  elec- 
trons. Are  there,  or  have  there  been,  any 
atoms  with  a  negative  nucleus  and  positive 
electron©  ? 

Such  a  supposition  would  readily  account 
for  all  combinations,  except  possibly  in  the 
case  of  the  amphoteric  elements.  ^  Consider 
the  union  of  hydrogen  and  chlorine,  an  elec- 
tro-positive nucleus  in  the  former  case  and 
an  electro-negative  nucleus  in  the  latter. 
Union  is  caused  by  a  +  electron  from  the 
chlorine  neutrahsing  an  electron  of  the 
opposite  sign  from  the  hydrogen.  (On 
separating  Jne  two  atoms,  the  equal  and 
oppositely  charged  electrons  are  restored  to 
their  original  positions  in  the  resipec- 
tive  atoms.)  The  hydrogen  part  of 
the  hydrochloric  acid  molecule  would  be 
electro  +,  and  as  in  the  former  case  may  be 
able  to  effect  combination  with  an  electro- 
negative element  other  than  the  chlorine 
with  which  it  is  already  combined. 
Through  the  loss  of  one  of  its  +  electrons 
the  chlorine  is  electro-negative  and  likewise^ 
may  be  able  to  effect  combination  with  an 
electro  +  atom  or  radicle.  Even  the  ampho- 
teric elements  need  not  offer  serious  trouble. 
We  have  to  account  for  the  combination  of 
two  electro-positive  atoms  in  the  molecule 
in  H2,  and  of  two  electro-negative  atoms  in 
CI,.  In  such  cases  the  union  may  be 
effecteo  by  the  +  nucleus  in  one  atom  at- 
tracting the  electron  in  the  other  atom 
thus : 


Hydrochloric  acid  forms  several  well- 
defined  hydrates,  e.g.,  HCl.H^O  imd  HCl.- 
2H2O.  How  do  the  acid  and  water  com- 
bine? The  signs  qpposite  the  symbols  in- 
dicate whether  the  atom  is  electro-positive 
or  negative.  It  is  presumed,  for  the  rea- 
sons given  above,  that  ^-i-nhination  with  an 
atom  or  group  of  opposite  sign  may,  in  cer- 
tain circumstances  be  effected  (Figs.  XXII. 
and  XXIII.) : 


H 


CI 


"(oh)  —  H 


<"F-.  g    til) 


(T'i3  22) 


APRIL  6,  1923. 


THE  CHEMICAL  NEWS. 


211 


(F.g    23) 


The  thickened  lines  in  Fig.  XXIII.  show 
the  position  of  the  main,  principal  or  domi- 
nant valency. 

Ammonium  chloride  may  be  derived  in 
the  same  way  from  ammonia  and  hydro- 
chloric acid,  as  in  Fig.  XXIV.  : 


Cl 


H 


(Tig    24-) 


Nitrogen  is  slightlv  more  ttian  trivalent 
towards  hydrogen,  pes m  v  not  tetravalent, 
but  the  hydrc^n  and  chlorine  of  the  hydro- 
chloric acid,  approaching  it  at  the  same 
time,  make  it  appear  to  be  pentavalent.  the 
chlorine  partially  returning  the  electron  it 
has  received  from  the  hydrogen,  which  now 
becomes  slightly  electro-positive  towards 
the  nitrogen  which  is  now  in- a  position  to 
transfer  (partially)  an  electron  to  the  chlor- 
ine. The  return  of  the  electron  from  the 
chlorine  to  the  hydrogen,  and  from  the  hy- 
drof^tm  to  the  nilrogen,  and  lastly  from  t 
nitrogen  to  the  chlorine,  may  not  be  com- 
plotrd  but  by  readjustments  in  their  elec- 
tronic orbits  these  three  elements  are  in 
equilibrium.  Ammonium  chloride  would 
be  represented  as  in  Fig.  XXV.,  the  arrows 
showing  the  direction  in  which  the  electrons 
tend  to  be  transferred. 


(P.'3  25) 


Unlike  many  rings,  the  ring 

is  easily  ionisable  in  the  presence  of  water. 
Sulphuric  Acid.— Here  sulphur  is    electro- 
positive to  oxygon  (Fig.  XXVI,): 


•H 


H 


(Tig    2b) 


The  water  combines  with  the  SO,  one 
hydrogen  joining  on  to  an  oxy;^t'n  and  the 
oxygen  in  the  water  directly"  linking  with 
the  central  atom,  sulphur.  '  There  is  then 
a  redistribution  of  valency  as  there  are  now 
four  atoms  or  groups  joined  to  the  sulphur, 
with  the  result  that  valency  a  disappears. 
This  is  an  exothermic  action,  and  part  of 
the  heat  evolved  may  be  due  to  the  rear- 
I'angement  of  the  valencies. 


Fig.  XX  VII.  shows  the  dibasio  nature  of 
the  acid,  whereas  an  alternative  method  of 


212 


THE   CHEMICAL   NEWS. 


APEIL  6,  1923. 


linkages  (Fig.  XXVIII.)  would  lead  to  the 
formation  of  a  closed  ring  which  are  often 
unionisable. 


.^3/ 


A-  ^y 


(T-.cj    28) 


Pig.  28  may  represent  a  temporary  iso- 
meric form  which  passes  into  the  compound 
represented  by  Fig.  27  by  the  oxygen  atom 
at  the  extreme  right  joining  on  to  the  sul- 
phur. The  former  arrangement  is  to  be  pre- 
ferred, not  only  because  the  valencies  are 
the  usual  valencies  of  these  elements,  but 
because  it  shows  the  formation  of  the  sul- 
phates in  a  more  straightforward  «ay, 
thus: — 


To  Su-lbhoLr.: 


Suliphuric  acid  and  the  sulphates  form 
hydrates,  and  the  first  molecule  of  water 
seems  to  occupy  a  unique  position,  and  is 
more  difficult  to  drive  off  than  the  other 
molecules  of  water.  For  this  reason  the 
following  formula  is  given : 


,H- 


X 


O. 


M O' 


(-Fi^  30) 


Four  other  molecules    of  water    can    be 
added,  thus : 

(See  Fig.  31.) 


Many  rings  are  non-ionisable,  but  a  solu- 
tion of  copper  sulphate  is  readily  precipi- 
tated by  a  solution  of  BaCl, ;  evidently  the 
above  rings  are  very  unstable  in  aqueous 
solution. 

A  few  example®  of  non-ionisable  rings  will 
now  be  given. 


(Tis  31) 


etc. 


APRIL  6,  1923. 


THE   CHEMICAL   NEWS. 


21;' 


Chromium  trichloride.  —  Three    crystal- 
line hydrates  are  known,  CrClg-GHjO,    two 
green  and  one  violet.      Werner  represented 
these  as  follows : 


[Cr  (OH^),  CI3]  CI    +    2  H,0 
[Cr  (OH,)^  CI]  CI,  +  H^O 
[Cr  (OH3).]  CI3 


The  chlorine  outside  the  square  brswskete 
is  ionic. 

I  prefer  to  think  that  the  anhydrous 
chloride  combines  with  three  molecules  of 
water  and  forms  three  closed  rings,  thus : 


H.OH 


H.OH 


or 


H.OH' 


(fio,  32) 


None  of  the  chlorine  is  ionic.  The  chro- 
mium appears  to  be  hexad.  Considering  ome 
ring  (1st  formula),  the  chlorine  receives  an 
electron  from  the  chromium,  and  with  it  it 
compensates  the  hydrogen  to  which  it  is 
directly  attached,  and  enables  it  to  hold  the 
OH  grouip  and  also  to  link  up  the 
chromium. 


If  another  molecule  of  water  is  added  to 
the  molecule  it  breaks  up  the  first  ring  and 
the  chlorine  which  is  freed  beoouiee  ionic 
(Fig.  XXXIII.): 


H.OH^         Ci y^  OH 


Onft-thlirdL    o-f 
the  c.hlor«;n*  i« 


Cl^  MxO  Hx^ 

(Fig    33) 

The  second  und  third  rings  are  broken  up 
by  successive  molecules  of  water: 


H^O^      CI — 7H.OH 
-CI 


CI 


Tu>0-tV»irdL»    Off 
LomVct 

l\ 

(P.'S  34-) 
H^O.       CI        .HxO  All    •*  tV* 

\  «r  cV>lorin«  i» 

H^O— C^— H^O  LOnJc. 

y7  V>V  (VcoUt   fc-m.) 


An  alternative  method  would  be  to  link 
the  water  and  chlorine  as  in  the  second  for- 
mula. The  final  form  is  the  same  in  each 
case. 

Thus  chromium  ia  attached  by  principal 
and  subsidiary  valencies  to  6,  7,  8,  or  9 
atoms  or  groups.  Six  of  these  are  water 
molecules  in  the  last  case  and  undoubtedly 
these  water  molecules  will  exercise  valency 
towards  each  other  to  form  polymM*  simi- 
lar to  di-  and  tri-  hydrol  in  liquid  and  sohd 
water.  In  any  ciisee  the  valencies  usually 
given  to  chrcmiium  cannot  hold,  because  if 
these  six  molecules  had  a  single  resultant 
residual  valency  towards  the  nuclear  chro- 
mium atom  the  valency  of  the  latter  would 
be  4.  To  mark  the  valencies  between  the 
chromium  and  the  chlorine  and  to  ignore 
the  molecules  which  are  included  in  the 
complex  ion  is  simply  shelving  the  matter. 
The  heat  change  accompanying  every 
chemical  and  physical  change  effects  a 
change  in  the  energy  of  the  system,  and  the 
valency  of  any  and  every  atom  will  be 
altered  in  some  degree.  xnene  is  no  valid 
argument  against  hydrogen  becoming  dyad 
or  triad  and  oxygen  pentad.  The  weight 
carried  by  a  person  depends,  to  some  ex- 
tent, on  the  distribution  of  the  load.  The 
following  seems  to  be  the  simplest  way  ol 


^u 


Tflfi   CHEMICAL   NfiWB. 


APEiL  6,  1928. 


reipresenting  the  complex  ion,  the  dotted 
lines  showing  the  weak  valencies  (Fig. 
XXXV.) : 


OH— H 


^H — oh' 


-RiuLS     t+>*      CI— 7H.OH       ^ir^g      IS 

V>on-Loni.S<xble,    u3V>«.r«<v.S  tVi«.    vA.n- 
Sto-bk    r«nq     |.r«.»ent    in   «».mr«or>vU.m 
cViloridLft.     »&-  — . 

H — >N 

(P.3   35)  • 
(To  be  cu.ttnueu.) 


COMPOUNDS  OF  SODIUM 
CARBONATE  WITH  FATTY  ACIDS. 

By  J.  F.  Weinberg. 
[Editorial  Note.  —  This  oommunica- 
tion  was  sent  under  seal  to  the  late  Sir 
Wilham  Crookes,  F.R.S.,  on  December 
26,  1919.  Recently,  efforts  to  get  into 
tovioh  with  the  author  have  failed.  The 
seals  were  thereupon  broken,  and  the 
article  is  now  published.] 

Preparation. 

Fatty  acids  in  a  melted  state  readily 
combine  with  crystallised  sodium  carbonate 
(10  ag.)  when  melted  in  its  water  of  crystal- 
lisation. A  series  of  comipounds  is  formed 
of  a  chemical  character,  rnuch  resembling 
sodium  bicarbonate,  its  composition  being 
represented  by  the  formula: 


X  H,0 


^^A     ^(c'h„_  ,00), 

Properties. 

These  compounds  can  with  great  advan- 
tage be  used  instead  of  soap. 

The  effect  on  the  skin  is  milder,  no  caus- 
tic soda  being  present  or  set  free  by  hydro- 
lysis. 

The  effect  during  ablutions  is  very  re- 
markable. 


The  exudation  from  the  human  skin  is  a 
solution  of  organic  nitrogen  compounds  in 
volatile  fatty  acids. 

In  foul  linen  these  volatile  fatty  acids  are 
soon  evaporated,  leaving  a  residue  insoluble 
in  caustic  soda  and  insoluble  in  soap. 

Therefore,  soap  will  never  make  foul 
linen  clean,  scrubbing  and  bleaching  agents 
being  indisipensable. 

However,  this  residue  is  easily  soluble  in 
a  hot  aqueous  solution  of  the  above-men- 
tioned compounds.  It  is  also  soluble  in  hot 
dilute  hydrochloric  acid  (0.1  per  cent.), 
which  seems  to  account  for  the  action  of 
chlorine  in  the  presence  of  moisture. 

Boiling  for  half  an  hour  in  a  1-2  per  cent, 
aqueous  solution  of  the  compounds  just  de- 
scribed, will  clean  the  foulest  linen, 
mechanical  treatment^  as  well  as  bleaching 
agen^  being  altogether  superfluous. 
Preparation  on  a  Large  Scale. 

The  fat  to  be  used  is  saponified,  then  de- 
composed by  sulphuric  or  hydrochloric 
acid.  Any  other  process  may  likewise  be 
used  to  obtain  the  fatty  acids. 

The  fatty  acids  are  simply  melted,  and  in 
this  state  added  to  sodium  carbonate  (10 
HjO)  melted  in  its  water  of  crystallisation. 

When  the  mixture  is  stirred,  the  reaction 
is  complete.  No  carbonic  acid  is  set  free, 
all  of  the  water  of  crystallisation  may  re- 
main in  the  product. 

Fatty  acids  prepared  from  Sunlight  soap 
(the  melting-point  of  the  acids  was  27°  C.) 
give  a  product  of  very  much  the  same  ap- 
pearance, only  being  a  little  harder. 

The  proper  proportions  are  approximate- 
ly :  1  part  of  fatty  acids  to  ^  part  of  carbon- 
ate of  soda  (10  HjO).  However,  an  excess 
of  carbonate  of  soda  seems  advisable.  Good 
results  were  obtained  with  :  1  part  of  car- 
bonate of  soda,  1  part  of  fatty  acids. 


CONCENTRATED  BORATE    OF  LIME. 
By  E,  L.  Fleming. 

Crude  borate  of  lime  contains  28.2  per 
cent,  anhydrous  boracic  acid.  Its  value 
delivered,  at  7s.  3d.  per  unit,  is  £10  5s.  per 
ton,  which  does  not  pay  cost  of  collection 
and  transport.  If  it  is  dried  and  contains 
43  per  cent.  A.B.A.  its  value  delivered  is 
£15  13s.  per  ton. 

By  removing  63  per  cent,  of  the  worth- 
less material  associated  with  the  borate  of 
lime,  freshly  drawn  from  the  deposit,  a 
concentrated  borate  is  produced  containing 


APRIL  6,  1923. 


THE  CHEMICAL  NEWS. 


215 


75  per  cent.  A.B.A.,  and  its  value  delivered 
is  £27  68.  per  ton.  lae  process  s  quite  sim- 
ple, the  materials  used  for  its  production 
being  pioducts  of  the  countries  where  the 
borate  of  lime  is  located.  The  approxi- 
mate cost  of  production  at  the  Boratera,  fw 
one  ton  of  concentrated  borate,  working 
with  the  smallest  plant,  with  an  output  of 
300  tons  per  ann.  being  £12  per  ton.  It 
may  be  worked  with  unskilled  native  labour. 
The  plant  for  producing  concentrated  bor- 
ate can  be  obtained  fft>m  a  well-known  firm 
of  chemical  engineers  in  England. 

The  advantages  possessed  by  concen- 
trated borate  75  per  cent.  A.B.A.  are  that 
by  boiling  it  with  half  its  weight  of  58  per 
cent,  alkali,  it  produces  200  per  cent,  of  its 
weight  in  crystal  borax.  The  solid  refuse 
only  amounts  to  7  per  cent.  There  is  a 
saving  of  42  per  cent,  in  transport,  when 
compared  with  calcined  borate  44  per  cent, 
anhydrous  boracic  acid. 

In  Argentina,  borate  of  lime  ground 
covering  an  area  of  76,000  hectares  has 
been  recorded  in  the  State  Mining  Roll. 
The  level  at  which  these  borateras  are 
located  is  reached  by  the  Central  Northern 
liailway,  at  Tres  Cruces.  In  Bolivia,  by 
the  Arica-la  Paz  Railway  at  Charana.  In 
Chile,  by  the  Antofagasta  and  Bolivian 
Railway  at  Asootan.  In  Peru,  by  the  Are- 
quipa  Railway  at  Pampa  de  Arrieros. 

"nie  borate  of  lime  owurs  in  three  distinct 
formations : 

(1)  In  layers  on  the  surface  of  the 
ground. 

(2)  In  banks,  five  or  six  feet  in  depth. 
(8)  In  the  form  of  "potatoes"  or  rounded 

masses,  scattered  through f>ut  the  soil. 


ACTIVE  HYDROGEN:   NEW 

METHODS    OF  PREPARATION. 

By  Y.  Vbnkatramaiah. 

Continuing  his  researches  on  the  activa- 
tion of  hydrogen,  the  author  has  elaborated 
four  more  new  methods  of  activating  the 
gas.  The  new  methods  are  : 
•  (a)  The  burning  of  oxygen  in  hydrogen. 
— The  hydrogen  and  oxygen  utilised  in  all 
the  experiments  conducted  was  prepared  by 
electrolysing  a  solution  of  barium  hydrox- 
ide. The  gases  were  purified  and  dried  in 
the  usual  way. 

The  combustion  of  oxygen  and  hydrogen 
wa«  carried  out  in  a  specially  constructed 
apiparatus  kept  cool  at  0°  C.      The  combus- 


tion tube  was  of  platinum,  of  12  mm.  in- 
ternal diameter.  The  oxygen  flame  was 
nearly  six  inches  in  height.  The  unbumt 
hydrogen  was  drawn  out  through  a  tube 
kept  in  iced  water,  on  to  cold  powdered 
sulphur,  and  the  presence  of  hydrogen  sul- 
phide was  tested  by  using  a  lead  acetate 
pa^er. 

(6)  The  surface  combustion  of  hydrogen 
and  oxygen  on  platinum. — In  this  experi- 
ment a  platiuum  wire  3  metres  in  length 
and  0.4  mm.  in  diameter  was  wound  round 
a  glass  rod  frame  10  cm.  in  breadth  and  12 
cm.  in  length.  The  wire  was  electrically 
heated  by  placing  the  frame  in  a  suitable 
apparatus  into  which  a  proper  mixture  of 
oxygen  and  hydrogen  could  be  introduced 
containing  slight  excess  of  the  latter.  The 
presence  of  activated  hydrogen  in  the  un- 
combined  gas  was  recognised  in  the  usual 
way. 

(o)  High  tension  arc  in  hydrogen.  —  A 
high  tension  arc  was  established  between 
two  silver  electrodes  5  mm.  in  diameter. 
The  electrodes  were  kept  1\  cm.  apart.  A 
large  induction  coil  whose  primary  could  be 
fed  with  a  current  up  to  20  amperes  was 
used  along  with  a  Wehnelt  interrupter.  The 
presence  of  active  hydrogen  in  the  gas 
drawn  out  wm  tested  in  the  usual  manner. 

(d)  High  t(^mperature  arc  in  hydrogen. — 
In  this  case  hvdrogen  was  conducted  into 
arcs  established  between  metalhc  elec- 
trodes 1  cm.  in  diameter,  of  gold,  platinum, 
and  silver  fixed  in  a  suitable  apparatus.  The 
olectrofles  wen-  kept  fed  with  a  current  of  6 
anxperes  under  220  volts  pressure.  The 
presence  of  the  active  gas  in  the  hydrogen 
drawn  out  from  the  arcs  was  tested  as  pre- 
viously described.  In  the  case  of  silver, 
activaticm  of  hydrogen  was  possible,  while 
in  the  case  of  gold  and  platinum  it  was  not. 
An  explanation  for  this  discrepancy  seems 
to  be  in  the  absorption  of  active  hydrogen 
by  thin  films  of  metals  in  the  case  of  gold 
and  platinum  which  are  known  to  absorb 
larger  quantities  of  hydrogen  than  silver  it- 
self.— (From  the  Proceedings  of  the  Science 
A880ciotion,  Maharajah's  College,  Viziana- 
gram,  Dec,  1922.) 


COMPRESSIBILITY,   INTERNAL 

PRESSURE,  AND  ATOMIC 

MAGNITUDES. 

By  Theodore  W.  Richards. 

The  contraction  of  elements    in  the  for- 
mation of  compound«  has  been    evaluated 


216 


THE    CHEMICAL   N*!WS. 


APEIL  6,  1923. 


from   the    determined    compressibilities     of 
the  individual  elements. 

la  the  pressure-volume  curves  for  sodium 
and  potassium,  which  extend  over  a  range 
of  45,000  atmospheres,     considerable   iden- 
tity  with   Bridgeman's   values  {Proc.    Am. 
Acad.  Arts  Sei.,  1922,  LVIII.)  is  disclosed, 
and  the  assumption  that  thej  are  more  or 
less  accurate  is  justifiable.      The  extant  ir- 
regularities are  considered  due    to  the  vol- 
ume,  rather  than  the  pressure  or  the  two 
together,  and  the  ultimate  pressure  is  com- 
puted as  the  sum  of  internal  and  externa!, 
giving  an  equation  of  the  type:     (p+P)  /  v 
=  K;  where  p   =   the  external,    and  P   = 
the  initial  internal  pressure.  A  close  study 
into  the  curves  revealed  a  formula  notable 
for    its    simplicity:      (V-B)   (p+P)    =    K. 
According  to  this,  the  B  portion  acts  as  if 
it  were  incompressible,  and  "the  relation  of 
the   total   pressure    (external  plus   internal) 
to  volume  is  simply  hyperbolic.       Tabula- 
tion of  the  K-volumes  shows  similarity  be- 
tween the  calculated    and  observed  values 
of  V. 

The  curve  seems  to  have  bearing  upon 
the  contraction  which  occurs  when  potas- 
sium and  chlorine  combine  to  form  potas- 
sium chloride.  The  sum  of  the  gram- 
atoms  of  these  elements  is  70.5  cc,  and 
the  reduction  takes  place  over  a  range  of 
33.0  cc,  the  final  volume  being  37.5  cc. 
The  range  of  compressibility  of  chlorine  is 
nearly  that  of  potassium;  thus,  if  potas- 
sium at  44,000  atmospheres  is  reduced  to 
half  its  original  volume,  the  average  P  of 
potassium  chloride  is  of  the  same  order. 

As  separate  from  monatomic  molecules, 
polyatomic  molecules  demand  recognition 
of  the  fact  that  two  or  more  internal  pres- 
sures must  exist;  those  caused  by  chemi- 
cal affinity  and  those  due  to  material  co- 
hesion. The  polyatomic  (urve,  then,  will 
be  comiplex;  one  with  a  hyperbola  similar 
to  that  of  K,  and  the  other  almost  horizon- 
tal, corresponding  to  the  greater  pressure 
on  certain  parts  of  the  atoms.  The  two 
curves  may  be  roughly  depicted  by  one  hy- 
perbola. 

Phosphorus  trichloride  presents  an  in- 
stance. The  behaviour  of  a  millilitre  as  far 
as  12,000  atmospheres  conforms  to  the 
equation  (p+6200)  (V-0.67)  =  2050;  the 
large  value  of  B  corresiponding  to  unit  ini- 
tial volume. 

There  has  been  no  first-hand  data  com- 
puted for  chlorine,  as  the  subjection  of  fhis 
element  to  high  pressures  is  difficult  in 
modem  apparatus.     Some  figures  were  ob- 


tained, however,  which  admitted  of  plaus- 
ible calculations  over  the  chloride  range. 
The  contentions  are  based  upon  observance 
of  the  respective  compressibilities  of  chloro- 
form and  carbon  tetrachloride,  and  by  com- 
paring chloroform  with  bromoform  (Eieh- 
ards  and  Stull;  Carnegie  hist.  Puh.;  1903, 
yil.,  44).  The  comparison  rendered  the 
indicative  equation:  — 


^ 


i8 


CI 


=  ^  X 


Br 


CHBr, 


this  conclusion  being  drawn  from  the  fact 
that  the  differences  between  the  boiling 
points  of  chlorine  and  bromine,  and  the 
two  derivatives  mentioned,  are  aipproxi- 
niately  identical. 

Phosphorus  trichloride  seems  to  throw 
some  light  upon  the  problem.  The  com- 
pound contains  rather  over  f  of  its  weight 
of  chlorine,  and  the  phosphorus  must  ob- 
viously be  com^pressed  to  a  smaller  bulk 
than  either  white  or  red  phosphorus.  A 
study  of  the  two  volumes  shows  that  the 
chlorine  is  in  a  similar  condition  to  inde- 
pendent liquid  chlorine.  From  these  m- 
ferences,  a  curve  depicting  the  behaviour 
of  liquid  chlorine  may  be  obtained;  it  be- 
ing confirmed  by  the  compressibilities  of 
both  bromine  and  iodine. 

The  numerous  data  comply  invariably 
with  observations  contained  in  an  earlier 
communication;  but  the  modified  prm- 
ciples  clarify  to  a  considerable  extent  the 
curious  actions  of  many  solids  and  liquids, 
and  further  discussion  upon  some  of  them 
will  follow  in  the  near  future. 

[Substance  of  a  Contribution  from  the 
Wilcott  Gibbs  Memorial  Laboratory  of 
Havard  University ;  quoted  from  the  Journ. 
Amer.  Chem.  Soc,  1923,  XLV.,  422.] 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


ROYAL  SOCIETY  OF  ARTS. 

Indian  Section, 

Friday,  April  6th,  1923,  at  4  p.m. 
Postal  and  Telegraph  Work  in  hidia,  by 

Geoffrey    Rothe    Clarke,     Esq.,    C.S.I. 
O.B.E.,   I.C.S.,    Director-General  of  Posts 
and  Telegraphs  in  India. 

The  Right  Hon.  Lord  Montagu  of  Beau- 
lieu,  K.C.I. E,,  C.S.I.,  will  preside. 


I 


APRIL  6,  1923. 


THB   CHExMICAL   NEWS. 


217 


SOCIETY  OF  GLASS  TECHNOLOGY. 

The  President,  Prof.  W.  E.  S.  Turner, 
D.Sc,  presided  at  the  meeting  of  the 
Society  of  Glass  Technology,  held  in  the 
University,  Birmingham,  on  Wednesday, 
March  21st,  1923.  The  papers  presented 
were  all  contributions  from  the  Department 
of  Glass  Technology,  The  University,  Shef- 
field. 

The  first  one,  entitled  A  Rapid  Method  of 
Testing  the  Durability  of  Glassware,  by 
Mr,  H.  S.  Blackmore,  Miss  Violet  Dim- 
BLEBY,  and  Prof.  W.  E.  S.  Turner,  was 
read  by  Miss  V.  Dimbleby,  who  was  thus 
the  first  lady  to  read  a  paper  before  the 
Society.  The  pa(per  presented  an  account 
of  a  simple  and  rapid  method  for  determin- 
ing whether  a  sample  of  glass  would  with- 
stand weathering  sufficiently  to  enable  it  to 
fulfil  certain  purposes.  The  test  consisted 
of  the  fact  that  when  a  very  dilute  solution 
of  one  part  in  1,000  of  the  alkaloid  naroo- 
tine  hydrochloride  is  heated  to  boiling  in- 
side a  glass  vessel,  the  alkaloid  is  thrown 
out  of  soIutif>n,  and  can  be  seen  as  a  tine 
preciipitate  if  the  glass  is  of  pow  quality.  If 
this  occurred  at  the  end  of  ten  minutes' 
heating,  the  glass  was  to  we  condemned ;  if 
within  twenty  minutes,  the  glass,  although 
better,  was  still  unsatisfactory. 

Good  glasses  ought  to  show  no  sign  of 
deposit  when  heated  at  the  boiling  point  for 
an  hour.  It  was  pointed  out  that  this  list 
differed  from  all  the  others  previously  de- 
vised and  used,  in  that  it  required  no  spe- 
cial chemical  knowledge,  could  be  carried 
out  with  very  simple  apiparatus,  and  there- 
iorv  was  a  test  which  could  be  applied  in 
any  factory.  The  test  was  shown  to  be 
thoroughly  satisfactory  by  a  large  number 
of  trials  on  all  kinds  of  glassware. 

The  two  other  papers  contributed  were : 
The  Corrosion  of  Fireclay  Refractory 
Material  by  Glass  and  Glass-making 
Materials,  by  Mr,  Donald  Turner  and 
Prof.  W.  E.  S,  Turner,  and  The  Effect  of 
Saltcake  in  Corroding  Fireclay  Materials, 
by  Miss  Edith  M.  Firtii,  Mr.  F.  W,  Hod- 
kin,  and  Prof.  W,  E,  S,  Turnbr,  These 
two  papers  were  taken  together  and  pre- 
sented by  Prof.  Turner,  who  detailed  ex- 
perimental evidence  showing  that  in  glass 
melting  the  corrosion  of  the  pots  or  of  the 
tank  blocks  was  most  severe  during  the 
early  stages  of  the  melting  of  the  batch. 
The  corrosion  due  to  the  plass  itself  was 
proved  to  be  very  much  less. 

Of  the  glass-making    materials,     sodium 
nitrate,  potassium  nitrate,  and  borax  were 


particularly  corrosive.  Kesistauce  to  cor- 
rosion could  be  improved  by  tiring  the  pots 
or  blocks  at  1,400°  before  the  charge  of 
batch  was  inserted.  At  temperatures  round 
about  800  or  900*0.,  saltcake  was  not 
nearly  so  corrosive  as  soda  ash.  At  the 
temperature  of  the  melting  furance,  how- 
ever, it  appeared  to  be  more  corrosive,  and 
it  was  demonstrated  by  a  series  of  experi- 
ments that  as  the  proportion  of  saltcake 
increased,  so  did  the  extensiveness  of  cor- 
rosion, even  in  batches  in  which  coke,  as  a 
reducing  agent  or  the  saltcake,  was  present 
throughout. 

During  the  forenoon  a  party  of  members 
visited  the  Longbridge  Works  of  Messrs, 
Austin  Motor  Co.,  Ltd.,  Northfield. 


INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

Seventieth  General  Meeting. 

At  the  House  of  the  Royal  Society  of 
Arts,  John  Street,  Adelphi,  W.C,2. 

On  Tuesday,  10th  April,  1923,  the  follow- 
ing paper  will  be  read : 

Poirero  No.  4.  A  History  of  One  of 
Mexico's  Earliest  and  Largest  Wells,  by 
A.  E.  Chambers,  M.Inst. P,T.,  Assoc.M.- 
Inst.C.E. 

The  chair  will  be  taken  at  5.80  p.m.  by 
the  President,  H.  Barringer,  M.Inst.C.E,, 
M.I.Mech.E.,  M.LN.A.,  M.Inst.  Mar. 
£ng. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 
Wireleas  Section  meeting,  in  the  Lecture 
Theatre  of  the  Institution,  aa  Wednesday, 
nth  April,  1923,  at  6  p.m.     (Light  refresh- 
ments at  5.80  p.ni.) 

The  Application  of  a  Revolving  Magnetic 
Drum  to  Electric  Relays,  Siphon  Recorders 
and  Radio  Transmitting  Keys  (Experimen- 
tal Demonstration),  by  N.  W.  McLachlan, 
D.Sc.  (Eno.),  Member, 


GENERAL  NOTES. 


BRITISH  DYER  "  BOOM." 

New  Plant  and  an  Order  from  Germany. 

Extensive  new  plant  is  being  installed  at 

the  Huddersfield  works  of  the  British  Dye- 

etufis  Corporation  to  meet  the  growing  de- 


218 


THE   CHEMICAL   NEWS. 


APRIL  6,  1923. 


mand  created  hy  the  situation  in  the  Rulir 
and  hy  a  greater  public  confidence  in  Brit- 
ish acids,  intermediates  and  djestufEs. 

There  has  recently  !  een  a  considerable 
increase  in  production  of  acids,  intermedi- 
ates and  dyestuffs.  This  may  be  due  in  part 
to  the  occupation  of  the  il\ihr,  but  is  due 
mainly  to  the  strengthening  of  confidence 
in  the  quahty  and  uniformity  of  British 
dyes.  Dje  users,  moreover,  are  always 
looking  for  a  continuous  supply  of  the  right 
goods  almost  as  much  as  for  the  right  goods 
themselves.  That  is  one  reason  why  to-day 
many  of  them  regai'd  the  Reparation 
material  with  much  less  favour  than  they 
did  twelve  months  ago. 

Inquiries  are  coming  even  from  the  Con- 
tinent. A  week  or  two  ago  one  came  from 
Brussels  for  mixed  acid,  and  only  the  other 
morning  there  was  another  from  Germany 
for  nitric  acid.  This  is  something  abso- 
lutely novel  for  the  English  chemical  indus- 
try, and  is  symptomatic  of  the  general  out- 
look. V 


In  the  House  of  Commons  recently,  Mr. 
Short  asked  the  President  of  the  Board  of 
Trade  if  he  could  state  the  total  imports  of 
alizarine  and  other  anthracene  dyes  during 
the  years  1913  and  1922  ies,pcctively. 

Lieut. -Colonel  Buckley,  Secretary  to  the 
Overseas  Trade  Department,  replied :  The 
imports  into  the  United  Kingdom  of  alizar- 
ine and  anthracene  dyestuffs  during  the 
year  1913  amounted  to  60,813  owts.,  valued 
at  £272,245.  In  the  year  1922  the  imports 
of  alizarine  dyes  amounted  to  11,387  cwts., 
valued  at  £60,607.  Owing  to  a  change  in 
classification  which  became  operative  in 
January,  1920,  separate  particulars  of  the 
imports  of  anthracene-  dyes  in  1922  are  not 
available. 


THE  PHOTOGRAPHIC  FAIR. 

The  Photographic  Fair  held  at  Holland 
Park  Hall,  W.,  from  March  15  to  24,  was 
characterised  by  a  good  disiplay  of  exhibits. 

Numerous  photographic  manufacturers 
showed  the  latest  productions  and  devices 
in  general  apparatus,  hand  and  folding  re- 
flex camera®,  lenses,  new  films,  ultra-rapid 
plates,  &c.  Good  specimens  of  silver  ni- 
trate, gold  chloride,  potassium  platini- 
chloiide,  etc.,  were  exhibited  by  a -well- 
known  firm  of  manufacturers  of  photo- 
graphic chemicals. 


Besides  these  there  were  also  exhibits  of 
radiography,  photomicrography,  press 
photography,  and  colour  reproduction.  A 
section  on  "spirit  photography"  was  ar- 
ranged by  the  Editor  of  Light. 

Some  first-class  prints  by  the  profession- 
al photographers  of  other  countries  were 
also  shown  at  one  stand. 


PYRIDINE  SIMONSENS  OIL  AND 
WOOD  NAPHTHA. 

The  Department  of  Overseas  Trade  have 
received  a  request  from  a  Durban  firm  to 
be  put  in  touoh  with  firms  in  the  United 
Kingdom  who  are  in  a  position  to  supply 
pyridine,  simonsens  oil  and  wood  naphtha. 
These  materials  are  required  for  the  de- 
naturing of  alcohol  for  the  manufacture  oi 
methylated  spirits. 

The  name  and  address  of  the  applicant, 
together  with  further  particulars,  may  be 
obtained  by  United  Kingdom  firms  inter- 
ested upon  application  to  the  Department 
of  Overseas  Trade,  35,  Old  Queen  Street, 
Westminster,  London,  S.W.I  (Room  52). 
Reference  number  10856/ ED /CP  should  be 
quoted. 


CZECHO- SLOVAK    CHEMICAL 
INDUSTRY. 

In  the  year  1922  only  50  per  cent,  of  the 
larger  Czecho- Slovak  chemical  factories 
were  working,  and  the  smaller  ones  were  in 
more  or  less  the  same  position.  The  reason 
for  the  small  demand  lay,  as  with  other 
branches  of  industry,  in  the  fact  that  prices 
were  higli  owing  to  fluctuation  in  the  Cen- 
tral Eurqpean  exchanges,  German  competi- 
tion, etc.,  and  consumption  was  conse- 
quently restricted,  the  result  being  a  crisis 
on  the  chemical  market.  One  circumstance 
is  common  to  all  these  causes,  namely, 
that  they  are  beyond  the  control  of  the  pro- 
ducer, so  that  the  manufacturer  himself 
can  do  nothing  to  remove  them.  Before 
the  war,  the  chemical  industry  in  Czecho- 
slovakia was  in  a  position  to  compete  with 
any  other,  and  had  a  large  share  in  the  ex- 
portation. Despite  the  unfavourable  con- 
ditions of  the  times,  the  industry  improved 
its  arrangements  and  methods  of  business, 
so  that  its  present  constitution  in  this  re- 
spect is  to-day  better  than  it  was. 


APBIL  6,  1923. 


THE   CHEMICAL   NEWS. 


219 


It  is  obliged  to  imjport  most  of  its  raw 
material  from  abroad.  Thus  more  especi- 
ally— pyrite  from  Spain,  phosphate  from 
America,  Africa  and  Australia,  salt  from 
Germany  and  Austria,  and  fats  from  over- 
seas. In  this  way  the  entire  Czech o- Slovak 
chemical  industry,  both  in  its  larger  and 
smaller  concerns,  is  dependent  on  the  one 
hand  on  the  importation  of  raw  material 
from  overseas,  while  on  the  other  it  must 
endeavour  to  export  the  finished  products, 
as  there  is  not  sufficient  demand  for  them 
in  Czeoho-Slovakia  itself. 

During  the  ipast  year  the  Czecho-Slovak 
chemical  industry  aimed  at  selling  off  the 
existing  supplies  and  at  covering  home  con- 
sumption, which  it  is  true,  wae  gradually 
diminishing.  The  decrease  in  exports  in 
1921  is  attested  by  the  following  statistics, 
but  it  should  be  borne  in  mind  that  the 
value  of  the  Czecho-Slovak  crown  two 
years  ago  was  not  as  high  as  it  is  now. 

Of  the  chemical  products  which  have 
chiefly  to  be  considered,  the  following  ex- 
ports were  effected :  — 

1920  for  1,480  million  crowns. 

1921  for    -870 

1922  for      280 

The  unemployment  figures  in  the  Czecho- 
slovak chemical  industry  for  January, 
1922,  expressed  as  630,  rose  to  2,084  by 
September,  1922,  of  which  18  per  cent,  re- 
ceived doles  direct  from  the  State,  and  42 
per  cent,  were  supported  by  various  indus- 
trial concerns.  The  figures  of  last  quarter 
are  significant :  in  October  there  were  2,804 
unemployed  workmen  in  the  industry,  and 
subsequently  in  the  month  of  November 
there  is  a  gradual  change  for  the  better, 
with  only  1,626  unemployed.  The  decrease 
in  wages,  which  became  a  necessity  last 
year,  was  carried  through  with  less  diffi- 
culty than  was  anticipated. 

In  consequence  of  the  rise  of  prices  in 
Germany,  it  would  seem  that  Czecho- 
slovakia will  again  be  able  to  supply  the 
demands  from  abroad,  and  her  chemical  in- 
dustry is  to-day  actually  in  a  position  to 
compete  with  England,  Belgium,  and 
America  in  very  many  articles.  As  regards 
its  organisation,  it  should  b6  pointed  out 
that  the  Czecho- Slovak  chemical  indus- 
tries comprise  22  sections,  of  which  each 
one  forms  a  link  between  the  undertakings 
of  the  individual  branches  of  the  industry. 
The  entire  Union  is  affiliated  to  the  Central 
Federation  of  Czecho-Slovak  Industries. 


CZECHO-SLOVAKIA. 
Demand  for  British  Chemicals. 

The  Acting  Commercial  Secretary  at 
Prague  reports  to  the  Department  of  Over- 
seas Trade  that  the  French  occupation  of 
the  Ruhr  district  and  the  present  industrial 
situation  in  Germany  are  undoubtedly  hav- 
ing their  effect  on  the  local  market,  but  the 
increased  demand  arising  out  of  the  abnor- 
mal conditions  obtaining  in  Germany  has, 
as  yet,  scarcely  been  noticeable,  owing  to 
the  fact  that  the  stocks  on  hand  in  this. 
country  have  been  sufficiently  large  to 
cover  all  requirements.  In  view  of  the 
general  depression  in  the  textile  industry, 
even  the  demand  for  aniline  dyes  has  been 
almost  imperceptible,  yet  in  normal  times 
the  Czecho-Slovak  requirements  in  dyes 
were  so  large  as  to  be  an  item  of  great  im- 
portance even  to  the  largest  German  works. 
The  present  stocks,  however,  will  not  last 
for  any  great  length  ol  time,  and  there  is 
no  doubt  that  sooner  or  later  there  will  be 
a  shortage  of  aniline  dyes  and  higher  prices 
will  be  seen,  especially  as  German  prices 
have  now  practically  attained  the  level  of 
those  ruling  in    the   international   market. 

?'he  effect  of  the  oocuipation  of  the  Ruhr  on 
he  Czecho-Slovak  heavy  chemical  trade 
has  been  to  arrest  the  falling  tendency  of 
prices. 

Lower  prices  were  expected  for  acetic 
acid,  soda,  borax,  and  chloride  of  lime,  but 
in  view  of  the  temporary  alienation  of  Ger- 
man competition  no  reduction  whatever 
has  taken  place,  and  local  prices  are  still 
two  or  three  times  higher  than  German 
prices,  and  oft<'n  higher  than  those  ruling 
in  the  Western  States. 

Following  are  the  market  prices  of 
chemicals  per  kilo  ruling  in  Prague  on  the 
8th  March:  — 

Czech  Crowns. 

Acetone  21.00 

Alum  ,'. 4.35 

Formic  Aeid   (80  per  cent.)  ....  12.30 

Benzoic  Acid      38.00 

Sulphate  of  Magnesia  1.40 

Borax   Crystals  6.50 

Boric  Acid    11.00 

Chloride  of  Barium 3.20 

Chloride     of   (chlorinated)  limo       'J. CO 

Chloride  of  Potassium   10.00 

Chrome  Alum  7.00 


220 


l^E   CHEMICAL   NEWS. 


APillL  6,  1923. 


Czech  Crowns. 

Dextrin  3.00 

Green  Vitriol  or  Copperas  0.60 

Acetic  acid  80  per  cent 18.00 

Yellow   cyanide    of     Potassium  30.00 
Sulphate  of  Soda  (powder)     ...       0.90 

Sulphate  of  Soda  (crystals)  ....  0.80 

Permanganate  of  Potash   15.00 

Nitrate  of  Potassium   7.00 

Oxalate  of  Potassium  19.00 

Blue  Vitriol       8.00 

Lime  8.00 

Oxalic  Acid       13.00 

Paraffin  3.50 

Sal  Volatile  98/100  5.90 

Liquid  Ammonia  0.910   5.30 

Nitric  Acid  36°  Be  3.00 

Hydrochloric  acid  20-22  p.c.   ..  0.95 

Shellac  T.N.  Orange  64.00 

Suliphide   of   Sodium    3.80 

Sulphide  in  pieces   1.80 

Sulphuric  Acid  66  per  cent.   ...  1.25 

Tartaric   Acid       25.00 

Turpentine    (French)   19.50 

White  Vitriol       2.80 

Japan  Wax       12.50 

Camauba  Wax       16.00 


In  the  House  of  Commons,  Mr.  Darbi- 
shire  asked  the  President  of  the  Board  of 
Trade  if  he  had  received  a  communication 
from  the  British  Chemical  Trade  Associa- 
tion, which  was  addressed  to  the  Secretary 
of  State  for  Foreign  Affairs  and  passed  on 
to  him,  containing  proposals  for  the  setting 
uip  of  a  licensing  office  in  the  Cologne  area, 
which  should  be  competent  to  deal  with  all 
consignments  of  British  goods  consigned  to 
the  United  Kingdom  or  elsewhere  overseas 
on  British  firms'  account;  and,  if  so,  did  he 
intend  to  endeavour  to  get  it  adopted  by 
the  Inter- Allied  Ehineland  High  Commis- 
sion? 


Lieut. -Colonel  Buckley  said  that  he  had 
received  the  communication  referred  to. 
There  were  three  licensing  offices  (Bad 
Ems,  Dusseldorf,  and  Essen)  dealing  with 
their  respective  areas.  To  set  up  a  fourth 
at  Cologne  dealing  with  British  trade  would 
add  to  the  confusion. 


DEATH  OF  Sm  JAMES  DEWAR. 

By  the  death  of  Sir  James  Dewar, 
F.R.S.,  the  world  in  general  and  physical 
science  in  particular  are  the  poorer. 

His  work  on  the  liquefaction  of  air,  nitro- 
gen, oxygen,  hydrogen,  etc.,  represents 
one  of  the  many  great  scientific  achieve- 
ments of  the  last  century.  This  work  led 
up  to  his  invention  of  the  vacuum  flask 
which  bears  his  name,  and  which  was 
adapted  to  every-day  domestic  use  in  the 
form  of  the  Thermos  flask. 

These  discoveries  not  only  led  him  into 
further  investigations,  but  also  promipted 
others  to  follow  along  lines  which  were  only 
possible  as  a  result  of  his  work. 

He  was  for  many  years,  and  until  his 
death  on  March  27,  connected  with  the 
Royal  Institution,  at  whose  meetings  many 
of  his  discoveries  were  first  announced 
Here  he  followed  and  maintained  the  illus- 
trious examples  of  great  predecessors.  Al- 
most all  the  important  scientific  societies 
throughout  the  world  have  honoured  him  at 
some  time  or  another. 


NAPHTHENIC  ACIDS  FROM 
JAPANESE   PETROLEUM. 

By  Y.  Tanaka  and  S.  Nagai. 

On  acidifying  the  waste  lye  from  the  re- 
fining of  25-26°  Be  petroleum  distillate,  a 
thick  brown  oil  S.G.  0.9853  and  acid  value 
68.8,  sulphur  content  0.89  per  cent,  was 
obtained.  It  emulsified  with  water,  and 
gave  an  ether  soluble  copper  salt  indicative 
of  naphthcnic  acids.  Other  compounds 
were,  hovNcver,  present.  The  naphthenic 
acids  were  separated  and  purified  by  hydro- 
lysis of  their  methyl  esters,  the  final  pro- 
duct being  a  light  yellow  viscous  liquid, 
S.G.  0.9918,  refractive  index  1.4824,  acid 
value  254.3,  mean  mol.  wt.  221,  iodine 
value  nil.  By  careful  fractionation  of  the 
methyl  esters,  trideca,  tetradeca,  and  pen- 
ta  decanaphthenic  acids  were  isolated. — 
(From  J.  Amer.  Chem.  Soc,  1923,  XLV., 
764-6.) 


APRIL  6.  1923. 


THE    CHEMICAL    NEWS. 


221 


CORRESPONDENOE. 


THE  AUTHENTICITY  OF  THE  LATIN 
WORKS  OF  (rEBBR. 

To  the  Editor  of  The  Chemical  News. 

Sir,— I  was  much  interested  to  read  Mr. 
E.  E.  Whale's  letter  on  the  above  topic,  in 
your  issue  for  March  9,  and  the  excellent 
repOTt  of  Mr.  Holmyard's  lecture  on 
"  Arabian  Alchemy  and  Chemietry," 
which  appeared  in  the  previous  issue.  In 
that  report  you  were  kind  enough  to  in- 
clude my  own  remarks  to  which  1  would 
draw  Mr.  Whale's  attention — which  per- 
haps sufficiently  define  my  own  iposititMi 
towards  the  question  of  Geber  in  the  Hght 
of  Mr.  Holmyard's  researches;  but  it  may 

Eossibly  be  or  use  if  I  briefly  expand  these 
ere.  Liki'  Berthelot,  I  know  no  Arabic, 
anu  in  common  with  him  and  other  writers 
Ml  the  history  of  chemistry,  I  had  to  rely, 
when  writing  Alchemy:  Ancient  and  Mod- 
em, upon  the  translations  of  Geber's  origi- 
nal works,  which  Bertndot  had  had  pre- 
pared for  the  purposes  of  hi«  own  studies. 
Judging  from  these,  no  other  conclusioQ 
seemed  possible  than  that  which  Berthelot 
himself  drew,  namely,  that  the  Latin  words 
asoribed  to  Geber  are  sp'inous.  For,  where- 
as these  Latin  works  are  definite  and  prac- 
tical treatises,  the  Arabic  works  are  highly 
mystical  in  character.  Moreover,  these  lat- 
ter works  make  no  mention  of  the  famous 
sulphur-mercury  theory  of  the  metals 
which  play  so  important  a  part  in  the  liatin 
works.  Mr.  FTolmyard,  it  is  true,  in  con- 
troverting this  argument,  has  not  produced 
the  Arabic  originals  of  the  T^atin  works ;  but 
he  has  di8cM>vered  other  Arabic  MSS.  the 
undoubted  work  of  Geber — such  as  The 
Book  of  Properties  in  the  British  Museum 
— which  are  exactly  like  tnose  in  character; 
works  which  describe  many  prcu;tical  pre- 
parations and  make  mention  of  the  sulphur- 
mercury  theory;  and  he  suggests  that  the 
Arabic  MSS.  of  Geber's  which  Berthelot 
had  translated  were  not  the  thetnical  works 
of  Geber,  but  religious  works  in  which 
Geber — as  a  chemist— naturally  made  use 
of  chemical  symbolism. 

1  entirely  agree  with  Mr.  Whale  that  it  is 
higlily  d«^sirnble  that  adequate  translations 
should  be  made  of  the  various  Arabic  MSS. 
in  question,  and  it  is  to  be  hoped  that  Mr. 
Holmyard  might  he  persuaded  to  undertake 


t>his  important  work.  A  translation  of 
Geber's  Book  of  Properties,  for  example, 
the  MS.  of  which  is  in  the  British 
Museum,  would  be  esipecially  welcome. 
Until  sucu  translations  have  been  made  it 
may  be  as  well  to  retain  an  open  mind  con- 
cerning the  question  of  the  authenticity  of 
the  Latin  works ;  but  certainly  the  evidence 
for  reversing  the  decision  arrived  at  by 
Berthelot,  which  Mr.  Holmyard  has  al- 
ready put  forward,  is,  to  my  mind,  very 
convincing. 

As  to  the  different  spellings,  "  Geber  " 
and  "  Dschabir,"  these  are  merely  differ- 
ent transliterations  of  the  same  Arabic 
name,  and  do  not  refer  to  different  indi- 
viduals.— Yours,  etc., 

H.   Stanley  Redgrove, 
B.Sc.  A.I.C,  F.C.S. 

191,  Camden  Road,  N.W.I. 
March  10.  1923. 

[Owing  to  an  error  on  the  part  of  the 
printers,  a  portion  of  Mr.  Redgrove 's  let- 
ter, which  appeared  in  the  issue  of  March 
23,  was  inadvertently  omitted.  We  pub- 
lish above  tho  letter  in  full,  and  tender 
apologies  to  Mr.  Redgrove  and  our  readers. 
—Ed.,  C.N.] 


NOTICES  OF  BOOKS. 

Olue  and  Gelatin,  by  Jerome  Alexan- 
der. Pp.  236.  New  York:  The  Chemi- 
cal Catalog  Co.  Inc..  19,  East  24th  St. 
1928.     Price  3  dollars. 

The  publication  of  this  monograph  under 
the  directi(»i  of  the  American  Chemical 
Society  is  well  justified  from  the  points  of 
view  of  the  principles  of  physical  chemistry 
which  it  touches  and  the  industrial  import- 
ance of  these  substances  as  well  as  by  their 
long  use. 

Tne  subject  is  a  difficult  one.  Much  in- 
formation is  scattered  through  the  scienti- 
fic literature,  but  often  under  unexpected 
headings. 

Another  difficulty  that  the  author  must 
have  encountered  is  the  unequal  quality  of 
the  work  published,  esipecially  concerning 
their  colloidal  properties. 

Most  attention  has  here  been  devoted  to 
well  known  theories  which  are  expounded 
and  discussed  in  the  light  of  the  properties 


222 


THE    CHEMICAL   NEWS. 


APBIL  6,  1923. 


of  glue  and  gelatin,  and  especially  with  re- 
ference to  recent  work  on  the  latter. 

In  til©  chapter  on  their  chemistry,  the 
different  estimations  and  calculations  of  the 
molecular  weight  of  gelatin  are  given.  It 
is  interesting  to  note  that  the  most  recent 
computation  puts  this  at  about  10,300. 

With  regard  to  the  testing  of  glue  and 
gelatin,  it  is  pointed  out  that  no  single  test 
can  satisfactorily  grade  a  commercial  sam- 
ple. Many  tests  are  necessarily  of  an  em- 
pirical nature,  and  this  must  continue  until 
a  more  exact  knowledge  of  the  chemical 
constitution  of  these  bodies  is  forthcoming. 

There  are,  however,  certain  specifications 
that  can  be  determined  and  must  be  com- 
plied with  in  the  case  of  gelatin  intended 
for  human  consumption. 

This  raises  the  question  how  to  distin- 
guish gelatin  from  glue ;  there  is,  in  fact,  no 
sharp  distinction.  But  gelatin  for  food 
must  not  contain,  e.g.,  SO,,  As,  Cu,  Zn,  or 
indeed,  any  injurious  body. 

The  author  is  to  be  congratulated  on  this 
compilation,  of  interest  both  to  technolo- 
gists and  physical  chemists. 


Anorganische  Chonie,  von  Dr.  F. 
Ephraim.  Zweite  und  dritte  verbesserte 
Auflage.  Pp.  VIII.  +  742.  Dresden  and 
Leipzig:  Verlag  von  Theodor  Steinkopff. 
1923.  Price  unbound  Bs.  6d.,  bound  10s. 
2d. 

There  are  now  so  many  textbooks  on  In- 
organic Chemistry  that  ther^  seems  little 
need  for  new  publications  covering  the 
general  theory  and  description  of  this  sub- 
ject. 

Prof.  Ephraim  has,  however,  written  one 
which  has  gone  through  two  or  three  edi- 
tions in  the  course  of  a  few  months,  from 
quite  a  new  standpoint,  and  which  deserves 
the  attention  of  chemists,  and  certainly  has 
justified  the  publication  of  yet  another 
Inorganic  Cheviistry. 

This  readable  volume  opens  with  an  ac- 
count of  the  present  views  concerning  the 
structure  of  the  atom,  followed  by  a  brief 
description  of  the  elements  and  general 
chemical  theory.  The  essential  principles 
of  physical  chemistry  are  included. 

In  the  next  chapter,  the  compounds  of 
the  halogens  are  described,  beginning  with 
those  with  hydrogen.     The  hydraoid  salts. 


the  oxides,  oxy-acids,  and  compounds  of 
the  elements  with  one  another  complete 
this  section. 

Chapter  three  deals  with  the  oxides  of 
hydrogen,  of  the  metals,  and  the  acidic 
(higher  and  amphoteric)  metal  oxides.  Fol- 
lowing are  chapters  on  the  other  elements 
in  convenient  groups.  The  mode  of  treat- 
ment is  along  the  same  lines,  viz.,  first  the 
hydrogen-compounds,  then  the  oxides  and 
salts,  and  finally  the  halogen  and  cyanogen 
compounds  are  described. 

The  inter-metallic  compounds  and  metal 
hydrides,  the  rare  earths,  and  the  radio- 
active bodies  all  have  separate  chapters 
allotted  to  them. 

By  this  arrangement  the  periodic  system 
and  other  generalisations  are  made  aippar- 
ent. 

Prof.  Ephraim 's  stimulating  and  compre- 
hensive volume  could  well  be  of  service  to 
those  advanced  science  students  studying 
German.  Advanced  workers  and  lecturers 
in  inorganic  chemistry  will  certainly  notice 
many  interesting  points  in  connection  with 
the  mode  of  presentation  of  even  the  most 
recent  developments  in  chemistry. 

J.G.F.D. 


The  Chemical  Technology  and  Analy- 
sis of  Oils,  Fats  and  Waxes,  by  Dr.  J. 
Lewkowitsch,  M.A.,  F.I.C.  Sixth  edi- 
tion, entirely.  Revised  by  G.  H.  War- 
burton.  Vol.  III.,  pp.  VIII.  +  508. 
London:  Macmillan  &  Co.,  Ltd.,  St. 
Martin's  Street,  W.C.     1923.     36s.  net. 

The  publieation  of  Vol.  III.  of  Dr.  Lew- 
kowitsch's  compendium  on  Oils,  Fats  and 
Waxes,  now  revised  and  brought  up-to-date 
by  Mr.  Warburton,  completes  the  sixth 
edition  of  this  well-known  standard  work  of 
reference;  Vols.  I.  and  II.  having  appeared 
last  year. 

The  appearance  of  Vol.  III.  has  been 
awaited  somewhat  impatiently  by  those 
who  have  had  frequent  occasion  to  consult 
this  work,  since  it  contains  the  subject  in- 
dex of  the  whole  edition. 

T'he  matter  of  this  volume,  in  addition  to 
useful  statistics  and  tabular  information, 
contains  muc"h  that  is  valuable  to  technical 
chemists,  analysts  and  others  requiring 
authoritative  information  on.  this  important 


APRIL  6.  1023. 


TKE  CHEMICAL  NEWS. 


223 


and    ever-expanding    branch    of    industrial 
chemistry. 

The  British  Association  for  the  Advance- 
ment of  Science  have  issued  as  a  reprint  the 
Reiport  on  Absorption  Spectra  and  Chemi- 
cal Constitution  of  Organic  Compounds. 
The  Committee  responsible  for  the  report 
consisted  of  Prof.  I.  M.  Heilbron,  Prof.  E. 
C.  C.  Baly,  and  Prof.  A.  W.  Stewart;  and 
they  have  collected  and  reported  upon  the 
experimental  work  and  theories  put  for- 
ward by  numerous  investigators  in  this 
field. 


Readable  School  Chemistry,  by  J.  A. 
Cochrane.  B.Sc.  Pp.  XI.  +  84.  Lon- 
don: G.  Bell  &  Sons,  Ltd.,  Portugal  St.. 
W.C.2.     1928.     Pride  28. 

Few  elementary  chemistry  textbooks 
really  appeal  to  young  pupils  just  beginning 
the  subject. 

It  is  nob  proposed  to  enter  into  the  causes 
of  this  here,  beyond  stating  that  Mr.  Coch- 
rane has  written  a  volume  which  will  ap- 
peal to  them.  The  subject  is  developed 
historically,  and  the  book  is  evidently  in- 
tended to  supplement  the  practical  work; 
f'sujh  fliapter  should  naturnlly  be  studied 
lifter  the  experimental  work  has  been  com- 
pleted. 

The  gradual  development  of  chemistry 
as  it  is  to-day,  is  traced  in  a  manner  calcu- 
lated to  sustain  and  stimulate  the  interest 
of  beginners.  Tn  particular,  the  chaipters 
on  Burning  and  Rusting  and  The  Air  and 
its  C<mstituents,  are  especially  well  writt^^n 
for  schoolboys. 

On  p.  3  the  author  accurately  indicates 
that  the  alchemical  period  dates  from  the 
Christian  era  to  1500  A.n..  and  not  from 
earlier  times. '  (Yet  on  p.  7  it  is  stated  that 
"  Egyptians  practised  alchemy  five  or  six 
thousand  years  ago.") 

This  little  volume  can  he  warmly  recom- 
mended fr>r  those  scholars  for  whom  it  is  in- 
tended. It  would  also  he  of  service  to  those 
who  do  not  intend  t^  pursue  the  subject 
very  deeply.  The  inclusion  of  several 
plates  of  historical  and  general  interest, 
and  itq  low  price,  are  additional  recommen- 
dations. J.G.F.D. 


The  Mathematical  Theory  of    Relativ- 
ity, by  A.  S.  ^DDlNGTON,    M.A.,  M.Sc, 
F.R.S.     lO^ius.  X  T^ins.     Pp.  X.  t  247. 
Cambridge:   The  University  Press.  Price 
20s.  net. 

The  Mathematical  Theory  of  Relativ- 
ity, by  A.  KoPFF.  Translated  by  H. 
Lew,  M.S.,  D.Sc.  F.R.S.E.  7iins.  x 
4iins.  Pp.  VIII.  +  214.  J^ondon : 
Methuen  &  Co.,  Ltd.,  36,  Essex  Street, 
W.C.     Price  8s.  6d.  net. 

Whereas,  during  recent  years  a  very  large 
number  of  popular  expositions  of  the  theory 
of  relativity  have  appeared,  English  and 
American  students  desirous  of  really  mas- 
tering the  subject  have  been  saddled  with 
the  double  task  (except  as  concerns  the 
helip  afforded  them  by  the  translations  of 
papers  by  Einstein  and  Minkowski,  which 
were  publshed  in  1920  by  the  University  of 
Calcutta)  of  studying  a  diffieult  subject  in 
a  foreign  language.  So  great  was  the  need 
that  it  might  be  said  that  almost  any  book 
dealing  with  the  maHiematics  of  the  theory 
of  relativity  would  be  welcome.  Especially 
welcome  indeed,  then,  is  this  brilliant  trea- 
tise by  Professor  Eddington,  and  not  less  so 
is  the  very  readable  translation  of  Professor 
Kopff's  fine  work.  Jn  many  ways  the  two 
books  show  marked  differences  in  the  treat- 
ment of  their  subject  matter;  and  each  has 
an  excellence  characteristically  its  own. 
Professor  Eddington'e  book  is,  perhaps,  the 
more  philosophical,  as  it  is  also  the  more 
novel  in  its  mode  of  presentation ;  but,  on 
the  other  hand,  it  is  the  more  difficult  to 
read  and  to  master.  The  fact  that  it  forms 
in  a  manner,  a  sequel  to  the  author's  pre- 
viously published  Space,  Time  and  Gravi- 
tation jiccf>vmts  for  its  somewhat  brief 
treatment  of  the  restricted  theory  of  rela- 
tivity, which  is  dealt  with  very  fully  in  Pro- 
fessor Kopff's  work.  Both  books  contain 
chapters  devoted  to  the  tensor  calculus, 
which  forms  the  necessary  mathematical 
apparatus  for  dealing  with  the  generalised 
theory,  to  a  discussion  t:f  which,  its  various 
aspects  and  consequences,  both  books  then 
pass.  Professor  Eddington 's  treatment  is 
the  fuller  here — the  problems  of  the  curva- 
ture of  Hme  and  space  and  of  worFd-geo- 
metry  general! v  being  discussed  at  con- 
siderable lenerth  with  special  reference  to 
the  views  of  Einstein,  de  Sitter  and  Weyl, 
Two  points  made  clear  in  the  "Introduc- 
tion" to  Professor  Eddington 's  book  must 
not  be  passed    over   in  this    all    too   short 


224 


THE  CHEMICAL  NEWS. 


APEIL  6,  1928. 


notice.  One  is  that  the  physical  qualities 
dealt  with  by  science  are  essentially  manu- 
factured articles.  "  Physical  quantities," 
he  writes,  "  are  not  properties  of  certain  ex- 
ternal objects,  but  are  relations  between 
these  objects  and  something  else."  The 
second  point  is  that  an  intrinsic  property 
of  a  measuring  instrument  must  appear  as 
a  uniformity  in  a  series  of  measurements 
made  by  it,  and  that  it  is  just  such  unifor- 
mities which  constitute  what  are  called 
"  laws  of  nature."  The  philosophical  im- 
portance of  such  inevitable  conclusions  of 
the  theory  of  relativity  as  these  can  hardly 
be  underestimated. 

Botli  t'lese  books  can  be  unreservedly 
recommended  to  students.  To  read  and  to 
master  one  of  them  is  to  gain  a  very  good 
working  knowledge  of  the  greatest  scienti- 
fic achovcmont  of  the  present  century.  But 
certainly  the  student  who  is  keen  will  not 
be  content  with  this.  He  will  read  and 
master  them  both.  H.  S.  Eedgrove. 


BOOKS  RECEIVED. 


The  Spectroscope  and  its  uses  in  General 
Analytical  Chemistry,  by  T.  Thorne  Baker, 
A.M.I.E.E.,  F.R.P.S.  Pp.  X.  +  208. 
Second  Edition.  1923.  Messrs.  Bailh^re, 
Tindall  &  Cox,  8.  Henrietta  Street,  Covent 
Garden,  W.C.2.     7s.  6d.  net. 


The  Phase  Rule  and  its  Applications,  by 
Alexander  Findlay,  M.A..  Ph.D.,  D.Sc. 
Pp.  XVI.  +  298.  Fifth  Edition.  1923. 
Messrs.  Longmans,  Green  &  Co.,  39,  Pater- 
noster Row,  E.G. 4.     10s.  6d.  net. 


Laboratory  Manual  of  Physical  Chemis- 
try, by  Albert  W.  Davison  and  Henry  S. 
van  Klooster.  Pp.  VTTI.  +  182.  1922. 
Messrs.  Chapman  &  Hall,  11.  Henrietta 
Street,  Covent  Garden.  W.C.2.     10s.  net. 


This  list  is  specially  compiled  for  The  Chemical 
News,  hv  Messrs.  Rayner  &  Co..  Registered  Patent 
Agents,  of  5.  Chanoery  Lane.  London,  from  whom 
nil  information  relating  to  Patents.  Trade,  Marke, 
and  Designs  can  be  obtained  gratuitously. 


Latest   PaU'nt    Applications. 

6861— Booer,  J.  R.— Preparation  of  salts  of  boric 
acid.    March  9. 

6737— British  Dyestaffs  Corporation  Co..  Ltd.— 
Manufacture  of  formaldehyde  or  its  poly- 
mers.   March   8. 

7009— Consortium  Fir  Elektrochemische  Indus- 
trie Ges.— Manufacture  of  anhydrides  of 
fatty   acids.    March   10. 

6.598— Teclino-Chemlcal  Laboratories,  Ltd.— 
Separating  solids  from   liquids.    March  7. 

650e— Weber,  W.— Process  for  treating  ammo- 
nium chloride  lyes  in  iron  vessels.  March?. 

7747— Aktieselkabet  Hydropeat.— Manufacture  of 
colloidal  solutions  of  ferric  oxide.  March  17. 

7770_Briti8h  Cellulose  &  Chemical  Manufactur- 
ing Co.,  Ltd.— Treatment  of  cellulose  ace- 
tate, etc.    March   17. 


Abstract  Puhlishpd  this  Week. 

191854— Dyes.— Soc.     of     Chemical      Industry       in 
Basle;   Basle,   Switzerland. 

Triarylmethane  dyes  are  obtained  by  condens- 
ing phenyl-chloroform  or  a  substitution  deriva- 
tive or  homologue  thereof,  or  l-chloro-2-naphthyI- 
ohloroform,  with  naphthnl  or  a  substitution 
product  thereof  having  a  free  4-poKition,  in  pre- 
sence of  a  substance  neutralising  acid;  addition 
of  a  catalyst,  for  instance  copper  or  alcohol,  is 
advantageous.  The  dyestiiffs  derived  from  1- 
naphtliol-2-carboxylic  acid  dye  wool  grey  tints 
changed  bv  afterohroming  to  green  or  blue  tints 
fast  to  fulling  and  potting;  they  may  also  be 
dyed  or  printed  on  chrome-mordanted  fabrics,  or 
used  in  sintrle-bath  processes.  According  to  ex- 
amples dve'^tufls  are  obtained  from  «  -naphthol 
and  phenVl-chloroform  in  the  presence  of  caustic 
soda,  and  from  l-naphthol-2-carboxylic  acid  and 
phenyl-chloroform  in  presence  of  copper  powder 
and  cnustic  soda,  lime,  or  magnesia.  The  several 
chlorphenyl chloroforms,  and  the  sulpho  deriva- 
tives of  l-naT>hthol-2-oarbo*ylic  acid,  such  as  1- 
naphthol-7-suli)ho-2-carboxYlic  acid  are  also  men- 
tioned as  suitable  components. 

Messrs.  E'lynei  &  Co.  will  obtain  printed  copies 
of  the  pnbli'^hed  Specifications,  and  forward  on 
I>ost  fre«  for  the  price  of  li.  6d.  each. 


APRIL  13,  1923. 


THE  CHEMICAL  NEWS. 


225 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3287. 


THE  INTERACTION  OF  AMMONIUM 

HYDRATE  AND  MERCUROUS 

.BROMIDE. 

By  J.  G.  F.  Druce,  M.Sc.  (Lond.), 
R.Nat. Dr.  (Pragub). 

Some  time  ago,  on  account  of  its  theo- 
retical and  photographic  interest,  the 
action  of  ammonium  hydrate  upon  mer- 
curous  chloride  was  quantitatively  investi- 
gated (see  The  Chemical  Neufs,  1921, 
CXXIII.,  153). 

It  was  concluded  that  the  results  were 
expressed  hy  the  equation:  — 

2NH,0H  +  Hg,  CI,  =  NH,  Kg,  CI  + 
NH^Cl  +  2H,0. 

The  action  of  ammonium  hydrate  upon 
mercurous  bromide  has  now  been  examined 
in  a  similar  manner. 

For  this  purpose  mercurous  bromide  was 
prepared  by  precipitating  an  acidified  solu- 
tion of  mercurous  nitrate  with  slight  ex- 
cess of  potassium  bromide.  The  almost 
white  precipitate  was  filtered  off  with  the 
aid  of  a  filter  pump,  and  washed  repeatedly 
with  warm  water  to  remove  any  potassium 
nitrate  or  acid  adhering  to  it.  It  was 
finally  drained  and  dried. 

0.9380  gram  was  placed  in  a  stoppered 
flask  with  about  26  cc.  of  water.  Twenty 
cc.  of  a  normal  solution  of  ammonium  hy- 
drate were  added.  The  stopper  was  re- 
placed, and  the  mixture  was  shaken  for  a 
few  minutes  and  allowed  to  stand  few  two 
days.  The  black  residue  was  then  removed 
as  quickly  as  possible  by  tiltrati<M,  and  was 
washed  with  distilled  water.  Filtrate  and 
washings  w(>re  made  up  to  200  cc. 

The  residual  ammonia  was  estimated  by 
titrating  lots  of  20  cc.  of  this  diluted  fil- 
trate with  decinormal  hydrochloric  acid. 
The  average  volume  of  acid  required  in 
these  experiments  was  16.7  cc.,  which  cor- 
responds with  0.5836  gram  ammonium 
hydrate  in  the  whole  filtrate.  Therefore 
0.1164  gram  had  reacted  with  the  mercur- 
ous bromide. 

The  quantity  of  ammonium  bromide 
fonned  was  determined  hy  taking  three  lots 
of  20  cc.  of  the  diluted  filtrate  obtained 
above  and  boiling  for  five  miniates  to  expel 
the  free  ammonia.     This  solution  was  then 


titrated  with  fiftieth  normal  silver  nitrate 
solution.  The  average  volume  required  in 
the  three  experiments  was  8.35  cc,  which 
indicates  that  the  total  filtrate  contained 
0.1632  gram  ammonium  bromide. 

Thus,   0.1164    gram    of  ammonium    hy-. 
drate  reacted  with  0.9380  gram  of  mercur- 
ous bromide,    forming  0.1632  gtam  of  am- 
monium bromide. 

These  results  indicate  that  two  molecules 
of  ammonium  hydrate  act  on  one  of  mer- 
curous bromide  and  one  molecule  ammo- 
nium bromide  is  produced  a 

The  other  product  of  this  interaction  was 
the  "  black  precipitate,"  which  could  be 
NH,  Hgj  Br,  or  a  mixture  of  NH,  Hg  Br 
and  finely  divided  mercury. 

At  the  end  of  the  article  previously  cited, 
the  same  question  was  considered  in  con- 
nection with  the  corresponding  chloro- 
compound,  and  the  ocwiclusion  was  drawn 
that  the  substance  was  a  compound,  since 
it  did  not  appeju-  to  amalgamate  with 
copper. 

The  black  precipitate  obtained  in  these 
exiperiments  amalgamated  readily  when 
rubbed  on  a  bright  piece  of  pure  copper 
when  freshly  prepared. 

When  washed  quite  free  from  ammonia 
it  did  not  amalgamate  so  readily,  and  when 
dry,  amalgamation  was  still  more  difficult 
but  could,  nevertheless,  be  effected. 

This  strongly  suggests  that  the  black 
precipitate  is  a  mixture. 

Additional  support  fix*  this  has  been  ob- 
tained by  boiling  the  substance  with  a 
strong  solution  of  ammonium  bromide.  By 
this  means  the  free  mercury  was  obtained 
in  the  fonn  of  a  fair-sized  globule,  whilst 
the  white  mercuric  bromo-amide,  NHj  Hg 
Br,  dissolved.  This  latter  substance  crys- 
tallised out  when  the  hot  saturated  solu- 
tion cooled. 

Thus  it  has  been  established  that  when 
ammonia  acts  upon  mercurous  bromide, 
the  reaction  may  be  expressed  by  the 
equation :  — 

Hg,  Br,  +  2NH,0H  =  NH,  Hg  Br  +  Hg 
+  NH.Br  +  2H,0. 
It  was  thought    of  interest  to    ascertain 
whether  by  using  excess  of  mercurous  bro- 
mide with   ammrmium  hydrate,     any    free 
acid    could    be  liberated    as  the    following 
equation  suggested  :^- 
NH.OH  +  Hg,  Br,  ^  NH,  Hg  Br  +  H  Br 
+  H,0  +  Hg. 
With  this  in  view,-  8.5  grams  mercurous 
bromide  were  ground    up  in  a  mortar  with 


226 


THE  CHEMICAL  NEWS. 


APEIL  13,  1923. 


20  cc.  of  water  and  5  cc.  of  normal  ammo- 
nium hydrate.  When  drops  weae  tested 
with  phenol-phthalein,  methyl-orange,  and 
litmus,  all  three  indicators  showed  that 
the  mixture  was  neutral,  therefore  no  free 
hydrobromic  acid  could  have  been  foi-med. 

Since  it^  was  clearly  proved  that  the  in- 
soluble product  of  the  interaction  of  am- 
monium hydrate  and  mercurous  bromide 
was  a  mixture  of  mercury  and  mercury 
bromo-amide,  it  was  deemed  imiportant  to 
further  investigate  the  corresponding  pro- 
duct from  mercurous  chloride. 

On  careful  examination  it  was  found  that 
the  wet  "black  precipitate"  just  as  it  was 
prepared,  readily  amalgamated  with  pure 
copper,  but  less  readily  when  free  from 
ammonia  and  least  easily  when  dry. 

Finally,  when  this  "black  precipitate" 
was  boiled  with  a  strong  solution  of  am- 
monium chloride  the  mercury  ran  together 
to  form  one  globule,  whilst  on  cooling  the 
supernatant  liquid  it  deposited  the  infusible 
white  precipitate. 

The    reaction    betvyeen    ammonium    hy- 
drate   and  mercurous    chloride  is  thus    in 
accordance  with  the  equation:  — 
Hg2  CI2  +  2NH4OH  =  NH,  Hg  CI  +  Hg  + 
NH,  CI  +  2H;0. 


The  International  Institute  of  Agricul- 
ture, Home,  has  issued  a  communication 
comparing  the  world's  crops  of  1922  with 
pre-war  figures. 

The  statistics  collected  indicate  that  the 
production  of  maize  in.  Europe  is  now  only 
62  per  cent,  of  that  grown  annually  before 
the  war.  The  world's  vintage  is  21  per 
cent,  above  the  average  1909-1913  figure. 

Other  important  data  are  given. 


CALCIUM  AKSENATE  FOR  THE 
U.S.A. 

The  Commercial  Counsellor  at  Washing- 
ton (Mr.  J.  J.  Brodenck)  reports  that  three 
firms  of  wholesale  druggists  in  Now  Orleans 
are  desirous  of  receiving  samples  and  quo- 
tations for  the  supply  of  calcium  arsenate. 
One  of  the  firms  also  desires  to  import 
arsenic  as  well  as  Paris  green. 

Furt.her  particulars,  together  with  the 
names  and  addresses  of  the  applicants, 
may  be  obtained  by  United  Kingdom  firms 
on  application  to  the  Department  of  Over- 
seas Trade  (Room  52). 


VALENCY. 

By  William  R.  Fielding,  M.A.,  M.Sc, 
(Vict.). 

Senior  Science  Master,  King  Edward  VII. 

bchool,  Lythavi. 

(Continued  from  Page  214.) 

The   Cohaltammines. 

C0CI3   (NH3)3,     which    is    non-ionisable, 
may  be  written  thus :  — 


Co(nh^.HCi)3:- 


ov 


Co  (NH2.HC1)3. 

As  the  chlorine  is  linked  up  with  hydro- 
gen as  well  as  cobalt,  neither  the  chlorine 
nor  the  nitrogen  are  exerting  their  maxi- 
mum "pull"  on  the  cobalt,  and  the  latter 
is  open  to  the  attack  of  other  negative 
groups.  Each  additional  ammonia  mole- 
cule breaks  up  a  ring  (two  rings  in  the  sec- 
ond formula),  and  the  heat-change  affects 
the  valency  of  everything  in  the  coniiplex 
molecule.  The  action  of  successive  mole- 
cules of  ammonia  may  be  represented 
thus :  — 


APRIL  13,  1923. 


THE  CHEMICAL  NEWS. 


227 


[CoCl3(NH3)3]    =  Co(NH,.HCI)3 

[CoNH3),(NH,.HCl)]Cl3 
[Co(NH3)JCl3 
*rom  formula  I.  in  Fig,  36,    four  iso- 
mers of  [Co(NH3)JCl2    could    be    secured 
thus :  — 


NHj 


NHvH 


CI     NMa-H 


NH-, 


,C1 


NHi-H 


CI        NM;t.M 


NHvH 


CI 


NH, 


Cl      C^ 


(Piq    37) 


NH, 


and  from  formula  II.  in  the  ^ame  Fig.  four 
isomers  (two  being  mirror-images),  thus:  — 


NH,.H 


J 44.rs»H» 


Vt.NUv 


H.NWi 


CI     H.NHj 

*^**»  NHvM 

(pig    38) 

If  tile  NH3  nets  as  a  single  unit  and  not 
as  II.NH.H  and  NH,.H,  the  last  two  are 
alike,  as  are  also  the  two  former. 

When  all  the  chlorine  has  been  replaced 
by  ammonia  the  final  form  will  present  th^ 
following  appearance  (a  plane  figure  is  used 
to  show  valencies  only):  — 


:N 


/ 


M 


H 


H 


(•Pi 3  3q) 


N 


M 


M 


Co  is  hexad;  nitrogen  is  pentad  in  three 
cases  and  tetrad  in  three  other  cases ;  it  can 
become  pentad  all  round  by  joining  direct 
to  the  central  atom.  Cobalt  will  then  have 
a  valency  of  nine,  six  joining  electro-nega- 
tive nitrogen  atoms,  and  three  joining  elec- 
tro-negative chlorine  atoms.  This  high 
valency  is,  in  a  way,  a  kind  of  reflected 
glory,  and  owing  to  borrowing  electrons 
from  the  six  electro-negative  nitrogen 
atoms  it  is  able  to  ionise  the  three  chlorine 
atoms. 

A  similar  procedure  is  adopted  in  evolv- 
ing the  formula  of  cobalt  pentammine  con- 
taining the  CO3  group.  In  carbonates  (Fig. 
40)  the  metal  is  not  joined  directly  to  the 
carbon. 


N<x 0 


CP  .■  9  40^) 


Four     molecules    of    ammonia    combine 
with  the  Co(CO,)X,  thus:  — 


^Jlr Co -N-H 


H 


H 


H-N—H 


■Cl- 


H~N-H 


(F  •  3   4^1) 

Here  Co  is  triad,  nitrogen  triad  and  te- 
trad, hydrogi'u  dyad  and  monad,  oxygen 
dyad  and  tetrad,  and  chlorine  triad.  The 
two  tetrad  nitrogen  atoms  an*  each  joined 
to  three  liydrogen  atoms  which  are  func- 
tioning as  dyads;  these  three  atoms  will 
not  utilise  as  much  of  the  valency-strength 
of  the  nitrogen  atom  to  which  they  are  at- 


228 


THE  CHEMICAL  NEWS. 


APRIL  13,  1923. 


tached  as  the  three  atoms  of  hydrogen  in 
NH3  do;  these  N  atoms  are  thereby  able  to 
effect  hnkages  with  the  cobalt  which  is  like- 
wise not  extended  to  its  full  valency- 
capacity  because  it  is  joined  to  three  atoms 
which  are  functioning  as  tetrads  and  triads, 
their  usual  valencies  being  dyad  and 
monad  respectively.  These  two  nitrogen 
atoms  may,  and  probably  do,  connect  up 
with  the  cobalt,  and  the  valencies  are 
shown  in  dotted  lines. 

The  fifth  ammonia  can  now  be  added, 
and  it  tackles  the  chlorine  end  of  the  mole- 
cule.    The  following  formula  is  suggested: 


H— N —  H CI H — INl-H 


(T'ic^  4-2) 


The  chlorine  atom  is  now  ionised,  when 
the  following  redistribution  of  valencies 
occurs : — 


An  alternative  method  would  be  to  group 
the  NH3  molecules  without  attempting  to 
exiplain  how  two  pentavalent  nitrogen 
atoms  link  each  other.  Nitrogen  would  be 
pentavalent  throughout,  and  bonds  num- 
bers 1  and  2  would  be  cancelled,  (These 
bonds,  which  are  not  shown  in  the  figure, 
join  the  cobalt  atom  and  the  two  lower  N 
atoms.) 

The  group  =C  =  0  behaves  differently 
towards  ammonia  according  to  the  group 
to  which  it  is  joined.  With  acetaldehyde, 
etc.,  it  forms  an  addition  compound,  as  in 
Fig.44. 


CH^.C 


(j^  i  q    4-4") 


and    with    formaldehyde, 
tetramine  (Fig.  45):  — 


hexamethylene- 


tCH^^O 


-f-4-NH^     =(cHOt  N^. -1- bH^O. 


=  CH 


N 


\ 


M 


CH=c CH^- 


CH^^ CH,: N 


CH 


(P  .  c,    A-S) 


I 


APRIL  13.  1923. 


THE  CHEMICAL  NEWS. 


229 


Conclusions. 
(1)  Valency  is  a  variable  property  of  ele- 
ments, the  variability  depending  on  the 
element,  the  temperature,',  the  pressure, 
and  the  element  or  elements  with  which  it 
is  combined. 

(2)  In  many  simiple  chemical  actions  the 
Law  of  Conservation  of  Principal  Valencies 
holds,  the  temperature  remaining  con- 
stant; but 

(3)  In  an  exothermic  action  the  degree 
of  polymerisation  is  greater  than  the  aver- 
age calculated  from  the  constituents.  That 
is,  as  the  amount  of  energy  in  the  system 
is  reduced  the  degree  of  polymerisation  is 
increased.  This  is  in  agreement  with  the 
known  facts  that  p  is  reduced  as  tempera- 
ture rises,  except  in  the  case  of  endother- 
mic  compounds. 

(4)  As  p  is  increased  the  usual  valency  of 
elements  must  be  increased  also.  This 
may  Ik-  oxipTained  by  the  following  linkages : 

(a)     A— B 


(b) 

A— B 

A— B 

(c) 

A— B 

1 
A— B 

(d) 

A— B 

aLb' 

ic) 

A— B 

-B 

(5)  Where  two  electro-positive  or  two 
electro-negative  atoms  are  linked  together, 
one  may  be  regarded  as  electro- positive  to 
the  other,  this  being  effected  by  a  change 
in  the  electronic  orbits  or  by  the  nuclei 
attracting  each  others  free  electrons. 

(6)  By  carefully  selecting  the  most  suit- 
able conditions  of  temperature,  pressure, 
elements,  etc.,  and  making  use  of  the 
changes  in  valency  following  every  physi- 
cal and  chemical  change  and  also  by  judi- 
cious "loading"  of  the  central  atom, 
valencies  can  be  increased  beyond  those 
generally  associated  with  the  element.  As 
Co,  Ft,  Cr,  etc.,  can  be  joined  to  six  atoms 
or  groups  as  well  as  to  several  atoms  which 
are  ionised  in  solution,  their  valencies  in 
the  solid  state  (where  some  degree  of  poly- 


merisation will  almost  certainly  take  place) 
will  be  considerably  higher  than  the  num- 
ber of  the  group  to  which  these  elements 
belong  in  the  Periodic  Table.  Their  valen- 
cies may  be  reduced  by  suipposing  that  the 
co-ordinated  elements  exert  a  single  result- 
ant valency  towards  the  central  atom. 

(7)  When  compounds  decompose  on 
heating,  melting,  or  boiling,  the  valency  of 
the  two  elements  for  each  other  must  be 
zero  at  that  particular  temperature  and 
pressure. 

(8)  Several  instances  have  been  given 
where  it  is  suggested  that  an  atom  "com- 
pensates" or  "accommodates"  another 
atom  in  the  matter  of  electrons.  Thus 
hydrogen  often  functions  as  a  dyad,  where 
its  electron  may  be  supposed  to  be  shared 
between  two  electro- negative  atoms. 

January  11th,  1923. 


THE  INFLUENCE  OF  HUMIC  ACIDS 

ON  THE  ASSIMILATION  OF 

PHOSPHORIC  ACID. 

By  K.  Mack. 

Phosphoric  acid  occurs  in  the  soil  in  the 
form  of  primary,  secondary  and  tertiary 
phosphates  of  the  alkalies,  alkaline-earth 
metals,  aluminium,  iron  and  manganese. 
It  is  perhaps  also  present  as  the  tetraphos- 
phate  of  certain  metals.  The  water  of  the 
soil  which  contains  phosphate  ions  be- 
comes separated  from  the  insoluble  phos- 
phates through  the  action  of  calcium,  mag- 
nesium, aluminium  and  iron-hydrates, 
magnesium  and  iron-carbonates  and  cer- 
tain silicates.  Through  the  activity  of  soil 
bacteria,  which,  during  resipiration,  pro- 
duce carbon  dioxide  and,  in  disintegrating 
organic  substances,  produce  acetic,  lactic, 
butyric,  and  valeric  acids,  the  insoluble 
phosphates  become  partly  soluble  again. 
In  soils  rich  in  organic  substances,  a  large 
quantity  of  humic  acids  is  formed  which 
renders  the  phosphates  soluble.  Phos- 
4)horic  acid  is  found  in  the  soil  not  only  as 
a  mineral,  but  also  in  the  form  of  organic 
compounds,  such  as  phosphatids  (lecithin), 
phytine  and  nucleoproteids,  as  is  shown  by 
the  work  of  Stoklasa  and  others.  These 
orgnnic  combinations  are  due  to  the  re- 
mains of  plants  incorporated  in  the  soil 
(stubble,  roots,  etc.).  Stoklasa  observed 
that  the  pho.^phoric  acid  combinations 
found  in  the  soil  are  much  more  energetic- 
ally assimilated,  under  the  notion  of  bac- 
tcrin.  tlmn  pure  insoluble  phosphates.  He 
also  concluded  that  the  soil  contains  other 
forms  of  phosphates  than  those  recognised 


230 


THE  CHEMICAL  NEWS. 


APRIL  13,  1923. 


hitherto,  notably  easily-assimilated  humo- 
phosphates. 

The  writer  has  made  a  series  of  experi- 
ments with  the  object  of  determining  the 
effect  of  humic  acids  on  the  various  phos- 
phates. The  acid  used  was  extracted  from 
peat,  which  was  treated  with  sulphuric 
acid  to  separate  the  alkaline  humates :  10 
grs.  of  pulverised  "  humic  "  acid  were 
added  to  a  quantity  of  phosphate  corres- 
ponding to  0.01  gram-molecule  of  phos- 
phoric acid  and  the  whole  was  left  for  48 
hours  in  a  litre  of  water,  and  was  fre- 
quently stirred.  The  results  nroved  that 
humic  acids  render  soluble  the  following 
quantities  of  phosphate,  expressed  in  per 
cent,  of  phosphoric  anhydride :  29.45  per 
cent,  of  di-calcium  phosphate,  28.46  per 
cent,  of  tri-calcium  phosphate,  12.54  per 
cent,  of  tertiary  aluminium  phosphate, 
and  7.46  per  cent,  of  tertiary  iron  phos- 
phate. Humic  acids  therefore  dissolve  in- 
soluble phosphates.  They  act  on  di-cal- 
cium phosphate  in  the  same  way  as  on  tri- 
calcium  phosiphato. 

Humic  acids  act  differently  when  alkalis 
are  present.  Thus,  humate  of  ammonia 
renders  soluble  less  tri-calcium  phosphate 
than  in  the  former  case  (23.08  per  cent. 
PjOg  as  against  28.46  per  cent.),  but,  on 
the  other  hand,  much  more  tertiarj^  alu- 
minium phosphate  (23.77  per  cent.,  as 
against  12.54  per  cent.),  and  tertiary  iron 
phosphate  (20.37  per  cent.,  as  against  7.46 
per  cent.). 

With  metallic  oxides,  humic  acids  and 
humates  are  capable  of  forming  complex 
combinations,  containing  the  metal  in  the 
anion.  Thus,  ammonium  humate  may 
combine  with  aluminium  and  iron  phos- 
phates to  form  compounds  containing,  be- 
sides iron  and  aluminium,  phosphoric  acid, 
otherwise  known  as  salts  of  a  "  humo- 
phosphoferric  "  acid  and  a  "  humophop- 
phoaluminic  "  acid.  Pure  humophospho- 
ferric  acid  has  been  isolated;  it  is  a  bitu- 
minous, blackish -brown  substance,  soluble 
in  alcohol  up  to  2.65  per  cent. 

In  a  soil  rich  in  bone  and  lime  phos- 
phates only  3.5  per  cent,  of  phosphoric  an- 
hydride were  found  to  be  present,  which 
agrees  with  the  fact  that  marshy  soils  rich 
in  lime  are  not  very  fertile.  From  a  garden 
rich  in  mineral  and  organic  fertiliser,  25.27 
per  cent,  of  anhydride  were  obtained. 

The  excess  of  bases  over  phosphoric  acid 
shoM's  that  the  latter  is  present  especially 
as  a  basic  phosphate.  In  soils  with  an  al- 
kaline reaction,    aluminium  and  iron  phos- 


phates are  combined  with  the  humic  basis, 
which  explains  their  greater  fertility. 

Humophosphoferric  and  huinophospho- 
aluminium  acids  therefore  serve  to  supply 
plants  with  phosiphoric  acid,  and  perhaps 
with  iron  and  aluminium  in  a  form  wliich 
can  be  easily  assimilated.  This  was  fully 
confirmed  in  a  series  of  experiments  in 
which  beets  were  cultivated  in  various  nu- 
tritive solutions,  of  which  some  were  ex- 
clusively mineral  while  others  contained 
humate  of  ammonia.  After  18  days,  there 
was  still  considerable  quantity  of  phos- 
phoric acid  in  the  first  solutions,  while  the 
second  contained  no  further  traces.  Other 
experiments  are  being  made.  Already  pre- 
parations of  peat  and  ashes  used  as  fertili- 
sers, and  the  addition  of  iron  hydrate  to 
the  ordinary  fertilisers  have  given  good  re- 
sults. 

The  writer  concludes  by  saying  that 
greater  importance  should  be  attached  to 
raw  phosphates  containing  oxide  of  iron, 
such  as  those  of  Bavaria  and  the  Hartz 
mountains ;  he  isn  ot  in  favour  of  the  use  of 
superphosphates,  which  eventually  render 
the  soil  too  acid.  The  use  of  manure,  on 
the  other  hand,  should  be  widely  developed. 
In  regions  where,  from  climatic  or  econo- 
mic reasons,  it  is  impossible  to  rear  live- 
stock, peat  may  be  used  with  advantage, 
for  it  not  only  renders  phosiphoric  acid  as- 
similable, but  also  furnishes  nitrogen,  and 
is  a  good  medium  for  bacteria. — (From  the 
Chem.  Zeit,  XL VI.,  pp.  73-5.) 


GENERAL  NOTES. 


GERMANY'S  POTASH  INDUSTRY. 

An  extract  forwarded  to  the  Department 
of  Overseas  Trade  by  the  Commercial  Sec- 
retary at  Cologne  states  that  a  number  of 
potash  works  in  Central  Germany  have 
been  compelled  to  restrict  work  owing  to 
unfavourable  sale  conditions.  During  1922 
boom  conditions  prevailed  on  the  potash 
market,  but  in  January  of  this  year  sales 
had  already  weakened,  and  the  sale  figures 
did  not  equal  those  of  January,  1922. 
Fears  were  expressed  that  inland  business 
would  suffer  a  considerable  decrease  this 
,year.  These  fears  have  now  been  realised. 
The  German  agricultural  industry  has 
greatly  restricted  its  orders  during  the  past 
few  weeks,  and  in  part  has  stopped  them 
altogether,  the  cause  of  which  is  to  be 
found  in  the  disparity  between  the  costs  of 


APRIL  13,  1923. 


THE  CHEMICAL  NEWS 


231 


iproduction  and    the  sale  prices  for  agricul- 
tural products. 

It  was  to  be  foreseen  that  the  improve- 
ment of  the  mark  and  the  accompanying 
price  reduction  would  also  have  its  dark 
side.  In  the  interests  of  guaranteeing  food 
supplies,  special  attention  will  in  the  near 
future  have  to  be  given  to  agricultural 
conditions.  The  price  reducti<»i  in  com, 
potatoes,  etc.,  is  in  no  [proportion  to  the 
reduction  in  the  costs  of  production,  and 
landowners  are,  therefore,  no  kmger  in  a 
position  to  devote  the  same  expenditure  as 
heretofore  to  the  supply  of  artificial 
manure. 

It  goes  without  saying  that  the  potash 
industry  has  been  hard  hit  by  the  decline 
of  the  inland  demand,  and  a  great  number 
of  potash  works  have  had  to  restrict  work. 
Exiport  sales  do  not  recompense  for  the 
loss  of  the  inland  business.  The  potash 
business  with  America  has  not  justified  ex- 
pectations, and  it  is,  moreover,  reported 
that  the  Alsatian  potash  works  are  doing 
their  best  to  obtain  the  American  market, 
and  are  imder-bidding.  The  American  far- 
mer is,  therefore,  assuming  a  certain  aloof- 
ness, expecting  no  doubt  that  the  German 
potash  works  will  also  soon  be  compelled 
to  reduce  their  prices. 

The  price  question  is  to-day,  in  fact,  the 
essential  point  in  the  sale  problem.  On  the 
one  hand,  should  the  present  prices  be  re- 
tained, there  is  no  hope  of  increasing  sales, 
and  the  closing  down  of  works  will  be  un- 
avo'dable.  A  reduction,  on  the  other 
hand,  endangers,  in  view  of  the  increased 
costs  of  prcxluction  and  especially  in  view 
of  the  increased  wages,  the  financial  basis 
of  the  potash  industry,  which  has  only 
just  been  re-established.  As,  however,  in 
the  present  conditions,  the  economic  policy 
of  the  various  industrial  groups  is  dictated 
in  the  first  place  by  general  economic  wn- 
sons,  the  potash  industry  will  no  doubt 
decide  upon  a  reduction  of  its  prices,  in 
order  to  revive  inland  sales. 


THE 


ECONOMIC    POSITION    IN 
CZECHO-SLOVAKIA. 


The  British  Vice-Consul  at  Prague  (Mr. 
J.  W.  Taylor)  has  forwarded  to  the  Depart- 


ment of  Overseas  Trade  a  survey  of  the  in- 
dustrial situation  in  Czecho-Slovakia,  by 
Dr.  Hodac,  the  Secretary-General  of  the 
Federation  of  Czecho-Slovak  Industrials. 
Dr.  Hodac's  statements  are  always  care- 
fully considered. 

An  improvement  has  taken  place  in  the 
sale  of  coal  and  coke,  in  the  output  of  pig- 
iron,  steel  and  rolled-iron  manufactures. 
At  the  end  of  December,  three  blast  fur- 
naces were  in  operation;  to-day  seven  are 
being  worked;  but  even  now  no  less  than 
15  are  idle.  This  imiprovement  is  con- 
nected with  special  temporary  causes. 

On  the  other  hand,  unemployment  in 
the  engineering  trade  has  shown  no  im- 
provement. 

In  the  chemical  industry,  a  bigger  de- 
mand for  sulphuric  acid  has  been  noted  in 
connection  with  the  use  of  coke.  Those 
branches  of  industry  which  were  doing 
comparatively  well  last  autumn,  and  which 
felt  the  crisis  only  later,  viz.,  the  varnish 
factories  and  the  technical  chemical  in- 
rlustry,  are  now  fooling  the  slump  in  the 
same  way  as  the  colour  factories  do.  Em- 
ployment in  th(>  wood  pulp  industry  is 
go<)<i ;  in  the  paper  industry  it  has  improved 
somewhat  in  regard  to  a  few  kinds  only. 
There  has  been  a  considerable  demand  for 
leather  of  all  kinds. 

The  position  in  the  glass  industry  re- 
mains unfavourable.  In  the  window  glass 
branch  there  are  about  9()0  workmen  em- 
ployed out  of  5, 000.  In  the  bottle  factories 
700  workmen  are  employed,  instead  of 
3,. 500.  In  the  mirrrir  nnd  cM«?t  glass  fac- 
tories only  1.4*10  workmen  are  employed 
out  of  2,400.  Ai  the  end  of  l^eeomher  the 
number  of  workmen  eniiployed  in  the 
manufncturv'  of  li'>llow  glass  was  7,804, 
and  in  Febniarv  ^.375,  hut  the  normal 
number  is  20.000. 


liieut. -Colonel  Buckley  informed  Mr. 
Graham  White  that  the  following  state- 
ment showed,  for  each  of  the  years  speci- 
fied, the  quantity  and  the  declared  value  of 
the  imports  into  the  United  Kingdom, 
registered  as  consigned  from  the  United 
States  of  America,  of  intermediate  coal  tar 
products  used  in  tlie  manufacture  of  dyes, 
and  of  finished  dyestuffs  obtained  from 
coal  tar,  respectively! 


232 


THE  CHEMICAL  NEWS. 


APRIL  13,  1923. 


1920. 
Quantity. 
Cwts. 


Description. 

Intermediate  coal  tar 
products  used  in  the 
manufacture  of  dyea 
(including  aniline  oil 
and  salt  and  phenyl 
glycine)        44,527 

Finished  dyestuffs  ob- 
tained from  coal  tar     15,636 


Value. 


736,221 

532,897 


1921.  1922. 

Quantity.       Value.      Quantity.     Value. 
Cwts.  £.  Cwts.  U. 


1,324 

1,218 


27,891 
35,576 


1 

150 


8 

1,444 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


ROYAL  INSTITUTION  OF  GREAT 

BRITAXNT'. 
The  Friday  evening    discourse  on    April 
13  was  delivered  by  W.  H.  Eccles    D.Sc, 
F.R.S.,   M.LE.E.,   M.R.I.        His    subject 
was  Studies  from  a  Wireless  Lahoratory. 

On  Monday,  April  9,  the  General  Meet- 
ing was  held. 


ROYAL  SOCIETY  OF  ARTS. 

The  Cantor  Lecture  (1)  ,entitled  Nitrates 
from  Air,  was  delivered  on  April  9  by  E. 
KiLBURN  Scott,  M.I.E.E.,  A.M. Inst. C.E. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

Ordinary  Meeting, 

Held  at  the  Chemical  Society's  Rooms, 
Burlington  House,  on  April  4,  Mr.  P.  A. 
Ellis  Richards,  President,  in  the  chair. 

Certificates  were  read  for  the  first  time  in 
favour  of  Mr.  Robert  C.  Grimwood, 
A.C.G.,  F.C.,  D.I.C.,  A.I.C.,  and  for  the 
second  time  in  favour  of  Messrs.  John 
Myers,  F.I.C.,  and  John  Loudon  Buchan- 
an, F.I.C. 

The  following  were  elected  members  of 
the  Society  :  Messrs.  Joseph  John  Valen- 
tine Backes,  A.R.C.Sc,  A.I.C.,  D.I.C. ; 
Francis  Fenelm  Donovan,  B.Sc.  (Lond.); 
Alfred  Edward  Johnson,  B.Sc.  (Lond.), 
F.I.C,  A.R.C.S.I. ;  Ernest  Victor  Jones, 
F.I.C;  S.  Gordon  Liversedge,  F.I.C; 
Samuel  Gordon  Stevenson,  A.I.C ;  Rich- 
ard William  Sutton,  B.Sc. Tech.  (Mane), 
A.I.C;  Laurence  Bamett  Timmis,  M.Sc. 
(Tech.)  Mane,  A.I.C. 


The  following  paipers  were  read:  — 

Physiological  Standards,  by  Dr.  Stanley 
White. 

Abstract. 
Since  many  important  drugs  used  in 
medicine  da  not  lend  themselves  to  chemi- 
cal standardisation  it  is  necessary  to  adopt 
physiological  standards.  A  number  of  in- 
dividual drugs,  including  digitalis,  ergot 
and  cannabis  indica  were  dealt  with,  and  a 
method  described  of  arriving  at  the  mini- 
mum lethal  dose  on  frogs,  and  so  estab- 
lishing a  heart  tonic  unit.  The  standard- 
isation of  Pituitrin  was  discussed,  and 
physiological  methods  for  determining  the 
presence  of  the  three  vitamins.  The  paper 
was  illustrated  by  numerous  slides. 

The  Estimation  of  Boric  Acid,  in  "Liquid 
Eggs"  and  other  Foodstuffs,  by  G.  W. 
MoNiER-WiLLiAMS,  M.A.,  Ph.D.,  F.I.C. 

Abstract. 

The  author  draws  attention  to  the  irre- 
gular results  sometimes  oibtained  with 
Thompson's  method  owing  to  loss  of  boric 
acid  by  precipitation  as  calcium  borate 
during  the  removal  of  phosphates.  A 
method  is  described  in  which  phosphoric 
acid  is  removed  by  precipitation  is  magne- 
sium ammQniuna  phosphate,  the  subse- 
quent titration  of  the  boric  acid  being  car- 
ried out  by  Thompson's  method. 

An  Investigation  into  the  Chemistry  of 
the  Reinsch  Test  for  Arsenic  and  Anti- 
7nony,  and  its  extension  to  Bismuth,  by  B. 
S.  Evans,  M.B.E.,  M.C,  B.Sc,  F.I.C 

Abstract. 

A  summary  of  the  literature  relating  to 
the  reaction  is  given.  A  method  is  de- 
scribed for  determining  the  velocity  of  the 


APRIL  13.  1923. 


THE  CHEMICAL  NEWS. 


233 


reaction,  and  a  number  of  curves  are  given 
showing  the  influence  on  the  reaction  velo- 
city of  varying  chloride,  acid  strength,  or 
arsenic  (antimony,  etc.)  ,  also  the  effect  of 
adding  ouipric  or  cuprous  salts.  The  pro- 
ducts of  the  reaction  are:  — 

P"or  Arsenic — the  compound  CujAsj. 

For  Bismuth — the  element  Bismuth. 

For  Antimony — the  compound  CujSb, 
followed  by  deposition  of  the  element  anti- 
mony. 

In  all  cases  cuprous  chloride  goes  into 
solution. 

An  attempt  was  made  to  elucidate  the 
mechanism  of  the  reaction,  and  a  number 
of  experiments  are  described  leading  to  the 
conclusion  that  it  is  due  to  reduction  of  the 
arsenio  (or  antimony,  etc.)  by  a  film  of  hy- 
drogen on  the  surface  of  the  copper.  Under 
certain  given  conditions  the  test  used  quali- 
tatively can  be  made  sensitive  to  lese  than 
0.01  mgrm.  per  100  cc. 

It  is  suggested  that  a  determination  of 
the  reaction  velocity  carried  out  in  any 
doubtful  liquid  will  readily  show  whether 
any  substance  is  present  which  would  in- 
terfere with  the  test. 


THE  OPTICAL  SOCIETY. 

A  meeting  was  held  at  the  Imperial  Col- 
lege, Imperial  Institute  Road,  on  Thurs- 
day, April  12th.  The  following  papers 
were  read  and  discussed:  — 

The  Hilger  Microscope  Interferometer, 
by  F.  TwYMAN,  F.Inst. P. 

On  the  Form  of  the  Wave  Surface  of  Re- 
fraction,  by  A.   WiiiTWELL,   M.A. 

Mr.  J.  H.  Barton  also  exhibited  a  new 
research  microscope  of  original  design. 

By  the  courtesy  of  Messrs.  The  Had  Icy 
Cnmpuny,  makers  of  gold-filled  Sipectacle 
frames  and  mounts,  a  visit  Has  been  ar- 
ranged to  their  works  at  Portsmouth  Road, 
Surbiton,  Surrey,  on  th(>  afternoon  of 
Thursday,  April  26,  1923.  Fellows  and 
Members  desiring  to  avail  themselves  of 
the  privilege  of  visiting  these  works  should 
advise  the  Hon.  Secretary  (Business)  at 
the  Imperial  College,  not  later  than  Satur- 
day, April  21. 


THE  INSTITUTION    OF  ELECTRICAL 
ENGINEERS. 

An  ordinary  meeting  was  hold  on  Thurs- 
day, April  12.    A  paper  entitled  The  X-Ray 


Examination  of  Materials,    wa«  read  by  A. 
G.  Warren,  Member. 

At  the  conclusion  of  the  lecture,  Mr.  E. 
E.  Brooks  exhibited  some  lantern  slides 
illustrating  lines  of  electric  force. 


THE  INSTITUTE  OF  METALS. 
A  General  Meeting  of  the  Institute  of 
Metals  will  be  held  at  the  Institution  of 
Mechanical  Engineers  Storey's  Gate,  West- 
minster S.W.I,  on  Wednesday  May  2, 
1923  at  8  p.m.  when  the  thirteenth  annual 
May  Lecture  will  be  delivered  by  Dr.  W. 
RosENHAix,  F.R.S.,  Vice-President,  on 
The  Inner  Structure  of  Alloys. 


IRON  AND  STEEL  INSTITUTE. 

The  Annual  Meeting  of  the  Institute  will 
be  held,  by  kind  permission  of  the  Council 
of  the  Institution  of  Civil  Engineers,  at 
Great  George  Street,  Westminster,  on 
Thursday  and  Friday,  the  10th  and  11th  of 
May,  1928. 

PROORAMMB  OF  PrOCEEDINOS. 

Thursday,  May  10th. 

10  a.m. — General  meeting  of  members. 
The  Council  will  present  their  Reiport  for 
the  year  1922.  The  hon.  treasurer  will 
present  the  statement  of  accounts  for  1922. 
Scrutineers  will  be  appointed  for  the  ex- 
amination of  voting  papers.  Election  of 
Council.  Presentation  of  the  Bessemer 
Medal  to  Dr.  W.  H.  Maw. 

A  resolution,  formal  notice  of  which  was 
given  at  the  autumn  meeting,  on  Septem- 
ber 5th,  1922,  of  the  alteration  of  By-Law 
10,  relating  to  the  election  of  the  Presi- 
dent, will  be  submitted.  The  terms  of  the 
present  by-law  aro  as  follows : 

"  The  Prosidont    shall  be  elected    for 
two  years,    and  shall  not  be  eligible    for 
re-election  until  after  an  interval." 
The  terms  of  the  resolution  are : 

"  That  the  By-Law  shall  be  altered  as 
follows :  'The  President  shall  be  elected 
for  one  year, '  and  to  omit  the  words : 
'  and  shall  not  be  eligible  for  re-election 
until  after  an  interval.'  " 
A  selection  of  the  following  pampers  will 
be  read  and  discussed  in  the  afternoon  ses- 
sion, and  also  during  Friday,  May  11 :  — 

C.  A.  Ablett,  Economic  Principles  gov- 
erning the  use  of  Electrical  Power  in  Iron 


234 


THE  CHEMICAL  NEWS. 


APEIL  13,  1923. 


and  Steel  Works. 

J.  O.  Arnold,  F.R.S.,  On  the  co-relation 
of  the  Chemical  Constitutions  of  "Triw 
Steels"  to  their  Micrographic  Structures. 

C.  R.  Austin,  Some  Mechanical  Proper- 
ties of  a  series  of  Chromium  Steels. 

L.  E.  Benson  and  F.  C.  Thompson, 
Some  Experiments  on  Grain-growth  in  Iron 
and  Steel. 

H.  C.  H.  Carpenter,  F.R.S.,  The  Pro- 
duction of  Single  Metallic  Crystals  and 
some  of  their  properties. 

F.  Clements,  British  Steel  Works  Gas 
Producer  Practice. 

T.  P.  CoLCLOUGH,  The  Constitution  of 
Basic  Slags — its  relation  to  Furnace  Re- 
actions. 

C.  H.  Desch  and  A.  T.  Roberts,  Some 
Properties  of  Steels  containing  Globular 
Gementite . 

C.  A.  Edwards  and  C.  R.  Austin,  A 
Contribution  to  the  Study  of  Hardness. 

J.  E.  Fletcher,  Some  Characteristics  of 
Moulding  Sands  and  their  Graphical  Repre- 
sentation. 

D.  Hanson  and  J.  R.  Freeman,  The 
Constitution  of  the  Alloys  of  Iron  and 
Steel. 

E.  J.  L.  Holman,  Note  on  a  Value  for 
the  Surface  Tension  of  Iron  Sulphide. 

K.  Honda  and  T.  Murakami,  The  Struc- 
tural Constitution  of  Iron-Carbon-Silicon 
Alloys. 

J.  J.  A.  Jones,    The  Acl  Range  in  Alloy 

Steels. 

J.  W.  Landon,  Change  of  Density  of 
Iron  due  to  Overstrain. 

F.  C.  Langenberg,  An  Investigation  of 
the  behaviour  of  certain  Steels  under  Im- 
pact at  different  Temperatures. 

T.  Matsushita,  Some  Investigations  on 
the  Quenching  of  Carbon  Steels. 

L.  Northcott,  A  Note  on  Temper  Car- 
bon. 

H.  O'Neill,  Variation  of  Brinell  Hard- 
ness Number  with  Testing  Load. 

T.  F.  Russell,  The  Potential  Energy  of 
Cold  Worked  Steel. 

J.  Stead,  The  Cold  Working  of  Steel 
with  reference  to  the  Tensile  Test. 

E.  R.  Sutcliffe  and  E.  C.  Evans,  The 
Reactivity  of  Coke  as  a  factor  in  the  Fuel 
Economy  of  the  Blast  Furnace. 

F.  C.  Thompson  and  A.  Goffey,  The 
Changes  in  Iron  and  Steel  below  400°  C. 

J.  H.  Whitley  and  A.  Braithwaite, 
Some  Observations  on  the  effect  of  small 
quantities  of  Tin  in  Steel. 


THE    INSTITUTION   OF  PETROLEUM 
TECHNOLOGISTS. 
The  following    paper    was    read    at    the 
Royal  Society    of  Arts  on  Tuesday,    April 
10,  1923:  — 

Potrero  No.  4.  :  A  History  of  One  of 
Mexico's  Earliest  and  Largest  Wells,  by  A. 
E.  Chambers,  Assoc.M.I.C.E, 

Potrero  No.  4  is  one  of  the  largest  pro- 
ducers in  Mexico,  having  given  over  one 
hundred  million  barrels  of  oil  before  salt 
water  appeared.  Its  technical  history  is 
little  known,  and  it  is  in  the  hope  that  a 
detailed  description  of  the  life  of  this  well 
will  interest  the  members  that  this  paper 
is  presented  to  the  Institution. 

The  career  of  the  well  was  an  eventful 
one;  it  was  brought  in  uncontrolled  in 
December,  1910,  brought  under  control  in 
March,  1911,  developed  large  seepage 
areas  in  its  vicinity  early  in  1914,  caught 
fire  in  August  of  that  year,  was  extin- 
guished early  in  April,  1915,  produced 
under  partial  control  for  nearly  four  years, 
until  December,  1918,  when  its  production 
turned  to  an  emulsion,  which  continued 
until  April,  1919,  when  the  well  was  finally 
closed  in. 

It  is  situated  in  the  State  of  Vera  Cruz, 
some  50  kilometres  north-west  of  Tuxpam. 

The  specific  gravity  of  the  crude  oil  was 
0.931°  at  60°  F.,  its  temperature  at  the  well 
was  147°  F.,  and  the  pressure  when  the 
well  was  closed  in  was  found  to  be  825  lbs. 
per  square  inch. 

At  first,  all  endeavours  were  devoted  to 
saving  the  oil,  but  it  was  soon  apparent 
that  the  quantity  being  produced  was  too 
great  to  attempt  storing  it;  a  careful  calcu- 
lation made  in  December,  1910,  showed 
that  the  well  was  then  flowing  at  the  rate 
of  100,000  barrels  in  24  hours.  The  Buena 
Vista  River,  previously  mentioned,  is  the 
natural  drainage  for  the  area  where  this 
well  is  situated,  and  it  was  down  this 
stream  that  immense  quantities  of  oil 
flowed  and  were  burnt  many  kilometres 
away. 

It  was  evident  that  the  only  thing  to  do 
to  save  this  well  and  its  production,  was  to 
bring  it  under  control.  Owing  to  the  great 
pressure  and  volume  of  oil,  no  ordinary 
method  could  be  used,  and  several  schemes 
were  suggested;  finally,  however,  an  appli- 
ance, now  fairly  well  known  under  the 
name  of  a  "  Bell  Nipple,"  was  devised  and 
successfully  installed  in  January,  1911. 


APRIL  13.  1923. 


THE  CHEMICAL  NEWS 


235 


On  August  14,  1914,  a  severe  lightning 
storm  visited  the  neighbourhood,  and  set 
fire  to  the  gas  escaping  from  the  well ;  this 
gas  fire  melted  some  lead  gaskets  in  the 
joints  of  the  flow  line  near  the  well  head. 
The  oil  from  these  joints  caught  fire,  also 
the  oil  leaking  from  the  bell  nipple;  the  fire 
rapidly  spread  to  the  seepages,  and  very 
quickly  this  large  area  was  completely  in- 
volved. It  was  unfortunate  that  the  occur- 
rence coincided  with  a  period  of  great  revo- 
lutionary activity  and  when  the  American 
Government  had  actually  advised  its 
nationals  to  leave  Mexico.  Practically  all 
the  skilled  American  oilfield  wM-kers  had 
therefore  left  Potrero,  leaving  operations  in 
charge  of  a  small  number  of  British  and 
other  nationalities.  These  few  men  were 
inadequate  to  deal  with  the  fire  in  its  early 
stages,  and  before  others  could  get  on  the 
scene,  the  fire  had  assumed  enormous  pro- 
portions. 

By  March  24,  1915,  the  fire  wag  totally 
extinguished,  and  all  that  remained  of  the 
well  tf>  be  seen  was  a  large  earthen  mound 
with  numerous  gas  piipea  sticking  out  from 
it.  After  a  few  weeks  the  action  of  the  gas 
on  the  clays  forming  the  mound  bad  con- 
verted them  into  a  loose  powdery  material, 
and  the  gases,  instead  of  coming  only  from 
the  gas  pipes,  were  exuding  from  all  over 
the  moimd.  It  was  thought  that  this  con- 
dition of  affairs  should  not  be  allowed  to 
remain,  as,  if  through  lightning  or  any 
other  cause,  the  gases  became  ignited,  it 
was  difficult  to  feel  certain  that  some 
serious  damage  might  not  eventually  occur. 
The  whole  mound  was,  therefore,  covered 
with  a  reinforced  concrete  coyer ;  the  cover 
being  designed  by  the  use  of  suitable  steel 
frames  to  be  entirely  self-supporting,  and, 
in  fact,  to  form  a  species  of  inverted  cup 
placed  over  the  earthen  mound  but  not  in 
contact  with  it.  Numerous  pipes  were  in- 
serted in  this  concrete  cap,  and  the  gas 
coming  therefrom  was  led  away  and  burnt 
at  flares  at  a  safe  distance.  The  well  in  this 
condition  produced  without  misadventure 
until  December,  1918. 


SOCIETY  OF  CHEMICAL    INDUSTRY. 

Birmingham  and  Midland  Section. 

The  following    papers    were  read  at    the 
meeting  on  March  27:  — 


Oil  Hydrogenation,  by  E.  J.  Lush,  M.A. 

The  physical  conditions  of  the  addition 
of  hydrogen  to  oils,  by  means  of  nickel, 
acting  as  a  catalyst,  lent  themselves  natur- 
ally to  continuous  working.  The  catalyst 
being  a  solid,  the  oil  a  liquid,  and  the  sub- 
stance producing  the  desired  change,  viz., 
hydrogen,  a  gas,  it  should  be  possible  to 
distribute  nickel  throughout  a  closed  ves- 
sel, keeip  the  vessel  full  of  hydrogen,  and 
allow  oil  to  run  in  at  one  end  and  out  at  the 
other — the  speed  of  flow  regulating  the  de- 
gree of  hydrogenation. 

Reaction  between  Ammonia  and  Sodium 
Hypohromite,  by  D.  R.  Nanji,  M.Sc,  and 
W.  F.  Shaw,  M.Sc 

When  ammonia  is  added  to  excess  of  al- 
kaline sodium  hypohromite,  it  is  decom- 
posed. That  this  reaction  is  not  the  only 
one  that  occurs  has  not  been  recognised  by 
certain  investigators  since  it  has  been  sug- 
gested as  the  basis  of  volumetric'  estima- 
tions of  ammonia.  Ammonia  is  decom- 
posed by  adding  it  to  excess  of  sodium  hy^ 
pobromite,  the  excess  of  the  latter  being 
determined  after  addition  of  potassium  io- 
dide, by  titrating  the  liberated  iodine  with 
thiosulphate. 

The  authors'  results  prove  that  this  basis 
is  not  sufficiently  accurate. 

The  Eatimation  of  Acetone  and  of  Ethyl 
Alcohol  in  a  mixture  of  the  two,  by  J.  H. 
BusuiLL,  B.Sc. 

The  object  was  to  estimate  these  sub- 
stances in  con^paratively  small  quantities 
in  the  products  of  fermentation  by  various 
bacteria.  The  method  of  estimating  ace- 
tone by  Rakskit  was  preferred  to  others. 
The  method  used  by  Northrop  and  his  co- 
workers for  estimating  alcohol  by  oxidising 
with  potassium  dichromate  and  sulphuric 
acid  was  criticised.  The  author  prefers  to 
estimate  the  specific  gi'avity  of  the  mix- 
ture which,  together  with  the  acetone  con- 
tent, gives  the  alcohol  present.  For  this, 
acetone  gravity  tables  up  to  1  per  cent,  had 
to  be  constructed. 

A  known  volume  was  made  slightly  alka- 
line wth  soda  and  distilled,  the  distillate 
being-  made  to  a  definite  volume.  The 
gravity  of  this  solution    is  then  taken    and 


236 


THE  CHEMICAL  NEWS. 


APEIL  13,  1923. 


the  acetone  estimated.  By  means  of  the 
acetone  tables  the  gravity  of  the  acetone 
present  can  be  found,  and  from  this  and 
the  gravity  of  the  mixture  the  alcohol  may 
be  estimated. 


HYDROHEPATOSIS,  A  CONDITION 
ANALOGOUS  TO  HYDRONEPHROSIS. 
By  Philip  D.  McMaster  and  Peyton  Rous. 

Eockefeller  Institute  of  Medical  Research, 
New  York. 

Read  before  the  Academy,  Nov.  15,  1922. 

The  changes  which  follow  obstruction  to 
the  common  bile  duct  in  human  beings  are 
highly  various;  and  clinical  and  autopsy 
records  yield  few  clues  to  the  factors  re- 
sponsible for  this  diversity.  We  have 
attempted  to  come  at  them  by  animal  ex- 
periment. 

The  fluid  found  in  the  distended  ducts 
above  an  obstruction  that  has  endured 
some  time  may  be  heavily  loaded  with  bile 
pigment  and  mucus,  green-black  and  tarry, 
or  so  wholly  devoid  of  these  constituents, 
despite  a  pronounced  jaundice  of  the  tissues 
in  general,  that  it  is  colourless,  limpid  and 
watery.  All  gradations  between  such  ex- 
tremes are  met  with.  We  have  shown  in 
previous  papers^ '^  that  in  the  absence  of 
infection  all  are  traceable  to  the  differing 
influences  of  the  gall-bladder  and  ducts 
upon  the  bile  first  pent  in  the  channels. 
The  ducts  elaborate  a  secretion  of  their 
own,  which,  thin  and  colourless,  tends 
gradually  to  replace  the  bile ;  whereas  the 
gall-bladder,  by  virtue  of  special  abilities  to 
concentrate  the  bile^  and  add  mucus  there- 
to, acts  to  fill  the  passages  with  one  so 
thick  and  inspissated  that  the  secretion 
just  mentioned  dilutes  it  but  slowly  and 
never  replaces  it  perfectly.  When  the  gall- 
bladder fails  to  exert  its  characteristic  m- 
fluences,  as  happens  sometimes  after  in- 
jury to  the  organ,  the  fluid  collecting  m  it, 
and  in  the  ducts  as  well,  is  a  colourless 
"white  bile"  similar  to  that  contained  m 
obstructed  ducts  unconnected  with  the 
receptaculum  fellece. 

These  are  the  findings  after  total  ob- 
struction. The  changes  taking  place  when 
the  liver  continues  to  secrete  into  the  pro- 
per channels  but  against  a  pressure  ob- 
stacle, have  not  only  theoretical  interest 
but  a  practical  one  as  bearing  upon  the 
development    of     gallstones.         We     have 


studied  them  with  the  aid  of  a  method 
whereby  in  dogs  the  common  duct,  and 
very  probably  the  duct  of  any  gland  lying 
within  the  peritoneal  cavity,  may  be  per- 
manently intubated  and  the  secretion  col- 
lected. The  method  depends  upon  the 
ability  of  the  omentum  to  limit  the  spread 
of  infection.  When  a  rubber  tube  is  con- 
nected with  an  intraperitoneal  duct  and  led 
directly  through  the  abdominal  wall,  it 
ordinarily  comes  away  within  a  few  days  as 
the  result  of  an  ascending  purulenoe.  But 
if  the  tube  be  so  bent  upon  itself  that  a  con- 
siderable stretch  of  it,  sheathed  in  omen- 
tum, is  interposed  between  the  duct  and 
the  exit  wound,  infection  does  not  travel 
along  it  and  it  remains  permanently  in 
place.  The  pressure  obstacle  necessary  to 
the  observations  was  found,  in  some  in- 
stances, in  the  tissue  adhesions  that  de- 
veloiped  about  a  balloon  for  bile  collection 
which  was  interpolated  in  that  part  of  the 
tube  system  lying  within  the  abdomen.  As 
the  adhesions  gradually  thickened  and  con- 
tracted, they  brought  to  bear  an  increasing 
resistance  to  the  expansion  of  the  balloon. 
In  other  instances,  in  which  the  balloon 
was  placed  outside  of  the  animal  in  a  basket 
moored  to  the  skin,  small  gallstones  form- 
ing in  the  lumen  of  the  glass  canula  placed 
in  the  common  duct  interfered  as  they  en- 
larged with  the  passage  of  the  bile.  Which- 
ever the  type  of  obstacle  the  same  series  of 
changes  in  the  bile  took  place.  From  day 
to  day,  as  the  pressure  against  which  the 
fluid  was  secreted  became  greater,  it  gradu- 
ally lost  the  characters  distinguishing  it  as 
bile.  While  still  fairly  copious,  it  contained 
less  and  less  bilirubin,  cholesterin  and  bile 
salts.  Only  faint  traces  of  these  substances 
were  present  in  the  last  scanty  specimens 
obtained  before  obstruction  became  com- 
plete. The  final  fluid  distending  the  ducts 
was  a  "  white  bile  "  such  as  has  already 
been  mentioned,  that  is  to  say,  no  bile  at 
all,  in  the  ordinary  sense  of  the  term. 

A  comparison  of  the  liver  changes  with 
those  occurring  in  other  glands  after  duct 
obstruction  has  proved  enlightening.  These 
changes  have  been  best  studied  in  the  kid- 
ney. In  this  organ  the  pressure  under 
which  the  retained  secretion  is  held  inter- 
feres with  the  venous  flow — and  it  does  this 
in  the  liver  as  well,  a  point  which  we  have 
brought  out  in  a  previous  paper. ^  Both 
organs  continue  to  secrete ;  but  the  secre- 
tion is  now  turned  back  into  the  body. 
There    is  in  both    a  progressive    connective 


APRIL  13.  1923. 


THE  CHEMICAL  NEWS. 


237 


tissue  proliferation,  and  an  accompanying 
parenchymal  atrophy.  The  atrophy  may 
become  complete  when  only  one  kidney  is 
affected;  but  when  the  outflow  of  urine 
from  all  o  the  renal  tissue  is  interfered  with 
death  ensues  long  before  the  alterations 
(progress  so  far.  Similarly,  obstruction  of 
the  bile  ducts  from  but  a  portion  of  the  liver 
leads  to  a  complete  parenchymal  atrophy 
in  the  region  concerned*;  whereas  if  the 
common  duct,  which  drains  all  of  the 
organ,  be  occluded,  the  individual  dies  at  a 
time  when  the  hepatic  changes  are  still  re- 
latively slight. 

A  striking  early  change  in  the  kidney  is 
sacculation,  and  the  sac  may  come  to  con- 
tain several  litres  of  a  watery  fluid  devoid 
of  the  characters  of  urine — whence  the  name 
for  the  condition,  hydronephrosis'  Ob- 
struction of  the  duct  from  the  liver  leads  to 
a  marked  distention  of  the  bile  channels, 
but  the  organ  itself  does  not  bag  out,  a 
difference  scarcely  surprising  when  one 
considers  that  the  maximum  pressure  de- 
veloped upon  biliary  obstruction  is  ex- 
tremely low  (350  mm.  of  the  bile  itself,  in 
the  dog),  whereas  on  renal  obstruction  it  is 
high  (from  650  to  900  mm.,  in  terms  of 
bile).  The  fact  that  the  fluid  ultimately 
found  in  the  distended  ducts  from  the  liver 
has,  in  the  absence  of  gall-bladder  in- 
fluence, none  of  the  characters  of  bile,  hns 
been  sufficiently  indicated.  When  secretion 
takes  place  against  a  pressure  obstacle 
there  is  a  reduction  both  in  the  total  out- 
put and  in  the  percentage  output  of  some 
substances,  exactly  as  with  the  kidney." 
Whether,  as  in  the  case  of  the  latter  organ, 
the  percentage  output  of  certain  other  sub- 
stances IB  increased,  remains  to  be  deter- 
mined. 

Prom  this  comparison  it  will  be  seen  that 
the  changes  consequent  upon  biliary  ob- 
struction and  upon  renal  obstruction,  re- 
spectively, are  essentially  similar  in  type. 
They  are  indeed  the  changes  which  follow 
obstruction  to  the  ducts  of  glands  in  gene- 
ral ;  and  the  differences  between  the  renal 
and  hepatic  manifestations  of  them  are 
traceable  merely  to  incidental  peculiarities 
of  the  glands  concerned.  These  facts  would 
long  ago  have  been  recognised,  were  it  not 
for  the  complicating  activities  during  biliary 
obstruction  of  an  extraneous  organ,  the  gall- 
bladder. As  indicating  the  essential  like- 
ness of  the  hepatic  to  the  renal  changes,  we 
Would  suggest  that  the  term  hi/drohepatoaia 


be  aipplied  to  the  condition  found  after  ob- 
struction to  the  outflow  of  bile.  When  the 
contents  of  the  obsti-ucted  ducts  have  been 
altered  through  the  gall-bladder  activity, 
the  hydrohepatosis  is  concealed,  in  a  very 
real  sense ;  but  when  this  has  not  happened, 
and  the  distended  ducts  are  in  consequence 
filled  with  "  white  bile,"  there  is  a  mani- 
fest hydrohepatosis.  But  the  terms  have 
little  importance  as  compared  with  the 
understanding  that  they  are  supposed  to 
convey. 

1  Rous,  P.,  and  McMaster,  P.  D.,  J.  Ex- 
per.  Med.,  Baltimore,  1921,  XXXIV.,  47. 

"  Rous,  P.,  and  McMaster,  P.  D.,  Ibid., 
1921,  XXXIV.,  75. 

'  Rous,  P.,  and  Larimore,  L.  D.,  ibid., 
1920,  XXXII.,  249. 

*Nas8e,  Verhandl.  deutsch.  Ges.  Chir., 
1894,  Berlin,  XXIII.,  Pt.  2,  525. 

*  Cushny,  A.  R.,  The  Secretion  of  the 
Urine,  London,  New  York,  Bombay,  Cal- 
cutta, and  Madras,  1917. 


[Reprinted  from  the   Proceedings  of 
Academy  of  Sciences  of  the  U.S.A.] 


the 


CORRESPONDENCE. 


THE  HEAT  OF  FORMATION  OF 
STIBINE. 

To  the  Editor  of  The  Chemical  Mews. 

Sir, — I  would  like  to  point  out  that  in 
nearly  all  the  English  textbooks  on  chemis- 
try the  heat  of  formation  of  Stibine  for  one 
molecule  is  given  as  -84.5  calories.  This 
value  was  found  by  Berthelot  and  Petit 
{compt.  rend.,  1889,  CVIII.,  546-550)  from 
the  heat  of  formation  of  the  bromide 
SbH,  +  4Br,  =  SbBr.  +  3HBr. 

In  1908.  however,  A.  Stock  and  W. 
Wrede  (Ber.,  1908,  XLI.,  540-543)  found 
the  heat  of  formation  of  stibine  by  decom- 
posing the  gas  quantitatively  into  its  ele- 
ments by  an  electric  spark.  The  value  they 
obtained  for  one  molecule  was  -34  cals. 

This  latter  paper  appears  to  have  been 
little  noticed  by  EngUsh  authors,  for  we 
find  J.  Thomlinson  (The  Chemical  News, 
1900,  XCIX.,  133)  assuming  the  earlier 
value.  His  results  are  valueless  in  the 
light  of  the  experiments  of  A.  Stock  and 
W.  Wrede. 


238 


THE  CHEMICAL  NEWS. 


APBIL  13,  1923. 


In  most  of  the  German  textbooks  on 
chemistry,  the  value  -84  cals.  is  now  taken 
instead  of  the  previous  one  of  -84.5  cals. — 
Yours,   &c., 

Edward  J.  Weeks,  B.Sc,  F.C.S. 
The  Sir  John  Cass  Institute. 
April  4,  1923. 


NOTICES  OE  BOOKS. 
Oxidations  and  Reductions  in  the  Ani- 
mal Body,  by  H.  D.  Dakin,  D.Sc, 
F.I.C.,  F.R.S.  Second  edition.  Long- 
mans, Green  &  Co.,  London,  1922.  6s. 
net. 

It  is  eleven  years  since  the  first  edition  of 
this  monograph  appeared,  and  during  this 
period  much  progress  has  been  made  in  un- 
ravelling the  mechanism  of  the  various  re- 
actions which  occur  in  the  animal  body. 
This  advance  has  been  general  rather  than 
sipecific,  and  accordingly  the  arrangement 
of  the  subject  matter  follows  very  closely 
that  of  the  first  edition,  and  it  is  only  in 
dealing  with  the  biochemistry  of  the  carbo- 
hydrates that  considerable  alterations  have 
been  rendered  necessary  in  order  to  incor- 
porate the  results  of  recent  investigations. 
This  monograph  is  devoted  to  the  consider- 
ation of  oxidation  and  reduction  processes 
of  the  animal  body,  from  the  standpoint  of 
the  structure  of  the  substances  undergoing 
change.  The  purely  biological  aspects  and 
also  the  thermo  dynamics  of  the  problems 
of  oxidation  and  reduction  have  been 
omitted  as  being  outside  the  scope  of  the 
work.  The  necessity  for  this  intensive 
study  of  intermediary  metabolism  is  justi- 
fied owing  to  the  developing  ajppreciation 
of  the  fact  that  different  proteins,  fats,  and 
sugars  are  not  physiologically  equivalent, 
and  that  certain  definite  chemical  groups 
subserve  special  functions  in  the  animal 
organism. 

As  the  author  points  out,  the  oxidations 
and  reductions  occurring  in  the  living  body 
are  so  closely  interwoven  with  other  types 
of  reaction,  especially  those  involving  con- 
densation and  hydrolysis,  that  their  con- 
sideration, apart  from  other  metabolic 
changes,  is  becoming  unduly  artificial,  and 
will  probably  be  abandoned  in  the  near 
future.  If  this  turns  out  to  be  so,  we  trust 
that  the  author  will  be  chosen  to  give  us 
that  more  extensive  view  of  metabolic 
changes  when  the  time  arrives.  The  only 
blemish  to  be  found  in  this  monograph    is 


the  presence  of  a  large  number  of  small 
errors  due  to  faulty  proof  reading  and  care- 
lessness in  setting  up  the  type. 

An  excellent  bibliography,  and  an  index 
complete  a  book  which  we  have  no  hesita- 
tion in  recommending  to  all  interested  in 
biochemistry. 


Vital  Factors  of  Foods — Vitamins  and 
Nutrition,  by  Carleton  Ellis,  S.B., 
F.C.S. ,  and  Annie  L.  Macleod,  Ph.I). 
Pp.  XVII.  +  391.  London:  Chapman 
&  Hall,  Ltd.,  11,  Henrietta  St.,  W.C.2. 
1923.     Price  25s. 

Not  so  many  years  ago  it  was  believed 
that  a  balanced  diet  should  contain  pro- 
tein, fat,  carbohydrates,  and  certain  salts 
in  correct  proportions,  and  then  the  animal 
body  would  continue  to  thrive.  Great  im- 
portance was  attached  to  the  calorie  or 
energy  value  of  foods. 

To  these,  investigations  of  the  past  de- 
cade have  added  the  essential  inclusion  of 
accessory  food  factors  or  vitamins. 

It  is,  perhaps,  surprising  that  substances 
which  play  so  vital  a  role  in  nutrition 
should  have  escaped  discovery  for  so  long, 
but  it  is  now  definitely  established  at  least 
three  accessory  factors  are  necessary,  viz., 
the   fat-soluble,    growth-promoting   Vitamin 

A,  the  water-soluble,  anti-neuritic  Vitamin 

B,  and  the  anti-scorbutic  Vitamin  C,  (Con- 
tinued investigations  may  lead  to  the  defi- 
nite characterisation  of  a  fourth.) 

It  has  come  to  be  realised  that  a  number 
of  maladies  are  not  caused  by  the  presence 
of  toxins,  as  previously  supposed,  but  by 
the  absence  of  vitamins. 

The  authors  have  given  a  careful  account 
of  the  discovery  of  the  existence  of  these 
three  vitamins  and  their  specific  functions. 
They  have  also  indicated  the  different  re- 
quirements of  these  in  the  food  of  children 
and  adults. 

Little  is  known  at  present  concerning  the 
chemical  properties  of  the  vitamins,  and 
still  less  of  their  structure.  The  attempts 
of  Funk  and  others  to  isolate  pure  vitamin 
are  recorded.  In  this  and  other  connec- 
tions the  original  literature  has  been 
quoted  and  searched  very  thoroughly,  so 
that  all  existing  knowledge  on  the  subject 
has  been  ably  summarised. 

Very  few  errors  have  been  noted,  but  re- 
ferences are  not  quoted  uniformly.  This 
very   minor  defect  will,    doubtless,     be   re- 


APRIL  la,  1923. 


THE  CHEMICAL  NEWS. 


239 


moved  in    the  next  edition,    which  should 
not  be  long  in  appearing. 

In  their  comprehensive  treatise  the 
authors  have  dealt  with  the  subject  authori- 
tatively in  a  lucid  manner  which  cause  the 
book  to  appeal  to  the  general  public  as  well 
as  to  scientists. 


The  Generation  and  Utilisation  of 
Cold.  A  general  discussion  held  by  the 
Faraday  Society.  Pp.  136.  London : 
The  Faraday  Society,  10,  Essex  Street, 
W.C.     1923.    Price  lOs.  6d. 

From  time  to  time  the  Faraday  Society 
holds  discussions  upon  physico-chemical 
subjects  of  both  scientific  and  industrial 
interest.  These  deliberations  are  printed 
in  the  Tranaactiona  of  the  Society,  but  in 
order  to  give  them  a  wider  publicity  the 
Socifty  also  issues  them  in  the  form  of 
Reprints. 

The  present  volume  is  an  account  of  a 
general  discussion  on  the  Generation  and 
Utilisation  of  Cold,  which  was  held  jointly 
by  the  Faraday  Society  and  the  British 
Cold  Storage  and  Ice  Associati(Mi  laet 
October. 

Part  I.  deals  with  the  laboratory 
methods  of  Liquefaction.  Prof.  H.  Kam- 
merliiigh  Onnes  has  contributed  an  article 
on  the  lowest  temperature  yet  obtained, 
and  an  account  of  the  apparatus  and 
methods  adopted  to  attain  low  tempera- 
tures in  the  Leiden  Cryogenic  Laboratory 
is  given  by  Dr.  C.  A.  Cn.mmelin;  both  con- 
tributions are  fully  illustrated.  This,  the 
more  academical,  portion  concludes  with  a 
short  pmper  on  Ethyl  Chloride,  by  Prof.  C. 
F.  Jenkins,  and  an  account  of  the  discus- 
sion on  the  laboratory  mtthrxls  of  liquefac- 
tion in  which  a  number  of  eminent  authori- 
ties participated. 

Part  II.  contains  the  contributions  on 
the  Industrial  Meth(Kls  of  Liquefaction 
and  the  practical  ii<pplications  of  low  tem- 
peratures. After  a  general  survey  by  K.  S. 
Murray,  follow  papers  by  M.  Georges 
Claude,  E.  A.  Griffiths,  A.  J.  Bremner, 
Dr.  E.  Griffiths  and  J.  H.  Aubery,  and 
Cosmo  Jones.  All  these  contributions  deal 
with  some  special  aspect  of  technical  im- 
portance. 

The  industrial  importance  of  the 
achievements  in  this  field  can  scarcely  be 
over-estimated. 


Laboratory  Manual  of  Physical  Chem- 
istry, by  Albert  W.  Davison  and  Henry 
S.  VAN  Klooster.  Pp.  VIII.  +  182. 
London:  Chapman  &  Hall,  Ltd.,  Hen- 
rietta Street,  W.C.     1922.     Price  10s. 

Lecturers  in  physical  chemistry  and 
laboratory  demonstrators  should  find  this 
manual  both  useful  as  a  guide  and  helpful 
to  indicate  to  students  the  exact  apparatus 
needed  for  a  given  experiment  and  the 
method  of  arranging  it. 

In  practical  nhysical  chemistry  this  is 
an  advantage  since  it  is  seldom  possible  for 
all  students  to  commence  simultaneously 
with  the  same  experiments. 

Each  experiment  is  set  out  in  a  clear  and 
concise  manner.  The  object  is  first  stated, 
references  are  then  quoted,  frequently  in 
three  categories — textbooks,  laboratory 
manuals  and  original  articles.  A  list  of 
apparatus  and  chemicals  required  comes 
next,  and  is  followed  by  the  method  of  pro- 
cedure. There  is  then  a  blank  scheme  with 
instructions  for  entering  observations  and 
measurements.  Penally  the  calculations 
required  are  indicated.  Blank  sheets  and 
graph  paper  have  been  introduced,  so  that 
the  manual  can  also  serve  firstly  as  a  note- 
book and  later  as  a  reference  volume. 

As  regards  the  experiments  selected, 
these  follow  the  usual  lines,  except  that 
the  procedures  have  been  modified  in  many 
cases.  Some  of  the  methods  have  not  ap- 
peared previously  in  textbooks. 

Students  who  complete  those  described 
cannot  fail  to  obtain  a  good  general  ac- 
quaintance with  practieal  physical  chemis- 


Messrs.  The  Eastman  Kodak  Company, 
of  Rochester,  N.Y.,  have  orwardcd  us  their 
fifth  volume  of  Abridged  Scientific  Publi- 
cations— now  being  published  annually. 

The  172  pp.  have  been  filled  with  various 
papers  compiled  from  research-records  of 
the  Kodak  Laboratories,  which  were  ipub- 
lished  in  a  wide  range  of  scientifiq  periodic- 
als during  the  year  1921. 

From  the  collection,  one  may  judge  that 
the  science  of  photography  will  develop 
enormously  during  the  next  few  years.  L. 
Silberstein  has  included  a  most  mteresting 
paper  upon  the  proipagation  of  light  in  ro- 
tating systems,  and  S.  E.  Sheppard  (very 
much  in  evidence  throughout    the  volume) 


240 


THE  CHEMICAL  NEWS. 


APBIL  13,  1923. 


criticises  Mr.  Eenwick's  theory  that  "  it 
is  .  .  .  silver  which  first  undergoes 
change  on  exposure  to  Hght  "  in  discussing 
the  contention  that  the  highly  dispersed 
silver  halide  is  converted  into  a  more  con- 
densed one. 

It  is  to  be  regretted  that  various  formu- 
lae have  been  omitted  from  L.  A.  Sones'  and 
C.  E.  Fawkes'  paper  upon  the  Reduction  of 
Developing -out  Papers,  as  the  arguments 
and  observations  seem  incomplete  without 
them.  Also,  the  experimental  apparatus 
described  on  p.  75  seems  a  trifle  vague,  and 
could  well  do  with  more  explanatory  illus- 
tration than  that  on  p.  81. 

However,  the  work  is  admirably  edited 
and  printed.  Perhaps,  to  render  it  more 
complete,  the  entire  papers  could  well  have 
been  inserted,  instead  of  congests;  and 
their  sources  kept  free  of  the  matter  by  in- 
cluding them  in  the  contents-table. 


BOOKS    RECEIVED. 

Atomic  Theories,  by  F.  H.  Loring.  Pp. 
X.  +  218.  Second  edition,  revised.  1923. 
Messrs.  Methuen  &  Co.,  Ltd.,  36,  Essex 
Street,  W.C.2.     12s.  6d.  net. 


Elements  of  Glass-Blowing,  by  H.  P. 
Waran,  M.A.,  Ph.D.  Pp.  VIII.  +  113. 
1923.  Messrs.  G.  Bell  &  Sons,  Ltd.,  York 
House,  Portugal  Street,  W.C.2.  2s.  4d. 
net. 


Wavelength  Tables  for  Spectrum  Analy- 
sis, by  F.  TwYMAN,  F.Inst. P.  Pp.  VIII. 
+  106.  1923.  Messrs.  Adam  Hilger,  Ltd., 
75a,  Camden  Eoad,  N.W.I.     7s.  6d.  net. 


Bulletins  issued    by    the     U.S.     Depart- 
ment of  the  Interior,  Bureau  of  Mines:  — 

No.  218:     The  Technology    of  Slate,    by 
Oliver  Bowles.     Pp.  132.  Price  20  cents. 


No.  201 :  Prospecting  and  Testing  for  Oil 
and  Gas,  by  R.  E.  Collom.  Pp.  170. 
Price  25  cents. 


This  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Ck).,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trada  Marks, 
and  Designs  can  be  obtained  gratuitously. 


Latest  Patent  Applications. 

7505 — Coley,  H.  E. — Maniifacture     of  barium  sul- 
phide and  hydroxide.    March  15. 

7473 — Spence,    H. — Preparation  of     titanium   com- 
pounds.   March   15. 

7407 — Waterloo    Chemical   Works,    Ltd. — Manufac- 
ture of  ferrio  hydroxide.    March  14. 
Specificntions   Published   this    Week. 

193881— Hybinette,  N.  V.— Separating,  plating  and 
refining  of  metals  by  electrolysis. 

193894 — Oompagnie  Francaise  Thomson-Houston.— 
Production  of  boron  and  boron  oxide  for 
use  in  purifying  copper  castings. 

171094— Pollak,  Dr.  F.— Manufacture  of  conden- 
sation products  from  fodmaldehyde  and 
urea,  thiourea,  or  their  derivatives. 

1939ia— British  Cellulose  &  Cliemical  Manufactur- 
ing Co.,  Ltd.,  and  Bader,  W. — Treatment 
of  cellulose  acetate  products. 

198934— Accioly,  F.  De  M.— Treatment  of  mineral 
and  othed  oils  for  the  production  of  vola- 
tile liquids  adapted  for  use  as  fuel. 

193967— Hailwood,  E.  A.— Annealing  lehr. 


Abstract  Published  this  Week. 

192298— Alkaloids— Boehringer  Sohn,  C.  H.,  and 
Stenzi.  H.,  Nieder-Jngelheim-on-Rhine, 
Germanp. 

Papaverine  nitrite  is  prepared  by  the  action  of 
salts  of  nitrous  acid  on  soluble  salts  of  papaver- 
ine; tlie  product  is  freed  from  papaverine  by 
means  of  solvents  such  as  benzene,  toluene,  tetra- 
hydronaphthalene,  or  alcohol.  The  reaction  may 
also  bp  effected  in  the  presence  of  one  of  the  above 
mentioned  solvents,  examples  of  each  method  be- 
ing given.  The  product  exhibits  the  tissue  dilat- 
ing properties  of  its  components  in  an  enhanced 
degree. 

Messrs.  Eayner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  price  of  Is.  6d.  each. 


APEIL  20,  1923. 


THE  CHEMICAL  NEWS. 


241 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3288. 


CANADIAN  CHEMICAL  SUPPLIES. 
The  Exploitation  of  Capital. 

Mineral  secretions  in  the  prairie  districts 
have  not,  in  the  past,  been  regarded  as  suf- 
ficiently extensive  to  warrant  the  attention 
of  industrial  enterprise.  Dr.  Charles  Cam- 
sell,  deputy  minister  of  mines,  and  Dr.  A. 
W.G.  Wilson,  chief  engineer  of  the  mineral 
resources  division,  have  now  issued  a  report 
show  ing  the  activity  in  producing  chemicals 
from  the  alkali  deposits  of  Manitoba,  Sas- 
katchewan, Alberta,  and  British  Columbia. 

A  few  details  showing  the  progress  might 
t)e  of  interest.  A  plant  costing  $500,000.00 
has  been  constructed  at  Dana,  Sask.  (the 
ipronerty  of  the  Salts  and  Chemicals,  Ltd.), 
and  is  operating  upon  the  brines  of  the  Mus- 
kiki  Lake,  23  miles  west  of  Humboldt.  The 
est'mated  output  of  the  plant  is  30,(X)0 
tons  of  salt  cake  per  annum,  in  addition  to 
Epsom  and  other  salts.  The  Bishopric  and 
Lent  Co.  have  founded  a  working  at  Freder- 
ick Lake,  five  miles  south-west  of  Dunkirk, 
Sask.  It  is  hoped,  at  a  very  early  date,  to 
produce  200  tons  per  day  of  salt  cake ;  its 
present  output  being  about  50  tons.  An 
experimental  plant  has  been  devised  for 
the  Soda  Deposits,  Ltd.,  at  Fusilier,  Sask.; 
here  exists  a  very  pure  deposit  of  sodiuTii 
sulphate,  some  of  which  has  already  been 
shipped. 

Other  companies  which  are  exploitinu 
these  districts  are:— The  Basque  Chemical 
Co.,  at  a  lake  15  miles  west  of  Ashcroft. 
B.C.,  for  crude  magnesium  sulphate;  and 
the  Lillooct  Soda  Co.,  at  a  place  60  miles 
north  of  Clinton,  B.C.,  for  sodium  carbon- 
ate 

Quoting  from  Natural  Resources,  pub- 
lished by  the  Department  of  the  Interior, 
Ottawa:  "The  operations  of  these  com- 
panies tend  to  bring  before  the  public  the 
possibilities  of  the  western  provinces  in  the 
mineral  field,  and  should  forni  the  nucleus 
of  the  ever- increasing  industry  which,  in 
time,  should  prove  of  great  importance  to 
the  whole  of  Canada." 

The  Mines  Branch  of  the  Department  of 
Mines,  Ottawa,  have  organised  a  thorough 
investigation  into  the  localities  and  extent 
of  the  unworked  deposits,  mainly  for 
Glauber's  salt,  salt  cake,  Epsom  salt,  sodn 
ash,  and  baking  sodas.     The  seoretions  are 


believed  to  contain  profitable  amounts  of 
magnesium  salts,  and  acid  sodium  carbon- 
ate. The  investigations  are  in  charge  of 
Mr.  S.  H,  Cole,  of  the  Department  of 
Mines.  J.M. 


THE    PROBLEM    OF    SUBSTITUTION 

IN    THE    BENZENE    NUCLEUS    AND 

THE    THOMSON-LEWIS-LANGMUIPi 

THEORY    OF    CO- VALENCE. 

By  Ronald  Eraser  and  James  Ernest 
Humphries. 

The  work  of  the  organic  chemists  who 
have  directed  their  attention  to  the  prob- 
lem of  substitution  in  the  benzene  nucleus 
falls  naturally  under  two  heads :  sipecula- 
tion  on  the  mechanism  of  substitution  and 
the  study  of  the  directive  influence  of  sub- 
stituents  already  present  in  the  nucleus. 
The  present  paper  deals  only  with  the 
second  part  of  the  problem,  though  it  is 
realised  that  the  two  are  probably  inter- 
dependent, and  the  possible  effect  of  addi- 
tion preceding  substitution  has  been  kept 
onstantly  in  view. 

Modern  theories,  as  exemplified  by  the 
ideas  of  Lapworth,  Fry,  Vorlander,  Prins, 
and  Fliirscheini,*  agree  in  regarding  orien- 
tation as  occasioned  by  a  differentiated 
condition — polarity  or  state  of  strain — of 
alternate  carbon  atoms.  These  theories 
inevitably  bear  among  themselves  a  certain 
formal  analogy,  and  the  ideas  here  de- 
veloped are  no  exceiption.  They  agree 
more  particularly  with  those  of  Lapworth 
and  Fry  in  possessing  an  electrical  basis- 
Nothing  is  postulated,  however,  as  to  the 
constitution  of  the  benzene  nucleus,  ex- 
cept that  it  is,  of  course,  regarded  as  a 
six-membered  ring;  and  we  consider  that 
the  state  of  the  molecule  after  the  entry  of 
a   substituent   and    resulting   from   its   pre- 


*  The  foUcrving  references  may  be  given 
to  the  papers  of  these  authors:  Lapworth, 
Mem.  ^fan-.  Phil.  Soc,  1920,  LXIV.,  ii., 
1;  T.,  1022,  CXXL.  416;  Fry,  The  Elec- 
tronic Conception  of  Valence  and  the  Con- 
stitution of  Benzene,  1921;  VorUindcr, 
Ber.,  1919,  LIL  (B),  268;  Prins.  Chcvi. 
Weei-hlad,' 19\H.  XV..  571;  Flurscheiw,  .1 . 
pr.  Chcm..  1902,  LXVI.,  321;  ibid.,  1905, 
LXXL,  497. 


242 


THE  CHEMICAL  NEWS. 


}  PEIL  20,  1923. 


sence  is  the  important  factor  in  orienta-  j 
tion  (c/.,  Mills,  J.  Soc  Chem.  Ind.,  1921,  i 
XL.,  417,  R.,  in  his  review  of  Fry's  mono-  \ 
graph).  j 

We  have  taken  as  our  basis  the  Thom-  ; 
son-Lewis-Langmuir  theory  of  co-valence, 
and  on  this  foundation  have  built  uip  an 
electronic  interpretation  of  Lapworth's 
Principle  of  Induced  Alternate  Polaritie.s, 
as  already  elaborated  by  Kermack  and 
Eobinson  (T.,  1922,  CXXL,  427).  We  &re 
not  prepared  at  the  present  stage  to  differ- 
entiate between  the  relative  sizes  of  the 
octets  surrounding  positive  and  negative 
centres,  and  for  our  present  purpose  tiiis 
appears  to  be  of  secondary  importance. 
The  development  of  the  theory  is  based  on 
the  following  three  postulates.  In  order 
to  avoid  the  introduction  of  unnecessary 
synonyms,  we  shall  adopt  in  the  sequel  the 
terminology  used  by  Kermack  and  Robin- 
son (loc.  cit.). 

Postulate  1 :  The  tendency  of  a  disin- 
tegrated octet  is  towards  further  disrup- 
tion; and  of  a  nearly  completed  octet  to- 
wards completion. 

Postulate  2 :  The  tendency  towards 
octet  stability  of  an  atom  with  nearly 
completed  octet  is  greater  than  the  ten- 
dency to  octet  instability  of  an  atom 
with   disruption   only   incipient. 

Postulate  3 :  The  more  nearly  a  group 
approaches  octet  stability,  the  greater 
the  ease  of  replacement  at  that  point. 
It  will  be  observed  that  Postulate  2  is 
simjply  a  statement  in  terms  of  octets  of 
the  conclusion  arrived  at  by  Briggs  (T., 
1908,  XCIIL,  1564;  ihid.,  1917,  CXI., 
253;  ihid.,  1919,  CXV.,  278),  viz.,  that 
negative  fields  are  in  general  stronger  than 
positive  gelds.  Further,  the  relation  of 
the  carbon  atom  to  Postulate  2  is  of  im- 
portance. It  is  generally  recognised  that 
carbon  is  unique  in  that  it  occupies  the 
middle  position  in  the  first  series  of  the 
periodic  system,  and  is  the  first  member  of 
its  group,  containing  the  fewest  number  of 
electrons.  It  follows,  then,  that  in  a  chain 
of  carbon  atoms  of  alternately  positive  and 
negative  character,  the  positive  centres 
tend  to  increasing  positive  character,  and 
the  negative  centres  to  increasing  negative 
character.  Some  interesting  consequences 
of  this  element's  electrical  individuality 
will  appear  in  the  sequel. 

Postulate  3  requires  further  discussion. 
We  are  of  opinion  that  the  distinction  be- 
tween polar  and  non-polar  compounds  is 
merely  one  of  degree,  and  our  views  in  this 


respect  are  those  of  Briggs  (T.,  1921, 
CXIX.,  1879),  and  of  Kermack  ;ind  Robin- 
son (loc.  cit-).  The  extreme  case  of  octet 
stability  is  evinced  in  compounds  whicii 
have  come  to  be  known  as  polar,  where  an 
atom  surrounded  by  a  completed  octet  can 
actually  exist  free  as  an  ion  {e.g.,  sodium 
chloride).  There  are  evidently  all  grada- 
tions of  octet  stability  from  such  extreme 
cases  to  those  of  typically  non-polar  com- 
pounds such  as  carbon  dioxide,  where  octet 
stability  is  apparently  only  possible  so 
long  as  there  is  electron-sharing  among  the 
octets.  It  is  practically  a  universal  rule 
that  the  reactivity  of  compounds,  as 
measured  by  the  velocity  of  reaction,  is 
greater  in  the  case  of  ionised  than  of  non- 
ionised  bodies,  although  some  doubt  is 
thrown  on  the  complete  generality  of  this 
statement  by  the  work  of  Kahlenberg  (J. 
Phijs.  Chem.,  1902,  VI.,  1;  and  subse- 
quent papers.  Compare,  however,  Stieg- 
litz's  discussion  of  Kahlenburg's  results, 
Qualitative  Chemical  Analysis,  Part  1., 
1912,  pp.  84-87).  Thus,  although  we  do 
not  anticipate  ionisation  as  a  cause  of  the 
reactivity  of  a  substituent  possessing  a 
stable  octet,  we  do,  as  a  result  of  the  con- 
sideration of  the  above  gradation  in  re- 
activity, regard  increasing  octet  stability 
as  parallel  with  increasing  likelihood  of 
lability. 

The  Brown  and  Gibson  Rule. 
Of  the  many  empirical  rules  which  have 
been  from  time  to  time  proposed  to  sum- 
marise the  directive  influence  of  substitu- 
ents  on  an  entering  group,  undoubtedly  the 
best  known  is  that  of  Brown  and  Gibson 
(T.,  1892,  LXL,  367).  It  was  unfortunate 
that  Brown  and  Gibson  based  at  least  part 
of  their  rule  on  the  lack  of  knowledge  of 
certain  reactions  (c/.,  Holleman,  Bull 
Soc.  Chim.,  1911,  IV.,  series  9,  1-14). 
Brown  and  Gibson  based  their  rule  on  the 
oxidisability  or  otherwise  of  the  compound 
HX,  where  X  is  the  substituent,  whereas 
the  real  basis  of  the  rule  is  rather  the  ten- 
dency to  oxidation  or  reduction  of  the  sub- 
stituent itself.  On  the  electronic  theory  of 
oxidation  and  reduction,  oxidation  means 
loss  of  electrons,  reduction  gain  of  elec- 
trons. The  ortho-para  directive  substi- 
tuents  lifted  by  Brown  and  Gibson  have  in 
each  case  the  atom  which  is  linked  to  the 
nucleus  in  a  state  approaching_  octet  sta- 
bility, hence  loss  of  electrons  {i.e.,  oxida- 
tion) is  resisted  (Postulate  1);. while  in  the 


APRIL  20,  1923. 


THE  CHEMICAL  NEWS. 


243 


case  of  the  naeta-directive  substituents, 
viz.,  NO2,  COOH,  SO3H,  COCH3,  the 
octets  of  N,  C,  S,  C,  are  in  a  state  of  in- 
cipient disruiption    due  to  the  effect  of  the 

negative  (octet  stable)  O,    ';•  -^  ,  0,,  OCH3 

respectively  (c/.,  Kermack  and  Robinson, 
loc.  cit.):  hence  loss  of  electrons  (i.e.,  oxi- 
dation) is  favoured  (Postulate  1).* 

In  short,   negative   (octet  stable)    substi- 


5  V^^  - 


Fig.  1. 


*  CCIj  is  listed  by  Broicn  and  Gibson 
among  the  ortho-para  directive  substitu- 
ents,  by  Vorldnder  (loc.  cit.)  among  the 
met  a -directive  substituents.  SpreckeU 
(Ber.,  1919,  LII.,  B,  315)  has  obtained  the 
meta  nitro  compound  under  conditions 
which  preclude  hydrolysis.  This  it  in  com- 
plete agreement  with  the  octet  view,  for 
the  carbon  atom  in  CCI3,  being  attached  to 
three  negative  {octet-stable)  chlorine$,  i$  a 
positive  centre,  and  hence  falls  into  the 
meta-directive  class.     Cf-,  also  below. 

It  is  convenient  to  note  here  the  meta- 
directive  nature  of  the  ammonium  salt 
group,  as  investigated  by  Vorldnder  and 
SiebeH  (Ber.,  1919,  LII.  [B] ,  288).  On 
nitrating  C,H,N(CH.,),NO,,  for  instance, 
the  meta  compound  is  obtained.  It  is  evi- 
dent that  the  condition  of  octet  stability  in 

+  -  +- 
C,H,N(CH,)3NO,  is  as  shoum,  the  signs  + 
and  -  indicating  polarity  as  resulting  from 
octet  instability  and  octet  stability  respec- 
tively; the  N  atom  attached  to  the  nucleus 
being  a  positive  centre,  the  whole  group 
would  be  expected  to  direct  meta. 

We  might  mention  here  that  some  of  the 
ortho-para  directive  substituents,  com- 
prised of  a  side  chain  (Vorldnder,  loc.  cit.), 
present  a  difficulty  inasmuch  as  the  in- 
duced polarity  of  the  nucleus  would  appear 
to  differ  from  case  to  case,  as,  for  example, 
in  CHXOOH,  •CH,CH,COOH,-CFT. 
CHCOOH,  nil  these  groups,  hoioever,  be- 
ing ortho-para  directive. 


tuents  direct  ortho-para ;  positive  (octet  un- 
stable) substituents  meta.j: 

From  the  above  argnment  the  state  of 
polarity  of  the  carbon  atoms  in  a  mono- 
substituted  benzene  compound  containmsr 
(1)  an  ortho-ipara  directive  substituent  X 
(Fig.  1,  a),  and  (2)  a  meta  directive  sub- 
stituent Y  (Fig.  1,  b)  readily  follows.  In 
Fig.  1,  a,  the  octet  of  X  tends  to  comple- 
tion; hence  the  electrons  shared  with  C, 
are  drawn  into  X,  making  Cj  positive;  C, 
can  now  appropriate  electrons  shared  with 
the  unstable  system  C,,  acquiring  negative 
polarity;  C,  assumes  positive  polarity,  and 
£0  on.  In  Fig.  1,  b,  containing  Y  in  a 
state  of  incipient  disruption,  the  polariv'' s 
are  obviously  as  shown  (cf.,  Lapworth, 
Mem.  Man.  Phil.  Soc.,  1920,  LXIV.,  ii,  1). 

A  consideration  of  the  figures  will  show 
that  whatever  is  the  cause  of  ortho-para 
substitution  in  Fig.  1,  a,  will  cause  meta 
suBstitution  in  Fig.  1,  b.  The  elucidation 
of  these  causes  involves  a  special  consider- 
ation of  the  position  of  hydrogen  with  re- 
f^ard  to  octet  stability.  We  regard  the 
condition  corresponding  to  octet  stability 
of  hydrogen  as  ropros(  nt€d  by  the  nucleus 
with  no  electrons.*  On  this  view,  the 
hydropen  atom  should  be  almost  entirely 
lacking  in  a  tendency  to  acquire  an  elec- 
tron, and  become  the  negative  hydrogen 
postulated  by  Fry  (op,  cit.,  pp.  20-27,  p. 
W).  Our  views  receive  strong  support  fr>m 
the  arguments  of  Stioglitz  (J.  Amer.  Chem. 
Soc.,  1922,  XLIV.,  1293)  against  the  exist- 
ence of  negative  hydrogen  in  benzene  com- 
pounds. 

f  Attention  should  be  directed  at  this 
point  to  the  use  of  the  terms  positive  and 
negative  applied  to  the  groups  mentioned, 
in  view  of  the  fact  that  in  discussions  on 
orientation  the  terms  are  used,  arbitrarily 
and  in  general,  un'th  the  opposite  meaning. 
This  has  already  been  noticed  by  Davies 
(T.,  1922.  CXXL,  footnote  to  p.  786).  The 
same  writer  (T.,  1922,  CXXI.,  809)  dis- 
proves the  statement  made  by  one  of  us 
(Fraser,  T.,  1922,  CXXI.,  195)  that  the 
directive  influence  of  substituents  was 
partly  dependent  on  their  volume.  The 
statement  above  is  nona  preferred. 

*  These  remarks  bring  hydrogen  (and 
the  metals)  into  line  with  Postulate  2, 
which  was  stated  in  such  a  form  as  to  make 
more  obvicms  its  application  to  the  com- 
mon organic  elements,  which  lie  to  the 
right  of  the  Periodic  Table. 


244 


THE  CHEMICAL  NEWS. 


APRIL  20,  1923. 


The  main  consideration  seems  to  be 
rather  the  state  of  the  carbon  atom  to 
which  the  hydrogen  is  attached.  In  a  car- 
bon atom  of  negative  polarity,  the  octet  is 
comparatively  firmly  held;  hence  the  hy- 
drogen attached  to  it  is  to  a  great  extent 
deprived  of  its  electron;  the  converse  hold- 
ing with  a  carbon  atom  of  positive  polarity. 
Bearing  in  mind  the  unique  position  of 
hydrogen  with  regard  to  octet  stability,  it 
is  evident  that  the  hydrogen  nuclei  at- 
tached to  negative  carbon  atoms  are  in  a 
condition  for  ready  substitution  (Postu- 
late 3). 

Thus  it  is  evident  (Fig.  1)  that  the 
ortho-para  hydrogens  in  Fig.  1,  a,  are  in  a 
condition  for  ready  substitution,  while  in 
(b)  it  is  the  meta  hydrogens  which  are 
the  more  easily  replaced.  It  is  seen  that 
the  essential  difference  between  the  two 
types  of  substitution  is  brought  out  with 
exceptional  clearness  on  this  view;  and, 
further,  the  ortho-para  directive  influence 
of  X  on  the  one  hand,  and  the  meta- 
direotive  influence  of  Y  on  the  other,  is  as 
it  should  be,  independent  of  the  nature  of 
the  entering  groujp. 

The  special  reactivity  of  the  hydrogen 
in  the  para-position  to  an  ortho-para  direc- 
tive substituent  follows  immediately  from 
the  above  considerations,  inasmuch  as 
(Fig.  1,  a),  there  is  a  reinforcing  negative 
influence  on  the  polarity  of  the  4-carbon 
atom. 

Entry  of  Positive  Groups. 

It  is  well  known  that  most  of  the  radicles 
which  can  be  introduced  directly  (i.e., 
without  the  action  of  catalysts),  into  the 
benzene  nucleus  are  positive  (octet  un- 
stable). This  follows  at  once  from  the  pre- 
ceding considerations.  We  have  computed 
the  number  of  electrons  present  in  the 
typical  positive  radicles,  COOH,  SO3H. 
and  NO2,  with  the  following  results:  (1) 
COOH,  charge  +  1,  has  sixteen  electrons 
available  for  the  formation  of  octets ;  adopt- 
ing the  Hantzsch-Lapworth  structure  for 
carboxyl,  it  is  found  that  the  carbon  atom 
contains  only    six  electrons  in  the    sheath, 

thus :  C   i  :J  H.       If  the    group    replace    a 

hydrogen  nucleus,  the  carboxyl  carbon  can 
readily  complete  its  octet  by  sharing  with 
the  negative  (octet  stable)  carbon  atom  in 
the  nucleus,  the  octet  of  this  atom  being 
left  complete  by  the  removal  of  the  hydro- 
gen nucleus.     (2)   SO3H.     In  sulphonation 


H„SO^  reacts  as  OH-  and  SO3H+ ;  on  this 
basis,  the  SO3H  radicle  contains  twenty- 
four  electrons  available  for  octet  formation. 


This  leads  to  the  structure  H  :  O  :  S 


;-o: 


o: 


in  which  the  sulphur  atom  contains  only 
six  electrons  in  the  sheath.  (3)  NOg.  In 
nitration,  HNO3  reacts  as  OH-  and  NO2; 
on  this  basis  the  number  of  electrons  in  the 
NO2  radicle  available  for  octet  formation  is 

eighteen;  this  leads  to  the  structure '^s  '  •' 

•'  6. 

in  which  the  unstable  centre,  N,  again  con- 
tains six  electrons  in  the  sheath.  Similar 
arguments  regarding  the  replacement  of 
hydrogen  apiply  to  cases  (2)  and  (3)  as  hold 
in  (1). 

It  is  clear  that  a  negative  (octet  stable) 
substituent  will  not  possess  an  electron 
content  able  to  give  the  easy  attainment  of 
octet  formation  such  as  is  possible  in  the 
cases  cited  above  for  positive  substituents, 
and  hence  we  should  not  expect  the  nega- 
tive class  to  be  so  readily  susceptible  to 
direct  introduction  into  the  nucleus. 

It  is  possible  that  we  have  here  an  under- 
lying reason  for  the  greater  stability  of 
compounds  of  the  type  (b)  (see  Fig.  1)  than 
those  of  type  (a)  (Cf.  Vorlander,  loc.  cit.). 

The  Holleman  Series. 

The  relation  between  octet  stability  and 
directive  influence  can  now  be  discussed. 
Consider  a  typical  case  of  a  di-substituted 
derivative,  CgH^XY,  where  the  octet  stabil- 
ity of  X  is  greater  than  that  of  Y. 


(."t) 


if 


Fig.  2. 


It  follows  from  the  relative  stabilities  of 
the  octets  of  X  and  Y  that  the  polarities  of 
the  carbon  atoms  should  be  as  illustrated 
in  Fig.    2  (a)    rather    than    that    shown  in 


APRIL  20,  1923. 


THE  CHEMICAL  NEWS. 


245 


2  (b).  Generalising,  it  can  be  stated  that 
the  relative  directive  power  of  substituents 
follows  a  descending  order  of  octet  staoil- 
ity,  and  this  seems  to  us  to  be  the  real  i:ii- 
plication  of  the  Holleman  series. 

Holleman  (Pie  direhte  Kinfuhrung  von 
Substituenten  in  den  Benzolkem,  1910, 
466-469)  points  out  that  the  directive  ten- 
dencies of  the  commoner  substituents  fol- 
low the  descending  order:  OH,  NH,.  CI.  1, 
Br,  CH,,  COOH,  SO3H,  NO,.  The  t€a- 
dency  to  octet  stability  doubtless  follows 
the  descending  order :  0>N>-C  (c/. 
Briggs,  Phil.  Mag.,  1921,  vi.,  XLIL.  449- 
450);  this  accounts  for  the  position  of  OH, 
NH2,  CH3,  it  being  remembered  that  the 
kernel  octets  are  attached  to  positive  hydro- 
gen nuclei.  The  greater  volumes  of  CI.  Br, 
I,  agree  with  their  comparatively  low  place 
in  the  series,  increase  in  electropositiveness 
with  increase  in  volume  being  a  well  estab- 
lished tendency  which  is  readily  interpreted 
electrically.*  One  would  expect  fluorine 
to  bo  above  hydroxyl  in  the  series  (see 
below).  That  all  ortho-para  directive  sub- 
stituents precede  the  mcta  follows  from 
Postulate  2.  Considering  the  meta-direc- 
tivo  substituents  among  thenoaelves,  it  is 
evident  that  electrons  are  more  easily 
drawn  from  the  labile  carbon  atom  than 
from  the  more  electropositive  sulphur.  The 
larger  volume  of  sulphur  as  compared  with 
nitrogen  agrees  with  its  high  position,  the 
effect    of     electropositiveness    being     here 


opposite  to    that  obtaining    in    the    ortho- 
para  directive  series. 

All  possible  cases  of  the  entry  of  the 
third  groujp  into  a  disubstituted  derivative 
will  now  be  considered. 

In  the  disubstituted  compounds  repre- 
sented above,  X^  and  Xj  are  ortho-para 
directive  (octet  stable)  substituents;  Y, 
and  Yj  are  meta  directive  (octet  unstable) 
substituents. 

Case  1 :  Fig.  3,  i.  The  induced  polari- 
ties of  the  carbon  atoms  is  as  shown  in  (a) 
and  (b),  according  as  the  influence  of  X,  or 
Xj  predominates.  Since  the  inductive 
effects  are  opposed,  t^ere  will  be  an  equili- 
brium between  the  two  electromers,  as  in- 
dicated above. 

{To  be  Continued.) 


*  The  position  of  iodine  relative  to  chlor- 
ine and  bromine  offers  a  curious  anomaly. 
Owing  to  the  differences  of  opinion  existing 
with  reaard  to  the  arrangement  of  electrons 
in  the  heavier  atoms  {Bohr,  Nature,  1921, 
CVII.,  104;  Bury,  J.A.C.8.,  1921,  XLIIl., 
1602),  we  have  not  attempted  to  account 
for  it. 


f     ♦J^, 


A 


-77 


<-7 


% 


V 


X 


Fig.  3. 


246 


THE  CHEMICAL  NEWS. 


APEIL  20,  1923. 


INTERVIEW  WITH  COMMERCIAL 

SECRETARY  ON  TRADE  WITH 

POLAND. 

Mr.  R.  E.  Kimens,  C.M.G.,  Commercial 
Secretary  to  His  Majesty's  Legation  at 
Warsaw  will  be  in  attendance  at  the  De- 
partment of  Overseas  Trade  for  one  week, 
commencing  on  April  18.  During  that 
period  he  is  prepared  to  interview  by  ap- 
pointment United  Kingdom  manufacturers 
and  merchants  interested  in  trade  with 
Poland. 

Application  for  interviews  with  Mr. 
Kimens  should  be  addressed  without  delay 
to  the  Comptroller-General,  Department  of 
Overseas  Trade,  35,  Old  Queen  Street, 
London,  S.W.I.  The  reference,  4672  T.G., 
should  be  quoted  in  all  applications. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


ROYAL  SOCIETY  OF  ARTS. 

On  Monday,  April  16,  the  second  Cantor 
Lecture  on  Nitrates  from  Air  was  delivered 
by  E.  KiLBURN  Scott,  M.I.E.E.,  A.M.- 
Inst.C.E. 

On  Wednesday,  April  18,  at  the  Ordinary 
Meeting,  Mr.  Hal  Williams,  M.I.Mech.E., 
M.I.E.E.,  M.I.Struct.E.,  gave  a  lecture 
on  Modern  Abattoir  Practice  and  Methods 
of  Slaughtering.  W.  Phen^  Neal,  Alder- 
man of  the  City  of  London,  late  Chairman 
of  the  Cattle  Markets  Committee  of  the 
Corporation,  presided. 

On  Friday,  April  20,  at  4.30  p.m.,  there 
will  be  a  joint  meeting  of  Dominions  and 
Colonies  and  Indian  Sections.  A  Review 
of  the  Base  Metal  Industry,  with  Special 
Reference  to  the  Resources  of  the  British 
Empire,  will  be  given  by  Sir  Richard  A. 
S.  Redmayne,  K.C.B.,  M.Sc,  M.Ikst.- 
C.E.,   M.I.Mech.E.,   F.G.S. 

The  Rt.  Hon.  Lord  Emmott,  G.C.M.G., 
G.B.E.,  will  preside. 


THE  GEOLOGICAL  SOCIETY  OF 
LONDON. 

The  following  communication  was  read 
on  March  28,  Further  Researches  on  the 
Succession  and  Metamorphism,  in  the  Mona 
Complex,  by  Edward  Greenly,  D.Sc, 
F.G.S. ,  Dr.  Herbert  H.  Thomas,  M.A., 
Vice-President,  in  the  chair. 


At  the  meeting  held  on  Wednesday, 
Ajpril  18,  the  following  communication  was 
read:  The  Structure  of  the  Bowmore-Por- 
taskaig  District  of  Islay,  by  John  Frederick 
Norman  Green,  B.A.,  F.G.S. 

At  the  meeting  to  be  held  on  May  2, 
Prof.  J.  Joly,  D.Sc,  F.R.S.,  F.G.S.,  will 
deliver  a  lecture  on  The  Bearing  of  some 
Recent  Advances  in  Physical  Science  upon 
Geology. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 
At  the  Ordinary  Meeting  in  the  Lecture 
Theatre  of  the  Institution,  Savoy  Place, 
Victoria  Embankment,  W.C.2,  on  Thurs- 
day, April  20,  1923,  a  paper  on  The  Drive 
of  Power  Station  Auxiliaries  was  presented 
by  L.  Breach,  Member,  and  H.  Midgley, 
Associate  Member. 


THE  FARADAY  SOCIETY. 
At  a  general  discussion  on  Alloys  Resis- 
tant to  Corrosion,  held  jointly  at  Sheffield 
by  the  Faraday  Society,  the  Sheffield  Sec- 
tion of  the  Institute  of  Metals,  and  the 
Manchester  Metallurgical  Society,  on  April 
13,  the  following  papers  were  read:  — 

Heat  and  Acid  Resisting  Alloys,  by  J. 
Ferdinand  Kayser,  Assoc.  Met. 

A  short  account  was  given  of  the  "  heat 
and  acid  resisting  "  properties  of  nickel- 
chromium  and  nickel-chromium-iron  alloys. 
Most  of  the  literature  dealing  with  this 
type  of  alloy  has  been  of  a  commercial 
nature,  and  has  contained  grossly  exagger- 
ated claims  concerning  the  high  M.P.,  re- 
sistance to  furnace  gases,  etc.  Scientific 
literature  on  the  subject  is  somewhat 
scanty. 

The  first  alloys  made  in  this  country 
were  binary  alloys  consisting  of  two  parts 
nickel  to  one  part  of  chromium.  Although 
the  addition  of  chromium  to  nickel  lowers 
the  melting-point  until  the  percentage  ex- 
ceeds 58,  alloys  containing  more  than  about 
50  per  cent,  of  chromium  are  almost  impos- 
sible to  cast  on  account  of  their  extreme 
viscosity.  There  is  nothing  to  be  gained  by 
the  use  of  an  alloy  containing  more  than  35 
per  cent,  of  chromium.  Furnace-parts, 
case-hardening  boxes,  etc.,  if  made  from  a 
binary  alloy,  usually  contain  from  25  to  35 
per  cent.  The  alloys  with  lower  percent- 
ages   are    used  for   resistance  wire.       Pure 


d 


APRIL  20,  1923. 


THE  CHEMICAL  NEWS 


24? 


nickel  wire  was  formerly  used  for  that  pur- 
pose, but  was  far  from  satisfactory  on 
account  of  its  tendency  to  become  brittle  if 
used  at  temperatures  above  about  700''  C. 
Addition  of  10  per  cent,  of  chromium  com- 
pletely prevents  this,  and  nickel-chromium 
wire  can  be  used  at  1,000-1. 050**  C.  with- 
out any  appearance  of  brittleness. 

The  hardness  of  the  alloys  increases  with 
increasing  chromium,  but  before  the  alloys 
become  so  hard  as  to  be  useful  for  making  a 
cutting  tool,  they  become  very  brittle  and 
break  under  the  Brinell  ball  before  showing 
a  hardness  higher  than  about  400. 

The  high  cost  of  metallic  chromium  (ap- 
proximately 58.  per  lb.)  soon  led  to  the 
chromium  being  introduced  as  ferro-chro- 
mium.  All  alloys  containing  not  less  than 
10  per  cent,  chromium  together  with  not 
more  than  about  28  to  30  per  cent,  iron  are 
equally  resistant  to  oxidation,  and  the  per- 
missible percentage  of  iron  depends  upon 
the  magnitude  of  the  stress  they  will  be 
called  upon  to  withstand. 

Besides  iron,  nickel,  and  chromium  there 
are  frequently  considerable  percentages  of 
other  elements  present,  the  most  important 
being  carbon,  silicon,  aluminium,  mangan- 
ese, and  copper. 

Silicon  is  often  added  t-o  nickel-chromium 
alloys,  and  iip  to  2  per  cent,  the  physicnl 
properties  do  not  appear  to  be  much 
affected,  but  elaborate  investigations  con 
ceming  that  point  have  not  been  made. 
The  addition  of  5  per  cent,  of  silicon  and  up- 
wards gives  an  intensely  brittle  and  hard 
alloy.  Such  a  high  silicon  also  materially 
reduces  the  resistance  of  the  alloys  to  the 
action  of  sulphur  dioxide. 

Nickel  and  aluminium  form  an  inter- 
metallic  compound  NiAl,  characterised  by 
a  very  great  heat  of  formntion  and  a  melt- 
ing-point higher  than  1.700"  C,  i.e.,  about 
300°  C.  higher  than  the  meltink-point  of  its 
most  difficultly  fusible  constituent.  When 
aluminium  is  added  to  a  molten  bath  rff  a 
nickel-chromium,  or  nickel-chromium  iron 
alloy,  there  is  a  violent  endothermic  re- 
action and  a  precipitate  is  formed.  It  may 
seem  hard  to  detect  a  precipitate  in  an 
opaque  liquid,  but  this  is  not  difficult.  The 
examination  of  microsections  of  samples 
quenched  out  in  water  from  the  molten 
state  showed  the  presence  of  crystals  of 
such  a  size  and  shape  that  they  couFd  not 
have  formed  in  the  solid  state,  and  must 
have  been  present  in  the  liquid. 

Corrosion  Resisting  Properties.— K\cko\- 
chromium  alloys    offer  a  perfect  resistance 


to  the  corrosive  action  of  the  atmosiphere  in 
presence  of  hard,  soft  or  sea  water.  Stain- 
less steel  should  be  con-ectly  heat-treated 
and  free  from  surface  scale  or  pit  marks. 
No  heat-treatment  is  necessary  in  the  case 
of  nickel-chromium  alloys.  Name  plates 
have  been  cast  with  the  lettering  in  relief 
and  exposed  to  atmospheric  action  after 
first  sand  blasting  all  over  and  then  grind- 
ing the  lettering  cMily,  and  after  several 
years  aiv  quite  free  from  corrosion.  In 
towns  such  name  plates  become  covered 
with  a  greenish  deposit,  but  this  is  identical 
with  that  found  on  window  panes,  etc.,  and 
can  be  removed  as  easily. 

Samples  to  be  tested  were  all  weighed 
and  mea.sured  beforehand.  Samples  of 
each  alloy  were  in  every  case  tested  at  room 
temperature  and  100"  C.  The  duration  of 
the  tests  was  varied  fw  different  rates  of  at- 
tack. When  necessary,  the  samples  were 
weighed  both  before  and  after  the  test,  and 
from  the  loss  of  weight  the  rate  of  loss  in 
grams  per  sq.  metre  per  hour  was  calcu- 
lated. 

The  alloys  were  all  readily  soluble  in 
aqua  regia,  hydrochloric  acid,  and  sulphuric 
acid,  but  not  soluble  in  nitric  acid. 

Other  acids  tried  were  20,  30  and  50  per 
cent,  acetic,  30  per  cent,  citric,  sulphurous, 
monochloracetic,  and  75  per  cent.  pBoe- 
phorio. 
Monel  Metal,  by  John  Arnott,  A.I.C. 
Monel  metal  may  be  said  to  be  primarily 
an  engineering  material  with  excellent  phy- 
sical properties  and  good  resistance  to 
many  corrosive  agencies.  Its  sphere  of  use 
is  therefore  diff(^ront  frcwn  that  of  the  truly 
acid-resisting  metals,  such  as  the  iron- 
silicon  alloys,  which  have  to  be  employed 
in  certain  cases  in  spite  of  their  poor 
mechanical  properties. 

Its  composition  and  physical  properties 
are  fairly  well  known.  Cold-rolled  and  cold- 
drawn  metal  are  now  used  to  quite  a  con- 
siderable extent. 

An  important  property  is  its  retention  of 
strength  and  ductility  at  temperatures 
above  normal. 

At  750*  F.,  the  highest  steam  tempera- 
ture in  use  in  this  country,  money  metal 
retains  85  per  cent,  of  its  strength. 

Monel  metal  is  very  little  affected  by  ex- 
posure to  fairly  pure  air.  A  sheet  freely  ex- 
posed to  the  elements  at  Cathcart  was 
bright  after  five  mcmths  and  showed  no 
change  in  weight.  In  air  which  is  most  im- 
pure, it  becomes  discoloured,  but  the  attack 
does  not  extend    beyond  the  surface  layers. 


248 


THE  CHEMICAL  NEWS. 


APEIL  20,  1923. 


It  is  unaffected  by  wet,  saturated  or 
superheated  steam.  Sea  water  does  not 
affect  it. 

Monel  metal  usually  is  not  suitable  for 
use  with  strong  acids,  as  in  acid  manufac- 
ture. It  is  readily  soluble  in  concentrated 
nitric  acid,  and  is  attacked  by  strong  hydro- 
chloric and  sulphuric  acids,  especially  if 
they  are  impure.  Sulphurous  acid,  even 
when  very  dilute,  attacked  monel  meta! 
violently,  leaving  a  deposit,  largely  consist- 
ing of  sulphide. 

Monel  metal  is  not  affected  by  alkalie? 
and  only  to  a  slight  extent  by  the  majority 
of  solutions  of  neutral  salts  at  ordinary  tem- 
peratures. 

Monel  metal  is  thus  suitable  for  parts 
which  have  to  resist  (1)  sea  water,  (2)  im- 
pure water  such  as  is  found  in  many  canals 
and  in  mines,  (3)  steam,  (4)  dilute  acid 
solutions  such  as  are  used  in  many  indus- 
trial operations,  (5)  alkaline  solutions  of  all 
kinds. 

The  Mechanism    of  the    so-called    "Dry 
Corrosion"  of  Metals,  by  Ulick  R.  Evans. 
Experiments  on    the  behaviour    of    "ap- 
parently    dry"     metals,      roughened     with 
emery,  show  that  no  corrosion  occurs  when 
they  are  kept  over  sulphuric  acid,  and  only 
slow,  sujperficial    corrosion    when  they    are 
kept    over    water.      The  rate    of    attack    is 
greatly  increased  by  the  presence  of  volatile 
electrolytes  in  the  air,  sulphur  dioxide  being 
most  dangerous  to  iron  and  nickel,  ammo- 
nia to  copper  and  its  alloys,    and  hydroggn 
chloride  to  zinc  and  aluminium;    hydrogen 
sulphide  and  carbon  dioxide    somewhat  in- 
crease the  rate  of  rusting  of  iron,    but  pro- 
duce   only    superficial     changes    on    other 
metals.     Contrary    to  popular    belief,    the 
corrosion    of  iron  is  not  caused    by  the  pre- 
sence of  ammonia.     Corrosion  of  metals  by 
volatile  electrolytes  appears  to  require  the 
presence  of  some  moisture,  but  proceeds  in 
air  which  is  distinctly  unsaturated.    Special 
phenomena  occur  at  the  contact  of  dissimi- 
lar metals,     apparent  electrochemical    pro- 
tection being  observed  in  some  cases. 

The  phenomena  are  best  explained  if  we 
consider  that  electrochemical  action  occurs 
in  the  adherent  (usually  invisible)  film  of 
moisture.  Volatile  electrolytes  increase  the 
condiwtivity  of  the  film  and  thus  accelerate 
corrosion.  Where  they  tend  to  produce 
hygroscopic  corrosion-products,  they  bring 
about  the  absorption  of  further  moisture 
and  thus  increase  the  thickness  of  the  film; 
in  several  cases  (zinc  in  hydrogen  chloride, 
copper    in  ammonia,    nickel  in  sulphur    di- 


oxide) the  metal,  originally  dry,  soon  begins 
to  shed  liquid  copiously,  and  in  such  cases 
corrosion  is  very  serious. 

The  Resistance  to  Corrosion  of  Stainless 
Steel  and  Iron,  by  J.  H.  G.  Monypenny, 
Chief  of  the  Research  Laboratory,  Brown 
Bayley's  Steel  W^orks,  Ltd.,  Sheffield. 

To  the  almost  exclusive  use  of  stainless 
material  for  cutlery  purposes  over  a  con- 
siderable period  may  be  ascribed  the 
opinion  that  stainless  steel  has  a  definite 
composition  and  a  small  range  of  mechani- 
cal properties.  There  is,  however,  a  whole 
range  of  steels  in  which  the  main  variable 
is  carbon,  precisely  in  the  same  manner  as 
this  element  is  the  prime  factor  in  produc- 
ing hard  and  soft  steels.  In  addition  to  this 
the  presence  in  varying  amounts  (either 
through  accident  or  design)  of  other  ele- 
ments such  as  silicon,  manganese,  or  nickel 
may  have  appreciable  effects.  Variations  in 
one  or  more  of  these  elements  inay  have 
quite  apprc'ciable  effects  on  the  resistance 
to  corrosion  of  the  stainless  material. 

In  addition  to  differences  in  chemical 
composition,  the  properties  of  the  material 
may  be  profoundly  modified  by  varying 
forms  of  heat  treatment,  and  such  varia- 
tions have  pronounced  effects  on  the  degree 
of  resistance  to  corrosion. 

Heat  treatment — hardening,  tempering 
and  annealing — all  influence  the  final  pro- 
ducts in  various  ways. 

A  study  has  been  made  of  the  resistance 
of  stainless  material  to  various  corroding 
agents. 

Tap  water  is  without  action  on  stainless 
steel,  either  hardened,  or  hardened  and 
tem^pered.  The  author  has  had  a  number 
of  small  samples  turned  from  a  hardened 
and  tempered  bar  over  which  tap  water  had 
been  allowed  to  trickle  for  over  twelve 
months,  and  there  is  not  the  slightest  signs 
of  attack.  These  samples  are  contained  in 
a  wide  glass  tube  attached  to  a  water  tap, 
the  latter  being  opened  slightly,  thus  allow- 
ing water  to  trickle  over  the  samples. 

Samples  of  stainless  steel  and  iron  in  the 
hardened  and  tempered  condition  were 
partly  embedded  in  a  block  of  wood  and  the 
latter  then  fixed  to  a  jetty  at  a  point  be- 
tween high  and  low  water  marks.  The 
samples  were  thus  alternately  wet  and  dry. 
Ater  six  months  they  were  quite  bright  and 
practically  unattacked,  there  being  only  a 
few  minute  pits. 

River  and  well  waters  have  in  general  no 
appreciable  action  on  stainless  material. 
This  is  shown  by  the  large  number  of  pump 


APRIL  20,  1923. 


THE  CHEMICAL  NEWS. 


24§ 


rods  and  otht-r  fittings  which  are  in  success- 
ful use  in  many  parts  of  the  country  for 
pumping  such  water. 

Ammonia,  alkalies  and  alkaline  carbon- 
ates in  all  strengths  of  solution  appear  Co 
have  no  effect  on  stainless  material. 

It  may  be  doubted  whether  the  results  of 
experiments  in  which  samples  of  stainless 
steel  (or  any  other  metal)  are  placed  or  sus- 
pended in  beakers  containing  solutions  of 
various  salts  are  of  any  great  practical 
value.  The  results  obtained  simply  refer  to 
the  conditions  under  which  the  test  was 
carried  out,  and  will  vary  as  these  condi- 
tions vary.  With  stainless  material,  when 
corrosion  does  take  place,  it  almost  invari- 
ably starts  at  the  point  of  support,  and 
often  is  entirely  confined  to  that  point.  In 
such  cases,  therefore,  the  amount  of  corrf>- 
sion,  or  even  the  presence  or  absence  of  cor- 
rosion, will  depend  on  how  the  sample  is 
supported.  It  is  not  intended,  therefore,  to 
give  a  list  of  how  stainless  samples  behaved 
when  immersed  in  various  solutiMis.  Speak- 
ing generally,  it  may  be  said  that  many 
such  solutions  have  little  or  no  effect  cm 
stainless  material,  and  where  corroeion  dots 
take  place  it  proceeds  much  slower  than 
with  ordinary  steel. 

The  results  with  solutions  of  a  few  salts, 
however,  are  of  some  interest. 

Ammonium  chloride  solutiMis  are  well 
known  as  corroding  agents.  They  have  a 
staining  and  pitting  action  on  stainless 
material  the  e.xtent  of  which,  however,  de- 
pends on  the  concentration  of  the  solution. 
With  dilute  solutions  the  attack  is  very 
slow,  oven  when  hot. 

Ferric  chloride  solutions  attack  the  steel 
even  when  fairly  dilute  (e.g.,  1  per  cent.). 

Copper  chloride  solutions  also  attack  the 
steel.  With  strong  solutions  a  deposit  of 
copper  is  formed,  and  the  steel  is  eaten 
away  fairly  rapidly.  With  dilute  solutions, 
on  the  other  hand,  pitting  take»  place  and 
very  little  copper  is  deposit<'d. 

Copper  sulphate,  nitrate,  and  acetate 
solutions,  on  the  other  hand,  have  no  action 
on  the  steel.  The  presence  of  copper  sul- 
phate also  appears  to  retard  greatly,  and  in 
some  cases  to  prevent  the  attack  of  dilute 
sulphuric  acid  on  stainless  material. 

Hydrochloric  and  sulphuric  acids  attack 
stainless  steel  or  iron  rapidly.  The  action 
of  these  acids  on  high  chromium  steels  has 
been  known  for  a  considerable  time,  and 
hence  it  is  not  necessary  to  devote  further 
attention  to  them.  Sulphurous  acid  also 
attacks  stainless  material,  probably  to  some 


extent  owing  to  the  presence  in  it  of  sul- 
phuric acid. 

Nitric  Acid.  —  The  attack  of  nitric  acid 
present  several  interesting  features.  Very 
dilute  solutions  attack  stainless  material 
slowly,  the  rate  of  attack  decreasing  with 
increasing  content  of  chromium,  and  with 
decreasing  carbon  content.  The  stronger 
acids  used  in  analytical  work  (e.g.,  S.G. 
1.20  and  1.42)  are  practically  without  action 
on  the  steel.  This  fact  aippears  to  be  fairly 
known,  and  since  acids  of  S.G.  1.20  attacks 
ordinary  steel  very  rapidly  this  reagent  is 
useful  should  stainless  material  be  accident- 
ally mi.xed  up  with  ordinary  steel.  With 
prolonged  attack  (e.g.,  lasting  a  month  or 
six  weeks)  of  acids  of  these  strengths,  the 
surface  of  the  steel  is  coloured  a  purplish 
tint  but  there  is  no  appreciable  alteration 
in  weight.  The  colour  thus  produced  bears 
some  rtsomblance  to  a  **  temper  colour," 
and  is  probably  of  a  similar  type  to  the  lat- 
ter. If  a  polished  microsection  be  treated 
in  this  way,  it  is  found  that  the  background 
is  coloured  while  the  carbide  remains  bril- 
liantly white. 

With  a  typical  stainless  steel  containing 
0.82  per  cent,  carbon  and  12.2  per  cent, 
chromium  the  maximum  attack  with  dilute 
acids  (at  atmospheric  temperatures)  oc- 
curod  at  about  normal  strength. 


ROYAL  INSTITUTION  OF  GREAT 

BRITAIN. 
The  Friday  evening  discourse  on  April 
20,  at  9  o'clock,  will  be  delivered  by  W.  J. 
S.  LocKYKR,  M.A.,  F.R.A.S.,  Director, 
Norman  Lockyer  Observatory.  The  subject 
is  The  Qrowth  of  the  Telescope. 

On  Tuesday,  April  17,  Sir  Arthur  Keith, 
M.D.,  LL.D.,  F.K.S.,  Sec.  R.I.,  Fullerian 
Prof,  of  Physiology,  gave  a  lecture  on  The 
Machinery  of  Human  Evolution :  How  Old 
Structures  are  Lost. 

On  Thursdav.  April  19,  Prof.  A.  O.  Ran- 
KiNE,  O.B.E.,  D.Sc,  lectured  on  Transmis- 
sion of  Speech  by  Light.     (Lecture  II.). 

At  a  General  Meeting  of  the  members  of 
the  Royal  Institution,  held  on  the  9th  inst., 
the  Duke  of  Northumberland  (President), 
in  the  chair,  a  resolution  of  condolence 
with  Lady  Dewar  on  the  death  of  Sir  James 
Dewar  was  moved  by  the  President  and 
carried  unanimously. 


250 


THE  CHEMICAL  NEWS. 


APBIL  20,  1923. 


Mr.  Arrol  Moir,  Professor  A.  O.  Kan- 
kine,  Lady  Wallace,  and  Miss  Williamson 
were  elected  members. 


SOCIETY    OF    GLASS    TECHNOLOGY. 

The  Sixth  Annual  General  Meeting  of 
the  Society  was  held  in  Sheffield,  on  Wed- 
nesday, April  18,  1923. 

After  other  business,  the  Presidential 
address,  entitled.  The  Year  in  Review  in  the 
World  of  Glassmahing,  was  delivered. 

Afterwards  a  general  discussion  on  Works 
Organisation,  opened  by  a  paper  entitled 
Organising  for  Production  from  Pot  Fur- 
naces, by  W.  W.  Warren,  A.M.I.C.E., 
A.M.I.E.E.  Other  speakers  presented  the 
case  for  Tank  Furnace  Works. 

Fifth  Annual  Dinner. 

The  attention  of  members  is  directed  to 
the  fact  that  the  Fifth  Annual  Dinner  of 
the  Society  will  be  held  this  year  in  Lon- 
don, following  the  meeting  on  May  16. 

Members  are  requested  to  keep  this  date 
open  so  that  a  good  attendance  may  be 
assured.  Full  particulars  will  be  announced 
later. 


THE  CHEMICAL  SOCIETY. 

At  the  Ordinary  Scientific  Meeting,  on 
Thursday,  April  19,  the  following  papers 
were  read  :  — 

The  Influence  of  Nitro-groups  on  the  Re- 
activity of  Suhsfituents  in  the  Benzene 
Nucleus.  Part  VII.  Reactions  of  2:5-  and 
4  ■.5-dinitro-m-xylenes,  by  K.  Ibbotson  nnd 
J.  Kenner. 

The  Chemistry  of  the  Three-carhon  Sys 
tern.     PaH  I.  The  Influence    of  the    Cyclo- 
hexane  ring  on  the  af^-fSy  Change,    by  S.  F. 
Birch,  G.  A.  K.  Kon,  and    W.    S.    G.    P. 
Norris. 

On  the  promotion  of  Catalytic  Reactions. 
Part  I.,  by  S.  Medsforth. 


PHYSICS  AND  SEWAGE  DISPOSAL. 
At  a  meeting  of  the  Birmingham  and 
Midland  Section  of  the  Society  of  Chemical 
Industry,  on  Tuesday,  April  10,  this  sub- 
ject was  discussed  in  an  important  paiper  by 
Mr.  F.  E.  O'Shaughnessy,  A.E.C.Sc, 
F.I.C.,  Consulting  Chemist  to  the  Birming- 
ham, Tame  and  Rea  District  Drainage 
Board. 

The  paper  was  a  thesis  dealing  with  the 
physical  properties  of  the  principal  compo- 


nents of  normal  sewage  (i.e.,  of  the  water 
on  the  one  hand  and  the  usual  polluting 
bodies  on  the  other)  as  affecting  those 
operations  preliminary  to  disposal,  com- 
prised under  the  heading  of  "  Treatment," 
which  are  of  a  preparatory  character  and 
for  the  purpose  of  facilitating  disposal. 

To  this  end  the  pubHshed  work  of  a  num- 
ber of  leading  experts  is  critically  reviewed 
in  support  of  the  views  advanced  by  the 
author. 

A    clear    distinction    is     made    between 

Treatment  "  and   "  Disposal." 

Emphasis  is  laid  on  a  statement  of 
Fowler's,  viz. :  "  The  subject  of  sewage  dis- 
posal is  mainly  a  question  of  the  separation 
of  solids  from  liquids." 

This  separation  has  been  difficult  because 
of  the  physical  character  of  much  of  the 
solid  matter  present  in  sewage,  viz. :  its 
colloidal  or  gummy  character,  which  causes 
it  to  adhere  tenaciously  to  water. 

The  author  refers  to  his  own  published 
results,  showing:  — 

That  faecal  solids  pass  into  colloidal  solu- 
tion in  water  by  agitation  to  200-250  parts 
per  100,000; 

That  this  is  the  chief  source  of  colloidal 
solids  in  normal  sewage ; 

That  the  amount  varies  in  different 
sewages. 

The  effect  of  various  methods  of  treat- 
ment of  sewage  are  discussed :  Simple  sedi- 
mentation, chemical  precipitation,  biologi- 
cal action  (anaerobic  and  aerohic).  It  is 
shown  that  whereas  the  visible  suspended 
solids  in  sewa^ge  are  for  the  most  part  read- 
ily separated,  the  bulk  of  the  colloidal 
solids  are  held  very  tenaciously  by  the 
water  of  the  sewage. 

The  colloidal  solids  are  very  partially 
thrown  down  by  simple  sedimentation. 
Chemical  precipitation  effects  only  partial 
removal  even  when  large  amount  of  chemi- 
cals are  added,  and  when  in  moderate 
amount  improves  the  liquor  for  the  bacteria 
bed.  Anaerobic  action,  whilst  removing  col- 
loids, makes  the  liquor  very  offensive ;  aerobic 
treatment  is  the  only  means  of  precipitat- 
ing colloidal  solids  whilst  leaving  the  liquid 
in  a  satisfactory  condition. 

It  is  known  that  as  aeration  is  effective 
and  complete  so  the  rate  of  removal  of  these 
troublesome  solids  is  also  effective. 

That  considerations  of  this  character  and 
the  observed  suddenness  with  which  they 
are  brought  down  in  the  top  of  a  percolation 
bed    suggest    that,     given    an    appropriate 


APRIL  20,  1923. 


tTHE  CHEMICAL  NEWS 


251 


agent,  their  removal  should  be  easy  and 
rapid. 

The  remarkable  work  of  F.  Wallis  Stod- 
dart,  F.I.C.,  F.C.S.,  is  reviewed,  which  in- 
dicated that  given  a  limpid  sewage  liquid 
which  had  been  freed  from  colloidal  solids 
by  appropriate  means,  the  quantity  of 
liquid  which  could  be  put  through  a  suit- 
able percolation  bacteria  bed  might  be  im- 
mensely increased,  even  to  10  or  20  million 
gallons  per  acre.  The  authw  then  indi- 
cates that  the  technique  provided  by 
Messrs.  Ardern  and  Lockett  in  the  acti- 
vated sludge  process  has  furnished  the  key 
to  the  solution  of  this  problem.  That  a 
modified  use  of  this  technique  which  for 
purposes  of  distinction  the  author  proposed 
to  call  the  flocculated  sludge  process,  is  the 
appropriate  means  of  dealing  with  collMdal 
matter  in  solution. 

In  regard  to  the  activated  sludge  proposi- 
tion, the  merits  and  demerits  are  discussed. 
Advantages  are :  Completicm  of  sewage 
ipurificatioo  in  one  tank  in  one  operation ; 
elimination  of  nuisance,  reduction  of  area, 
and  production  of  valuable  ertiliser. 

The  objects  are :  Existing  works  dis- 
carded ;  sludge  problem  more  complex ;  eco- 
nomical recovery  of  sludge  problematical ; 
extravagant,  i.e.,  prolonged  aeration,  high 
oxygen  demand  by  sludge,  alteraticai  of  phy- 
sical character  of  sludge,  etc. ;  slow  rate  of 
solution  of  oxygen  in  water  the  central  phy- 
sical fact  here;  in  many  cases  protection  re- 
quired Cor  aeration,  ihe  iprooedure  in  this 
process  is  arbitrary,  its  objective  largely 
Cf>mmercial  (conserving  manurial  elements) 
and  must  stand  or  fall  on  finaoeial  merits. 

As  to  flocculated  sludge  process  (a  modi- 
fication of  the  activated  sludge  process), 
three  operations  are  involved :  Agitation  of 
sewage  and  flocculated  sludge  with  air  for  a 
time  to  bring  about  clarificatioQ  of  the  sew- 
age and  partial  purification  of  the  liquor; 
seiparation  of  sludge  from  treated  sewage, 
and  re-aeration  of  separated  sludge. 

This  mode  of  procedure  may  be  applied 
to  the  whole  sewage  (less  grit,  etc.)  as  in 
the  activated  sludge  process  or  after  any 
desired  degree  of  preliminary  sedimenta- 
tion. The  advantages  are  :  A  wide  choice 
of  procedure  is  available,  for  the  procoss 
may  be  incorporated  with  existing  iplant; 
greatly  increased  volumes  of  liqiiid  may  be 
put  on  bacteria  beds ;  nuisance  (odour  and 
flies)  may  be  eliminated;  and  the  expensive 
teration  period  may  be  reduced  to  reason- 
able proportions. 

The  theory  of  flocculated  sludge  process 
is  next  discussed.       Evidence  is  given  that 


the  purification  of  sewage  is  effected  by  two 
distinct  meanjs :  By  (physical  agents  which 
bring  about  flocculation  of  colloidal  solids ; 
and  by  biological  agents  which  bring  about 
oxidation  of  the  dissolved  impurities.  In 
the  activated  sludge  technique  the  real  floc- 
culating agent  is  the  sludge.  Evidence  is 
given  that  the  condition  of  the  sludge  is 
much  more  important  than  its  quantity, 
and  that  with  the  procedure  advocated  in 
the  flocculated  sludge  process  very  remark- 
able and  rapid  purification  may  be  obtained 
with  greatly  reduced  volume  of  sludge. 
Thus  the  flocculated  sludge  is  apparently 
the  vehicle  for  the  transference  of  energy. 
By  eliminating  easily  seiparable  material 
from  the  sewage  the  oxygen  demand  of  un- 
profitable or  useless  elements  is  reduced 
and  consequently  the  efficiency  of  the 
action  very  greatly  increased. 

The  whole  question  of  sludge  treatment 
is  presented  thus:  — 

The  bulk  of  the  solids  may  be  separated 
from  the  bulk  of  liquid  in  the  crude  sewage 
quite  readily. 

When  separated,  the  peculiar  physical 
properties  of  the  solids  assert  themselves 
thus:  (a)  The  solids  (sludge)  adhere  most 
tenaciously  to  about  9  times  their  weight 
of  water;  (b)  the  sewage  liquor  adheres 
with  great  tenacity  to  about  20-25  per  cent, 
of  the  solids  of  the  cniginal  sewage. 

The  problem  presented  in  each  case  is 
the  same,  viz.  :  the  modification. of  the  phy- 
sical character  of  the  colloidal  solids. 

In  the  case  of  the  sludge  this  change  is 
conveniently  effected  by  the  inoffensive  in- 
tensive, anaerobic  digestion  of  the  sludge  as 
by  the  Imhoff  Tank  or  by  the  method  of 
separate  digestion  as  at  Birmingham  (Eng- 
land), and  Baltimore  (U.S.A.),  and  else- 
where. It  is  claimed  that  the  cost  of  the 
latter  method  is  relatively  low. 


NOTE  ON  THE  PREPARATION  OF 
SARCOLACTIC  ACID. 

By  John  Missenden,  B.Sc. 

This  substance,  also  known  as  6-a-hy- 
droxypropionic  acid,  8-a-CHj.CH(0H).- 
CO. OH,  may  be  prepared  from  proteinous 
tissue,  mainly  intercostal,  by  boiling  the 
flesh  for  several  hours  until  the  fibres  seipar* 
ate  and  present  a  greyish  appearance.  The 
liquid  so  obtained,  subsequent  to  filtration, 
is  fairly  abundant  in  saroolactic  acid,  and 
should  be  carefully  evaporated  to  a  thick 
syrup,  care  being  taken  that  no  burning  on 


252 


THE  CHEMICAL  NEWS. 


APRIL  20,  192S. 


the  sides  of  the  vessel  takes  place.  Immer- 
sion of  this  vessel  in  strong  brine  is  a  satis- 
factory process. 

While  at  a  temperature  of  about  40"  C, 
2.5  volumes  of  alcohol  (75  per  cent.)  should 
be  added,  and  the  whole  made  up  to  6  vol- 
umes with  water.  Again,  the  evaporation 
to  a  syrup  takes  place,  and  the  whole  is 
slightly  acidified  with  a  few  drops  of  sul- 
phuric acid,  and  filtered.  The  acid  is  then 
extracted  with  ether,  and  purified  by  con- 
version into  a  convenient  metallic  salt. 

This  method  of  preparation  takes  several 
days,  but  seems  the  speediest  way  of  ob- 
taining the  pure  product.  There  is  no  ob- 
jection to  assisting  the  filtration  of  the 
acidified  extract  by  the  careful  addition  of 
water,  but  subsequent  procedure  makes  this 
undesirable.  Muscular  tissues  surround- 
ing the  abdomen  and  femur  in  the  human 
body  form  a  plentiful  source  of  the  sub- 
stance, but  the  regions  of  the  lactic  organs 
at  the  front  of  the  thoracic  cavity  yield  the 
best  supply. 


GENERAL  NOTES. 


DYESTUFFS    (IMPORT  REGULATION) 
ACT. 

Applications  for  Licences  in  March. 

The  following  statement  relating  to  ap- 
plications for  licences  under  the  Dyestuffs 
(Import  Regulation)  Act,  1920,  made  dur- 
ing the  month  of  March,  1923,  has  been  fur- 
nished to  the  Board  of  Trade  by  the  Dye- 
stuffs  Advisory  Licensing  Committee. 

The  total  number  of  applications  received 
during  the  month  was  539,  of  which  459 
were  from  merchants  and  dealers.  To  these 
should  be  added  the  30  applications  out- 
standing on  1st  March,  making  a  total  for 
the  month  of  569.  These  were  dealt  with 
as  follows :  — 

Granted. — 405      (of    which    376    were 

dealt  with  within  seven  days  of  receipt). 
Referred  to  British    makers  of    similar 

products. — 105  (of  which    96  were    dealt 

with  within  seven  days  of  receipt). 

Referred  to  Reparation  supplies  avail- 
able.— 37    (all  of  which  were  dealt    with 

within  two  days  of  receipt). 

Outstanding     on      Slst     March.  —  22 

(mostly    received    immediately  prior    to 

Easter). 

Of  the  total  number,  569,  of  applications 


received,    467,    or  82  per  cent.,    were  dealt 
with  within  four  days  of  receipt. 


IMPORT  OF  CHEMICALS  INTO 
GUATEMALA. 

The  Acting  British  Vice-Consul  at  Guate- 
mala reports  that  by  virtue  of  an  Ordinance 
dated  30th  December,  1922,  and  published 
in  the  "  Official  Gazette  "  of  23rd  January 
last,  certam  chemical  and  medicinal  sub- 
stances may  be  imported  by  persons  not 
licensed  as  pharmacists  or  druggists. 

A  list  of  such  chemical  and  medicinal 
substances  is  available  and  may  be  con- 
sulted by  United  Kingdom  firms  interested 
on  application  to  the  Department  of  Over- 
seas Trade,  35,  Old  Queen  Street,  London, 
S.W.I.     (Reference  7683/F.L.). 


ECLIPSE    TESTS. 

Further  Confirmation  of  Einstein's 
Theory  of  Relativity. 

The  photographs  of  the  total  eclipse  of 
the  sun  last  September  have  now  been 
carefully  examined  and  measured.  Com- 
pared with  their  real  positions,  the  stars 
thus  photographed  near  the  ecliprsed  sun  all 
showed  the  displacement  which  should  aip- 
pear,  supposing  Einstein's  theory  to  be 
true. 

Close  on  the  announcement  that  the 
Canadian  plates  show  practically  the  Ein- 
stein shifts  comes  news  from  the  Lick  Ob- 
servatory of  similar  confirmation.  The 
Lick  expedition,  which  went  to  Avi^tralia, 
was  very  elaborately  equipped  for  the  pur- 
poses of  the  test,  and  obtained  a  series  of 
photographs  of  the  region  around  the 
eclipsed  sun  which  showed  over  eighty  stars, 
some  of  them  as  faint  as  the  tenth  magni- 
tude. The  mechanical  work  of  measuring 
the  plates  for  star  positions,  which  necessi- 
tated determining  them  with  accuracy  to  a 
small  fraction  of  a  second  (or  on  the  scale 
of  the  plates  to  about  the  5,000th  part  of  an 
inch),  and  the  mathematical  discussion  of 
the  actual  values  of  the  displacements  has 
taken  several  months. 

Thus  Relativity  has  successfully  survived 
the  two  eclipse  tests  to  which  it  has  been 
subjected,  that  of  1919  and  that  of  last 
year. 


APRIL  20,  1923. 


THE  CHEMICAL  NEWS. 


253 


NOTICES  OF  BOOKS. 

Atomic  Theories,  by  F.  H.  Luring. 
Second  edition,  revised.  Pp.  XII.  +  218. 
London:  Methuen  &  Co.,  Ltd.,  36,  Essex 
Street,  W.C.2.     1923.     12s.  6d.  net. 

During  the  last  few  years,  atomic  and 
sub-atomic  science  has  developed  so  greatly 
that  only  the  specialist  has  been  able  to 
keep  well-iniorined  by  careful  and  constant 
perusal  of  the  original  literature.  Mr.  Lor- 
ing's  volume  on  the  atomic  theories  has 
therefore  been  of  great  strvicf  for  the  gene- 
ral scientific  reader  an.xious  to  gain  a  clear, 
oom[)rehensive,  and  up-to-date  knowledge 
of  this  subject. 

The  author  has  availed  himself  of  the  op- 
iport unity  afforded  by  the  publication  of  n 
second  edition  to  introduce  the  results  and 
conclusions  of  investigations  which  have 
been  announced  since  the  first  edition  (re- 
viewed in  The  Chemical  Neu'8,  1022. 
CXXIV.,  158)  appeared. 

It  may  be  pointed  out  that  the  totraho- 
dral  arrangement  of  the  carbon  atom  given 
in  Fig.  19,  page  90,  is  not  adhered  to  on 
page  110,  Fig.  33.  Presumably  the  author 
had  in  mind  that  the  electrons  might  shift 
thiir  positions  in  the  carbon  atom  to  meet 
the  positions  in  the  attached  oxygen  atoms. 
The  tetrahedral  arrangement  in  the  carbon 
atom  would  obviously  do  equally  well,  for 
one  oxygen  atom  need  only  be  orientated 
accordingly. 

The  additions  include  the  author's  Wedge 
Periodic  Table  of  the  Elements,  and  a  fuller 
table  of  isotopes  is  given  on  pages  191  and 
198. 

A  few  minor  corrections  have  also  been 
made,  and  difticult  passages  re-written,  so 
that  the  book  can  now  claim  to  be  a  stand- 
ard work,  since  it  deals  with  all  the  theories 
relating  to  the  atom,  and  discusses  their 
experimental  foundations.  It  will  be  read 
by  an  increasing  number  of  students  of 
Chemistry  and  Physics,  and  by  others  in- 
terested in  the  latest  develoipments  and 
views  concerning  the  Atom. 


,tion.  Pp.  VIII.  +  134,  with  25  illustra- 
tions. London:  Messrs.  J.  &  A.  Church- 
ill, 7,  Great  Marlborough  St.  1923.  6s. 
6d.  net. 

The  exposition  of  main  physical  proiper- 
ties  of  the  subject,  together  with  absence  of 
a  quantity  of  tedious  calculation  seems  to 
be  the  keynote  of  this  edition ;  in  wliich  has 
been  added  some  important  notes  upon  the 
properties  of  thin  films,  polarised  mole- 
cules, and  boundary  lubrication.  As  Dr. 
Willows  exiplains  in  his  preface,  the  work 
indicates  the  possible  connections  between 
surface  tension  and  other  chemical  and 
physical  properties  of  liquids,  **  and  .  .  . 
opens  up  many  fascinating  avenues  for  re- 
search." 

Some  confirmed  observations  of  Eotvos, 
the  Hungarian  chemist,  have  been  dealt 
with,  in  order  to  show  how  these  relation- 
ships are  more  or  less  apparent,  and  the 
evolution  of  Dr.  A.  Ferguson's  formula 
!  il'hil.  Mag.,  Jan.,  1016),  a-d  =  <to  (1— b^)" 
for  showing  the  dependence  of  surface  ten- 
sion upon  critical  temperature  is  of  inter- 
est. On  p.  123  is  a  brief  paragraph  incor- 
porating some  points  upon  the  various 
stages,  of  tanning,  and  their  facilitation  by 
means  of  the  electric  charge  (i.e.,  the  elec- 
tro-combination of  the  tannins). 

The  work  is  an  f)ld  favourite,  and  the  pre- 
sent edition  should  prove  of  even  greater 
value  to  biologists  and  chemists.  We  can 
well  recommend  it  to  those  engaged  in  the 
study  of  colloidal  principles. 


Surface  Tension  and  Surface  Energy, 
and  their  Influence  on  Chemical 
Phenomena,  by  R.  S.  Willows,  M.A., 
D.Sc,    and    E.  Hatsciiek.      Third    Edi- 


Thr  SpectroHCope  and  its  U»es  in 
General  Analytical  Chemistry,  hv  T. 
...Tfiorxe  Baker,  A.M.I.E.E..  F.R.P.S. 
Second  Edition.  Pp.  X.  +  208.  London: 
Messrs.  Bailliere.  Tindall  &  Cox,  8.  Hen- 
rietta Street,  Covent  Garden,  W.C.2. 
1023.     7s.  6d. 

The  vast  development  of  sipectroscopy 
has  been  responsible  for  considerable  ex- 
tensions in  this  work.  In  1907,  when  the 
first  edition  was  issued,  the  spectroscope 
was  not  sufficiently  developed  to  render  it 
so  highly  important  in  quantitative  analy- 
tical processes,  although  its  efficiency  was 
fully  recognised.  Now,  the  most  rnodem 
instruuK'nts  and  their  most  recent  applica- 
tions have  necessitated  much  of  the  text 
being  recast. 

Laboratory  usages  have  been  dealt  with 
in    an     extensive    manner,      spectrophoto- 


254 


THE  CHEMICAL  NEWS. 


APRIL  20,  1923. 


gapliy  taking  prominent  space.  The  book 
would  hardly  be  complete  without  giving 
details  of  the  infra-red  spectrometer  of 
Messrs.  A.  Hilger,  Ltd.,  which  the  author 
has  described  and  illustrated  in  a  manner 
clearly  demonstrating  the  fundaments  of 
series-refleetion-refraction  throug'h  the 
thermqpile-slit. 

In  the  final  chapter,  attention  is  paid  to 
the  X-ray  spectra.  The  examination  of 
metals  by  this  means  has  produced  some 
new  results  which  are  discussed  throughout 
the  brief  treatise  upon  the  subject;  but 
greater  attention  could  have  been  paid  to 
the  monochromatic-radiation  filters,  which 
must  vary  with  the  substance  examined, 
and  the  nature  of  the  anti-cathode  target. 

Good  illustration  (for  which  Messrs.  A. 
Hilger,  Ltd.,  Watson  Sons,  Ltd.,  and  J. 
J.  Griffin  &  Sons,  Ltd.,  are  largely  respon- 
sible) and  oompositorial  excellence  crown  a 
very  lucid  and  self-explanatory  text ;  a  most 
useful  work  in  every  way. 

We  are  in  receipt  of  Skinner's  Cotton 
Trade  Directory  for  1923.  (London  :  Messrs. 
Thomas  Skinner  &  Co.,  Gresham  House, 
London,  E.C.2.  Price  12s.  6d.  net).  It  is 
a  handy  and  compact  volume,  and  contains 
much  information  of  value  to  those  inter- 
ested in  the  personnel  and  progress  of  the 
cotton  industry. 


The  proprietors  of  Current  Opinion  (The 
Industrial  League  and  Council,  82,  Victoria 
St.,  London,  S.W.I)  have  sent  us  their 
"first  birthday"  number.  The  general 
tone  of  the  publication  tends  to  be  qptimis- 
tic  of  trade  revival,  and  figures  are  quoted 
which  justify  the  optimism.  There  is  little 
doubt  that  such  periodicals  as  Current 
Opinion  help  greatly  in  the  co-ordination  of 
individual  enterprise,  and  we  wish  the  pro- 
prietors and  editor,  G.  C,  Lawrence,  Esq., 
every  success. 

The  issue  of  Nature  for  April  7  contains 
further  correspondence  relating  to  the  dis- 
covery and  identity  of  Hafnium. 

In  a  letter  On  Urhain's  Celtium  Lines, 
H.  M.  Hansen  and  S.  Werner,  of  Universi- 
tetets  Institut  for  teoretisk  Fysik,  Copen- 
hagen, write : 

Through  an  examination  of  the  very  care- 
ful measurements  of  the  spectra  of  the  rare 
earths  published  during  the  last  few  years 
by  Eder,  we  have  learned  in  the  meantime 
that  the  greater  part  of  Urbain's  celtium 
lines  have  been  observed  by  this  author 
(Wiener  Ber.,  Ila,  vol.  124.  1915)  in  the 
spectrum  of  a  preparation  of  the  rare  earth 


element  cassiopeium  or  lutetium.  The  dis- 
covery of  this  element  (atomic  number  71) 
was  announced  in  1905  by  Auer  von  \V els- 
bach,  to  whom  the  former  name  is  due, 
while  the  name  lutetium  was  proposed  in 
1907  by  Urbain,  who  published  at  the  same 
time  the  first  list  of  lines  of  its  optical  spec- 
trum [Comptes  rendus,  t.  1907,  145,  p. 
759). 

In  the  table  they  give  the  wave-lengths 
of  the  celtium  lines  from  Urbain's  paper 
and  the  corresponding  wave-lengths  and  in- 
tensities from  Eder's  measurements  of  the 
cassiopeium  spectrum. 

There  is  close  accordance  in  the  values  of 
the  relative  intensities  in  the  two  cases, 
which  we  think  justifies  the  identification  of 
the  lines  also  in  the  few  cases  where  the 
difference  between  the  wave-lengths  is 
slightly  greater  than  is  to  be  expected  from 
the  usual  accuracy  of  Urbain's  measure- 
ments of  wave-lengths  or  rare  earths.  Only 
a  few  of  these  lines,  denoted  by  an  asterisk, 
were  included  in  Urbain's  original  list  of 
the  lutetium  lines. 

It  is  of  interest  to  add  that  in  a  recent 
note  (Comptes  rendus,  t.  176,  1923,  p.  496), 
which  first  came  to  our  notice  after  the 
above  was  written,  dealing  with  the  dis- 
covery by  Coster  and  Hevesy  of  the  ele- 
ment hafnium  with  atomic  number  72,  Ur- 
bain himself  directs  attention  to  the  parti- 
cular behaviour  of  the  lines  ascribed  by 
him  to  celtium,  and  expresses  the  conjec- 
ture that  these  lines — the  observation  of 
which  was  the  basis  for  his  belief  in  the 
presence  of  a  new  element  in  his  prepara- 
tion— may  actually  constitute  the  spark 
spectrum  of  the  element  71. 

D.  Coster  and  G.  Hevesy  also  contri- 
bute another  letter  On  Celtiuvi  and  Haf- 
nium.    Among  other  matters  they  state  : 

Only  two  lines  of  the  element  72  were 
claimed  to  have  been  detected  by  Dauvil- 
lier,  and  even  in  the  case  of  the  most  in- 
tense of  these  lines  we  meet  with  the  diffi- 
culty that  it  falls  in  the  same  place  in  the 
spectrum  as  the  strongest  zirconium  line  in 
the  second  order.  As  an  argument  against 
ascribing  this  line  to  zirconium,  Urbain 
states  that  the  optical  spectrum  of  his  pre- 
parations did  not  show  any  zirconium  line. 
An  investigation  of  Urbain's  spectrum  of 
the  "celtium"  preparation,  however,  does 
not  show  any  line  of  the  hafnium  spectrum 
either.  If  the  possibility  of  the  presence  of 
one  of  these  elements  in  Urbain's  prepara- 
tion can  be  taken  seriously  into  considera- 
tion, it  shoTild  be  expected  that  zirconium 
would  be  present    in  greater    amount.       in 


APRIL  20,  1923. 


THE  CHEMICAL  NEWS. 


255 


fact,  zirconium  was  likely  to  be  more  abun- 
dant in  the  original  mineral  than  hafnium, 
and  a  purification  of  rare  earth  preparations 
from  zirconium  and  not  simultaneously 
from  hafnium,  by  treating  with  oxalic  acid 
or  any  other  method  mentioned  by  Urbain, 
is  scarcely  imaginable  in  view  of  the  close 
similazity  of  the  chemical  properties  of 
these  elements.  As  mentioned  in  our  pre- 
vious letters,  however,  the  two  lines  as- 
cribed by  Dauviliier  to  the  element  72  were 
lying  4  X-units  distant  from  our  Hf-lines, 
which  is  distinctly  more  than  the  limit  of 
experimental  error,^  whereas  the  lines  of 
the  elements  70  and  71  measured  by  Dau- 
viliier (Comptea  rendua,  vol.  174,  p.  1347, 
1022)  on  the  same  plates  closely  agree  with 
the  measurements  of  the  same  elements 
obtained  by  Coster  {Phil.  Mag.,  vol.  44,  p 
546,  1922),  As  the  two  lines  according  to 
Dauviliier  were  extremely  faint,  they  may 
easily  be  explained  to  be  of  some  other 
ori<,'in. 

It  is  of  interest  to  note  that,  at  various 
times,  announcements  have  been  made  as 
to  the  complexity  of  zirconium.  In  1845 
Svanberg  claimed  that  in  decampoeing  zir- 
cons be  discovered  a  new  element, 
"  norium,"  with  a  lower  atomic  weight 
than  zirconium.  His  and  Sjogren's  (1853) 
statements  were  later  dis,proved  by  the 
work  of  several  investigators,  including 
Marignac.  In  1864  Nylander  reported  the 
existence  of  two  earths  in  zircona.  Five 
years  later,  by  a  spectroscopic  investigation 
of  zirconium,  Sorby  was  led  to  announce 
the  discovery  of  "jargonium"  and  Church 
f>f  "  nigrium."  Finally,  in  1901,  Hofmnnn 
and  Prandtl  thought  that  they  had  found  in 
ouxenite  a  new  element  related  to  zir- 
conium. It  is  also  interesting  to  note  that 
Mendele^ff,  as  we  learn  from  Sir  T.  E. 
Thorpe's  letter  in  Nature  of  February  24. 
p.  252  (March  17),  suggested  that  the  ex- 
traordinarily discordant  values  for  the  ato- 
mic weight  of  titanium,  found  by  several 
chemists,  might  be  due  to  the  presence  of 
a  homologous  element  of  higher  atomic 
weight  in  their  material.  Whether  these 
statements  in  some  oases  may  be  explained 
by  the  presence  of  hafnium  in  the_ minerals 
and  (preparations  under  investigation,    it  is 

*  Dduvillier's  measurementa  carried  otd 
since  the  announcement  of  our  discovery, 
on  other  material  which  poaaibly  contained 
hafnium,  have  already  led  hiui  to  give  new 
vdlnra  for  the  aame  ivavc-lcngtha,  which 
arc  rcapectivchj  3.4  and  2.3  X-unila  larger 
Nature,  February  17,  1923). 


not  easy  to  decide.  The  intricate  chemistry 
of  zirconium,  and  the  great  chemical  simi- 
larity of  hafnium  with  this  element,  would 
in  fact  have  made  any  establishment  of 
hafnium  very  difficult  before  the  develop- 
ment o  fthe  powerful  method  of  X-ray  ana- 
lysis. 

A  Tested  Method  of  Laboratory  Organ- 
isation, by  Seymour    Pile,    M.A.    (Can- 
tab),   and  Regin.ald  G.  Johnston,    with 
an    introduction     by    W.    R.    Barclay, 
O.B.E.     Pp.  XI.  +  98.      London:  H.  F. 
&    G.    Witherbv,    326,    High    Holborn, 
W.C.     1923.    7s.  6d.  net. 
Birmingham    brass-founders    followed    a 
commendable    course    when    they    entered 
upon  their  co-operative  laboratory  scheme, 
and  put  into  being  the  Midland  Laboratory 
Guild,   Ltd.     The  hundreds  of  little  brass- 
works  in  and  around  the  district  were  sadly 
lacking  in  eftieient  laboratory  services  until 
this  great  centre  was  established ;  now  they 
have    facilities     at    least    equal    to     those 
possessed  by  the  enormous    steel  firms    of 
Lancashire  and  Yorkshire. 

Such  a  laboratory  needs  first-class  or- 
ganisation, and  Messrs.  File  and  Johnston 
have  described  in  their  book  how  this  has 
been  attained.  Not  only  the  construction 
and  equipment  of  the  building  have  been 
dealt  with,  but  also  the  personnel  and  the 
methods  of  analysis  and  costing;  and  the 
masterly  manner  of  enumeration  tells  of 
considerable  familiarity  with  the  inner  de- 
tail of  the  processes. 

The  chapter  upon  The  Scientiat  in  Rela- 
tion to  This,  That,  and  the  Other  is  some- 
thing unusual.  It  takes  the  scientific  mind 
to  pieces,  exposing  all  the  works.  Some  of 
these  works,  reduc«'d  to  their  first  prin- 
ciples, are  a  trifle  astounding,  as  they  typi- 
fy the  scientist  on  the  lines  of  human  per- 
fection, and  give  one  the  impression  that 
the  analytical  chemist  is  the  nearest  ap- 
proach to  the  ideal.  This  has  the  effect,  as 
do  most  other  chapters  in  the  book,  of 
creating  an  inspiring  atmosphere  around 
the  study  of  chemistry,  and  promoting 
what  is  essential  to  the  scientist — a  love  for 
his  work. 

Altogether,  the  book  must  tprove  valu- 
able. The  methods  it  describes  are  effi- 
cient, and  will  have  some  significant  bear- 
ing upon  future  laboratory  management; 
while,  as  a  text-book,  it  provides  excellent 
scope  for  the  foundation  of  new  idea^. 
Messrs.  Pile  and  Johnston  are  to  be  con- 
gratulated upon  it,  and  wished  every  suc- 
cess. 


256 


THE  CHEMICAL  NEWS. 


APRIL  20,  1923. 


We  have  received  a  coipy  of  the  1923  issue 
of  the  Directory  of  Paper  Makers  of  the 
United  Kingdom,  price  5s.  9d.  net.  It  has 
again  been  authentically  revised  and 
brought  up  to  date,  and  contains  informa- 
tion valuable  to  all  connected  with  this  in- 
dustry. 

It  includes  alphabetical  lists  of  paper 
makers;  paper  enamellers,  surfacers  and 
gummers;  mills;  trade  designations;  paper 
trade  customs,  and  other  useful  matter. 

The  following  Bulletins  have  been  pub- 
lished by  the  Department  of  the  Interior, 
United  States  Geological  Survey:  — 

Gold  and  Silver  in  1921,  by  J.  P.  Dunlop. 

Stone  in  1921,  bv  G.  F.  Loughlin  aiid  A. 
T.  Coons. 

Cement  in  1921,  by  Belle  W.  Bagley. 

Natural  Gas  Gasoline  in  1921,  by  E.  G. 
Sievres. 

Potash  in  the  Greensands  of  New  Jersey, 
by  George  Eodgers  Mansfield  (1922). 

Surface  Water  Supply  of  the  United 
States,  1918.  Part  IX.  :  Colorado  River 
Basin. 

Copper  Deposits  of  the  Tyrone  District, 
New  Mexico,  by  Sidney  Paige,  1922.    . 


BOOKS  RECEIVED. 

Inlx,  by  C.  AiNswoRTH  Mitchell,  M.A., 
F.I.C.  Pp.  VIII.  +  128.  1923.  Sir  Isaac 
Pitman  and  Sons,  Ltd.,  Parker  Street, 
Kingsway,  W.C.2.     3s.  net. 

Einfuhrung  in  die  Kolloidchemie,  von 
Prof.  Viktor  Poschl.  Pp.  XII.  +  158. 
1923.  Verlag  von  Theodor  Steinkkopft, 
Dresden  und  Leipzig.    3s.  lid.  net. 


This  list  is  specially  compiled  for    The  Chemical 

News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 

Agents,  of  5.  Chance i-y  Lane,  London,  from  whom 

all  information  relating  to  Patents,  Trada  Marks, 

and  Designs  can  be  obtained  gratuitously. 

Latest   Patent   Application^. 

7828— Desci) amps,   J.    J.— Facilitating^  physical    or 

chemical  reactions  in  piled  bodies.  Marcli  19. 


812(>— Farbenfabriken   vorui.,     F.     Bayer     &  Co.— 

Manufacture  ox   azo-dyes.     Marcli   2L 
7813— Verein     fux  Chemische     und     Metallugische 
Produktiun.— Production    of    chemically-pure 
hydrochloric  acid.     March  19. 
Specifications  Published   this    Week. 
194339 — Rardt,  H.— Process  for  precipitating  or  re- 
covering  metals   from   their   solutions. 
19462.5— Douglas,   R.    P.— Manufacture    of  sulphate 

of  ammonia. 
185124— Mathesius,  W.,  &  H.— Process  for  produc- 
ing lead  alloys  containing  strontium. 
Abstract  Published  this  Week. 
192438— Dyes;  intermediate  products.— Akt-Ges  fur 
Anilin-Fabrikation,  Berlin. 
o-Oxyazo  dyes  are  prepared  by  coupling  a  di- 
azotized  dilialogen-2-aminophenol,  containing  as  a 
fifth  substituent  a  halogen  atom  or  an  alkyl 
group,  with  an  oxynaphthalene  sulphonic  acid  or 
a  substitution  product  thereof  other  than  8-halo- 
gon-l-oxynaphthalene-5-sulphonic  acid.  Examples 
are  given  of  the  preparation  of  dyes  from  the  fol- 
lowing pairs  of  components  :— 3  :  4  :  6-tric]iior-2- 
aminopheuol  and  l-nai>hth()l-5-sulphonic  acid;  3: 
4 :  5-trichlor-2-aminop]ienol  and  l-acetylaniino-8- 
naphthol-4-sulphonic  acid;  3:  4:  5:  6-tetrachlor- 
2-aminoj>h?nol  and  2-naphthol-6-sulphonic  acid; 
4-metl)yl-3 :  5-dichlor-2-nniinophenol  and  1-acetyl- 
a'iiino-8-n;  pM  :  ol  4-3ulphonic  acid;  these  dye  wool 
with  chrome  mordants  reddish-blue,  blue,  red- 
dVh-viok't,  and  reddish-blue  shades  respectively. 
The  following  second  components  also  are  speci- 
fied :  —  l-naphthol-4-sulphonic  acid,  l-amino-8- 
naphthol-4-  ulphonic  acid,  l-amino-8-naphthol-2  : 
4-disulphnnic  acid,  l-benzoylamino-8-naplithol-4- 
sulphonic  acid,  1  -p-  toluonesiilphamino-8-naph- 
thol-4-sulplionio  acid,  l-phenylamino-8-nai>hthol-3  : 
6-disulphonic  acid,  2-benzoylamiuo-5-naplitliol-7- 
sulphonic  acid.  Specification  168,681  is  referred  to. 
3:4:  (i-Trichlor-2-aminophenol  is  made  from  1: 
2:4:  5-tetrachlorbenzene  by  replacing  one  chlor- 
ine atom  by  an  hydroxyl  group,  nitrating,  and 
reducing. 

3:4:  5-Trichlor-2-aminophenol  is  made  from  3: 
4 :  5-trichloraniline  by  diazotizing,  boiling,  ni- 
trating,  and   reducing! 

i-Methyl-i :  5-dichlnr-2-aminophenol  is  made 
from  4-amino-2:  6-dichlor-l-methylbenzene  by  di- 
azotizing, boiling,  nitrating,  and  reducing;  the 
4-amino-2 :  e-diohlor-1-methylbenzene  is  prepared 
by  dichlorinating  4-nitjolouene  and   reducing. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  publislied  Sj>ecifi(atious,  and  forward  on 
lost  free  for  the  price  of  Is.  6d.  each. 


PAMPHLETS. 

Science  by  Definition  Series, 

By  F.  H.  Loring. 

1.  DEFINITION  OF  RELATIVITY. 

2.  DEFINITION  OF  THE  AETHER. 

3.  DEFINITION  OF  EQUIVALENCE. 

4.  DEFINITION  OF  ISOTOPES. 

(Others  in  progress). 
Price  Is.  each  net.     Postage,   British  Isles 
Id.  each. 
"  A  little  series  called    '  Science  by  Defi- 
nition, '  in  which    the  author  relies    on  the 
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Times  Literary  Supplement. 
H.  O.  LLOYD  &  Co.,  Ltd., 

327,  Upper  Street,  London,  N.l. 


APRIL  27,  1923. 


THE  CHEMICAL  NEWS. 


267 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3289. 


CHEMICAL  INDUSTRY  AND  THE 
BRITISH  EMPIRE  EXHIBITION  (1924). 

For  the  first  time  in  the  histcM-y  of  great 
exhibitions,  the  chemical  industry  is  to  be 
represented  in  all  its  branches.  Hitherto, 
manufacturers  have  not  taken  sufficient  in- 
terest in  such  displays;  in  the  main,  for  two 
reasons.  Firstly,  the  reiputation  of  British 
heavy  cheinicals  was,  presumably,  too  well 
established  to  warrant  representation;  and, 
secondly,  fine  chemicals  and  tivt  stuffs  were 
tcK>  undeveloped  to  admit  of  the  manufac- 
turers thereof  indulging  in  such  heavy  ex- 
penditure. 

Quoting  from  the  Empire  Exhibition 
News  (February,  1923),  about  .TO  firms  have 
been  entered.  Home  nlknlis  nnd  the  com- 
plete range  of  coal  by-products  will  be  ex- 
hibited, as  well  as  fine  chcraicals  and 
domestic  materials.  A  mr>st  interesting 
feature  will  be  the  presence  of  the  leading 
scientific  societies  for  the  pmpose  of  illus- 
trating the  progress  (A  pure  and  applied 
chemistry  during  the  ipast  10  years;  this 
will  cover  the  periofl  of  the  bite  war. 

As  the  European  upheaval  depressed  the 
industry,  so  will  the  Exhibition  more  than 
revive  it.  Dyestuffs,  certainly,  will  benefit; 
while  the  general  lines  of  future  resenreh 
will  be  more  in  co-ordination  with  industrial 
requirements. 

Organisation  of  the  Chemirnl  Section  is 
being  undertaken  by  the  .Association  of 
British  Chemical  Afanufacturers,  and  it  is 
to  be  hoped  that  firms  will  do  thei^  ntrno^f 
to  arrange  for  exhibits — to  the  bonofit  of  all 
concernnd.  .T.  Af. 


THE    PROBLEM    OF    SUBSTTTUTTON 

IN    THE    BENZENE    NUCLEUS    AND 

THE    THOMSON-LEWIS-L.\NGMUIR 

THEORY    OF    CO- VALENCE. 

By  Ronald  Fkaser  and  James  Ernest 
Humphries. 

(Continued  from  Page  246.) 

The  electromer    present  in  greater    con- 
centration— a   factor   evidently     determin':>d 

by   thp  rolntive  octet  stabilities  of  X,     and 


Xj — will  react  with  greater  velocity  with 
the  entering  groujp;  and  the  resulting  tri- 
substituted  compound  will  predominate  m 
the  final  products.  If  X^  has  the  greater 
i  octet  stability,  further  substitution  will 
take  place  at  the  4  and  6  positions;  if  Xj, 
at  the  3  and  5  positions;  i.e.,  considered 
from  the  standpoint  of  X,  alone,  ortho- 
para  if  X,  is  negative  and  meta  if  X,  is 
iposLtive.  If  the  octet  stabilities  of  X,  and 
Xj  are  widely  different,  one  electromer  may 
be  present  in  such  small  concentration  that 
its  resultant  will  not  be  capable  of  defec- 
tion in  the  final  products.  On  the  other 
hand,  if  the  octet  stabilities  of  X,  and  X, 
are  of  the  same  order,  the  number  of  pro- 
ducts will  be  greater.  The  two  possibilities 
may  be  illustrated  by  the  iodination  of 
o-toluidine  (Wheeler  and  Liddle.  Amcr. 
Chem.  J.,  1909,  XLIL.  501),  and  the  nitra- 
tion of  o-chlwiK>luene  (Wibaut,  Rec.  Trav. 
Chim.,  1913,  XXXII.,  244). 

Similar  reasoning  applies  to  disubstituted 
derivatives  of  the  type  C.H^       X,(,)    X,(J 

Case  2,  IMg.  8.  ii.  In  this  case  the  octet 
tendencies  of  X,  and  X,  reinforce  each 
other,  and  a  single  electromer  exists.  Sub- 
stitution would  be  exipected  to  occur  at  the 
4  and  6  positions,  which  ie  in  agreement 
with  the  facts. 

Case  3.  This  is  similar  to  Case  1.  If 
the  octet  instability  of  Y,  is  greater  than 
that  of  Yj,  electromer  (a)  will  predominate, 
and  if  conversely,  electromer  (b).  Further 
substitution  will  proceed  accordingly. 

The  type  C.H,     Y,(,)      Y,(J    is  similar. 

Case  4.  A  single  electromer.  Further 
substitution  at  5. 

Case  5.  A  single  electromer.  The 
groups  X  and  Y  reinforce  each  other's 
natural  octet  tendency.  The  smooth  ni- 
tration of  the  nitrophenols  is  all  in  agree- 
ment with  this  statement.  The  type 
C,H,      X(,)      Y(J      falls  under  this  case. 

Case  6.  Equilibrium  between  electro- 
mers  holds  in  this  case ;  reference  to  Postu- 
late 2  indicates  that  the  direction  of 
equilibrium  will  be  that  shown  (Fig.  3, 
vi.),  and  hence  ortho-para  directive  sub- 
stituents  will  exert  the  greater  influence  in 
orientation. 

The  Effect  of  Conditions. 
One  of  the  main  difficulties  to  the  form- 
ulation of  definite  rules  summarising  'he 
facts  of  orientation  is  the  effect  of  condi- 
tions in  altering  the  relative  amounts  of 
the  final  products  of  a  reaction.  On  the 
octet  view,  this  means  thnf.  thp  equilibrium 


258 


THE  CHEMICAL  NEWS. 


APRIL  27.  1923. 


pictured  above  in  the  electromeric  equa- 
tions, or,  in  the  cases  where  a  single  elec- 
tromer  exists,  the  relative  octet  stabilities 
of  the  substituents,  is  altered.  In  either 
instance,  this  would  indicate  that  the  effect 
of  conditions  is  largely  one  of  electron 
transference . 

The  work  of  Biltz  (Z.  Elek.,  1911,  XVII., 
676)  has  shown  that  carbon  possesses  a 
very  high  characteristic  vibration  fre- 
quency; and,  as  stated  by  W.  C.  McC. 
Lewis  (System  of  Physical  Chemistry,  vol. 
III.,  62),  "  an  atom  possessing  high  fre- 
quency is  no  doubt  the  most  likely  type  of 
atom  to  allow  of  the  transference  of  elec- 
trons to  and  from  itself."  1'hat  electron 
energy  increases  with  rise  of  temiperature 
has  been  indicated  by  Kocnigsberger  (Z. 
Elek.,  1911,  XVII.,  289),  and  electron 
lability  must  also  be  affected  by  the  nature 
of  the  solvent  medium  (dielectric  constant, 
etc.).  It  is  along  these  lines  that  we  hope 
to  approach  the  problem  of  conditions. 
Replacements  and  Octet  Stability. 

The  term  "Replacement"  is  used  to  de- 
note the  exchange    of  one  substituent    for 


6*) 


another;  "Substitution"  refers  to  the  ex- 
change of  hydrogen  for  an  entering  group. 
It  seems  to  us  that  no  essential  distinction 
can  be  drawn  between  the  two  processes ; 
and  we  regard  substitution  merely  as  a 
special  case  of  replacement.  No  rule  of  re- 
placement corresponding  to  a  rule  of  sub- 
stitution has,  so  far  as  we  can  find,  been 
formulated;  but  consideration  of  our  re- 
marks on  the  special  case  of  the  "  octet 
stability  "  of  hydrogen  appears  to  lead  to 
some  degree  of  uniformity  in  this  respect. 
It  was  pointed  out  that  the  lability  of  hy- 
drogen was  conditioned  by  its  tendency  to 
give  up  its  electrons;  whereas  octet  com- 
pletion is  the  determining  factor  in  the 
lability  of  all  other  elements  attached  to 
the  nucleus.  In  other  words,  a  labile  hy- 
drogen is  attached  to  a  negative  carbon 
atom,  while  a  labile  radicle  other  than 
hydrogen  is  attached  to  a  positive  carbon. 

Thus,  any  rule  which  expresses  the  facts 
of  substitution  will  be  reversed  in  the  case 
of  replacement;  by  "reversed"  we  mean 
that  a  group  which  causes  substitution  in 
the  meta  position  will  favour  replacem,ent 
in  the  ortho-para  positions,  and  conversely. 


Q 


If  i 


Fig.  4.* 


For  example,  the  nitro  group  causes  substi- 
tution in  the  meta  position;  but  in 
the  hydrolysis  of  the  nitranilines,  re- 
placement of  NHj  by  OH  occurs 
at  the  ortho-para  positions  to  the 
nitro  group,  and  not  at  the  meta 
position.  Reasoning  on  the  same  lines  as 
those  employed  in  the  discussion  of  substi- 
tution, it  will  be  seen  (Fig.  4,  a  and  b), 
that  the  octet  stability  of  NH^  is  reinforced 
by  the  polarity  effects  of  the  nitro  group : 
whereas  in  Fig.  4  (c),  the  polar  tenden- 
cies of  NHj  and  NOg  are  opposed,  and  the 
lability  of  NH,  consequently  diminished.! 
We  have  found' the  above  rule  (which  is,  of 
course,  the  obverse  of  the  Brown  and  Gib- 


*  A  ringed  group,  thus  V!LJ  ,  is  used  here 
to  denote  lability  folloiring  on  octet  stabil- 
ity. 

f  Reference  to  Case  VI.  shows  that  m- 
nitraniline  exists  as  two  electromers,  the 
NHg  group  exerting  the  greater  directive  in- 
fluence. It  would  appear  that  the  lability 
of  a  group  is  m,ore  easily  influenced  by  one 
of  opposite  polar  tendency  than  is  its  direc- 
tive influence;  and  this  is  in  general  agree- 
ment with  our  views  on  reactivity.  In  this 
connection  it  should  be  noted  that  the  NH, 
group  in  aniline  itself,  while  exerting  fufl 
directive  power,  requires  the  reinforcement 
of  ortho  or  para  nitro  groups  to  render  it 
labile  in  hydrolysis;  and  m,any  other  simi- 
lar instances  could  be  cited. 


APRII,  27.  1923. 


THE  CHEMICAL  NEWS. 


259 


son  rule)  to  be  of  general  application  to  the 
simpler  cases. 

Another  interesting  rule  follows  from  the 
unique  electrical  character  of  the  carbon 
atom  discussed  above,  if  we  enquire 
how  the  tendency  there  mentioned  to- 
wards increasing  differentiation  of 
polarity  in  a  chain  of  carbon 
atoms  can  be  satisfied.  §  The  inductive 
effect  of  a  substituent  on  the  carbon  atoms 
of  the  nucleus  is  greater  the  greater  its  octet 
stability  {of.  discussion  of  the  Holleman 
Series);  hence  the  differentiation  of  pohir- 
ity  of  the  carbon  atoms  will  be  increased 
by  the  replacement  of  the  given  substituent 
by  a  group  of  greater  octet  stability.  The 
rule  may  therefore  be  stated  thus;  in  re- 
pla<;ements,  the  entering  group  is  one  of 
greater  octet  stability  than  the  group  re- 
placed. The  hydrolysis  of  the  nitranilinea 
is  a  case  in  ipoint,  and  many  others  have 
been  examined,  and  the  rule  found  to  hold.* 

A  striking  example  of  the  application  of 
the  rule  is  seen  in  the  work  of  Swarts 
(Bull.  Acad.  roy.  Belg.,  1920,  389) 
on  the  nature  of  the  CF,  group.  OF,  is,  as 
one  would  expect,  mota  directive. 
Unlike  C.HjCCl,.  C.H.rP,  can  be 
nitrated  under  ordinary  conditions  without 
hydrolysis  of  the  CF,  group.  This  is  pre- 
cisely what  we  should  expect  cm  the  octet 
view.  It  was  pointed  out  (see  last  week's 
issue)  that  fluorine  was  in  all  probability 
more  octet  stable  than  any  other  atom  or 
group;  therefore,  while  the  replacement  of 
CI  by  the  more  octet  stable  OH  group  is  to 


§  Th*".  rules  of  ^fichael  and  Markouni- 
hoff  way  he  i  consequence  of  this  property 
of  a  chain  of  carbon  atoms,  the  inductive 
effects  being  more  pranounced  when  the 
chain  is  unsaturated  (Kermack  and  Hobin- 
son,  he.  cit.,  pp.  430-432).  In  the  ex- 
amples CH,  :CHrOOH  +  HBr  =  BrCH,. 
CH,.COOH:  and  CH^.CBrrCH,  +  HBr  = 
CH,.CBr,.CH,,  the  reaction  has  taken 
plnce  tvhich  increases  the  polarity  (positive 
or  negative)  of  the  carbon  atoms. 

*  An  apparent  exception  to  the  rule  is  the 
action  of  PCI,,  o^t  phenols,  where  OH  is  re- 
placed by  CI.  The  chlorines  in  PCI,,  how- 
ever, may  be  in  an  exceptional  state  of  octet 
stability  (cf.  Thomson,  Phil.  Mag.,  1921. 
[vi.],  XLI..  521).  Tt  is  in  aqreement  with 
the  deductions  above  that  the  reaction 
takes  plice  more  readily  with  p-nitrophenol 
than  with  pheyiol  itself. 


be  looked  for,  replacement    of  F  by  OH  is, 
according  to  the  rule,  difl&cult  or  impossible. 

Hitherto  the  application  of  the  rule  has 
been  confined  to  the  entry  of  groups  of  an 
essentially  electronegative  character;  but 
we  have  found  that  the  important  class  of 
reduction  reactions,  where  a  group  is  re- 
placed by  hydrogen,  falls  equally  under  the 
rule.  In  a  recent  series  of  papers,  Mac- 
beth and  his  co-workers  (Henderson  and 
Macbeth,  T.,  1922.  GXXI.,  892;  Hirst  and 
Macbeth,  ibid.,  p.  904;  Macbeth,  ibid.,  p. 
1116)  have  pointed  out  that,  different  as 
are  the  structures  of  comp>ounds  with  halo- 
gens labile  towards  reducing  agents,  they 
have  in  common  the  possession  of  halogen 
with  a  strong  induced  positive  polarity — 
that  is,  on  our  view,  octet  unstable.  The 
octet  instability  in  the  cases  cited  by  these 
authors  appears  to  be  unusually  pro- 
nounced, and  hence  their  ready  replace- 
ment by  negative  (octet  stable)  groups  is 
not  to  be  expected.  Their  replacement  by 
hydrogen,  however,  which  tends  to  become 
electropositive  and  "octet  stable"  at  the 
same  time  (vide  supra),  is  in  agreement 
with  the  rule  and  with  its  underlying  foun- 
dation, viz.,  the  tendency  towards  increas- 
ing differentiation  of  polarity  of  the  carbori 
atoms.  The  replacement  of  the  halogen  by 
metals  in  this  class  of  compound  (Hender- 
son  and  Macbeth,  loc.  cU.  p.  895)  is  a  simi- 
lar example  of  the  rule.* 

It  is  important  to  note  here  the  finding 
of  Burton  and  Kenner  (T.,  1922,  CXXI., 
675),  that  in  the  removal  of  halogen  in  the 
reduction  of  halogenated  nitro-compounds, 
the  reduction  of  the  nitro  groups  to  amino 
groups  in  all  probability  precedes  the  re- 
moval of  the  halogen  (of.  the  examples 
cited  by  Burton  and  Kenner,  loc.  cit.,  and 
the  papers  of  Macbeth  and  his  co-workers 
mentioned  above).  The  present  theory 
would  predict  that  such  is  the  course  of 
these  reactions. 

Effect  of  Groi^ps  on  Each  Others 
Reactivity. 

We  can  now  refer  more  particularly  to 
the  loosening  or  tightening  effects  on  sttb- 
stituents  caused  by  other  groups  present  in 
the  nucleus,  as  has  been  referred  to  already 


*  The  activity  or  inertness  of  hnlogen  in 
the  compounds  cited  by  Kenner  (T.,  1914, 
CV..  2719)  and  explained  by  him  en 
Fliirscheim's  formulation,  can  be  equally 
well  interpreted,  along  the  above  lines,  on 
our  views. 


260 


THE  CHEMICAL  NEWS. 


APRIL  27,  1023. 


in  the  simpler  cases  (Fig.  4).  Among  the 
numerous  examples  examined,  may  be 
cited  the  following:  the  loosening  effect  of 
meta  directive  groups  on  substituents  in 
the  ortho-para  positions  (Schopf  and  his 
collaborators,  Ber.,  1889,  XXII.,  900,  et 
seq.;  Kenner,  loc.  cit.);  the  loosening  of 
ortho-ipara  directive  groups  on  substituents 
in  the  meta  position  (Kenner  and  Parkin, 
T.,  1920,  CXXVIL,  855;  Holleman  and 
Hollander,  Rec.  trav.  chim.,  1920, 
XXXIX.,  435;  Guia,  Gazzetta,  1921,  LI., 
i.,  307;  Burton  and  Kenner,  T.,  1922, 
CXXL,  489);  the  tightening  effect  of  ortho-. 
para  directive  groups  on  bromine  in  the 
para  position  (Meyer,  Ber.,  1921,  LIV., 
[B],  2265).  An  examination  of  these  will 
show  that  our  views,  and  in  particular  Pos- 
tulate 3,  are  capable  of  predicting  the 
observed  facts. 

The  Directing  Group  in  Polysubstituted 
Compounds. 
In  a  large  number  of  cases  examined  by 


Robinson  (Perkin  and  Robinson,  7'.,  1914, 
CV.,  2379;  Jones  and  Robinson,  7'.,  1917, 
CXI.,  906;  Gibson,  Simonsen,  and  Rau, 
T.,  1917,  CXI.,  73),  it  is  found  that  when 
a  negative  group  is  in  the  ortho-para  posi- 
tion to  a  positive  group,  they  neutralise 
each  other,  and  the  orientating  effect  is  ex- 
ercised by  the  second  positive  grouip.  The 
work  of  Davies  on  the  cumulative  effect  of 
the  chlorine  atom  and  the  methyl  and  sul- 
phonyl chloride  groups  on  substitution 
(Davies,  T.,  1921,  CXIX.,  853-876;  ibid., 
1922,  CXXL,  785)  affords  interesting  ex- 
amples of  the  applicability  and  otherwise 
of  the  Robinson  rule. 

In  attempting  to  determine  the  position 
taken  up  by  a  fourth  substituent  in  a  tri- 
substituted  derivative,  two  main  considera- 
tions are  of  importance,  viz.,  the  relative 
octet  stabilities  of  substituents  already  pre- 
sent, and  the  persistence  of  their  inductive 
effects  through  a  chain  of  carbon  atoms. 


Percentage  yield    of  corresponding 

nitro  comipounds    (substitution    at 

asterisk). 


The  substances  on  which  Davies  worked 
(Fig.  5)  contain  in  each  case  CHj  and  01 
in  the  ortho  relation,  the  SO^Cl  occuipying 
various  positions  relative  to  them.  The 
octet  stability  of  CI  being  greater  than  that 
of  CH3,  the  predominating  polar  state  of 
the  molecule,  in  the  absence  of  the  SO,CI 
group  would  be  as  indicated  in  Fig.  5,  la, 
iia,  iiia.  Consider  now  the  question  of  the 
persistence  of  induction.  In  Fig.  5  i.,  the 
inductive  tendency  of  CI  in  reversing  the 
natural  polarity  of  S0,C1  is  greater  than 
that  of  CH3,  which  has  the  opposite  ten- 
dency, owing  to  the  difference  in  the^  num- 
ber of  carbon  atoms  through  which  induc- 
tion has  to  be  eflfected.    On  the  other  hand, 


in  Fig.  5  ii.,  the  greater  inductive  power  of 
CI  as  compared  with  CH3  is  balanced  by 
the  weakening  effect  of  the  carbon  atoms 
intervening  between  CI  and  SO2CI.*  In 
Fig.  5  iii.,  the  SO2CI  and  CI  have  the  same 
polar  effects  on  the  nuclear  atoms.  The 
~  *  MorganTand  Jones  (T.,  1921,  CXIX., 
187)  on  nitrating  2-chloro  6-nitrotoiuene, 
obtained  90  per  cent,  of  the  compound  cor- 
responding to  iia  above,  and  5-10  per  cent, 
of  iib.  Reference  to  remarks  on  the  order 
of  the  meta  directive  s^ibstituents  indicates 
that  electromer  (,i)  can  exist  in  greater  con- 
centration when  an  NOj    group  is  in  place 

of  SO3CI. 


APRIL  27,  1923. 


THE  CHEMICAL  NEWS. 


261 


electromeric  equilibria  in  the  three  cases 
will  therefore  be  as  shown  in  that  figure, 
and  the  yields  of  the  nitration  products  are 
in  agreement.  Thus  it  will  be  seen  that 
the  present  theory  is  borne  out  by  the 
above  experiments;  whereas  the  Robinson 
rule  fails  in  the  third  example  (v.,  Davics, 
T.,  1922,  CXXI.,  786;  but  comjpare  foot- 
note to  same  page). 

The  results  of  Gibson,  Simonsen,  and 
Rau  (T.,  1917.  CXI.,  69)  on  the  nitration 
of  2-acetylamino-3-4-dimethoxy  benzoic 

acid  and  of  3-acetylamino-veratrole,  and  of 
Simonsen  and  Rau  (T.,  1917  CXI..  220)  on 
the  nitration  of  isomeric  acetylamino  meth- 
oxybenzoic  acids,  are  difficult  of  interpreta- 
tion on  the  octet  view,  ipartly  owing  to  the 
large  number  of  substituente,  and  hence 
the  difficulty  of  determining  their  mutual 
interdependence;  and  partly  to  the  diffi- 
culty at  the  present  stage  of  dogmatising 
with  regard  to  the  relative  octet  stabilities 
of  NHAc  and  OMe. 

In  the  above,  we  have  attempted,  on  the 
basis  of  the  Thomson-Lewis-Langm'.iir 
theory  of  co-valence,  to  connect  various 
thecM*ic8  and  rules  which  at  first  sight  may 
scorn  wide  apart;  to  give  ae  oon«istent  a 
biusis  lis  we  could  to  certain  observed  regu- 
larities; and  further,  to  formulate  general- 
isations which  may  be  of  use  in  classifying, 
and  perhaps  in  predicting  the  course  of, 
substitution  reactions. 

Supplementary  Note. 

It  should  be  observed  that  our  view  of 
the  mechanism  of  in(lu<tion  differs  some- 
what from  that  of  Kerinack  and  Robinson 
(Joe.  cit.),  inasmuch  as  actual  "appropria- 
tion" of  electrons  by  octvt  stable  centres  is 
postuliitt'd  by  us.  That  this  is  not  the 
opinion  of  Keniiack  and  Itoliinson  was  made 
clear  by  Professor  R(>i)inson  at  the  Hull 
meeting  of  the  British  Association.  1922. 
It  is  our  intention  to  attempt  to  obtain  ex- 
pori mental  evidence,  which  will  give  at 
least  a  fK>inter  as  to  the  correctness  or 
otherwise  of  our  ideas  on  thia  point. 

Chemistry  Department, 

University  of  Aberdeen. 

A  NEW  TEST  FOH  XTTRATKS. 
By  Ivor  G.  Xixon. 


The  i\iii<,'  lesr  lor  ii urates  possesses 
two  main  disacivaiifa^'es.  namely,  the  fer- 
rous sulphate    solution  does  not  keep    well. 


whilst  if  made    up  freshly  each    time,    the 
salt  dissolves  but  slowly    in  the  coid  water. 
It    appeared    possible    to  the    writer    that 
some    of  the    uitro-sulphonic    acids    of    the 
naphthalene  series,    which    are    noted    for 
their    intense  and    persistent  yellow  or    red 
colour  in  solution,  might  be  utilised  to  pro- 
vide   a  sensitive    test    for    nitrates    which 
would    be  free    from    these    disadvantages. 
These  nitro  acids  are  easily  formed  by  add- 
ing nitric  acid  to  a  solution  of  the  sulphonic 
acid  in  concentrated  sulphuric  acid,  tience  it 
would  appear  possible  that  the  addition  of  a 
few  dr(4>s  of  a  water  solution  of  one  of  tnese 
sulphonic  acids  to  a  mixture  of  the  suspec- 
ted nitrate,  in  water  solution,    with    an  ex- 
cess of  c<Miceutrated  sulphuric  acid,  should 
cause  a  distinctive  colour  to  be  developed  if 
a  nitrate  is  present.      This  test  was    tried, 
using  /3-naphthalene    sulphonic    acid,     but 
negative  results  were  obtained.     "  G  Salt  " 
(2:6:8  naphthol  dUulphonic  acid),  "Gam- 
ma acid"  (2:6:8  aminonaphthol  sulphcaiic 
acid),  "Schaflfer's  acid"  (2:6  naphthol  sul- 
phonic acid),  and  the  "Cleve's"  acids  (1:6 
and  1:7    naphthylamine  sulphonic    acids), 
however,  were  all  found  to  react  vigorously, 
giving  wine  red  solutions.    The  test  is  very 
sensitive,  with    "  G  Salt,"    for  instance    a 
distinct  red  colour   is  given    by  0.02    milli- 
grams of  nitrogen  as  nitric  acid,  whilst  with 
much    smaller    (juantities    a  faint    yellow 
colour  is  still  obtained.     Under  these  condi- 
tions, the  "Ring  Test"    gives  negative    re- 
sults.    Then'    is  no  need  to  cool  the    solu- 
tions during  the  tost,  as  must  be  done  dur- 
ing the  ring  t<'st.    Indeed,  it  was  found  that 
the     application    of    mwlerate    heat     often 
deepens  the  colour — thus  if  the  tost  mixture 
in  which  "G  Salt"  has  been    used  \<  boiled, 
the    colour    becomes    mcwo    intense,     and 
rather  bluer  in  tone.     Under  the  same  con- 
ditions for  "  Gamma  acid."    the  wine    red 
colour  of  the    solution  becomes    an    olive- 
green.     Nitrit«s    also  answer    to    the    test. 
The  general  method  of  procedure  is  as  fol- 
lows:— 

About  one  cubic  centimetre  of  the  sus- 
pected solution  i-;  mixed  with  aipnroxi- 
mately  an  equal  volume  of  concentrnted 
sulphuric  acid,  and  then  about  five  cubic 
centimetres  of  a  1  per. cent,  solut'on  f>f  "'(^ 
Salt"  slowly  added,  if  a  nitrate  or  nitrite  is 
present  an  intense  wine  red  colour  is  de- 
veloped. The  test  may  also  be  applied  ns 
a  ring  t<^st.  in  this  case,  the  nitrate  solution 
is  mixed  with  that  of  the  sulphonic  acid, 
and  concentrated    sulphuric    nci '  then  run 


262 


THE  CHEMICAL  NEWS. 


APRIL  27,  1923. 


down  the  side  of  the  test  tube.  A  red  ring 
is  formed  at  the  junction  of  the  two  hquids, 
and  on  shaking  the  tube,  this  colour  is  com- 
municated to  the  whole  of  its  contents. 


AN  EXPLANATION  OF  THE  THEORY 

OF  THE  ROTATION  OF  THE 

ATOMIC  NUCLEUS. 

By  Herbert  Henstoch, 

Part  I. 

In  a  previous  communication  {The 
Chemical  News,  1923,  CXXVL,  129)  the 
author  gave  a  general  description  of  the 
manner,  in  which  the  atomic  nucleus  iplays 
its  part  in  the  union  of  atoms,  together 
with  certain  effects  and  consequences 
which  must  follow  such  action.  It  is  now 
prriposed  to  describe  this  action  a  little 
more  in  defail,  and  to  attempt  to  show  its 
bearing  upon  some  of  the  difficulties  met 
with  both  in  inorganic  and  organic  chemis- 
try :  but  before  showing  its  applications  to 
concrete  cases,  it  has  been  thought  better 
to  give  a  general  explanation  here,  and  to 
defer  particularisations  to  the  future  parts 
of  this  series. 

This  hypothesis  in  no  sense  pretends^  to 
supersede  or  to  invalidate  the  theory  of  the 
Induced  Alternate  Polarity  of  Atoms,  but 
is  put  forward  as  an  explanation  ot  the 
underlying  cause  of  that  theory,  or,  to  be 
more  exact,  that  law;  for  alternate  polarity 
has  now  got  beyond  the  stage  of  theory  and 
is  beginning  to  be  recognised  as  an  actual- 
ity In  explanations  of  alternate  polarity, 
as,'  for  example,  that  given  by  Kermack 
an^  Robirison  (Trans.  Chem.  Soc.,  192^, 
CXXI  427)  the  idea  that  a  negative  atom 
appropriates  to  itself  some  of  the  electrons 
of  neighbouring  atoms,  and  that  a  positive 
ato  mtends  to  disintegrate,  may  or  may  not 
be  true ;  but  the  author's  point  is  tiiat  all 
such  features  are  merely  manifestations  or 
results  of  alternate  polarity  and  not  the 
cause  of  it,  the  cause  is  the  nucleus  of  an 
atom. 

If  this  hypothesis  be  applied  to  the 
Lewis-Langmuir  conception  of  the  atom, 
then  the  general  effect  of  the  nucleus  upon 
the  octet  will  be  seen  from  Fig.  1. 


Part  of  the  number  of  edges,  where  single 
valence  bonds  may  exist,  will  be  positive 
and  part  negative  in  the  same  atom,  so  that 
when  two  atoms  of  the  same  element  unite 
to  for  ma  molecule  they  both  have  similar 
potentialities  for  molecule  formation.  If 
we  imagine  such  an  atom  travelling  with 
one  of  its  negative  edges  in  front,  when  it 
meets  another  atom  similarly  situated  mov- 
ing to  meet  it,  the  second  atom  will  prob- 
ably rotate  as  a  whole  until  one  of  its  posi- 
tive edges  faces  the  first  atom,  when  union 
will  occur :  this  will  be  esipecially  the  case 
in  those  elements  strong  in  "permanent 
polarity"  (The  Cheviical  News,  loc.  cit.), 
but  it  is  more  than  probable  that  this  will 
occur  between  all  atoms  of  the  same  ele- 
ment. The  case  may  be  somewhat  differ- 
ent, however,  between  two  or  more  atoms 
of  different  elements :  an  atom,  strong  in 
permanent  polarity,  may  actually  rotate  the 
the  nucleus  of  another  much  weaker  one ;  as 
an  example,  a  chlorine  atom  may  rotate  the 
nucleus  of  a  carbon  atom,  but  would  not  ro- 
tate that  of  a  sodium  atom,  the  sodium 
atom  would  rotate  as  a  whole  till  a  positive 
edge  faced  the  chlorine,  just  as  would  be 
the  case  with  two  chlorine  or  two  sodium 
atoms.  This  effect  may  be  seen  from  Fig.  2. 


APBIL  27,  1923. 


THE  CHEMICAL  NEWS 


263 


If  A  and  B  be  two  chlorine  atoms,  and  A 
is  travelling  towards  B  with  its  edge  1-2  in 
front,  and  B  is  moving  towards  A  with  its 
edge  2-3  in  front,  then  the  whole  of  atom  B 
will  revolve  till  its  edge  1-2  faces  A.  If  A 
be  a  chlorine  and  B  a  sodium  atom  the 
same  thing  will  happen,  but  if  A  were  a 
chlorine  and  B  a  carbon  atom,  then  the 
union  might  be  made  between  A  1-2  and  B 
2-3,  but  the  nucleus  of  B  would  revolve 
through  an  angle  of  90°,  making  the  edge 
2-3  a  positive  one,  estpecially  if  the  carbon 
atom  were  already  combined  with  other 
jjtoms. 

In  working  out  the  various  problems,  the 
following  rules  have  been  found  to  .hold 
good  :  — 

(1)  The  normal  primary  valencies  in  any 
atom  will  be  wholly  confined  to  negative  or 
wholly  to  positive  edges.  ^^^^_^^^_ 


(2)  When  an  atom  unites  normally  by  its 
negative  edges  and  any  compound  is 
formed  where  a  positive  edge  comes  into 
play,  then  that  compound  will  be  an  un- 
stable one.  The  converse  for  normal  posi- 
tive edges  also  holds. 

(3)  The  nearer  together  the  nuclei  come  in 
a  molecule,,  the  more  unstable  it  will  be. 

(4)  Electrons  are  more  strongly  held  to 
the  nucleus  along  a  negative  edge  than 
along  a  positive  one. 

(5)  When  electrons  are  moved  from  one 
comer  to  another  in  the  octet,  a  strain  is 
caused  in  the  atom. 

(6)  Two  electrons  at  one  comer  in  a  bond 
are  a  source  of  weakness  in  the  bond. 

(7)  Distortion  of  the  octet  is  always  a 
source  of  weakness  in  the  molecule. 

A  chain  of  atoms  will  be  represented  es 
in  Fig.  3. 


H- 


-i- 


/ 

w 

w 

*^^~-^ 

■^^ — , 

^ 

X    \ 

/ 

r.'gizr 


The  normal  unsatisfied  valence  bonds 
will  lie  in  the  vertical  direction  in  each 
atom  in  accordance  with  rule  (1),  and  any 
union  along  a  horizontal  bond  will  be  un- 
stable, as  follows  from  rule  (2). 

Lapworth's  law  of  alternate  polarities  is 
here  clearly  demonstrated. 

A  double  bond  is  shown  in  Fig.  4. 

The  two  cube  faces  both  come  together. 
So  that  four  edges  touch  in  each  atom, 
which  eonstitut<'S  one  f>f  the  weaknesses  ..f 
the  double  bond,  since  in  the  case  of  the 
the  negative  atom  rules  (1)  and  (2)  both 
operate.      Also  the    nuclei    are  nearer    to- 


+ 


F^sH 


264 


THE  CHEMICAL  NEWS. 


APRIL  27,  1923. 


gether  than  they  axe  when  united  by  a 
single  bond,  hence  rule  (3)  operates,  which 
is  a  second  cause  of  weakness. 


A  treble  bond    may  be  seen    in  Fig.  5  re- 
presenting two  carbon  atoms. 


+ 


oc 


trv  . 


A-^TT 


In  the  negative  atom  the  nuclear  poles 
are  parallel  with  the  plane  of  x  y  z,  but  in 
the  positive  one  they  are  at  right  angles  to 
the  plane  oi  x  y  z. 

If  the  distorted  cube  representing  the 
positive  atom  could  be  taken  up,  turned 
over  and  applied  to  the  negative  one,  so 
that  X,  y  and  z  in  eacli  would  coincide,  then 
the  bond  would  be  complete. 

In  the  negative  atom,  the  electron,  from 
the  comer  of  the  octet  which  has  vanished, 
has  been  driven  down  to  z,  and  in  the  posi- 
tive atom  the  electron  from  z  has  been 
driven  to  m. 

There  are  at  least  three  sources  of  weak- 
ness in  this  bond : 

(1)  The  octet  is  distorted  and  electrons 
driven  from  the  corners  which  have  dis- 
appeared to  any  of  the  comers  x,  y  and  z. 
See  rules  5  and  7. 

(2)  In  the  two  triangles,  x  y  z 

1  xz  h   - 

2  xz  is  + 

1  yz  is   - 

2  yz  is  + 

1  xy  i?;    + 

2  xy  is  + 

In  the  negative  atom,  negative  and  posi- 


tive bonds  come  into  operation,  also  two 
positive  bonds  come  together.  See  rules  1 
and  2. 

(3)  The  two  nuclei  are  still  closer  together 
than  in  a  double  bond.     See  rule  3. 

A  treble    bond  is  therefore    a  very    weak 
one  when  acted  upon  by  other  atoms,  i.e., 
when  acted  upon  by  the  electricity   of  other 
atoms,  but  it  is  often  very  stable  to  heat,  as 
for  instance  in  the  case  of  acetylene.      The 
action  of  electricity    and  of    heat    upon    a 
bond  are  therefore    often  quite  different  and 
not  comparable ;  heat  may  or  may  not  (and 
more  often  does  not)    rotate  the  nucleus  cf 
an  atom  in  the  same  way  that  the    electri- 
city   of  another  atom  wilt    do.      These   two 
forces  are  often    confused  when  comparing 
the  relative  stability  of  compounds ;    a  sub- 
stance easily    decomposed  by  heat    is  often 
broken  up  by  different  causes    and  often  in 
different  ways  from    those  due  to  either    a 
current  of  electricity  or  the  electricity  of  an 
atom  :    as  an  example  might  be  mentioned 
the  deposition  of  copiper  from    a  solution  of 
cupric  nitrate  by  a  current  of  electricity  Crr 
by  metallic  iron,  whereas  heat  leaves  cuprie 
oxide  instead  of  the  metal.      Therefore,  un- 
less otherwise  specified,    a  weak  bond  may 
be  taken  to  mean  that  which  is  weak  in  an 
electric  sense  between  atom  and  atom. 


APRIL  27,  1923. 


THE  CHEMICAL  NEWS. 


265 


Distortion  of  the  octet  must  occur  in  a 
double  bond,  and  there  seems  no  reason  why 
it  should  not  do  so  in  all  atoms  where  there 
are  three  or  four  vacant  corners  to  the  cube ; 
in  fact,  some  kind  of  distortion  might  occur 
in  any  ancombinod  atom,  with  the  excep- 
tion of  those  of  the  inert  gases.  It  is  in- 
conceivable to  imagine  that  the  element 
cf.rbon  alone  has  the  form  of  what  might  be 
termed  a  distorted  cube.  In  the  case  of 
carbon  this  distortion  may  occur  not  only 
to  the  extent  of  the  complete  tetrahedron 
but,  as  will  be  shown  later,  partial  distor- 
tion of  the  cube,  between  it  and  the  tetra- 
hedron may  occur  when  carbon  is  in  the 
combined  state.  This  idea  may  be  extended 
to  the  octets  of  the  other  elements,  and  in 


-I- 


In  each  of  the  pairs,  th<  <  lectrons  are  to 
be  imagined  to  be  one  above  the  other  in 
planer  at  right  angles  to  the  plane  of  the 
paper,  and  not  in  the  iplane  oi  the  paper : 
this  also  a^pplies  to  double  and  treble  bcMids. 
II. — By  double  bonds: 

(a)  In  negative    atoms    the  four    elec- 
trons of  the  double  bond  are    alternately 


TIL     By  treble  bon.ls  : 

(a)  In  negiitiv*'  atoms  the  three  elec- 
trons, forming  the  bond,  are  jf>ined  two 
to  one  end  of  the  nucleus  and  one  to  the 


conjunction  with  the  direction  of  the  tubes 
of  force  emanating  from  the  nucleus  it  will 
be  found  caipable  of  explaining  many  ano- 
malous cases  of  vsdenoe,  together  with 
weakness  in  bonds  with  consequent  insta- 
bility of  molecules. 

The  usual  notation  suffices  to  show  the 
arrangement  of  electrons  and  bonds,  if  it  be 
remi  mbered  that  all  the  ordinary  unions 
are  made  normally 

T. — By  single  bonds: 

(o)    In    negative    atoms    by    electrons 

which  are  joined  to  opposite  ends  of    the 

nucleus. 

(h)     In    positive    atoms    by    electrons 

w^hich  are  joined  to  the  same  end  of  the 

nucleus. 


-   + 


•    «  •    • 


^    <$3c>»a 


A :  ^  :~Q 


•  •      •  • 


joined  to  either  end  of  the  nucleus  and  in 
the  H'maining  two  unions  the  electrons  of 
each  pair  arc  joined  to  opposite  ends  of 
the  nucleus. 

(b)  In  positive  at(»ns  double  bond  elec- 
tron pairs  are  joined  to  one  end  of  the 
nucleus,  the  other  two  valence  ipairs  to 
the  opposite  end. 


-     -f 


^  S<yyyt, 


-'^  'A'-^'. 


other;  the  two  electrons  forming  the 
single  bond  are  each  joined  to  opjpofiite 
ends. 

(6)  In  positive  at<Mns  all  three  electrons 


^66 


THK  CHEMICAL  NEWS. 


APRIL  27,  1923. 


of  the  treble  bond  are  joined  to  one  end  of 
the  nucleus,    and  the    two    single    bond 


electrons  to  the  other  end. 


+ 


-    + 


Here  it  cannot  be  seen  that  the  positive 
carbon  atom  shares  two  of  its  electrons  with 
the  negative,  which  latter  shares  but  one 
with  the  positive,  without  reference  to  Fig. 
5.  In  the  negative  atom  there  is  only  one 
"  single  bond,"  although  tliere  are  four 
electrons,  and  in  the  positive  atom  there  is 
a  single  electron  which  is  apparently  alone, 
but  the  true  significance    is  not  seen  with- 


GENERAL  NOTES. 


GERMANY'S  TRADE  INDUSTRY 
DURING  MARCH. 

The  Commercial  Secretary  at  Berlin 
(Mr.  J.  W.  F.  Thelwall)  has  forwarded  to 
the  Department  of  Overseas  Trade  a  sur- 
vey of  the  position  of  trade  and  industry 
during  March. 

It  appears  that  un,-occupied  Germany 
has  borne  the  cutting  off  of  her  most  im- 
portant industrial  area  comparatively  well. 
The  anticipated  shortage  of  coal  has  not 
set  in.  The  demand  for  pig  iron  and  steel 
was  also  met.  This  was  possible  owing  to 
the  existing  stocks,  and  increased  imports, 
especially  of  English  coal. 

In  the  textile  and  tobacco  industries 
there  were  further  indications  of  a  retro- 
grade movement,  while  employment  in  the 
remaining  industries  was  generally  satis- 
factory in  spite  of  high  costs  of  production 
in  consequence  of  the  use  of  English  coal. 
In  occupied  territory,  however,  works  were 
compelled  to  incur  heavy  unproductive  ex- 
penditure, and  their  free  development  was 
greatly  interrupted  by  the  blockade  and 
other  acts  of  intervention  by  the  occupying 
Powers.  They  were  forced  to  continue  to 
work  for  stock. 


OX  sc^/M  ^  <r  *  -^  * 


out  drawing  the  octets  and  putting  in  the 
lines  of  force,  when  the  matter  at  once  be- 
comes clear,  which  is  a  good  demonstration 
of  the  importance  of  the  lines  of  force  in 
any  cases  of  doubt  as  to  how  a  substance  :s 
constituted. 

Chemical  Research  Laboratory , 
School  Gardens, 
Shrewsbury. 


Mining. 

No  definite  information  with  regard  to 
the  coal  output  of  the  Rhenish-Westphalian 
coal  district  can  be  given.  In  the  Central 
German  brown  coal  district  a  not  incon- 
siderable increase  of  output  occun-ed. 
There  was,  however,  an  interruption  of 
sales  owing  to  a  smaller  deinand  on  the 
part  of  the  sugar  working-up  industry  and 
also  of  the  potash  industry.  The  demand 
for  Upper  Silesian  coal  also  partly  ceased. 
It  thus  appeared  that  buyers  had  quickly 
covered  their  requirements  as  a  result  of 
the  Ruhr  occupation,  and,  with  the  uncer- 
tain economic  situation  and  the  expected 
reduction  of  coal  prices,  were  not  yet  ready 
for  new  purchases.  The  gasworks  belong- 
ing to  couimunitios  particularly  showed  re- 
serve in  placing  new  orders. 

Potash  Industry. 

The  market  conditions  were  unfavour- 
able. In  particular  German  agriculture, 
whose  demand  in  this  month  is  usually 
great,  limited  its  purchases.  The  reason 
for  this  lay  partly  in  the  high  prices  of  pot- 
ash and  coal,  and  also  high  freights,  and 
partly  because  German  farmers  covered 
their  requirements  sufficiently  in  previous 
months  at  cheaper  potash  prices  and 
freights.     Foreign  trade  was  confined  with- 


APEIL  27,  1923. 


THfi  CHEMICAL  NEWS 


26? 


in  comparatively  narrow  limits:  only  for 
sulphate  of  potash  salts  was  the  demand 
satisfactory.  The  market  for  the  by-pro- 
ducts of  the  potash  industry  also  left  miuch 
to  be  desired. 

The  aluminium  industry  continued  to 
suffer,  and  the  outlook  for  the  near  future 
is  bad. 

The  electro-technical  industry  also  suf- 
fered from  lack  of  orders.  An  amiple 
demand  for  electrical  plant  of  all  kinds  ex- 
isted, but  there  was  nowhere  any  possibility 
of  raising  the  requisite  capital. 

In  general,  employment  in  the  electro- 
technical  industry  is  assured  tor  months 
ahead. 

Chemical  Industry. 
Owing  to  the  fact  that  nrices  in  the 
chemical  industry  had  reached  and  partly 
exceeded  the  world's  market  level,  foreign 
orders  declined.  Competition  with  foreign 
countries  was  rendered  partieularlv  difficult 
by  high  railway  freights,  ptrstal  fees,  and 
coal  prices.  In  exjpectation  of  a  reduction 
of  prices,  inland  customers  covered  cmly 
their  immediate  needs  in  small  quantities. 
There  was  still  in  stock  a  heavy  proportion 
of  goods  ipurchased  at  high  nrices  in  Janu- 
ary and  February  which  could  be  dispofted 
of  only  at  a  loss.  lousiness  in  chemically 
pure  reagents  and  pniparatious  was  almost 
completely  at  a  standstill,  owing  partly  to 
the  closing  of  all  institutes  and  universi- 
ties for  Easter. 

Indiarubber  Industry. 
The  position  was  unsatisfactory.  The 
shortage  of  German  coal  necessitated  in- 
oreasea  purchases  of  English  fuel.  Condi- 
tions on  the  inland  market  were  thoroughly 
unfavourable. 

Glass  Industry. 
In  the  sheet  glass  industry  the  supfply  of 
raw  materials  was,  in  general  sati8fact<>ry. 
The  eosts  of  manufacture  ,'ipproached  the 
world's  market  prices.  The  inland  demand 
continued  to  fall  off.  Bel^'ian  and  Czech 
glass  industries  greatly  injured  the  German 
industry  on  foreign  markets,  so  that  only 
very  few  sales  to  the  eastern  Border  States 
were  possible.  Exports  to  Italy,  Africa, 
and  America  were  small.  In  the  hollow 
glass  industry  a  stagnation  of  sales  set  in, 
resulting  in  restrictions  of  work." 
Fertilisers. 
Tha  market  for  nitrogenous  fertilisers 
was  slMi^tuiut.  Some  fa<'tories  in  occupied 
territovy  had  to  cease  work.  Prices  were 
such  that  (ierman  nitrogen  was  still  cheaper 
than  foreign  nitrogen. 


In  order  to  afford  farmers  who  have  not 
yet  placed  their  s,pring  orders,  the  possibil- 
ity of  ipurchasing  nitrogenous  fertilisers 
cheaply,  the  Nitrogen  Syndicate  has  de- 
cided .  to  sell  such  fertilisers  for  the  time 
being  at  reduced  prices,  quite  out  of  propor- 
ti<Mi  to  the  reduction  in  coal  prices  of  the 
1st  April.  The  lowered  prices  came  into 
tfieot  on  the  3rd  .\jpril. 

SCIENTIFIC  APPARATUS  FOR 
BRITISH  COLUMBIA. 

H.M.  Trade  Commissioner  in  Vancouver, 
British  Columbia  (Mr.  L.  B.  Beale)  reports 
that  the  authorities  of  the  University  of 
British  Columbia  aie  desirous  of  receiving 
from  U.K.  manufacturers  illustrated  cata- 
logues, full  f)articular8,  and  prices  of  scien- 
titic  apparatus. 

Further  particulars,  together  with  the 
names  of  the  enquirers,  may  be  obtained  by 
firms  interested  upon  application. 


The  Commercial  Secretary  at  Bucarest 
regions  that  the  Roumanian  Railroad  Ad- 
ministration invites  tenders  for  the  suppiy 
of  sulf>hatti  of  copper. 

Application  for  particular;?  should  be 
made  to  the  Department  of  Overseas  Trade, 
35,  Old  Queen  Street,  London,  S.W.I. 


THE   DYE   INDUSTRY. 

Nbw  Cabbkus  Ckbated  by  an  Act  of 
Pauliamemt. 

The  effect  u|>on  the  career  of  University 
men  of  new  conditions  in  the  Dyestuffs  In- 
dustry is  discussed  in  an  interview  by  Pro- 
fessor Arthur  G.  I'erkin,  F.R.S.,  the  head 
of  the  Departments  of  Colour  Chemistry 
and  Dyeing  at  Leeds  University,  where  the 
summer  term  has  just  opened. 

"  Although  the  number  of  students  en- 
tering our  Colour  Chemistry  and  Dyeing 
Department  is  falling,  he  said,  "it  still  re- 
mains much  higher  than  at  any  time  before 
the  war.  A  decrease  to  some  extent  is  in- 
evitable because,  in  the  first  place,  many 
ex-army  men  have  now  finished  their  train- 
ing, and,  at  the  same  time,  fees  have  of 
necessity  been  c^msiderably  increased.  This, 
I  am  afraid,  may  prevent  many  young  men 
from  taking  our  course. 

"  In  the  future  we  may  have  a  normal 
sixty    students    taking    our     three    years' 


268 


THE  CHEMICAL  NEWS. 


APEIL  27,  1923. 


course  either  for  the  Diploma  or  Ordinary 
B.Sc.  in  dyeing,  or  our  four  years'  course, 
leading  to  the  Honours  B.Sc.  in  colour 
chemistry.  In  this  case  some  twenty 
students  will  enter  the  dyeing,  colour 
chemistry  and  allied  industries  each  year. 
Much,  however,  depends  upon  Government 
action;  for,  if  they  repeal  the  Dyestuffs  Act, 
there  is  no  doubt  that  the  artificial  dyes  in- 
dustry will  become  moribund  in  this  coun- 
try. As  it  is,  the  forty-seven  students  wno 
left  me  this  year  have  all  obtained  positions 
not  only  in  colour  works,  but  in  wool  dye- 
ing, cotton  dyeing,  calico  printing,  artificial 
silk,  and  other  industries." 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  MINEIUL  OUTPUT  OF  YUKON. 

Figures  are  to  hand,  authenticated  by  the 
District  Gold  Commissioner,  Mr.  George  P. 
MacKenzie,  showing  the  output  of  gold, 
silver,  lead,  and  copper  from  this  territory. 
The  dominant  note  in  his  report  is  one  of 
sheer  optimism  that  the  future  holds  mucu 
good,  in  the  productive  sense. 

Conservative  quotations  show  the  total 
output  as  follows:  Gold,  $200,000,000;  sil- 
ver, 3,500,000  ozs.,  valued  at  $2,100,000; 
lead,  3,500  tons,  valued  at  $400,000;  cop- 
per, 12,000,000  pounds,  valued  at 
$2,700,000.  Two  million  ounces  of  the  sil- 
ver was  produced-  as  a  by-product  in  refin- 
ing placer-gold;  and  the  Mayo  district,  so 
long  unworkable  owing  to  difficulties  of 
transport,  has  so  far  developed  that  1,500 
claims  are  now  staked. 

It  has  long  been  feared  in  the  circles 
concerned  that  the  mines  were  becoming 
used  U|p,  and  that  very  little  metal  remains. 
Mr.  MacKenzie  refutes  this  belief,  ana  ter- 
minates an  interesting  report  with  the  fol- 
lowing paragraph:  — 

"  The  views  of  the  residents  of  the  terri- 
tory and  all  those  interested  in  its  mineral 
resources  and  production  are  now  most  op- 
timistic. The  life  of  the  placer  fields  is 
anything  but  over,  and  now  it  appears  cer- 
tain that  a  period  during  which  the  silver- 
lead  areas  of  the  territory  will  equal  or  ex- 
ceed the  gold  fields  in  the  production  of 
wealth  has  just  been  entered  upon,  wliile 
further  gold,  silver,  and  copper  deposits 
may  be  said  to  be  held  in  reserve  awaiting 
the  day  when  the  world  market  calls 
them." 


THE  KOYAL  SOCIETY. 
Thursday,  April  26. 

Papers  read :  — 

T.  R.  Merton,  F.R.S.,  and  R.  C.  John- 
son :   On  Spectra  associated  with  Carbon. 

R.  A.  Watson  Watt  and  E.  V.  Apple- 
ton,  D.Sc. :  On  the  Nature  of  Atmospher- 
ics. Communicated  by  Sir  Henry  Jackson, 
F.R.S. 

W.  A.  Bone,  F.R.S. ,  D.  M.  Newitt,  and 
D.  T.  A.  Townend  :  Gaseous  Combustion 
at  High  Pressures.  Part  III.  :  The  Energy 
absorbing  Function  and  Activation  of  Nitro- 
gen in  the  Combustion  of  Carbon  Monoxide. 

I.  Masson,  D.Sc,  and  L.  G.  F.  Dolley  : 
The  Pressures  of  Gaseous  Mixtures.  Com- 
municated by  Professor  F.  G.  Donnan, 
F.R.S. 

Papers  read  in  title  only  : — ■ 

W.  R.  BousFiELD,  F.R.S..  and  C.  Els- 
PETH  Bousfield  :  Vapour  Pressure  and 
Density  of  Sodium  Chloride  Solutions. 

F.  A.  LiNDEMANN,  F.R.S.,  and  G.  M.  B. 
DoBSON  :  A  Note  on  the  Temperature  of  the 
Air  at  Great  Heights. 

G.  H.  Hardy,  F.R.S.,  and  J.  E.  Little- 
wood,  F.R.S.  :  On  Lindelof's  Hypothesis 
concerning  the  Riemann  Zcta-fiinction. 


ROYAL    INSTITUTION. 

On  Thursday,  April  26,  Professor  J.  T. 
MacGregor-Mouhis  began  a  course  of  three 
lectures  at  the  Royal  Institution  on  Modern 
Electric  Lamps.  On  Saturday,  April  28, 
Dr.  Leonard  Williams  will  deliver  the  first 
of  two  lectures  on  the  Physical  and  Physio- 
logical Foundations  of  Character. 

The  Friday  evening  discourse  on  Ajnil  27 
will  bo  delivered  by  Mr.  C.  V.  Boys,  on 
Measurement  of  the  Heating  Value  of  Gas, 
and  on  May  4  by  Professor  Soduy,  on  the 
Origins  of  the  Conception  of  Isotopes. 


ROYAL  SOCIETY  OF  ARTS. 
On  Friday,  April  20,    there  was    a  joint 
meeting  of  the  Dominions  and  Colonies  and 
the  Indian  Soctu-iK.     Sir  Richard    A.    S. 


APlilL  27,  1923. 


THE  CHEMICAL  NEWS. 


269 


Hkumavnb,  K.C.li.,  M.Sc,  M.Inst.C.E., 
M.I.M.E.,  F.G.S,,  delivered  a  lecture  en- 
titled A  Hrvieu;  of  the  Banc  Mefnl  Industry, 
iritli  Special  Reference  in  the  licaourccH  of 
the  Br, fish  Evipire.  The  Ht.  Hoo.  Lord 
Emmr  tt,  G.O.M.G.,  G.B.E.,  .presided. 

On  Monday,  April  23,  Mr.  E.  Kilburx 
Scott.  M.I.E.E,,  A. M.Inst.C.E.,  gave  his 
(third)  Cantor  lecture,  Nitrates  from  Air. 

On  Wednesday,  April  25,  there  was  a 
coiifeieiice  c.n  The  Milk  Question  at  the  Or- 
dinary Meeting.  Short  papers  were  read  as 
follows:  (1)  The  Anjuments  for  Maintain- 
ing an  Oft'  n  Market  for  Freah  Milk,  by 
pROFKssoii  K.  Stenhouse  Wii.liams,  M.B.. 
B.Sc,  J..H.C.P.,  and  S.E.,  D.P.H.; 
Chnm/CH  in  the  Digestibility  and  Nutritive 
Value  of  Milk  Induced  by  Heating,  by  Pro- 
fessor J.  Cecil  Drummond,  D.Sc,  F.l.C. ; 
(3)  The  Effect  of  Heat  on  Some  Physiologi- 
cal Principles  in  Milk,  by  S  S.  Zilva. 
Ph.D.,  D.Sc,  F.l.C.  A  demonstratirin  of 
some  of  the  chemical  chimges  in  milk  on 
heating  to  various  temperatures  was  given 
by  Captain  .John  Ooldino,  D.S.O.,  F.l.C. 
and  Mrs.  A.  T.  R.  Mattick,  M.Sc.  Tho 
Rt.  Hon.  F.  D.  Acland,  M.P..  .presided. 

Arrangements  for  Mf.etin(;s  until  the 
End  of  the  Present  Skason. 

Monday,  April  30,  8  p.m.  (Howard  IjBC- 
ture) :  The  Development  of  the  Steam  Tur- 
bine, by  Stanley  S.  Cook  (Lecture  1). 

WVdnesday,  May  2,  8  p.m.  (Ordinary 
Meeting) :  Maurice  Drake,  The  Fourteenth 
Century  Revolution  in  Glass  Painting.  Pro- 
fessor \V.  K.  Fiethaby  will  preside. 

Monday,  May  7,  8  p.m.  (Howard  lec- 
ture): The  Development  of  the  Steam  tur- 
bine, by  Stanley  S.  Cook  (Lecture  2). 

Wednesday.  May  9.  8  p.m.  (Ordinary 
Meeting):  William  Arthur  Bone,  D.Sc.. 
Ph.D.,  F.K.S..  Professor  of  Chemical 
Teehnologv,  Imperial  College  of  Science 
and  Technology,  South  Kensington.  Re- 
cent Developments  in  Surface  Combustion. 
D.  Milne  Watson  M.A.,  LL.B..  Governor 
of  the  Gas  Light  and  Coko  Company,  will 
preside. 

Monday,  May  14.  8  p.m.  (Howard  Lec- 
ture):  The  Development  of  f  Sfeam  Tur- 
bine, by  Stanley  S.  Cook  (Lecture  8). 

Wednesday,  May  30,  4.30  p.m.  (Ordi- 
nary Meeting):  A.  J.  Sewell.  'I'he  History 
and  Development  of  the  Perambulator  and 
Invalid  Carriage. 

Friday,  .June  L    4.80  p.m.    (Indian    Sec- 


tion): Austin  Kendall,  l.C.S.  retd..  the 
Indian  Section  of  the  British  Empire  Ex- 
hibition, 1924. 

Friday,  Junelu,  4.30  p.m.  (Indian  Sec- 
tion;: Sir  John  H.  :Marshall,  CLE., 
M.A.,  LiTT.D.,  F.S.A.,  Director-General  of 
Archeology  in  India,  The  Influence  of  Race 
on  Early  Indian  Art.  (Sir  George  Birdvvood 
Memorial  Lecture.) 


ROYAL  MICROSCOPICAL  SOCIETY. 

The  sectiMi  of  the  Society  which  has 
been  formed  to  deal  with  the  Industrial  Ap- 
plications of  the  Microscope,  and  to  assist 
in  the  development  of  Industrial  Research 
in  Brit.sh  Industries,  held  a  meeting  on 
Wednesday,  April  '2'>. 

Messrs.  C.  Baker  exhibited  their  junior 
I  ngineer  metallurgical  microscope  and  the 
(iieenough  binocular  microscope. 

M' ssrs.  H.  &  J.  Beck,  Ltd.,  demon- 
strated a  new  research  outfit  for  metallurgi- 
cal \\(/rk,  including'  microscope,  camera, 
o|)tic4il  bench,  etc. 

The  Edison  Swan  Electric  Co..  Ltd., 
showed  their  projector  and  fuUolito  lamips. 

Mr.  Manse!l  P.  Swift  demonstrated  the 
use  of  Dichroisooi>e.s  iar  the  identification 
of  certain  gem  stones. 

Messrs.  W  v\'atson  A  Sons  exhibited 
petrological  mioroscopes. 

Mr.  J.  E.  Barnard,  F.Inst.P.,  F.R.M.S. 
gave  the  fir.-*t  of  a  scries  of  short  communi- 
cations on  The  .Manipulation  of  the  Micro- 
scope in  Industrial  Laboratories.  Part  I. : 
lUuminants  and  Illuntination. 

Dr.  Marie  C.  Stopbs,  D.Sc,  Ph.D., 
F.L.S.,  rt'au  a  pap<'r  entitled  The  Micro- 
scopical Examinati(m  of  Coal  in  relation  to 
Fuel  Economy  and  Efficiency. 

Future  meetings  will  be  held  a»s  follows: 

May  Irt:  Mr.  Leonard  Taverner, 
.\.R.S..M..  The  Principles  and  Application 
of  Technical  Mctallur(fical  Microscopy. 

Mr.  W.  M.  Ames.  M.A.,  B.Sc,  A.l.C, 
.ipplrcat'ims  of  the  Microscope  in  the  Man- 
ufacture of  Rubber. 

May  30:  yin.  Joseph  M.  Coon,  On  the 
Microscopical  Determination  of  Cassiterite 
in  Rock  Sections. 

Mr.  H.  B.  Milner,  The  Microscopical 
Investigation  of  Sands  for  various  Indus- 
trial Purposes. 

The  Industrial  Applications  Section  of 
the  Royal  Microscopical  Society  has  been 
formed  for  the  purpose  of    assisting  in  the 


270 


THE  CHEMICAL  NEWS. 


APETL  27,  1923. 


development  of  Industrial  Research  in 
British  ludii  tries,  and  holds  regular 
monthly  meetings  with  practical  demon- 
strations connected  with  the  reading  and 
discussion  of  communications  dealing  with 
Industrial  Research  problems. 

Enquiries  and  suggestions  are  solicited 
by  the  Honorary  Secretaries  to  the  Section  : 
W.  E.  Watson  Baker,  A.Inst. P.,  313,  High 
Holborn,  W.C.I,  C.  F.  Hill,  M.Inst.M.M., 
A. Inst. P.,  Moore,  Warrington. 


THE  CHEMICAL  SOCIETY  OF  JAPAN. 

The  following  papers  have  been  commu- 
nicated to  the  Society:  — 

Studies    on     Accelerators    of    Oxidation 
Part  I.      Action  of  Ferric    Sulphate    upon 
Potassium  Perwanqannte,  by  Bunsuke  Su- 
zuki and  Chujirz  Hamada. 

On  the  Oxidase-lihc  Action  of  Complex 
Salts  of  Metals.  Part  III.  Decomposition 
of  Hydrogen  Peroxide  by  Complex  Salts  of 
Kaneko. 

Influence  of  Heatinq  and  Oxidation  ov 
the  Vitamine  A  and.  B  of  Milk,  by  ITjoepa- 
BURO  Serine  and  Tamotsu  Okamurx. 

Studies  of  Metallic  Oxides  and  their  Hy- 
drates by  X-Eays.  Part  I.  X-Eay  Analy 
sis  of  Stannic  Oxide  and  its  Hydrates,  by 
NoBUG  Yamada. 

Braun's  Law  and  Thallous  Sulphate,  by 
Fusao  Ishikawa. 


The  Society  of  Motor  Manufacturers  and 
Traders,  Ltd.,  have  decided  to  organise, 
from  Thursdav,  November  22,  to  Saturday. 
December  1,  1923,  in  the  recently  enlarged 
Olvmpia.  pn  Exhibition  embracing  not  only 
the  various  types  of  commercial  motor 
vehicles  and  their  components  and  acces- 
so'ries,  but  also  plant,  machinery  and 
materials  used  in  the  construction,  main- 
tenance,  and  develoipment  of  roads. 

Th"  exhibition  will  be  divided  into  four 
sections :  Commercial  motor  vehicles  and 
body  work ;  accessories  and  components ; 
tyres;  and  road  plant,  machinery,  and 
materials. 

The  exhibition  manager  will  be  pleased  to 
supply  copies  of  the  conditions  and  forms 
of  application  for  space,  on  airmlication  to 
the  Society's  offices,  83,  Pall  Mall,  Lon- 
don, S.W.'l. 


CORRESPONDENCE. 


ATOMIC  THEORIES. 

To  the  Editor  of  The  Chemical  News. 

Sir,  —  With  regard  to  the  notice  of  the 
second  edition  of  my  Atomic  Theories, 
which  you  kindly  gave  in  your  last  issue, 
the  point  raised  by  the  reviewer,  concerning 
the  positions  of  the  electrons  in  the  carbon 
atom  is  certainly  an  interesting  one. 

At  the  time  of  writing  I  did  not  regard 
the  positions  of  the  electrons  as  absolutely 
assigned  and  always  definitely  fixed  to  cer- 
t-iin  cornel's  O'f  the  cube;  for,  even  suppos- 
ing the  arrangement  to  be  as  shown  by  Fig. 
19,  on  page  90,  which  is  the  one  expected 
when  the  four  electrons  are  free  to  take  up 
positions  of  equilibrium  in  the  outer  shell 
of  the  atom.  But  in  the  case  of  the  com- 
bination shown  in  Fig.  33  on  page  90,  it 
seems  probable,  as  your  reviewer  has 
pointed  out,  that  the  electrons  might  take 
up  changed  positions  to  meet  the  vacant 
places  in  one  of  the  oxygen  atoms,  if  this 
latter  happens  to  be  in  the  position  shown 
in  the  figure. 

If,  however,  one  of  the  oxygen  atoms  is 
orientated  through  an  angle  of  90  degrees, 
then,  of  course,  this  orientation  of  the  car- 
bon electrons  would  not  take  place.  The- 
electrons  would  have  the  positions  as  shown 
in  the  earlier  figure. 

Other  considerations  also  tend  to  show 
that  the  electrons  may  alter  their  positions 
in  the  atoms. 

I  am,  Yours,  &e., 

F.    H.    LORING. 

London.  S.W.i. 
April  21,  1923. 


NOTICES  OF  BOOKS. 

A  Comprehensive  Treatise  on  Inorganic 
and  Theoretical  Chemistry,  by  J.  W. 
Mellor,  D.Sc.  Vol.  HI.,  pp.  X.  +  927. 
London:  Messrs.  Lonemans,  Green  & 
Co.,  39,  Paternoster  Row,  E.C.4.  1923. 
Price  63s.  net. 

This  volume  covers  the  olemonts  Cu,  .\g, 
Au,  Ca,  Sr,  and  Ba,  and  the  mass  of  infor- 
mation it  contains  is  enormous.  Each 
element  is  dealt  with  from  historical,  geo- 
logical, physiological  and  purely  chemical 
aspects,  and  the  various  derivatives  are 
enumerated  separately.  The  last  three 
substances  are  collected  imder  the  heading 
of  alkaline  earths. 


APRIL  27,  1923. 


THE  CHE!\fICAL  NEWS. 


271 


There  is  no  doubt  that  the  work  covers 
every  by-way  in  the  scientific  knowledge  of 
the  el<•nn^nts,  and  the  time  and  labour 
spent  Ujpon  it  cannot  ho  described  other- 
wise than  as  colossal;  but  the  author  has 
made  the  great  mistake  of  adding  a  profu- 
sion of  references.  For  instance,  in  the 
chapter  upon  cupric  chloride  and  the  com- 
plex salts  thereof,  there  are  no  fewer  than  4 
pages  of  references,  with  70  lines  to  the 
page. 

Considerable  attention  has  been  (paid  to 
the  sources  of  the  elements  (i.e.,  the  com- 
position of  the  ores,  etc),  their  extraction, 
and  alloying.  Tn  fact,  er  mplete  deduction 
from  the  crude  ore  to  the  most  complex 
"R.P.  salt  is  f;ne  of  the  most  prominent 
features.  Qualitative  and  quantitative 
analyses  have  been  associated  with  the 
most  up-to-date  methofls  of  research,  and 
various  theoretical  discussions  are  incor- 
porated with  great  thoroughnesa. 

Efficiency  in  authorship  and  editorship  is 
evident  in  its  maximum  degn'e,  and  the 
work  is  most  valuable  for  complete  refer- 
ence. So  far.  it  is  incomiplete,  further 
volumes  being  in  preparation,  the  next  one 
dealing  mainly  with  the  radium  and 
actinium  families.  We  awnit  its  publica- 
tion with  interest,  and,  meanwhile,  place 
the  present  vohime  high  on  the  shelves  of 
great  works.  .T.M. 

FAe/mrnU  of  GlaitH-hlninnq,    bv    TT.  P. 

Waran.    M.A..    Ph.D..    F.Tnst.P.      Pf). 

IX.  +  116.    London:    Ci.    Bell    A    Sons. 

Ltd.,    Portugal    Street,    W.C.2.       1028. 

Price  2s.  4d.  net. 

Manipulative  skill  in  glass-blowing  can 
only  be  acquired  by  nntient  practice — prac- 
tice, it  may  be  mentioned,  along  the  correct 
lines.  ^  ... 

Students  show  very  unequal  capacities  m 
making  iprogress  in  this  direction,  whilst 
m\ich  depends  on  their  own  ability,  expert 
guidano^  coimts  for  much.  The  examples 
of  a  clever  maniipulator  greatly  help  them 
to  become  proficient. 

The  present  manual  on  this  fluhi'ect  will 
be  found  useful  to  students  and  inexperi- 
enced research  workers  called  upon  to  cnrrv 
out  cx^rtain  trlass-blowine  work,  whether  it 
he  merelv  the  ioining  of  two  tubes  or  the 
makine  of  vacuum  tubes  or  other  elaborate 
nipparatus.  The  principles  and  advice  given 
bv  the  niithor  are  sound,  and  the  illustra- 
tions are  very  clear. 

The  hook  should  certamly  ap,peal  to  a 
wide  circle  of  readers  among  chemists  and 
physicist*.  , 


Atoms,   by  Jean  Pbrrin.       Authorised 

translation    by    D.  Ll.    Hammick,    M.A. 

Second  English  eflition  revised.  Pp. 
-XV.  +  231.     London:    Constable  &  Co.. 

Ltd.,  Orange  Street,  W.C.2.     123.  Price 

8s.  6d.  net. 

The  second  English  translation  of  Prof. 
Perrin's  Les  Atonies,  which  has  now  been 
published,  has  been  based  upon  the 
eleventh  revised  French  edition. 

The  contents  have  been  revised  where 
necessary,  ^in  accordance  with  the  rapid 
advances  which  continue  to  be  made  in 
atomic  science. 

A  particularly  lucid  account  of  the  ex- 
periments and  views  of  Prof.  Perrin  and 
others  on  the  Brownian  movement,  radia- 
tion, light  and  quanta,  electrons,  etc.,  are 
given,  tog»ther  with  the  advances  in  the 
study  of  the  genesis  and  destruction  of 
atoms  by  various  investigators. 

In  th"  section  entitled  Appendix,  1921. 
then'  are  notes  on  recent  work  in  certain 
directions,  e.g..  Corpuscular  Swarms, 
Bohr's  Theory,  etc. 

This  English  edition  should  serve,  at 
least,  to  make  Prof.  Perrin's  work  more 
widelv  known,  both  here  and  in  America. 


Ink      by    C      Ainsworth     MixcnELi.. 

M.A..'P.l'.C.  Pp.  VITI.  +  128.  London: 

Sir  Isaac  Pitman  A  Sons,    Ltd.,    Parker 

Street.  Kingswav.  W.C.       1928.       Prico 

88.  net. 

Whilst  the  author  has  not  attempted  to 
compile  a  laborafory  or  works  manual,  he 
has  written  a  very  readable  and  informative 
volume,  which  contains  an  account  of  tho 
history  and  scientific  developments  of  the 
manuifacture  and  uses  of  inks. 

Sufficient  details  are  given  of  the  pro- 
cesses for  preparing  the  different  kinds  of 
inic  for  ordinarv  and  sipecial  purposes,  so 
that  a  clear  and  correct  impression  of  the 
methods  mav  be  obtained.  ,    .  , 

After  a  description  of  the  raw  materials 
for  makinjT  iron-gall  inks,  and  their  manu- 
facture, there  is  a  chapter  on  the  methods 
of  testing  inks  in  general.  Tn  this  and  other 
chapters  the  author's  special  knowledge  and 
experience  is  much  in  evidence.  Besides 
the  iron-gall  preparations  there  are  now 
numerous  others,  e.g.,  logwood  inks,  vana- 
dium inks,  and  those  made  from  aniline 
black  and  similar  dyestuffs.  Special  inks 
such  as  those  for  ef^pving,  tvpewnting  and 
printing,    and  Indian  inic,    nil  receive    ade- 


272 


THE  CHEMICAL  NEWS. 


APKIL  27,  1923. 


quate  treatment,  consistent  with  the  size  of 
the  book. 

The  information  contained  in  this  little 
volume  is  noticeably  free  from  industrial 
and  scientific  technicalities,  thus  making  A 
available  for  general  readers,  as  well  as  for 
chemists,  analysts  and  others  who  may  be 
specially  interested  in  the  subject. 


The  Recovery  of  Volatile  Solvents,  by 
C.  S.  EoBiNSON.  Pip.  188.  New  York: 
The  Chemical  Catalos;  Co.,  19,  East  24th 
Street.     1922.     Price  $2.50. 

It  is  only  of  late  that  the  recovery  of 
volatile  solvents  has  attained  any  import- 
ance in  industrial  chemistry.  The  subject 
has,  however,  been  well  investigated.  The 
author  of  the  present  volume,  who  has  him- 
self made  valuable  contributions  on  the 
subject,  is  of  opinion  that  future  improve- 
ments in  solvent  recovery  must  be  princi- 
pally in  the  designing  of  suitable  apparatus 
and  in  the  improved  application  of  known 
principles. 

Prof.  Eobinson  has  presented  a  good  and 
well  illustrated  account  of  these  fundamen- 
tal principles  and  their  technical  applica- 
tion. The  book  is  divisble  into  six  sections. 
The  first  six  chapters  give  the  important 
elementary  principles.  The  technical 
readers  of  this  volume  may  find  the  physi- 
cal chemistry  of  this  section  hard  reading, 
but  it  is  of  importance,  since  the  chemical 
engineering  involved  rests  upon  these  prin- 
ciples and  laws. 

The  second  portion  nf  the  book  (chapter?; 
VII. -XI.)  deals  with  the  application  of  solid 
absorbents.  The  third  ipart  deals  with  the 
recovery  of  vapours  by  condensing  and 
cooling  processes.  Part  four  (chapter  XX.) 
covers  the  methods  of  combined  cooling  and 
compression.  An  account  of  the  various 
methods  of  scrubbing  constitutes  part  five, 
and  a  long  and  excellent  abstract  of  the 
literature  constitutes  the  final  section. 

This  is  the  first  book  to  deal  exclusively 
with  solvent  recovery,  and  the  aiithor  is  to 
be  congratulated  upon  the  care  which  he 
has  given  to  the  compilation  of  this  valu- 
able contribution  to  technical  literature. 


8956- 


xHis  list  is  specially  compiled  for    The  Chemical 

News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 

Agents,  of  5,  Chanc^.-y  Lane,  London,  from  whom 

all  information  relating  to  Patents,  Trada  Marks, 

and  Designs  can  be  obtained  gratuitously. 

Latest   Patent   Applications. 

9004 — Chemical   Industry     in   Basle. — Manufacture 

of  soluble  acid  in  calcium     salts  of  inosite- 

phosphoric  acid.    March  29. 

8576 — Laporte,   Ltd.,  B. — Manufacture     of  barium 

peroxide.    March  26. 
8837 — Casselle  &  Co.,  Ges. — Manufacture    of  alky- 
lated derivatives  of  vat  dyestuffs.     March  28. 
8992— Soc.  I'Air  Liquide,  Soc.  Anon,  pour  TLtude 
et  rExploitation  Des  Precedes  G.   Claude^ 
Manufacture  of  nitrogen  peroxide.  March  29. 
-Verein  fur     Chemische  und     Metallurgische 
Produktion. — Production  of  chemically  pure 
sulphuric  acid.     Mai'ch  29. 
Specifications   Published   this    Week. 
194740 — Ca?ale,  Dr.  L. — Process  for     the  synthetic 

production  of  ammonia. 
1947^9— Waldberg,   A.-;-Electro-metallurgy     or    the 

electro-deposition  of  metals. 
181677 — Blanc,  G.  A. — Method  of  and  apparatus 
for  the  treatment  of  silicates  with  acids 
in  order  to  obtain  solutions  of  salts  free 
from  silica. 
188338 — K'nKlberger  &  Co. — Preparation  of  iron- 
free  chromium  compounds. 

Abstract  Published  this  Week. 
1P2941 — Phenol-aldehyde   condensation     products. — 
Byron,  J.  G.,  1,  Norfolk  Avenue,     Heaton 
Cliarelm,   near  Stockport;     and   Attwater, 
R.,  Hopwood  Street  Mills,  Preston. 
Phenol   or    cresol   is   condensed     with    formalde- 
hyde with  sodium  thiosulphate,    or  other  neiitral 
salt  of  thiosulphiiric  acid,  as  catalyst,  thus  effe,ct- 
ing  an  economy     in  formaldehyde,     light-coloured 
products  b?ing  obtained.     In  an  example  sulphur- 
free  oresylio     acid     is  fondens^ed     in  presence     of 
eodium  thiosulphate  with  formaldehyde    which  is 
added  in  four    equal  quantities  at  specified  inter- 
vals.    The  product  is  separated  from  the  aqueoiis 
layer  and  may  be  diluted  with  solvent.s  for  use  as 
a  varnish  or  may  be  incorporated  with  fillers  and 
hardened,  for  use  for  example  as  electrical  insu- 
lation. 

M"ssTS.  Rayner  &Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  price  of  Is.  6d.  each. 


PAMPHLETS. 


Science  by  Definition  Series. 

By  F.  H.  Loring. 

1.  DEFINITION  OF  EELATIVITY. 

2.  DEFINITION  OF  THE  AETHER. 

3.  DEFINITION  OF  EQUIVALENCE. 

4.  DEFINITION  OF  ISOTOPES. 

(Others  in  progress). 
Price  Is.  each  net.     Postage,   British  Isles 
Id.  each. 
"  A  little  series  called    '  Science  by  Defi- 
nition,' in  which    the  author  relies    on  the 
writers  o  recognised  authority." 

Times  Literary  Suppievient. 
H.  O.  LLOYD  &  Co.,  Ltd., 

327,  Upiper  Street,  London,  N.l. 


MAY  4,  1923. 


THE  CHEMICAL  NEWS. 


273 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3290. 

VALENCY  AND  RADIATION. 
By  F.  H.  LoRiNG. 

The  octet  theory  of  valency  is  bo  satisfac- 
tory in  most  cases  as  to  lead  cme  to  con- 
clude that  it  represents  a  tnith.  The  Bohr 
atom,  on  the  other  hand,  fits  in  so  well 
with  many  experimental  facts  of  8|>ectruni 
analysis  that  one  is  compelled  to  regard 
this  theory  as  also  true  in  the  main;  but 
there  is  a  conflict  between  t^ese  two 
theories  in  that  the  latter,  as  is  well  known, 
involves  electrons  revolving  in  planetary 
orbits  round  a  central  sunlike  nucleus; 
while  the  octet  theory,  though  it  in  no  way 
necessitates  the  electrons  being  at  absolute 
rest,  does  imply  that  they  cannot  circulate 
in  orbits  round  a  central  positive  nucleus. 
How,  then,  are  these  theories  to  be  recon- 
ciled with  each  other? 

Since  the  Bohr  theory  is  founded  on  the 
spectrum  of  hydrogen,  it  might  be  assumed 
that  with  one  comparatively  free  electron 
outside  the  nucleus,  as  in  the  case  of  the 
hydrogen  atom  which  is  more  easily  ionised 
than  helium  on  this  account,  it  would  ho 
free  to  absorb  energy  and  exprosa  it  poten- 
tially in  orbital  revolution;  then  give  it  up 
as  rmliation  when  settling  into  "stationary" 
or  steady  states  of  revolution  in  orbits  re- 
presenting less  energy,  and  when  this  occur- 
rence takes  place  it  involves  multiples  of 
energy  or  quanta  hz,  where  h  is  Planck'" 
constant  and  z  is  the  frequency  of  the 
radiation. 

When,  however,  other  clonionts  having 
atoms  of  more  complex  structure  are  con- 
sidered, difliculties  occur  both  in  the  Bohr 
theory  and  in  its  reconciliation  with  the 
octet  theory.  These  difficulties  have  been 
fully  realised  by  chemists  and  physicists, 
and  several  suggestions  have  been  made  to 
meet  the  difficulties  arising  therefrMn,  such, 
for  example,  as — 

1. — The  electrons  in  their  octets  vibrat- 
ing in  their  mean  positions  of  equilibrium, 
yet  retaining  their  "corner"  positions  aip- 
iproximately. 

2. — The  electrMis  revolving  in  small  or- 
bits round  axes  emanating  from  the  oornrr<; 
of  the  cube. 


3. — In  the  case  of  heUum,  the  electrons 
vibrating  in  semi-circular  tracks  round  a 
nucleus. 

4. — The  electrons,  in  the  case  of  hydro- 
gen only,  revolving  in  circular  and  elliptical 
orbits  round  a  nucleus. 

Now  it  will  be  seen  that  if  these  views — 
taken  in  a  reverse  order — are,  as  it  were, 
plotted,  they  fall  into  line,  for  the  first 
"plot"  (4)  is  a  circle  or  ellipse,  the  second 
(3)  is  a  semi-circle,  while  the  third  (1)  is  a 
more  restricted  vibration  and  No.  2  is  ruled 
out.  This  observaticai^  is  probably  not  a 
significant  one,  but  the'  transition  shown 
has  a  good  inverse  parallel  in  the  three 
states  of  matter:  solid,  liquid  and  gaseous. 
Similarly,  in  considering  valency,  it  is  well 
to  remember  that  the  "stationary"  state — 
so  to  speak — is  in  this  case  one  in  which  a 
certain  geometric  stability  has  been  reached. 

In  the  whole  demain  of  science  involv- 
ing energy  considerations,  inoomipatibilities 
of  these  kinds  appear.  The  quantum 
theory  and  the  ordinary  theory  of  radiation 
are  in  conflict  at  one  extreme,  while  they 
blond  at  the  other.  The  theory  of  relativity 
negatives  certain  ideas  of  Newton  whicli 
have  been  thoroughly  established  for  many 
years.  Here,  too,  at  the  extreme  of  great 
differential  speeds,  the  two  theories  are  in 
conflict,  the  Einstein  theory  giving  the  cor- 
rect answer  in  this  case.  At  the  other  ex- 
treme where  slow  speeds  are  involved, 
either  theory  will  give  the  correct  answer, 
I.e.,  the  introduction  of  the  relativity 
theory  does  not  modify  the  calculations 
arrived  at  by  \he  Newtonian  metho<l — the 
classical  mechanics.  In  valency  problems 
the  same  conflict  exists,  and  in  certain 
cases  the  answer  is  the  same  by  either 
theory,  e.g.,  the  ordinary  valence  theory  or 
that  centred  round  the  octet  theory,  but 
the  latter  seems  to  include  the  former,  that 
is  to  say  it  is  not  necessary  to  change 
theories  m  passing  from  one  extreme  to  the 
other. 

One  point  might  bo  made  here,  and  that 
is  that  the  reason  for  this  conflict  possibly 
lies  in  the  overlooking  of  some  important 
factor  common  to  the  conflicting  theories ; 
and  which,  if  aipprociated ,  would  help  to 
clear  up  matters.  First  order  fractional 
atomic  weights  were  cleared  up  by  iso- 
topes, although  calculations  had  been 
made  to  show  how  the  mass  might  become 
fractioned,"  as  it  were,  by  energy  condi- 
tions. The  discrepancies  between  New- 
tonian calculations  and  observed  motions  of 
bodies — electron  emissions  and   the  planet 


274 


THE  CHEMICAL  NEWS. 


MAY  4,  1923. 


Mercury — have  been  cleared  up  b}'  Ein- 
stein's theory,  which  formulates  the  rela- 
tive view  of  necessity  involved  in  the  elec- 
tron case,  and  similarly  in  the  case  of  Mer- 
cury, but  with  more  elaboration  as  space 
physios — so  to  sipeak — enters  into  these 
iproblems.  The  octet  theory  clears  up  out- 
standing difficulties  of  the  older  theories. 

Now  Bohr,  in  the  later  developments  of 
his  theory,  claims  that  the  octet  scheme 
involving  the  sharing  of  electrons  can  be 
considered  in  terms  of  electron  orbits  so  ar- 
ranged as  to  unite  the  atomic  nuclei  sub- 
stantially as  they  are  bound  according  to 
the  static  theory.  "  In  fact,  the  tendency 
seems  towards  a  Rutherford-Bohr-Lewis- 
Langmuir  atom  " — as  stated  in  my  Atomic 
Theories,  page  137.  It  is  profitable 
for  everyone  to  become  interested  in  the 
problems  that  are  engaging  the  attention  of 
many  of  the  leading  scientists  of  the  world. 


COMPEESSIBILITY,    INTERNAL 
PRESSURE  AND  ATOMIC 

MAGNITUDES. 

By  Theodore  W.  RicnARDS. 

Wolcott  Gibbs  ^femorial  Laboratory, 

Harvard  University. 

The  object  of  this  paper  is  primarily  to 
evaluate  the  respective  bulks  of  the  atoms 
of  elements  in  combination,  from  the  study 
of  the  compressibilities  of  the  individual 
elements  and  the  contraction  which  occurs 
during  combination.  The  outcome  led  also 
to  many  other  considerations  concerning 
the  forces  which  hold  molecules  together  in 
the  solid  and  liquid  state.  The  following 
points  in  particular  are  emphasised. 

1.  Internal  pressure  is  defined  for  the 
purpose  of  the  present  article  as  the  pres- 
sure exerted  by  the  force  of  affinity,  either 
chemical  or  cohesive. 

2.  Bridgman's  pressure- volume  rela- 
tions for  elements,  exiperimentally  deter- 
mined as  far  as  12,000  atmospheres,  are 
shown  to  be  represented  roughly  by  hyper- 
bolas of  the  general  type  :  (p+P)  ('V-B)  =  K. 
P  and  K  increase  and  B  diminishes 
with  increasing  external  pressure,  but  the 
simple  equation  just  given  serves  as  a  suffi- 
cient approximation  for  the  present  pur- 
pose, since  with  groat  press\ires  these  con- 
trary changes  partly  counterbalance  one  an- 
other. P  indicates  internal  pressure ;  B  is  a 
function  which  represents  the  fact  that  the 
atom  is  less  compressible  than  a  perfect  gas 
would  be  under  the  same  conditions  of  pres- 
sure,   volume  and  temperature.      In    such 


substances  as  copper,    gold,    etc.,    both    F 
and  B  are  very  large. 

3.  It  is  shown  that  Bridgman's  values 
for  the  pressure- volume  relations  of  potas- 
sium and  sodium  are  very  similar,  the  dif- 
ference being  chiefly  due  to  the  fact  that 
sodium  possesses  a  much  higher  internal 
pressure  than  potassium.  Therefore  it  is 
legitimate  to  use  the  sodium  values  as  a 
continuation  of  the  potassium  curve.  In 
this  way  a  curve  corresiponding  approxi- 
mately to  the  equation  (p  +  25,800)  {v- 
0.20)  =  20,650  for  the  compression  of  1.000 
cc.  of  potassium  from  zero  to  perhaps  40,000 
atmospheres  external  pressure. 

4.  From  my  own  values  for  the  compres- 
sibility of  chlorine,  bi'omine  and  iodine,  and 
Bridgman's  for  phosphorus  trichloride, 
similar  (although  less  trustworthy)  curves 
for  chlorine  and  bromine  are  constructed. 
These,  like  the  curves  of  all  other  poly- 
atomic substances  of  low  boiling-point,  are 
much  more  flexed  than  the  potassium 
curve.  The  reasons  for  this  greater  flexure 
are  indicated.  The  chlorine  curve  is  extra- 
polated by  means  of  the  equation  (p  + 
5,300)  {v  -  0.50)  =  2,650,  which  corres- 
ponds  to  the  curvature  under  the  highest 
pressures  employed  experimentally. 

5.  The  above  equations,  which  ^ivo  a 
reasonable  picture  of  the  compression  of 
these  solids  and  liquids  and  are  probably 
capable  of  moderate  extrapolation  without 
great  risk,  give  a  new  approximate  means 
of  estimating  internal  pressures. 

6.  From  these  curves,  reduced  to  a 
gram-atom  basis,  taking  account  of  the  in- 
ternal pressures  as  indicated  by  the  equa- 
tions in  the  several  combinations,  the  vol- 
umes of  these  components  in  combination 
and  the  atomic  diameters  in  the  salts,  a-? 
compressed  by  the  mutual  affinities,  we.'e 
computed.  The  atomic  diameters  thus 
computed  are  given  in  the  following  table  in 
comparison  with  earlier  values  which  1  com- 
puted by  an  entirely  different  method,  al-'j 
depending  upon  the  same  fundament'^J 
idea. 

Atomic  Diamrtrrs. 

New       Karlier 
values,    vahies. 

Potassium,  in  chloride  3.46  3.5 

Potassium  in  bromide  3.56 

Sodium  in  chloride  2.85  2.9 

Sodium,  in  bromide    2.92 

Chlorine,  with  potassium  ..     2.82  2.8 

Chlorine,   with  sodium    2.78 

Bromine,  with  potassium  ..     3.04  3.1 

Bromine,  with  sodium  3.03 


MAY  4,  1923. 


THE  CHEMICAL  NEWS. 


275 


I 


7.  The  compressibility  of  the  products, 
calculated  from  these  considerations,  cor- 
restponds  as  closely  as  could  be  expected 
with  the  actual  compressibilities  of  the 
compounds  in  question.  This  fact  con- 
firms the  results  of  the  extrapolation  of  the 
curves.  Otherwise,  the  extrapolation  might 
seem  excessive. 

8.  The  outcome  furnishes  a  striking 
quantitative  confirmation  of  the  theory  of 
atomic  compressibility,  which  has  been  a 
subject  of  so  many  earlier  contributions, 
and  supports  this  theory  in  every  respect, 
affording  important  aid  in  throwing  light 
upon  the  nature  of  the  atoms.  This  theory 
which  was  first  advanced  in  its  present  form 
in  1901,  maintains  that  the  chief  cause  of 
changing  atomic  volume  is  change  of  inter- 
nal pressure.  In  diflFerent  chemical  combi- 
nations atoms  must  be  subject  to  very  dif- 
ferent pressures  from  the  severa!  mutual 
affinities  which  bind  them  together.  Hence 
their  bulk  must  depend  chiefly  upon  the 
magnitude  of  these  pressures,  and  upon  the 
coniiprcssibility  of  the  elements  concerned. 
The  investigation  is  being  continued,  and 
highly  interesting  further  results  have  al- 
ready  been  obtained. — (From  the  Proceed- 
ings   of    the    U.S.    Natiorial    Academy    of 

Srirnrrs.    1023,   IX.,   73.) 


TITR  PETEf'TlOX  OF  TRACES  OF 
STIBINE. 

By  Edward  J.  Weeks,  B.Sc.,  F.C.S. 

In  some  work  on  the  preparation  of  sti- 
bine  it  was  found  necessary  to  devise  a 
method  by  which  slight  traces  of  this  sub- 
stance could  be  detected  quickly  without 
using  the  mirror  test. 

The  following  method  was  found  to  show 
the  presence  of  stibine  in  a  gas,  even  when 
it  wa«  only  present  to  the  extent  of  O.O.T 
per  cent,  by  volume. 

According  to  H.  Reckleben  (Bcr.,  1909. 
XLII.,  1458-1464)  the  action  of  stibine  on 
stiver  nitrate  is  as  below : 

SbH,  +  3AgN0,  =  Ag,Sb  +  8HN0, 
.\g,Rb  +  SAgNO,  +  3H,0  = 

6Ag   t  H^SbO,  +  fillNO, 

The  silver  is  deiposited  as  a  black  precipi- 
tate. 

Hence  n  glass  tube  was  taken  with  a  dia- 
meter of  about  T)  mm.  and  about  20  cm.  in 
length.  A  drop  of  silver  nitrate  was  in- 
serted in  the  tube  and  allowed  to  run  down 
the  sides  so  as  to  moisten  the  inside  of  the 


tube.       The    experimental    gas    was    then 
passed  through  the  tube,  and  a  brown  stain 
was    produced  at  once,    even  when    only  a 
trace  of  stibine  was  present. 
Sir  John  Cass  Institute. 
April  25,  1923. 


r.ENBRAL  NOTES. 


THE  MINERAL  PRODUCTION  OP 
NEW  SOUTH  WALES. 

Mr.  A.  Simpson,  H.M.  Trade  Commis- 
sioner at  Sydney,  has  forwarded  to  the 
Dept.  of  Overseas  Trade  a  statement  of  the 
mineral  production  of  New  South  Wales 
for  1922. 

It  is  stated  that  the  value  of  the  output 
of  minerals  for  the  year  has  been  ascer- 
tained to  be  €14,274,770,  an  increase  of 
£266.122  compared  with  the  previous  year, 
mainlv  owing  to  renewed  activity  on  the 
Broken  Hill  Field. 

The  aggregate  value  of  all  minerals  won 
to  the  end  of  1922  is  £850,113.801. 
Coal,  Coke,  and  Oil  Shale. 

The  quantity  of  coal  wrought  during  the 
year  amounted  to  10,183.133  tons,  a  de- 
crease of  610,254  tons  compared  with  1921. 

The  output  of  ch\  shale  for  the  year  is 
23.467  tons,  valued  at  £60,641 ;  a  decrease 
of  9,022  tons  and  £16.739  in  vahie  com- 
pared with  1921. 

The  diminished  smelting  operations  at 
Newcastle  and  Lithgow  had  a  very  serious 
effect  on  the  coke  manufacturing  industrv, 
the  production  for  1922  being  240.229  ton^. 
valued  at  €382.926  as  against  592,097  tons, 
valued  at  £1.029,694  during  the  previoiis 
vear. 

Gold. 

The  aggregate  of  gold  won  in  the  State 
up  to  the  end  of  1922  amounted  to 
14.873.939  ounces  fine,  valued  at 
£63,180,442.  The  production  for  1922 
showed  a  further  diminution,  the  yield 
being  25.222  ounces  fine,  valued  at 
£107,139.  Dredging  operations  contri- 
buted aipproximately  one  half  of  the  yield 
for  the  year,  the  principal  gold  producing 
mining  divisions  being  Gimdajjai  £18.028. 
Canbelege  £16,000.  Adelong  £15.915.  Hill 
End  £11.706.  and  Araluen  £8.155. 

The  yield  for  1922  represents  less  than  1 
per  cent,  of  the  total  value  of  the  mineral 
production  of  the  year,  and  this  brHnch  of 
the  industry  is  steadily  declining  in  favotir 
of  mining  for  economic  minerals. 


276 


THE  CHEMICAL  NEWS. 


MAY  4,  1923. 


Silver,  Lead,  and  Zinc. 

This  branch  of  the  industry  is  rapidlj^  be- 
coming normal.  Many  of  the  Broken  Hill 
Mines  were  in  active  operation  throughout 
the  year,  and  production  was  greatly  in 
excess  of  1921.  The  value  accruing  to  the 
State  from  the  products  of  the  silver,  lead 
and  zinc  mines  for  1922  amounts  to 
Jd3,731,566,  an  increase  of  £2,120,747  oom- 
ipared  with  1921. 

The  closing  down  of  the  Sulphide  Cor- 
poration Works  at  Cockle  Creek  has  re- 
sulted in  a  decreased  output  of  silver  and 
lead  (pig),  and  a  corresponding  increase  in 
the  despatches  of  ore  and  concentrates  for 
treatment  at  Port  Pirie. 

The  quantity  of  ore  raised  on  the  Broken 
Hill  Field  was  640,064  tons,  an  increase  of 
.22,731  tons  on  1921. 

The  output  from  the  Yorrandorie  field  is 
valued  at  £64,630,  an  increase  of  £14,056. 
Copper. 

The  value  of  the  outiput  of  copper  for 
1922  was  £36,233,  a  decrease  of  £5,034 
compared  with  1921.  Practically  all  the 
important  mines  remained  closed  during 
the  year,  but  as  the  market  is  showing  an 
upward  tendency,  an  augmented  produc- 
tion may  be  recorded  for  1923. 
Tin. 

The  value  of  the  tin  ores  produced  in 
1922  is  ;bi54,698,  or  a  decrease  of  £8,753 
comipared  with  1921, 

Tin  mining  was  restricted  on  account  of 
low  markets  and  high  costs,  and  in  the  New 
England  district  dredging  operations  were 
also  retarded  by  lack  of  water.  If  the  pre- 
sent price  of  tin  is  maintained,  the  outiput 
for  1923  should  show  a  marked  advance. 
Ironstone. 

The  production  of  pig  iron  from  the  New 
South  Wales  ores  amounted  to  54,856  tons, 
which  represents  a  considerable  decrease. 
Hoskins  Iron  and  Steel  Company,  Ltd.,  at 
Lithgow,  were  partly  closed  during  the 
year.  Prosipecting  operations  are  being 
carried  on  by  this  company  on  large  areas  in 
the  Goulbum,  Cunning,  Queenbeyan  and 
Tuena  Divisions. 

In  addition,  988  tons  of  ironstone,  valued 
at  £1,274,  were  raised  and  used  by  smelting 
comipanies  for  fluxing  purposes. 

Of  iron  oxide,  1,381  tons  were  raised  and 
used  for  the  manufacture    of  pigments  and 
by  gas  companies  for  purifying  purposes. 
Limestone. 

Of  Portland  cement,  187,800  tons  were 
manufactured  during  the  year  from  lime- 
stone raised  in  the  State  reipresenting  an  in- 


crease of  £14,466  in  value  as  compared 
with  1921. 

The  output  for  other  minerals  is  as  fol- 
lows : — Alunite  £740,  arsenic  £14,818,  as- 
bestos £11,418,  bismuth  £939,  chrome 
£1,095,  clay  £13,464,  diamonds  £1,300, 
dolomite  £800,  magnesite  £3,231,  mangan- 
ese £7,194,  marble  £1,900,  molybdenite 
£320,  opal  (noble)  £15,150,  platinum 
£1,182,  silica  £5,577,  sundry  minerals 
£6,942. 

Owing  to  the  low  prices  ruling  there  was 
no  production  of  antimony,  acheelite,  nor 
wolfram,  and  only  small  quantities  of  bis- 
muth molybdenite  were  obtained. 

Mining  for  chrome,  dolomite,  magnesite, 
manganese,  and  silica  was  very  seriously 
affected  by  the  reduced  operations  carried 
on  by  the  iron  and  steel  works. 


GERMANY'S     POTASH    AND 
NITROGEN    INDUSTRIES. 

Since  April  6  the  Potash  Syndicate  has 
introduced  a  small  price  reduction.  This  is 
of  little  avail  from  the  viewpoint  of  increas- 
ing sales.  The  general  opinion  is  that  the 
reduction  of  coal  prices  is  too  slight  to 
cause  reduction  in  potash  prices.  It  is 
also  thought  that  a  reduction  of  ipotash 
;prices  wouFd  hardly  bring  about  a  revival  of 
business,  as  the  agricultural  industry,  ex- 
pecting further  declines,  holds  back  its 
orders. 

The  position  of  the  potash  works  will 
soon  necessitate  short  time  working.  Many 
works  are  already  on  short  time,  and  prob- 
ably during  the  next  few  months  will  have 
to  work  on  stock  to  a  greater  extent  than 
ever.  Accumulation  of  stock  entails  heavy 
expenditure.  Proceeds  derived  from  export 
are  no  longer  so  considerable  as  formerly, 
and  thus  do  not  afford  the  necessary  com- 
pensation. The  rock  salt  business,  which 
used  to  bring  in  considerable  sums  to  the 
works,  is  at  a  complete  standstill.  Credit 
is  limited  and  the  complete  closing  down  of 
works  can  only  be  avoided  if  the  necessary 
working  capital  is  obtained,  and  nothing 
remains,  therefore,  but  to  have  recourse  to 
the  open  market. 

_  With  regard  to  nitrogen,  it  appears  that 
since  1913  the  German  consumption  of  ni- 
trogen has  doubled.  During  the  last  finan- 
cial year,  German  agriculture  required 
365,000  tons  of  nitrogen,  i.e.,  12.2  kilos  for 
every  2.47  acres.  These  arrangements  for 
increasing  the  productivity  of  German  agri- 
culture, which  have  been  reflected    in  har- 


MAY  4,  1923. 


THE  CHEMICAL  NEWS. 


277 


vest  results,  had  only  become  possible  by 
making  German  nitrogen  requirements 
more  independent  of  foreign  sources.  The 
Haber  Bosch  process  used  by  the  Badische 
Anilin  und  Sodafabrik  and  brought  to  its 
highest  technical  tperfection,  put  an  end  to 
the  former  monopoly  of  saltpetre. 

At  the  present  time  the  Leunawerk  works 
are  still  fully  employed,  but  anxiety  is  felt 
for  the  future.  Statements  to  the  effect 
that  the  demand  for  suliphate  of  ammonia 
has  greatly  diminished  and  has  even  come 
almost  to  a  standstill  have  been  confirmed. 


FAST  DYES. 

New  Record  Claimed  for  a  Lancashire 
Process. 

A  dyeing  process  discovered  in  Lanca- 
shire laboratories  achieved  what  is  claimed 
to  be  a  record  test  during  the  Drapery  and 
Textile  Exhibition,  recently  held  at  the 
Agricultural  Hall,  London. 

For  a  fortnight,  cambrics,  piques,  ratines 
and  zephyrs  in  various  ipinks,  blues,  reds, 
j^ri'cns,  and  other  shades  were  boiled  in  n 
mixture  of  strong  soap  and  soda  water.  Not 
one,  as  a  result  of  this  strenuous  treatment, 
showed  signs  of  fading. 

The  test  began  on  the  Monday  the  Ex- 
hibition opened,  and  the  materials  were 
boiled  continuously.  The  colours  are  all 
made  by  British  dyemakers,  and  this  pro- 
cess leaves  them,  for  the  entire  life-time  of 
the  materia],  absolutely  fast  to  boiling, 
bleaching,  sunlight  and  seaside  air. 


UNIVEKSITY  OF  LEEDS. 
Chemistry    Professorship. 

Dr.  li.  W.  Whytlaw-Gray,  O.B.E,. 
Ph.D.,  Fellow  of  University  College,  Lon- 
don, was  appointed  Professor  of  Chemistry 
at  the  University  of  Leeds  as  from  October 
1  next,  in  succession  to  Professor  Arthur 
Smithells,  F,R.S.  Dr.  Whytlaw-Gray  was 
educated  at  St.  Paul's  School,  London, 
and  at  University  College,  London.  From 
1900  to  1902  he  worked  under  Sir  William 
Ramsay  on  a  redetermination  of  the  atomic 
weight  of  nitrogen.  This  wwk  was  com- 
pleted in  the  laboratory  of  Professor 
Hiehard  Anschutz  in  the  University  of 
Bonn,  On  his  return  from  Germany  in 
V.)OC),  Dr.  Whytlaw-Gray  was  appointed  on 


Sir  William  Ramsay's  staff  at  University 
College,  London,  and  in  1908  he  became 
Assistant  Professor.  While  on  the  staff  of 
University  College,  Dr.  Whytlaw-Gray 
conducted  important  investigations  on  the 
physical  constants  of  gases,  and  was  asso- 
ciated with  Sir  William  Ramsay  in  the 
well-known  work  on  radium  emanation 
(niton).  This  work  involved  exceptional 
experimental  difficulties,  less  than  one- 
tenth  of  a  cubic  millimetre  of  the  gas  being 
available.  With  this  almost  infinitesimal 
quantity  Messrs.  Ramsay  and  Whytlaw- 
Gray  succeeded  in  determining  its  physical 
properties,  thus  proving  that  the  emanation 
bel<«iged  to  the  helium  family  of  elements. 
In  connection  with  this  very  delicate  work, 
Dr,  Whytlaw-Gray  constructed  a  specially 
designed  balance,  which  was  sensitive  to 
1  250  thousandth  of  a  milligramme.  Since 
1914  Dr,  Whytlaw-Gray  has  been  science 
master  at  Eton  College,  During  the  war  he 
also  acted  as  civilian  chemical  adviser  to 
the  Chemical  Warfare  Committee,  and  de- 
voted all  his  spare  time  to  research  on  the 
chemical  problems  involved  in  gas  warfare. 
This  work  has  been  continued  and  extended 
since  the  Annistice,  and  the  results  of  his 
investigations  have  been  exceptionally  im- 
portant. 


CERAMIC  DEPOSITS  OF 
SASKATCHEWAN, 

A  considerable  amount  of  interest  is  being 
displayed  by  ceramic  experts  in  the 
numerous  deposits  of  valuable  clays  to  be 
found  in  the  Province  of  Saskatchewan — 
these  ranging  from  the  lower  grades  used  in 
the  mnnufacinre  of  bricks  and  tiles  to  a 
kaolin  which,  it  is  claimed,  bums  as  white, 
if  nf>t  whiter,  than  the  British  product. 

In  this  connection  the  Provincial  authori- 
ties have  secured,  through  the  Saskatche- 
wan Bureau  of  Labour  and  Industries,  the 
services  of  a  fully-qimlified  ceramic  en- 
gineer, in  the  person  of  Professor  W.  G. 
W<«t;e8ter,  who  is  engaged  in  the  compila- 
tion of  data  for  the  perusal  of  prospective^ 
investors.  Although  the  investigations 
mude  up  to  the  present  are  only  in  their 
initial  stages,  the  Saskatchewan  Bureau  of 
Tiahour  and  Industries  is  desirous  of  bring- 
ing the  information  already  compiled  to  the 
attention  of  British  clay-workers,  and  has, 
therefore,  sent  over  to  the  High  Commis- 
sioner for  Canada  in  London  a  bulletin  on 
the    Clays    of  Saskatchewan,     which    it    is 


276 


*HE  CHEMICAL  NEWS. 


MAY  4,  1923. 


thought  may  interest  parties  in  Great 
Britain  likely  to  be  wilhng  to  undertake 
development  work  in  this  field  in  Western 
Canada. 

The  article  in  question,  with  aooomipany- 
ing  photographs,  may  be  consulted  at  the 
office  of  the  High  Commissioner  for  Can- 
ada, 19,  Victoria  Street,  London,  S.W.I, 


BKUGS  REQUIRED  IN  SWITZER- 
LAND. 

H.M.  Consul-General  at  Zurich  (Mr. 
Ernest  G.  B.  Maxse,  C.M.G.),  reports  that 
a  firm  of  wholesale  and  retail  druggists  in 
Schaffhausen,  is  desirous  of  purchasing 
pharmaceutical  and  druggists'  sipecialities ; 
or  preferably  of  securing  the  representation 
for  Switzerland  of  British  manufacturers  of 
such  goods. 

Application  for  further  particulars  re- 
garding this  enquiry  should  be  addressed  to 
the  Department  of  Overseas  Trade,  35,  Old 
Gueen  Street,  London,  S.W.I,  quoting 
reference  19094/ FW/CC. 


PHOTOGRAPHIC  MATERIALS  FOR 
ECUADOR. 

His  Majesty's  Consul-General  at  Quito 
(Mr.  R.  C.  Michell)  has  transmitted  a  re- 
port on  the  market  for  photographic 
materials  in  Ecuador,  a  copy  of  which  may 
be  obtained  by  British  firms  upon  applica- 
tion to  the  Department  of  Overseas  Trade, 
35,  Old  Queen  Street,  London,  S.W.I. 
(Ref.  No.  905/2/F.G./C.C.) 


F.B.I.  AND  RAILWAY  RATES. 

The  question  of  railway  rates  came  before 
the  Grand  Council  of  the  Federation  of 
British  Industries  on  April  18,  when  Sir 
Eric  Geddes  presided. 

The  following  resolution    was    passed  :  — 

"  That  the  President  be  authorised,  acting 
in  consultation  with  the  Transport  Com- 
mittee, to  lodge  an  application  with  the 
Railway  Rates  Tribunal  for  a  general  re- 
duction of  rates,  to  take  effect  on  August  1, 
if,  at  any  time,  he  should  consider  that 
the  situation  demands  such  action." 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Patpers  read  at  the  meeting  on  Thursday, 
April  26:  — 

W.  A.  Bone,  F.R.S.,  D.  M.  Hewitt, 
and  D.  T.  A.  Townend. — Gaseous  Combus- 
tion at  High  Pressures.  Part  III.  :  The 
Energy-absorbing  Function  and  Activation 
of  Nitrogen  in  the  Combustion  of  Carbon 
Monoxide. 

It  is  shown  that  nitrogen  can  no  longer 
be  regarded  as  an  inert  gas  in  the  combus- 
tion of  caxbon  monoxide,  because  when  pre- 
sent as  a  diluent  in  a  mixture  of  2C0  +  O2 
undergoing  combustion  in  a  closed  vessel 
under  high  pressure  it  exerts  a  peculiar 
energy-absorbing  influence  upon  the  sys- 
tem, far  beyond  that  of  other  diatomic  dilu- 
ents (e.g.,  excess  of  O^  or  CO)  or  even  of 
argon.  This  influence  (a)  retards  attain- 
ment of  maximum  pressure,  and  (b) 
diminishes  maximum  temperature  attained 
in  explosion,  in  a  much  greater  degree  than 
can  be  accounted  for  on  the  supposition  cf 
its  acting  merely  as  a  diatomic  diluent. 

The  energy  so  absorbed  by  nitrogen  dur- 
ing the  combustion  period  is  slowly 
liberated  as  the  system  cools  down  after  at- 
tainment of  maximum  temperature,  and 
consequently  the  rate  of  cooling  is  greatly 
retarded  for  a  considerable  time.  These 
effects  are  very  marked  in  the  case  of  a  car- 
bon monoxide-air  mixture  (2CO+O2+4N2), 
and  much  more  so  in  that  of  a  mixture 
(2CO+O2+6N2),  undergoing  combustion 
under  high  pressures.  In  consequence  of 
such  energy-absorption,  nitrogen  becomes 
chemically  "activated"  in  such  explosions, 
remaining  so  for  a  considerable  time  after 
attainment  of  maximum  pressure,  while 
slowly  reverting  to  its  normal  condition. 
Whilst  in  this  "activated"  condition  it  will 
combine  with  oxygen,  forming  oxides  of 
nitrogen. 

If  no  nitrogen  be  present  in  the  mixture 
exploded  (e.g.,  in  an  undiluted  mixture 
2C0  +  O2),  carbon  monoxide  bums  in  oxy- 
gen at  high  pressures  almost  (but  not  quite) 
as  rapidly  as  does  hydrogen.  Indeed,  it 
would  appear  as  though  the  usually  con- 
sidered "slow-burning"  character  of  carbon 
monoxide  as  compared  with  hydrogen  is  not 
so  much  inherent  in  the  gas  itself  as  it  is 
conditioned  by  the  presence  of  nitrogen  in 
the  burning  mixture. 


MAY  4,  1923. 


THE  CHEMICAL  NEWS 


279 


There  is  no  correspondinglj?  large  (if  any) 
energy- absorbing  effect  (other    than  purely 
"diluent")  when  nitrogen  is  present  in  hy- 
drogen and  oxygen  mixtures  similarly    un- 
dergoing combustion,  and  there    is  no  evi- 
dence of  nitrogen  being  then  activated.  In- 
deed,  the  presence    of    even  a  small    per- 
centage (two  or  three)  of  hydrogen  in  a  car- 
bon monoxide-air  mixture  undergoing  com- 
bustion is  sufficient  to  prevent  any  material 
activation  of  the  nitrogen.      It  would  thus 
seein  as  though    the  peculiar    influence    cf 
nitrogen  in    2C0  +  0^    explosiMis  is  due  to 
its  ability  to  absorb  the  particular    quality 
of  radiation  emitted  when  CO  and  :  ()  (but 
not  when  CO  and   :0H3)  react;  such  radia- 
tion is  known  to    be    of  a    different    wave- 
length from  that  emitted  during   the  flame- 
combustion  of  hydrogen.       In  other  words, 
there  seems  to  be  some  constitutional    cor- 
respondence between  CO  and  N,  molecules, 
whereby  the  vibrational  energy    (radiation) 
emitted  when  the  one  reacts  with   A)  is   of 
a  quality  readily  absorbed  by  the  other,  the 
two  aotmg  in  resonance. 

R.  A.  Watson  Watt  and  E.  V,  Applk- 
TON,  D.Sc. — On  the  Nature  of  Atmospher- 
ics. Coiiniiunicated  by  Sir  Henry  JacksiMi, 
F.U.S. 

The  paper  describes  observations  with  a 
cathode  ray  oscillograph,  on  the  tempwnl 
variations  of  the  electric  force  occurring  in 
radio  telegraphic  atmospherics.  It  is  shown 
that  approximately  faithful  reproductiwi  of 
tbe  field  changes  can  be  assured  by  using  .i 
highly  damped  antenna  whose  time  con- 
stant is  kept  much  less  than  the  duration  of 
the  ntnioeipheric. 

The  princiipal  constants  of  six  hundred 
typical  atmf)spheric8,  of  which  five  hundred 
were  delineated  by  an  "eye  and  hand" 
method,  are  examined.  A  bare  majority 
are  quasi-periodic,  consisting  normally  of 
one  complete  oscillation,  of  duration  2,000 
micro  seconds,  the  m^an  change  of  field 
being  0.128  volts  per  metre,  with  no  marked 
unbalanced  transport  of  electricity  on  the 
whole  group. 

A  second  group  of  almost  equally  fre- 
(juent  occurrence  consists  of  aperiodic  im- 
pulses, of  durati(Mi  generally  about  1,250 
micro  seconds,  but  frequently  reaching 
0.02')  of  a  second,  the  monn  change  of  field 
being  0.125  Volts  per  metre,  with  a  seven  to 
one  numerical  predominnnoo  of  discharges 
tending  to  carry  negative  electricity  to 
earth  in  the  receiving  antenna. 

The  form  of  the  aperiodic  type  of  atmos- 


pheric is  shown  to  include  a  period  of 
growth  to  maximum  field  strength  whose 
duration  is  Uttle  short  of  the  decay  period. 

I.  Masson,  D.Sc,  and  L.  G.  F.  Dolley. 
— The  Pressures  of  Gaseous  Mixtures. 
Comnmnicated  by  Prof.  F.  G.  Donnan, 
F.R.S. 

Measurements  have  been  made  at  25°  of 
the  compressibilities  up  to  125  Atm.  of 
ethylene,  argon,  oxygen,  and  a  series  of 
binary  mixtures  of  these. 

The  volume  of  a  compressed  mixture 
usually  exceeds  the  sum  of  the  separate 
volumes  of  its  two  components,  the  excess 
depending  on  the  molecular  ratio  of  the 
two  gases  chot>en  and  upon  the  pressure. 
Thus  with  an  equimolecular  mixture  of  ar- 
goa  and  ethylene  at  80  Atm.  the  volume  is 
greater  than  the  additive  value  by  24  per 
cent.  At  a  given  pressure  there  is  an 
"optimum"  ctHnposition,  and  with  a  given 
composition  there  is  an  optimum  pressure. 
Oxygen-ethylene  mixtures  behave  quanti- 
tatively in  the  same  way  as  argon-ethylene ; 
oxygen  and  argcm  when  nuxed  show  a  negli- 
gible volume  mcrt>a8e,  and  are  individually 
equally  compressible. 

It  is  further  shown  that  the  pressure  of  a 
mixture  at  high  densities  exceeds  the  sum 
of  those  measured  for  the  separate  constitu- 
ents; at  moderate  densities  it  is  definitely 
less.  The  former  occurrence  is  due  to  the 
actual  space  filled  by  the  molecules;  the 
latter  is  due  to  a  mutual  cohesicm  between 
eaoh.  The  significance  of  this  was  discussed. 

Papers  read  in  title  only : — 

T.  R.  Mkrtqn,  F.R.S.,  and  R.  C.  John- 
son.— 0»  Spectra  associated  with  Carbon. 

The  spectral  changes  due  to  the  admix- 
ture of  helium  to  vacuum  tubes  containing 
carbcm  compounds,  and  the  conditions  for 
isolating  the  band  spectra  associated  with 
carbon  have  been  investigated.  In  particu- 
lar the  "high  pressure  CO"  bands  can  be 
isolated  almost  completely  under  appro- 
priate conditions.  The  "comet- tail"  bands 
are  found  in  vacuum  tubes  containing  he- 
lium and  carbon  monoxide  under  appro- 
priate conditi<Mis. 

In  the  presence  of  helium  the  distribu- 
tion of  intensity  in  ili(!  comet-tail  bands  dif- 
fers nuirkedly  from  that  observed  by  Fow- 
\er  in  tubes  containing  carbon  monoxide  at 
very  low  pressures,  and  the  wave-lengths  of 
the  heads  of  the  bands  have  been  re- 
measured.     By  the  admixture  of  hydrogen 


280 


THE  CHEMICAL  T^EWS. 


MAY  4,  1923. 


the  comet-tail  bands  are  replaced  by  a  sys- 
tem of  triplet  bands  which  have  not  been 
isolated  hitherto,  and  the  wave-lengths  of 
the  heads  of  these  bands  have  been 
measured  and  found  to  fall  into  two  distinct 
band  series. 

In  helium  containing  a  small  quantity  of 
carbon  monoxide  a  new  Une-spectrum  has 
been  observed  under  suitable  conditions  of 
excitation,  and  it  is  believed  that  this  spec- 
trum is  to  be  attributed  to  carbon. 

W.  E.  BousFiELD,  F.E.S.,  and  C.  Els- 
PETH  BousFiELD. — VapouT  Pressure  and 
Density  of  Sodium  Chloride  Solutions. 

The  purpose  of  the  author's  was  to  ob- 
tain a  standard  set  of  V.P.  determinations 
at  18°  C.  for  aqueous  solutions  of  NaCl  at 
all  concentrations.  The  method  employed 
was  to  introduce  water  and  the  solution  into 
the  legs  of  a  V  tube  smmounting  a  baro- 
metric column  of  mercury.  Special  pre- 
cautions were  taken  to  exclude  air.  This 
necessitated  the  boiling  of  the  solutions  so 
that  they  became  of  unknown  concentra- 
tion. The  V.P.  observations  were  there- 
fore primarily  correlated  to  the  densities  of 
the  solutions.  To  correlate  with  the  con- 
centrations, a  complete  set  of  density  obser- 
vations at  18°  C.  were  made  on  solutions  of 
known  concentration  accurate  to  +  2  in  the 
fifth  place  of  decimals. 

Incidentally  a  method  of  determining 
molecular  weights  by  combined  observa- 
tions of  the  density  and  V.P.  of  dilute  solu- 
tions is  given. 

F.  A.  LiNDEMANN,  F.E.S.,  and  G.  M.  B. 
DoBSON. — A  Note  on  the  Temperature  «/ 
the  Air  at  Great  Heights. 

The  relatively  high  pressure  of  the  at- 
mosiphere  above  60  km.,  which  was  dis- 
cussed in  a  previous  paper,  would  appear 
to  be  due  to  absorption  of  an  appreciable 
amount  of  direct  solar  radiation.  Thus 
there  should  be  a  large  variation  in  tem- 
perature at  these  great  heights.  Various 
ways  in  which  such  a  variation  might  be 
shown  are  considered  and  some  evidence  of 
its  existence  is  found. 

G.  H.  Hardy,  F.E.S.,  and  J.  E.  Little- 
wood,  F.E.S. — On  Lindelof's  Hypothesis 
concerning  the  Riemann  Zeta-f unction. 

The  paper  contains  a  number  of  neces- 
s-ary  and  sufficient  conditions  for  the  truth 
of  the  hypothesis,  some  stated  in  terms  of 
the  Zeta-function  itself,  and  others  in 
terms  of  the  arithmetical    functions  which 


occur  in  the    "lattice-point  problems"     of 
Dirichlet  and  Piltz. 


EOYAL  INSTITUTION  OF  GEE  AT 
BEITAIN. 

The  Friday  evening  discourse  on  May  4, 
at  9  o'clock,  will  be  delivered  by  Frederick 
SoDDY,  F.E.S.  The  subject  is  The  Origins 
of  the  Conception  of  Isotopes. 

On  Tuesday,  May  1,  Sir  Arthur  Keith, 
M.D.,  LL.D.,  F.E.S.,  Sec.  E.I.,  Fullerian 
Prof,  of  Physiology,  gave  a  lecture  on  The 
Machinery  of  Human  Evolution:  (IV.)  Arc 
our  Bodies  Changing? 

On  Thursday,  May  3,  Prof.  J.  T.  Mac- 
Gregor-Morris,  M.I.E.E.,  M.E.I. ,  gave  a 
lecture  on  Modern  Electric  Lamps:  (II.) 
Glowing  Solids  in  Gases. 

On  Saturday,  May  5,  Leonard  Williams, 
M.D.,  M.E.I. ,  will  give  a  lecture  on  The 
Physical  and  Physiological  Foundations  of 
•  Character.     (Lecture  II.). 


EOYAL  SOCIETY  OF  AETS. 
On  Monday,  April  30,  the  Howard  Lec- 
ture on  The  Development  of  the  Steam.  Tur- 
bine, was  delivered  by  Stanley  S.  Cook, 
B.A.  (Cantab.),  M.I.N. A.,  M.I.M.  (Par- 
sons Marine  Steam  Turbine  Co.). 


THE  CHEMICAL  SOCIETY. 

At  the  Ordinary  Scientific  Meeting,  held 
on  Thursday,  May  3,  the  following  papers 
were  read :  — 

Change  of  Properties  of  Substances  on 
Drying.    Part  II.     H.  S.  Baker. 

The  Sodium  Salts  of  Phenolphthalein.  H. 
B  AS  sett  and  P.  Halton. 

The  Action  of  Thiosulphates  on  Cupric 
Salts.    H.  Bassett  and  E.  G.  Durrant. 

The  Conditions  of  Reaction  of  Hydrogeyi 
ivith  Sulphur.  Part  II.  :  The  Catalytic  Ef- 
fect of  Oxygen.  Part  III.  :  On  the  mech- 
anism of  the  Reaction  of  Hydrogen  with 
Sulphur  and  its  Catalysis  by  Oxygen.  E. 
G.  W.  Norrish  and  E.  K.  Eideal. 

Studies  of  Electrovalcncy.  Part  II.  : 
Co-ordinated  Hydrogen.     T.  M.  Lowry. 

Investigations  on  the  Dependence  of  Ro- 
tatory Poivcr  on  Chemical  Constitution. 
Part  XX.  :  The  Rational  Study  of  Optical 
Properties.     H.  Hunter. 


MAY  4,  1923. 


tSe  chemical  news. 


281 


I 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 

OTHEll  ANALYTICAL  CHEMISTS. 

A  meeting  of  the  Societj^  was  held  oa 
Wednesday,  May  2,  when  the  following 
papers  were  read:  — 

The  Quantitative  Determination  of  Hemp 
and  Wood  in  Papers  containing  these  two 
Fibres,  by  William  Dickson,  ij'.I.C. 

The  Estimation  of  Fat,  Lactose  and 
Moisture  in  Dried  Milks,  by  H.  Jephoott, 
M.Sc,  Jb'.l.C. 

The  Estimation  of  Lactose  by  the  Folaii- 
metric  and  Graviynetric  Methods,  by  A.  L. 
Bacuakach,  B.A.,  A. I.e. 

The  Melting  Foint  and  Iodine  Value  of 
Refined  Natural  D.  Camphor,  by  Maurice 
S.  Salamon,  B.Sc. 

The  Presence  of  Bariutn  and  Strontium 
in  Natural  Brines,  by  A.  G.  Francis,  B.Sc, 
F.I.C. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEEltS. 
At  a  meeting  of  the  Wireless  Section,  in 
the  Lecture  Theatre  of  the  Institution,  on 
Wednesday,  May  2,  Professor  C.  L.  For- 
TEscuE  dehvered  a  lecture  entitled  The  De- 
sign of  Inductances  for  High-Frequenoy 
Circuits. 


SOCIETY  OF  GLASS  TECHNOLooi. 

The  sixth  annual  general  meeting  of  the 
Society  of  Glass  Technology  was  held  in 
Sheffield,  on  Wednesday,  April  18,  the  Pre- 
sident, Prof.  W.  E.  S.  Turner,  D.Sc,  in 
the  chair.  The  formal  business  included 
the  election  of  the  following  officers  to  fill 
vacancies  arising  according  to  the  "Consti- 
tution and  liules"  of  the  Society: — 

President:  Prof.  W.  E.  S.  Turner,  D.Sc. 
(re-elected). 

Vice-Presidents:  E.  A.  Coad-Pryor,  B.A., 
W.  J.  Gardner. 

Members  of  Council:  F.  F.  8.  Bryson, 
M.A.,  B.Sc.,  F.Inst.P.,  Violet  Dimbleby, 
B.Sc,  Major  G.  V.  Evers,  Col.  S.  0.  Halse, 
T.  Teisen,  B.Sc,  C.E. 

Treasurer:  Joseph  Connolly  (General), 
Wm.  M.  Clark,  Ph.B.  (American).  ' 

Hon.  Secretary  :   S.  English,  M.Sc. 

Auditors:  Edward  Mcigh,  M.Sc.  7^rjini< 
Wood,  F.8.A.A. 

The  President's  mldrt'ss  on  The  Year  in 
Review  in  the  World  of  Glas8}naking,    was 


taken  as  read,    the  main    business    of    the 
meeting    being    a    general     discussion    on 
Works  Organisation.      Mr.  W.  W.  Warren 
(Messrs.       Lemington     Glassworks,     Ltd.) 
opened  the  discussion  with  a  paper  entitled 
Organising    for  Production    from  Pot    Fur- 
naces.      After  a  discussion    on    this    paper 
(which  had  already    been  presented  at    the 
Newcastle  meeting    in  February),    the  case 
for    "  Tank-furnace    wwks    organisation  " 
was  presented    by     Mr.    T.    C.  Moorshead 
(Messrs.    United    Glass    Bottle     Manufac- 
turers, Ltd.),  who  said  that  organisation  as 
applied  to  a  manufacturing  industry  might 
be    defined  as  a    combination    of  men    ar- 
ranged   or   distributed  in    parts    or    groups 
with  proper  officials,    managers,    and  fore- 
men, and  so  co-ordinated    that    they    were 
able  with  the    aid  of    such  machines    and 
tools  as  they  might  have  available,  to  pro- 
duce a  finished  article  efficiently.      If  they 
could  not  say  assuredly    that  each    of  their 
groups  was  convposed  of  capable  men,  each 
group  in  charge  of  a  capable  foreman,    the 
foremen  all  capable,  and  co-operating  under 
a  capable  su|)erintendent  <»*  shift  manager, 
or  whatever  they  might  call  him;  who  was 
responsible?      He    believed    that    the  man 
really  responsible    for  the    losses    in   plant 
efficiency  was  the  active  head  of  the  institu- 
tion.    He  endorsed    the  opinion  of    indus- 
trial engineers    and  efficiency  experts    who 
stated    that    the    average     manufacturing 
plant  had  only  50  per  cent,  efficiency,    and 
that  also    80  per  c<:>nt.  of  this    tremendous 
loss  of  efficiency    was  due  to  the  manager, 
or  to  a  lack  of  proper  or  efficient    manage- 
ment.   The  difficulties  which  beset  the  fac- 
tory manager  every  day  might  all  be  traced 
back  to  inefficiency  on  the  part  of  the  man- 
agement, and  probably  to  three  things:  — 
(1)  Lack  of  foresight;    (2)  lack  of  thorough 
knowledge    of  the    faotwy  operations;    (8) 
lack  of  initiative.       The    causes    for    these 
losses  could  be    grouped  under    five    head- 
ings:— (1)    Faulty  raw  material;    (2)  poor 
labour,    that  is,  incapable,  indifferent    and 
disloyal    employees ;    (3)  poor    attendance ; 
(4)    large  labour  turnover,    or  ratio  of  nien 
leaving  to  the  number   of  men  on  the  pay- 
roll;    (5)    machine    or  mechanical     break- 
downs. 

1. — Faulty  Raw  Material:  It  was  urged 
that  the  buyer,  or  preferably  a  works 
clicmist,  should  investigate  the  sources  of 
sujiiply  to  make  provision  for  constant  and 
regular  supplies,  keep  a  sufficient  quantity 
in  store  at  all  times  to  ensure  the  factory 
against  shut  downs  in  case  of  failure  of  de- 


282 


THE  CHEMICAL  NEWS. 


MAY  4,  1923. 


liveries,  to  analyse  frequently  the  materials 
for  purity ,  and  to  see  that  they  came  up  to 
sipecifications. 

2. — Poor  Labour  was  a  difi&cult  problem 
and  should  be  dealt  with  at  the  source. 

3. — Poor  Attendance  was  a  fundamental 
principle  in  dealing  with  their  difi&cult  prob- 
lems to  make  a  man's  work  interesting. 
This  might  be  done  first  of  all  by  being 
sure  that  employees  understood  what  they 
were  doing  and  why.  The  more  they  knew 
about  the  material  they  worked  with,  the 
better.  Weekly  managers'  and  foremen's 
meetings  are  held,  full  and  complete  re- 
cords or  minutes  of  which  are  kept  and 
copies  circulated  to  those  who  were  present. 
One  copy  is  also  sent  to  the  head  ofi&ce. 

4. — Large  Labour  Turnover:  To  prevent 
the  wastage  due  to  this,  work  should  be 
made  agreeable.  It  was  also  necessary  to 
regularise  it.  Every  man  should  be  given 
identity.  A  great  many  manufacturing 
plants  were  going  so  fur  as  to  make  a  care- 
ful analysis  of  each  piece  of  work. 

5. — Machine  or  Mechanical  Breakdowns 
were  the  least  wearisome  cause  of  efficiency 
loss.  In  nine  cases  out  of  ten,  machine 
breakdowns  were  due  to  lack  of  foresight; 
failure  on  the  part  of  the  man  responsible 
for  either  the  operation  or  upkeep  of  the 
particular  machine  to  anticipate  troubles; 
failure  to  see  that  spares  for  vital  parts  of 
the  various  machines  were  in  store,  and 
failure  to  keep  all  moving  parts  properly 
oiled  and  the  machines  clean,  all  of  which 
brought  us  back  to  the  human  element  and 
organisation. 

Mr.  Moorshead  concluded  his  paper  by 
emphasising  the  resiponsibility  that  rests  on 
the  foremen,  and  suggested  the  questions  a 
manager  might  ask  himself  in  selecting  his 
foreman  or  determining  his  capabilities. 

Col.  S.  C.  Halse  (Messrs.  J.  Lumb  &  Co., 
Ltd.)  said  that  at  his  works,  after  installing 
a  set  of  new  machines,  they  had  daily  con- 
ferences, including  everyone  really  con- 
cerned in  the  output  of  their  machines.  By 
analysing  the  figures  obtained  from  day  to 
day  they  had  increased  production,  anrl 
were  able  to  trace  neaxly  every  bottle 
dropped  on  to  the  conveyer. 


THE  INSTITUTE  OF  METALS. 

Dr.  W.  Eosenhain,  F.R.S.,  delivered 
the  thirteenth  annual  May  lecture  before 
the  Institute  of  Metals  on  Wednesday,  May 
2.     His  subject  was  The  Inner  Structure  of 


Alloys,  upon  which  much  debated  matter  a 
Hood  of  light  was  thrown. 

Manchester  Meeting. 
A  further  meeting  of  the  Institute  (the 
annual  autumn  gathering)  will  be  held  in 
Manchester  on  September  10-13.  A  ballot 
for  the  election  of  Members  and  Students 
desirous  of  particijpating  in  this  and  other 
meetings  will  take  place  on  July  12th,  the 
necessary  membership  particulars  being 
also  obtainable  from  the  Secretary,  Mr. 
Shaw  Scott,  The  Institute  of  Metals,  36-38, 
Victoria  Street,  S.W.I. 


PHYSICAL   SOCIETY  OF  LONDON. 

At  the  meeting  held  on  Friday,  April  27, 
the  following  papers  were  read:  — 

The  Analysis  of  Bubbles  in  Glass,  by  the 
Research  Staff  of  the  General  Electric 
Company,  London. 

A  Simple  Regenerative  Vacuum  Device 
and  Some  of  its  Applications,  by  H.  P. 
Waran,  Ph.D. 

Application  of  the  Eotvos  Torsion  Bal- 
ance to  the  Investigation  of  Local  Gravita- 
tional Fields,  by  C apt.  H.  Shaw  and  E. 
Lancaster- Jones,  B.Sc. 

Demonstrations  were  given  as  follows  : 

An  Electromagnetic  Inductor,  by  L.  F. 
Richardson,  F.Inst. P. 

An  Experiment  Demonstrating  Time-Lag 
in  Vision,  by  Dr.  F.  Ll.  Hop  wood. 

At  the  meeting  held  on  March  23,  Alex- 
ander Russell,  M.A.,  D.Sc,  in  the  chair, 
papers  on  A  Neiv  Moving-Coil  Galvanometer 
of  Rapid  Indication  and  ^u  Thermopile  for 
Measuring  Radiation,  by  Dr.  W.  J.  H. 
MoLii,  University  of  Utrecht,  were  read  by 
Mr.  R.  S.  Whipple  in  the  author's  absence. 

The  galvanometer  is  designed  to  secure 
rajpid  indication  and  steadiness  of  reading 
without  unduly  sacrificing  sensibility.  The 
coil  is  long  and  narrow,  and  therefore  of 
small  moment  of  inertia:  the  mirror  is 
supported  by  the  wires  forming  the  coil, 
between  which  it  is  slipped,  and  the  coil  is 
supported  between  an  upper  and  a  lower 
vertical  wire,  as  distinct  from  strips,  made 
of  silioium  bronze  and  put  in  tension. 

The  thermopile  is  designed  to  be  quick- 
reading  and  free  from  zero-errors,     as  well 


MAY  4,  1923. 


THte  CHEMICAL  NEWS 


283 


us  sensitive.  The  cold  junctions  are  in  con- 
tact with  metal  masses  which  keep  down 
their  temperature,  and  in  order  that  the 
hot  junctions  may  have  small  heat  capacity 
the  bi-metallic  straps  composing  the  ther- 
mopile are  made  of  plates  of  constantau 
and  manganin  silver-soldered  along  an 
edge,  rolled  in  a  direction  parallel  to  the 
edge  into  thin  foil,  and  then  cut  into  striips 
perpendicular  to  the  edge. 

Discussiun. 

Mr.  F.  E.  Smith  commented  on  the 
strikingly  dead-beat  character  of  the  indi- 
cations given  by  both  instruments.  He  sug- 
gested that  the  thermopile  strips  mig^t  be 
reduced  to  even  a  less  thickness  than  0.005 
1 1  mi.  by  solution  in  acid.  The  galvano- 
ijieter  seemed  to  have  been  designed  to  pro- 
duce what,  with  a  single  fibre  suspension, 
would  have  been  an  extremely  sensitive  in- 
strument, but  then  the  supporting  wires 
were  put  in  tension  to  reduce  the  periotl. 
Would  it  still  be  possible  in  these  oircum- 
stances  to  obtain  the  required  sensibility? 

Dr.  li.  T.  Beatty  recalled  the  time  when 
it  was  necessary  to  work  with  a  bismuth- 
iron  couple  of  great  heat-capacity  and  an 
insensitive  Thomson  galvanometer.  Later 
came  the  Paschen  astatic  galvanometer, 
l>ut  this  instrument  required  such  heavy 
])rotecti(>n  from  stray  magnetic  fields  that 
lew  cared  to  use  it.  Dr.  Moll's  improve- 
ments should  make  (possible  an  advance  >n 
I  Measurements  of  the  distribution  of  energy 
in  the  spectrum,  e.g.,  in  the  H  and  He 
spectra. 

Mr.  C.  R.  Darling  suggested  that  the 
apparatus  might  be  applied  to  measure  the 
listribution  of  energy  in  the  spectrum  of  u 
/low  lamp. 

Mr.  J.  Guild  inquired  if  the  present  gal- 
vanometer differs  materially  from  that  ex- 
hibited by  Dr.  Moll  three  years  ago,  and 
what  is  the  number  of  junctions  ^er  cm. 
in  the  linear  form  of  the  thermopile.  If 
silicium  bronze  is  similar  in  its  properties 
to  phosphor  bronze  the  tension  f>f  the  sup- 
porting wires  of  the  galvanometer  would 
nave  a  serious  effect  on  the  sensibility  of 
the  instrument. 

Mr.  L.  F.  Richardson  said  that  he 
thought  Dr.  Moll's  thermopile  admirabl'j 
for  indoor  use.  For  work  out  of  doors,  where 
a  rock  salt  cover  could  not  be  used  and 
jfusts  of  wind  could  not  be  excluded,  Mr. 
W.  H.  Dines  had  found  it  de.sirablo  to  make 
the  hot  and  cold  junctions  of  as  nearly  the 


same  thermal  capacity  as  |)ossible,    so  that 
air  currents  might  affect  both  equally. 

^Ir,  R.  S.  Whipple,  in  reply,  said  that 
the  difficulty  of  rolling  the  strijps  is  im- 
mense, and  Mr.  Smith's  suggestion  as  to 
solution  in  acid  was  well  worth  trying, 
though  there  might  be  difficulties  due  to 
unequal  chemical  action.  He  agreed  that, 
although  there  is  no  instrument  as  sensitive 
as  the  Paschen  galvanometer,  this  is 
troublesome  to  use. 

A  Note  on  Aberration  and  the  Doppler 
Effect  as  Treated  in  the  Theory  of  Relativ- 
ity, by  Capt.  C.  W,  Humb,  M.C,  B.Sc. 

In  older  text-books  aberration  is  ex- 
plained as  due  to  the  compounding  of  the 
velocity  of  light  with  the  velocity  of  the 
earth  relative  to  the  ether;  hence  at  first 
!>ight  the  phenomenon  appears  to  conflict 
with  the  principje  of  relativity.  The  paper 
gives  siuiple  methods  of  treating  this  prob- 
lem consistently  with  the  Restricted  Prin- 
ciple, and  of  finding  the  Doppler  effect.  In 
each  case  the  result  differs  from  the  non- 
relativity  result  by  tenns  of  the  second  and 
higher  orders  in  v/c. 

A  demonstratitm  was  shown  by  Mr.  C. 
R.  Daklino  and  Hon  C.  W.  Stopfohd,  en- 
titled Experiments  on  the  Production  of 
Electromotive  Forces  by  Heating  Junctions 
of  Single  Metals. 

When  a  circuit  is  closed  through  a  junc- 
tion of  a  oold  metal  with  a  hot  piece  of  the 
same  metal,  large  E.M.F. 's  are  often 
noticed.  As  examiple  a  bare  copper  wire 
was  connected  to  the  terminals  of  a  gal- 
vanometer. The  wire  was  cut  at  the  mid- 
dle, one  of  the  cut  ends  heated  and  brought 
into  cMitact  with  the  cold  end,  when  a  large 
deflectioo  was  obtained.  Electromotive 
forces  up  to  0.26  volt  may  thus  be  pro- 
duced. 

DisciiHsion. 

Mr.  J.  S.  G.  Thomas  called  attention  to 
an  account  of  experiments  somewhat  simi- 
lar given  by  Prof.  Carl  Benedicks  in  1920. 

Dr.  H.  Boms  said  he  hardly  underst(KKl 
why  Mr.  Darling  was  surprised  at  his 
strong  thermo-electric  fcM'ces.  When  he 
broke  his  copiper  wire  with  a  pair  of  pincers 
the  two  ends  of  the  wire  would  not  l-e 
stniined  equally.  Tli<;  one  end  of  his  iron 
rod  (and  of  his  graphite  rod)  was  groowd, 
th<«  other  filed  to  chisel  shape.  The  one  end 
was  heated  in  a  gas  flame  to  about  700®  C. ; 


^84 


THE  CHEMICAL  NEWS. 


MAY  4,  1923. 


the  temperature  gradients  were  very  steep, 
and  the  conditions  were  favourable  to  oxi- 
dation and  other  chemical  effects,  expul- 
sion of  gases  (from  the  graphite),  and  to 
pronounced  heterogeneity. 

Mr.  r.  E.  Smith  commented  on  the  ex- 
treme difficulty  of  treating  metals  in  any 
way  without  affecting  their  constitution. 
In  trying  to  make  a  junction  with  E.M.F. 
as  low  as  10-^  volts  he  had  found  it  impos- 
sible even  to  cut  silver  and  platinum  wires 
without  straining  them,  and  by  twisting 
the  wires  he  obtained  a  much  greater  effect. 
One  inference  from  the  omnipresence  of 
thermo-electric  voltages  is  that  in  the 
Wheatstone  Bridge  the  galvanometer  key 
ought  to  be  closed  before  the  battery  key, 
contrary  to  the  usual  practice. 

Dr.  l).  Owen  said  that  the  voltages  ob- 
tained aippeared  to  be  of  the  order  to  be  ex- 
pected from  thermo-electric  currents  at 
contacts  of  oxides  or  sulphides  of  the 
metals.  Had  the  authors  tried  the  effect 
with  platinum? 

Dr.  J.  A.  Harker  said  that  in  using  the 
Callendar-Grifiiths  Bridge  some  years  ago 
to  measure  the  resistance  of  copper  wire, 
he  had  found  that  if  the  wire  were  asym- 
metrically heated  two  different  values  of  its 
resistance  were  obtained  for  the  two  direc- 
tions of  the  current  through  the  bridge. 
The  two  values  drifted  further  ajpart  with 
lapse  of  time.  Lord  Kelvin  regarded  the 
phenomenon  as  a  modified  form  of  the  Kel- 
vin effect. 

Mr.  R.  S.  Whipple  asked  whether  the 
E.M.F.  obtained  is  affected  by  the  pres- 
sure at  the  junction.  If  the  effect  is  chemi- 
cal, the  compression  would  affect  the  thick- 
ness of  any  film  formed. 

Dr.  E.  H.  Rayner  said  that  thermo-elec- 
tric currents  were  formerly  dealt  with  very 
briefly  in  the  text-books.  He  would  like  to 
know  how  the  subject  is  now  handled  in 
the  class-room. 

Dr.  F.  LI.  Hop  wood  said  that  informa- 
tion bearing  on  the  subject  of  the  demon- 
stration could  be  found  in  the  published 
writings  of  Richardson  and  Benedicks. 

A  demonstration  of  The  Double  Refrac- 
tion due  to  Motion  of  a  Vanadium  Pent- 
o^ide  Sol,  and  Some  Applications,  was 
given  by  Mr.  R.  H.  Humphry,  M.Sc. 

The  effect  was  first  noticed  in  1915  by 
Freundlich,  Dieselhorst  and  Leonhardt.  In 
linear  flow  the  liquid  behaves  in  the  same 
way  as  a  plate  of  uniaxal    crystal  cut  paral- 


lel to  the  axis  and  placed  with  axis  parallel 
to  the  direction  of  flow. 

The  field  between  crossed  nicols  was 
shown  to  light  up  near  an  obstacle  inter- 
posed in  a  stream  of  the  liquid.  Similar 
effects  due  to  efflux  of  the  sol  from  a  jet,  to 
the  convective  stream  from  an  electrically- 
heated  wire,  etc.,  were  also  shown. 

Discussion. 

Mr.  E.  Hatschek  said  that  the  experi- 
ments called  for  exceiptional  cleanliness  as 
the  sol  is  very  sensitive  to  electrolytes. 
Aniline  blue  is  interesting  in  that  it  gives 
colour  effects;  it  has  a  well-marked  absorp- 
tion band,  and  behaves  Uke  a  positive  crys- 
tal to  wave-lengths  on  one  side  of  the  band, 
but  like  a  negative  crystal  to  wave-lengths 
on  the  other  side. 

Mr.  R.  W.  Paul  asked  whether  the  effect 
of  subjectinor  the  liquid  to  an  electrostatic 
field  had  been  tried. 

Mr.  J.  Guild  said  he  was  not  satisfied  as 
to  the  cause  of  the  double  refraction.  The 
colloidal  particles  are  too  large  to  have  the 
effect  of  molecules,  and  too  small  to  be  re- 
garded as  transmitting  light  after  the  man- 
ner of  glass  dust.  In  his  reading  of  ultra- 
microscopic  literature  he  had  come  come 
across  nothing  which  suggested  a  satisfac- 
tory explanation.  In  interpreting  the  ap- 
pearances obtained  by  Prof.  Coker's  method 
the  greatest  caution  is  necessary.  The  in- 
tensity of  the  effect  of  a  strain  or  a  stream- 
line depends  on  its  direction,  and  for  cer- 
tain directions- it  is  imipossible  to  detect  a 
strain  at  all. 

In  reply  to  the  discussion  Mr.  Humphry 
said  that  the  exiperiments  which  were 
shown  were  only  to  be  regarded  as  prelimi- 
nary, and  no  interpretation  of  the  observed 
effects  had  yet  been  attempted.  It  seemed 
possible  by  use  of  this  effect  to  throw  more 
light  on  stream  line  problems;  and  with 
bettor  apparatus,  designed  to  overcome  any 
tendency  towards  gelation,  useful  results 
might  be  obtained.  The  effect  of  an  elec- 
tric field  on  the  arrangement  of  the  par- 
ticles had  been  worked  out  by  Freundlich 
(Kapillar  Chemie,  1922),  who  also  ex- 
plained the  production  of  the  double  refrac- 
tion. It  is  true  that  with  stationary  nicol 
prisms  certain  stream  lines  are  accentuated, 
while  others  may  not  appear  at  all ;  but 
this  difficulty  would  be  overcome  by  having 
rotating  nicols.  The  more  delicate  means 
of  examining  polarised  light  might  show 
effects  which  were  missed  with  nicol 
prisms. 


MAY  4,  1923. 


THE  CHEMICAL  NEWS. 


285 


PHYSICS  IN  INDUSTRY. 

The  fourth  of  the  series  of  lectures  on 
this  subject,  which  are  Ijcing  deUvered 
under  the  auspices  of  the  Institute  of  Phy- 
sics, will  be  given  by  Dr.  J.  W.  Mellok, 
of  Stoke-on-Trent,  and  will  deal  with  The 
Application  of  Physics  to  the  Ceramic  In- 
dustries. 

Sir  J.  J.  Thomson  will  preside  at  the 
lecture,  which  will  be  delivered  in  the  hall 
of  the  Institution  of  Electrical  Engineers, 
Victoria  Embankment,  W.C.2,  on  Wednes- 
day, May  9,  at  5.30  p.m. 

A  ticket  of  admission  will  not  be  re- 
quired. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 
The  Design    of    Inductances    for    High- 
Frequency  Circuits,   by  Professor    C.    L. 
FoRTEScuE,  Member. 

This  paper  consists  of  an  investigation  •>! 
the  proportions  and  the  arrangement  of  the 
winding  of  high-frequency  inductances  in 
order  to  obtain  the  minimum  ratio  of  R/L 
Both  stranded  and  solid  wire  coils  are  deaR 
with,  and  the  unavoidable  limitaticms  aris- 
ing from  the  sipace-f actor  are  considered. 
Results  and  tables  are  given  which  enable 
simple  comparisons  to  be  made  between 
stranded  and  solid  wire  coils  having  either 
single-  or  multiple-layer  windings. 


CORRESPONDENCE. 


I 


CAUTION  TO  INVENTORS. 

To  the  Editor  of  The  Chemical  News. 

Sir, — In  case  the  matter  may  not  have 
been  brought  to  your  notice  already,  I 
should  like  to  draw  your  readers'  attention 
to  the  Caution  to  Inventors,  which  has 
been  inserted  by  the  Comptroller-General 
of  Patents  in  the  Illustrated  Official  Jour- 
nal at  the  request  of  the  Chartered  Insti- 
tiii,.  of  Patent  Agents:  — 


"  Inventors  are  advised  to  beware  of 
suggestions  such  as  are  now  being  issued 
from  a  German  source  to  the  effect  that, 
for  reasons  obscurely  stated  by  the  German 
writer,  the  British  inventor  should  co- 
pper: it<'  with  him,  and  in  particular  should 
send    him    by    registered    letter    a  sum   of 


money.     The  communication  is  fraudulent, 
and  on  no  account  should  money  be  sent." 
I  am, 

Yours  faithfully, 

Richard  B.  Pilciier, 
Registrar  and  Secretary. 
The  Institute  of  Chemistry, 

30,  Russell  Sq.,  London.  W.C.I. 
April  18,  1923. 


ARABIAN  ALCHEMY  AND 
CHEMISTRY. 

To  the  Editor  of  The  Chemical  News. 
Sir, — Perhaps  you  will  be  good  enough 
to  allow  me  to  answer  the  letters  of  Mr. 
Whale  (March  9),  and  Mr.  Redgrove  (April 
6),  on  the  question  of  Gi  ber.  I  would  first 
make  it  quite  clear  that  the  sole  conclusive 
iproof  of  the  identity  of  Geber  with  Jabir 
ibn  Hayyan,  the  famous  and  historical 
Muhommedan  chemist  of  the  8th  century, 
would  be  the  discovery  of  Arabic  originals 
of  the  Latin  works;  up  to  the  present  this 
discovery  has  not  been  made.  I  have  briefly 
outlined  my  position  in  an  article  in  Nature 
(Feb.  10,  1923),  to  which,  and  to  the  valu- 
able letter  of  Prof.  J.  R.  Partington  in  the 
following  number  of  the  same  journal,  per- 
haps Mr.  Whale  and  Mr.  Redgrove  will 
refer. 

There  are,  however,  one  or  two  additional 
facts  which  may  be  of  interest:    (1)    Oeber 
is  an  accurate  transliteration  of  tne  Arabic 
Jabir,  eajpecially    as  in    Egypt    and    many 
other  parts  of  the  Muhammadan  world  the 
letter  ;  (/  j  m)  is  sounded  as  hard  g;  (2)  ac- 
cording to  Darmstaldtcr,  Die  Alchemic  des 
Geber,  Berlin,  1922,    p.    184,    Vincent    de 
Beauvais  in  cap.  82  of  his  Speculum  Natur- 
ale,  Numberg,   1485,    refers    to    Geber    as 
Jober;     (3)    in    mediasval    Latin    chemical 
works  Geber    is  often    called    Geber    ebor 
Haon,  which  is  undoubtedly    a  translitera- 
tion of  the    Arabic    Jabir  ibn  Hayyan;    (4) 
Boerhaave  (1668-1738),  professor  of  chemis- 
try at  lieyden  University,  says  in  his  Ele- 
nienta  Chemiie    (Shaw's    English    transla- 
tion, 3rd  edition,  1753,  vol.  I.,  p.  26,  foot- 
note, that  GoliuB  (1596-1667),    professor  of 
mathematics  and  Arabic    at  the  same  Uni- 
versity, presented  Arabic  MSS.  of  Geber  to 
the  Leyden  public  library,    and  translated 
them  into  Latin;    the  translation  was,    he 
says,  published  at  first  in    folio  and  after- 
wards in  quarto,  under  the    title  of    Lapis 
Philonnphonim.        From    Boerhaave 's    de- 
scription of  this  translation  (U)c.  cit.)  it  is 


286 


THE  CHEMICAL  NEWS. 


MAY  4,  1923. 


clear  that  the  work,  if  not  actually  the 
Sumvia,  at  least  bears  the  closest  similar- 
ity to  it.  But  the  Sum  ma  and  other  Latin 
works  were  already  well  known,  and  had 
been  studied  for  some  throe  hundred  years. 
Why,  therefore,  should  Golius  go  to  the 
trouble  of  translating  them  from  the  Arabic 
unless  to  iprovide  a  more  accurate  text  ?  It 
seems  to  me  that  the  importance  of  this  ob- 
servation of  Boerhaave's  is  very  great.  At 
the  same  University  as  Golius,  and  practic- 
ally contemporary  with  him,  his  informa- 
tion must  almost  certainly  be  reliable;  he 
knew  the  Summa  and  other  Latin  works 
and  the  presumption  that  Golius'  transla- 
tion is  of  Arabic  originals  of  these  seems 
overwhelming.  If  it  were  otherwise,  surely 
Boerhaave  would  have  mentioned  the  fact. 
It  is  tantalising  tq  find  that  the  Leyden 
library,  if  Boerhaave  is  correct,  must  have 
lost  these  manuscriipts,  as  there  are  now  in 
it  none  which  can  be  regarded  as  originals 
of  the  Latin  works.  However,  fresh  dis- 
coveries of  Arabic  MSS.  are  continually 
being  made,  and  one  may  hope  that  other 
copies  of  the  works  translated  by  Golius 
may  be  forthcoming  in  the  future. 

(5)  The  names  of  many  works  attributed 
to  Geber  correspond  with  titles  of  works  of 
the  Arabic  Jabir  ibn  Hayyan,  as  given  in 
the  Kitab  at  Fihrist  and  elsewhere;  ex- 
amjple  (a)  De  claritate  alcheviice  with  The 
Book  of  Spendour,  (b)  Test  amentum  Geher 
with  The  Testament  of  Jabir,  (c)  The  Sum- 
m,a  with  the  Compendium.  Unfortunately 
Arabic  texts  of  these  are  not  yet  known. 

On  the  desirability  of  making  translations 
of  all  the  extant  Arabic  writings  of  Jabir 
ibn  Hayyan,  I  am  in  entire  agreement  with 
Mr.  Eedgrove  and  Mr.  Whale.  I  feel,  how- 
ever, that  translations  without  texts  are 
always  unsatisfactory,  but  since  publishers 
are  very  reluctant  to  undertake  the  expen- 
sive business  of  having  Arabic  type  set  up, 
there  seems  to  be  no  alternative.  I  have 
in  hand  a  translation  of  the  Book  of  Proper- 
ties, from  the  British  Museum  MS.,  and 
hope  to  publish  a  great  part  of  it  in  a  forth- 
coming book  on  Chemical  Theory  and  Prac- 
tice in  Islam,  which  I  am  preparing  for  the 
Trustees  of  the  Gibb  Oriental  Translation 
Fund. — I  am.  Sir, 

Yours,  etc., 

E.  J.  Holm  YARD. 

Clifton  College. 
April  19,  1923. 


LABORATOliY  ENQUIRY. 

To  the  Editor  of  The  Chemical  News. 
Sir,  —  Could  any  of  your  readers  supply 
me  with    the  address    of  a  laboratory    that 
would  make  up  a  sample  from"  a  formula? 
I  am,  Yours,  &c., 

Norman  Urwin. 
3,  Percy  Avenue,  Catchgate,  Durham. 
April  19,  1923. 


NOTICES  OF  BOOKS. 

Wavelength  Tables  for  Spectrum  Ana- 
lysis,   by  F.    TwYMAN,    F.Inst. P.      Pp. 
VIII.  +  106.      London:     Messrs.    Adam 
Hilger,  Ltd.,  75a,  Camden  Road,  N.W.I. 
19-23.     Price  7&.  6d.  net. 
This  comprehensive  treatise  is  not,  as  the 
title  conveys,  a  monotonous  page-sequence 
of    tables,    difficult    of  reference    and    with 
jumbled  data.       Instead,    it  is  a    first-class 
text-book  of  interesting  matter,  of  inestim- 
able value  to  the  analyst. 

Referring  to  the  author's  preface,  it  com- 
prises standard  wavelengths  from  2375  to 
8495  I.A.,  the  ipersistent  and  sensitive  lines 
of  most  of  the  elements  arranged  \inder  the 
name  of  each  element,  and  the  most  persis- 
tent and  sensitive  lines  rearranged  in  order 
of  wavelengths.  The  last  chapter  deals 
with  wavelengths  useful  in  the  determina- 
tion of  stellar  radial  velocities. 

In  his  explanatory  matter,  the  author  has 
rightly  paid  much  attention  to  the  results 
of  Hartley,  Pollok,  Leonard,  and  A.  de  Gra- 
mont,  briefly  sTiowing  records  of  their  re- 
spective works,  and  carefullv  tabulating 
their  data.  In  a  short  appendix,  the  con- 
densed sipark  produced  by  means  of  the 
Hemsalech  coil  (quoted  frequently  by  the 
authorities  mentioned  above)  is  described 
collectively  with  the  requisite  observations. 
The  value  of  this  book  is  not  to  be  esti- 
mated, and  we  recommend  it  highly  to  the 
notice  of  our  readers.  It  should  run  to 
many  editions. 


The  Phase  Rule  and  Its  Applications, 
by  Alexander  Findlay,  M.A.,  Ph.D., 
D.Sc,  F.I.C.  Fifth  edition.  Pp.  XVI. 
+  298.  London :  Longmans,  Green  & 
Co.,  Ltd.,  39,  Paternoster  Row,  E.G. 4. 
1923.  Price  10s.  6d.  net. 
In  the  course  of  the  rapid  developmerit 
of  the  various  sections  of  Physical  Chemis- 


MAY  4,  1923. 


THE  CHEMICAL  NEWS. 


287 


try,  in  recent  years,  increasing  attention 
has  been  paid  by  investigators  to  the  study 
of  heterogenous  equilibria.  This  has  neces- 
sitated a  very  complete  revision  of  some  of 
the  chaiptcrs  of  Professor  Findlay's  classical 
text-book  on  the  Phase  Rule,  which  we  are 
pleased  to  note  is  now  in  its  fifth  edition. 

Certain  sections  have  been  re- written, 
and  much  new  matter  (including  24  fresh 
diagrams)  has  been  incorporated.  The 
graphical  methods,  especially  those  initiat^^d 
by  Jiinecke,  of  representing  multi-compo- 
nent systems,  have  been  widely  used.  They 
are  fully  explained  for  the  benefit  of  stu- 
dents and  others  not  familiar  with  thi«: 
mode  of  exipressing  results. 

Doubtless  the  present  revised  edition  of 
this  volume  in  the  important  series  of  text- 
books on  Physical  Chemistry,  edited  by  Sir 
William  Ramsay  and  Prof.  F.  G.  Donnan. 
will  be  as  widely  and  assiduously  studied 
as  its  predecessors. 


The  Destructive  Distniatinn  of  Wood. 
by  H.  M.  BuNBURV,  M.So.  CBris.').  B.Sr. 
(Lond.).  Pp.  XTX.  +  320.  London: 
Benn  Brothers,  8,  Bouverie  St.,  E.C. 
1023.     Price  358.  net. 

Whilst  the  destructive  distillation  of  coal 
has  been  the  subject  of  numerous  treatises, 
very  little  attention  has  been  paid  to  the 
thermal  decomposition  of  wood.  This  is 
somewhat  surprising  in  view  of  the  fact 
that  the  distillation  of  wood  comes  next  in 
importance  to  that  of  coal. 

Mr.  Bimbury's  book  is  therefore  very 
welcome.  In  it  he  has  given  a  good  descrip- 
tion of  the  plant  and  iprocesses  used  in  th'^ 
distillation  of  various  types  of  wood.  Thi< 
is  followed  by  a  survey  of  the  iproducts  of 
these  thermal  decompositions  and  the  con- 
ditions influencing  their  respective  quanti 
ties  and  composition. 

The  treatment  of  the  technical  aspects  of 
the  subject  has  been  well  done,  and  whilst 
modem  processes  are  adequately  described, 
obsolete  methods  receive  historical  men- 
tion only. 

Tn  the  immediate  future  such  processes 
as  the  thermal  decomposition  of  wood  will 
receive  much  more  attention  than  thev 
have  hitherto  commanded,  especially  when 
it  is  realised  that  waste  wood  can  be  suc- 
cessfully treated. 

The  information  contained  in  Mr.  Bun- 
bury 's  book  will    be  found    of  value  to   in- 


dustrial chemists  and  others  interested  in 
this  subject.  It  is  a  contribution  to  the 
chemistry  and  technology  of  distillation 
which  deserves,  and  will  doubtless  obtain, 
a  place  in  all  scientific  and  technical 
libraries. 


PUBLICATIONS  RECEIVED. 

Nitrate  Fasts  and  Figures,  1923,  com- 
piled by  A.    F.    Brodie    James,    F.S.S 
London:    F.  C.  Mathiesons  &  Sons,  16, 
Copthall  Ave.,  E.C.    5s.  net. 
This  is  the    twentieth    year    of    issue    yt 
these  statistics,   which  tend   to  show    that 
the  period  of    depression  in  the  nitrate  in- 
dustry has  passed.     The  near  future  seems 
very  hopeful. 


Mysore    Agricultural    Calendar,    1923. 

Price  1  anna. 

This  publication  contains  much  useful  in- 
formation for  those  interested  in  its  54 
pages.  That  agricultural  problems  are  of  a 
scientific  nature  is  clearly  indicated  by  a 
perusal  of  the  various  methods  outlined  to 
combiit  pests. 


The  Official  Handbook,  issued  by  The 
British  Association  of  Trade  and  Tech- 
nical Journals,  Ltd.     London :   Silioian 
House.   Southampton  Row,  W.C.I.    Pp. 
102.     1923.     Is.  net.,  is  full  of  most  in- 
teresting data  concerning  the  advertising 
facilities  offered  by  technical  journals. 
The  restoration  of  trade  rests,  to  some  ex- 
tent, with  the  creation  of  a  revitalised  mar- 
ket-interest.      Prior    to    the  war,     British 
chemicals  were  in  a  general    state  of  pros- 
perity, but  a  damaging  cautiousness  is  ex- 
tant among  purchasers  now.     To  overcome 
such    an    attitude,     manufacturers     must 
make  judicious  use    of  industrial    publica- 
tions,   and    this  is  the  object    of  the    pub- 
lishers   of  the  Handbook :     to  advise    and 
keeip  advertisers  in  their  campaigns — large 
or  small. 

Much  important  information  bearing  up- 
on these  points  is  enclosed  in  the  prefaces. 
The  book  is,  in  fact,    a  complete  and    con- 
cise means  of  reference    for  nil  firms    who 
are  planning  publicity  schemes  in  1928. 


288 


THE  CHEMICAL  NEWS. 


MAY  4,  1923. 


W.  Heffer    &  Sons,    Ltd.,    Publishers, 

Cambridge,    have  in  the  press  a    volume 

entitled     The     Exi>crt     Witticss,     by     C. 

AiNSWORTH     Mitchell,     M.A.     (Oxon.), 

Editor  of  The  Analyst. 

This  book  is  written  on  similar  lines  to 
and  is  in  many  resipects  a  sequel  to  the 
author's  "  Science  and  the  Criminal," 
which  is  now  in  its  second  large  edition.  It 
gives  an  outline  of  the  latest  aipplications 
of  scientific  research  to  the  investigation  of 
criminal  problems,  and  also  an  account  in 
non-technical  language  of  the  use  of  ex- 
pert evidence  of  all  kinds,  illustrated  by 
reference  to  old  and  modem  trials. 

The  nine  chapters  deal  with  the  latest 
methods  of  identification  by  means  of  pat- 
terns on  the  feet;  by  the  pores  of  the  skin; 
by  the  detection  of  latent  prints  on  paper, 
etc. 

The  latest  scientific  methods  of  hand- 
writing are  also  described,  and  an  outline  is 
given  of  the  author's  methods  of  estimat- 
ing the  age  of  ink  in  writing.  In  the  de- 
scription of  Secret  Writing  there  is  an  ac- 
count of  the  scientific  evidence  given  at  the 
trials  of  German  spies. 

The  last  chapter  deals  with  expert  evi- 
dence in  art  and  with  the  application  of 
such  scientific  methods  as  the  use  of  X-rays 
to  identify  old  masters. 


Messrs.  Bailli^re,  Tindall  &  Cox,  8,  Hen- 
rietta St.,  Covent  Garden,  W.C.,  state  that 
the  price  of  Mr.  T.  Thome  Baker's  The 
Spectroscope  and  lis  Uses  in  General  Ana- 
lytical Chemistry,  published  by  them,  and 
reviewed  in  The  Chemical  News,  this  vol., 
page  253  (April  20),  is  8s.  6d.,  and  not  7s. 
6d.  as  originally  given  by  them. 


xHis  list  is  specially  compiled  for  The  Ghemica} 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chanoecy  Lane.  London,  from  whom 
all  information  relating  to  Patents.  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest   Patent  Applicntiovs. 

9622— Bakelite.  Ges.— Manufacture  of  condensa- 
tion products  from  phenols  and  aldehydes. 
April  6. 


910.') — Casale,  L. — Synthetic  production  of  ammo- 
nia.   April  5. 

9374 — Farbwerke  vorm.  Meister  Lucius  Bruning. 
—Converting  hydrocarbons,  etc.,  into  others 
containing  a  higher  number  of  carlwn  atoms. 
April  5. 

9369 — Naugiituck  Chemical  Co. — Manufacture  of 
diphenylguanidine.     April   5. 

Specifications   Published   this    Week. 

19.5113— Smythe,  R.  H.— Process  to  facilitate  clas- 
sification of  mineral  particles  and  to  re- 
duce losses  in  ore  dressing  by  the  aid  of 
chemical  substances. 

173237 — Westinghouse  Lamp  Co.— Process  for  the 
preparation  of  coherent  masses  of  the  rare 
metals  and  alloys  and  oxides  thereof. 

173757— Gerb-und  Farbstoffwerke,  H.  Renner  & 
Co.,  Akt-Ges. — Manufacture  of  salts  of  sul- 
phonated  coumarone   resins. 

195295 — Pedemonte,  A.  L.— Manufacture  of  pure 
alumina. 

Abstract  Published  this  Week. 

19320'!)— Chlorinating  organic  compounds.— 
Boake,  Roberts  &  Co.,  Ltd.,  Carpenters 
Road,  Stratford,  London,  and  Silberrad. 
O.,  Silberrad  Research  Laboratories, 
Buckhurst  Hill,  Essex. 

The  chlorimtion  of  organic  compounds,  more 
particularly  of  such  compounds  as  are  chlorinated 
with  difficulty  by  ordinary  methods,  is  carried 
out  by  means  of  snlphnryl  chloride  in  conjunc- 
tion with  aluminium  chloride  and  sulphur  chlor- 
ide. The  last  reagent  may  be  omitted  if  sub- 
stances, such  as  sulphur  and  carbon  bisulphide, 
capable  of  yielding  sulphur  chloride  under  the 
conditions  of  reaction  are  present.  An  example 
describes  the  chlorination  -if  p-dichlorbenzene  to 
yield  tetrachlorbenzene  with  lesser  amounts  of 
ibri-  penta-  and  hexachlorbenzene.  The  chlorina- 
tion of  anthraquinone,  indanthrene,  and  naph- 
thalene and  its  derivatives  is  also  referred  to. 

Messrs.  Ravner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
post  free  for  the  price  of  Is.  6d.  each. 


PAMPHLETS. 

Science  by  Definition  Series, 

By  F.  H.  Loring. 

DEFINITION  OF  KELATIVITY. 
DEFINITION  OF  THE  AETHER. 
DEFINITION  OF  EQUIVALENCE. 
DEFINITION  OF  ISOTOPES. 
(Others  in  progress). 
Price  Is.  each  net.     Postage,  British  Isles 
Id.  each. 
"  A  little  series  called    '  Science  by  Defi- 
nition,' in  which    the  author  relies    on  the 
writers  o  recognised  authority." 

Times  Literary  Supplement. 
H.  0.  LLOYD  &Co.,  Ltd., 

327,  Upper  Street,  London,  N.l. 


MAY  11,  1923. 


THE  CHEMICAL  NEWS. 


289 


THE  CHEMICAL  NEWS, 

VOL.  CXXVII.     No.  3291. 


NOTES  ON  THE  INDIAN  INDUSTRIAL 
REVIVAL. 

It  is  apparent  from  the  various  pieces  of 
news  received  that  India  is  undergoing  a 
revival  on  a  large  scale  in  the  chemical  in- 
dustry. Some  idea  of  this  progress  will  be 
gathered  from  the  following  notes,  compiled 
from  authoritative  sources:  — 

Bengal. — Dr.  Bose's  Laboratory,  Ltd., 
have  erected  a  plant  at  Belliaghata  for  the 
extensive  production  of  sulphuric  acid.  The 
plant  is  of  the  S.  Carves  type,  and  manu- 
factures 7  tons  per  day.  The  company  an- 
ticipate an  output  of  hydrochloric  and  nitric 
acids  later.  At  Kumardhubi,  large  fireclay 
and  silica  works  have  just  arrived  at  com- 
pletion, drawing  their  material  from  adja- 
cent deposits.  A  process  for  the  manufac- 
ture of  glass  from  an  anhydrous  sodium  sul- 
phate present  locally  has  been  adopted  by 
the  Belliaghata  Glassworks,  and  this  will 
render  output  more  cheap  and  of  bettor 
quality. 

Bombay. — Mr.  C.  B.  Amoula  and  Dr.  A. 
N.  Mi'Idrum  have  experimented  in  the 
manufacture  of  rennet  casein  [Joum.  In- 
dian Indus.  Lab.,  1923,  IIL  (i),  95),  and 
more  than  22  cwts.  have  boon  transported 
to  England  for  the  determination  of  its 
commercial  value. 

Central  Provinces. — At  Wardha,  a  new 
feature  is  presented  by  Messrs.  Ranade  A- 
Co.,  who  are  producing  a  red  oxide  paint  of 
high  quality. 

.Madras. — The  Godavari  and  Kistna  dis- 
tricts are  imdor  examination  for  the  produc- 
tion of  sodium  carbonate  and  the  general 
utilisation  of  alkaline  deposits.  Dr.  Mars- 
den,  the  industrial  (demist  fca:  the  Presi- 
dency, has  issued  his  report  and  opinions 
for  Government  consideration.  The  fac- 
tories under  construction  for  the  Kerala 
Soap  Institute,  Calicut,  should  be  com- 
pleted in  May,  and  its  gross  profits  are  esti- 
mated at  Rs.  12,500  per. annum. 

United  Provinces. — The  proprietor  of  the 
Nawab  Sugar  Factory  at  Shahabad  (Hardoi 
District)  is  in  negotiations  for  the  purchase 
of  an  up-to-date  sugar  refinery,  and  the  ter- 
mination of  the  deal  will  furnish  a  long-felt 
want.  The  Shr-Waha  liakshmi  Sugar  Cor- 
poration (Kheri  District)  has  followed  suit. 


and  is  cultivating  adjacently  on  a  wide 
commercial  basis.  Applications  and  repre- 
sentations have  been  made  for  the  forma- 
tion of  a  new  company  called  "  The  Lyall- 
pur  Sugar  Co.,  Ltd.,  Cawnpore,"  with  the 
considerable  caipital  of  five  lakhs  of  rupees. 

J.M. 


A  STUDY  IN  RHYTHMIC  SERIES 
OF  CHEMICAL  CHANGES. 

By  K.  C.  Viraraohava,  M.A. 

The  phenomenon  of  the  appearance  of 
one  of  the  products  of  a  reaction  in  a  homo- 
geneous or  heterogeneous  system,  in  a 
periodic  instead  of  a  continuous  manner, 
has  been  noted  in  many  cases,  and  the  clas- 
sical Liesegang  phenomenon  is  the  most 
studied.  Various  authors  have  interpreted 
it  differently.  There  are  the  super-satura- 
tion theorists,  adsorption  advocates,  and 
electrolyte  coagulationists. 

A  gel  is  not  essential  for  the  production 
of  this  phenomenon.  When  aspirin  is 
heated  just  to  its  melting  point  and  allowed 
to  (!Ool,  it  solidifies  in  the  form  of  concen- 
tric rings  round  a  circular  centre,  the  thick- 
ness of  the  rings  gradually  increasing  from 
the  centre  outwards.  Nor  is  the  phenome- 
non confined  only  to  a  solid,  or  liquid,  tr 
their  combined  phase. 

A  series  of  experiments,  "  on  the  forma- 
tion of  the  rhythmic  bands  by  the  inter- 
action in  narrow  tubes  of  such  gases  as  am- 
monia with  hydrogen  chloride,  hydrogen 
bromide  and  hydropon  fluoride ;  and  hydro- 
gen sulphide  with  ch'orine  or  sulphur  di- 
oxide, has  been  described  by  Koenig. 

The  typical  rhythmical  reactions  so  far 
studied  are  as  follows:  — 

Homogeneous  Systems. 

(a)  The  evolution  of  carbon  monoxide  by 
the  action  of  sulphuric  acid  on  formic  acid. 

(6)  The  evolution  of  carbcm  dioxide  from 
super-saturated  solutions. 

(c)  The  action  of  nitric  acid  on  a  mixture 
of  sulphuric  acid  and  formic  acid. 

((i)  Super-saturated  sodium  thiosulphate 
and  alum  solutions. 

(e)  The  solidifying  of  melted  aspirin. 

Heterookneous  Systems. 
(a)  Involving  the  alternate  formation  and 
decomposition  of  a  protective  Rim. 

(1)  The  decomposition  of  hydrogen  per- 
oxide in  the  presence  of  a  clear  film  of 
mercury. 


290 


THE  CHEMICAL  NEWS. 


MAY  11,  1923. 


(2)  The  interaction  of  calcium  carbon- 
ate and  acetic  acid. 
(6)  Involving  sloiv  diffusion. 

(1)  Silver  chromate  in  gelatin. 

(2)  Lead  chromate  or  iodide  in  agar. 

(3)  Lead  carbonate  in  silicic  acid. 

(4)  Interaction    of    mercurous    nitrate 
and  sodium  formate  in  agar. 

(5)  Hydrochloric     acid     with     sodium 
chloride  in  gelatin. 

The  reactions  which  take  place  on  some 
such  base  as  a  gelatin  or  agar-agar  layer, 
axe  very  complete.  The  concentration  of 
the  reacting  solutions,  'tenitperature,  light, 
impurities,  e.g.,  chlorine,  the  method  '>f 
preparing  the  gel,  the  age  and  nature  of  the 
gel,  peptisation,  all  influence  the  course  of 
the  reactions. 

In  all  these  reactions  diffusion  plays  an 
important  part,  for  instance,  in  the  Liese- 
gang  phenomenon  potassium  chromate  or 
,  dichromate  must  have  been  distributed  in 
the  gel  and  must  have  reached  a  o  rtain 
equilibrium  when  the  sol  had  set.  When 
new  forces  are  set  up,  e.g.,  by  introducing 
silver  nitrate,  equilibrium  is  upset,  and 
counter  influences  are  at  work  between  sil- 
ver ion  and  chromate  radical.  It  is  not 
known  if  the  chromate  ion  exists,  but  cer- 
tainly silver  chromate  is  precipitated.  Sil- 
ver chromate  is  seen  when  silver  nitrate 
solution  is  added  to  the  gel.  What,  then, 
diffuses?  If  it  is  silver  nitrate,  it  must 
pass  through  the  ring  of  silver  chromate, 
like  coipper  ferro-cyanide  in  a  porous  pot. 
Silver  chromate  will  then  function  as  a 
semipermeable  membrane  in  the  gelatin 
structure.  H.  M.  Fischer  and  D.  McLang- 
lin  have  found  that  all  substances  which 
give  satisfactory  Liesegang  rings  are  im- 
permeable toward  molecularly  dissolved 
substances  and  consequently  it  would 
seem  unlikely  that  after  the  formation  of 
the  first  ring  a  second  and  third  ring  could 
be  formed. 

It  has  been  said  that  the  chromate  also 
diffuses.  Only  as  a  resultant  of  the  diffu- 
sions of  chromate  and  nitrate  is  the  precipi- 
tate formed  in  periods.  In  an  experiment 
the  lower  portion  of  a  gel  was  completely 
deprived  of  its  chromate  before  the  reaction 
connpleted. 

Hugh  McGuigan  has  observed  that  the 
chromate  is  fixed,  and  remains  so,  unless 
an  attraction  force  is  exerted.  The  silver 
nitrate  wanders  on  through  the  ring  into 
the  clear  zone  until  it  is  sufficiently  close  to 
the  chromate  gelatin  to  exert  an  attraction 
which  again  draws  the  chromate  and  forms 


another  ring  and  clear  zone.  At  the  same 
time  the  chromate  exerts  a  pull  on  the  sil- 
ver, and  the  ring  is  formed  whore  the  forces 
are  balanced. 

Dr.  J.  N.  Friend  has  put  forward  the 
suggestion  that  colloidal  silver  chromate  is 
first  formed  and  the  organic  emulsoid  gela- 
tin retards  the  rate  of  precipitation,  but  all 
the  same,  diffusion  continues  until  the  col- 
loidal particles  have  grown  too  large  and 
then  begin  to  precipitate  out.  He  considers 
that  the  distance  between  the  rings  is  there- 
fore the  algebraic  sum  of  the  rates  of  diffu- 
sion and  precipitation.  Dhar  and  Chatter- 
jee  have  observed  that  peptisation  is  an 
important  factor  in  the  phenomenon  of 
periodic  precipitation.  Possibly  the  insol- 
uble silver  chromate  is  in  a  finely  dispersed 
state,  and  as  they  go  on  diffusing,  they 
grow  in  size  and  precipitate  out.  But  Wil- 
hams  and  Mackenzie  have  experimental 
evidence  to  infer  that  silver  chromate  did 
not  function  as  a  protected  coJloid  with  a 
slow  rate  of  diffusion,  and  diffused  only 
like  a  crystalloid.  The  precipitation  fol- 
lowed the  usual  rules  of  solubility  profUict. 

With  regard  to  circular  disposed  precipi- 
tation, W.  Moeller  concluded  that  the 
structure  of  the  gel  is  the  main  factor. 
Gelatin  jellies  contain  two  substances,  one 
of  which,  a-gelatin,  forms  a  structural  net- 
work and  the  sipaces  in  this  are  occupied  by 
/8-gelatin,  which  is  structureless.  Ehyth- 
mio  changes  in  the  structure  of  the  fibrillar 
network  are  suggested  to  be  responsible  for 
the  separation  of  foreign  substances  in 
rhythmically  distributed  layers.  According 
to  him,  Liesegang  rings  are  not  dependent 
on  chemical  interaction  of  substances  after 
diffusion  through  a  jelly  medium.  Forces 
are  called  into  play  which  indirectly  deter- 
mine a  rhythmical  alternation  in  the  co- 
agulation of  the  dispersed  phase. 

But  Prof.  H.  T.  Brown  believes  that 
two  opposing  diffusive  streams  of  reacting 
substances  produce  a  rhythmical  series  of 
zones  and  bands  which  follow  the  contours 
of  surfaces  of  equidensity.  Apparently  all 
bands  contain  particles  of  the  same  density. 
The  size  of  the  particles  may  also  differ  be- 
tween the  bands,  and  the  differentially  de- 
posited particles  might  show  colour  differ- 
ences. It  has  been  said  that  the  co](-ur  of 
dispersoids  differs  with  the  size  of  the 
particles. 

In  many  of  my  experiments  the  rings 
came  out  with  intervals  in  a  regular  rhyth- 
mical manner,  but,  after  some  time,  be- 
yond the  range  of  the  rings  but  contiguous 


MAY  11,  1923. 


THE  CHEMICAL  NEWS. 


291 


to  them,  several  bands  in  thin  films  were 
deposited  continuously  with  different 
colours.  It  has  been  observtd  that,  when 
the  concentration  of  the  two  reagents  ap- 
proximate to  equality,  the  precipitate  ap- 
pears to  be  continuous,  but  under  the 
microsooipe  it  is  seen  to  be  finely  banded. 
Even  with  the  naked  eyes,  the  alternate- 
coloured  continuous  bands  can  be  seen  on 
the  gelatin  layer.  Possibly,  when  there  is 
the  difference  in  concentration,  the  rings 
aippear  and  at  the  stage  when  the  concen- 
trations equalise,  the  precipitate  is  formed 
in  a  continuous  manner.  The  different 
colours  need  to  be  explained. 

The  suggestion  has  already  been  made 
that  the  existence  of  quanta  is  not  limited 
to  energy  alone.  Just  as  matter  has  been 
considered  for  centuries  to  be  discontinuous 
it  may  be  its  reactions,  too,  are  of  a  similar 
nature. 


THE  SIGNIFICANCE  OF  THE  EXPEBJ- 

MENTALLY    DETERMINED  CRYSTAL 

STRUCTURES  OF  THE  ALl'ALT 

POLYHALIDES. 

By  George  L.  Clark.* 

Jefferson  Physical  Laboratory .  Harvard 
University. 

By  means  of  a  new  and  powerful  methml 
of  X-ray  analysis  the  crystal  structures  of 
some  of  the  alkali  polyhalides  have  just 
been  determined  by  the  writer  in  associa- 
tion with  Professor  William  Duane.  Both 
the  details  of  the  method  and  of  the  analy- 
ses have  been  ipresentcd  in  other  nf>tes.'  It 
is  the  purpose  of  this  note  to  bring  the  new 
experimental  data  to  bear  upon  the  great 
uncertainty  concerning  the  real  constitution 
of  these  unique  compounds  which  has  pre- 
vailed since  their  discovery  30  years  ago  hv 
Wells  and  Wheeler.' 

Few  experimental  facts  concerning  the 
alkali  polyhalides  have  been  known  up  to 
the  (present  time,  except  that  solutions  of 
cesium  iodide,  for  example,  are  able  to  dis- 
solve iodine,  or  bromine  or  chlorine,  and 
produce  crystals  whose  chemical  analyses 
may  be  expressed  by  the  empirical  formiilfp 
Csl,.      Csl,,      CsIBr^,     CsBrI,,       CsICl,, 

'  National  Research  Fellow. 

^  Clark  and  Duane,  Proceedings  TLS. 
Acad.  Sci.,  1922.  VIII.,  90. 

'  Wells  and  Wheeler,  Zs.  anorg.  Chem., 
1892,  I.,  442. 


CsIBrCr,  etc.  Wells  and  Penfield*  found 
that  the  trihalides  crystallise  similarly  and 
may  even  be  isomorphous.  Stability 
measurements  by  the  writer  and  by 
Ephraim''  show  that  the  trihalides  form  a 
remarkable  continuous  series,  in  which 
maximum  dimensions  of  the  atoms  are 
favourable  to  stability:  thus  Cslj  is  most 
stable,  while  CsClg,  KBr,  or  Nalg  do  not 
exist;  and  KI3,  KbErl^  and  CsBrj  are  all 
equally  stable.  These  measurements  also 
indicate  very  clearly  that  all  salts  which 
contain  iodine  form  one  stability  and  crys- 
tal lographic  series,  and  those  containing 
bromine  in  the  absence  of  iodine  another; 
in  other  words,  the  heaviest  halogen  atom 
has  a  defining  influence,  so  that  such  a 
formula  as  CsBrlj  might  more  properly  be 
written  CsI.Brl. 

It  has  been  suggested  that  in  the  alkali 
polyhalides  the  metal  may  have  a  .higher 
primary  valence,  as  is  true  of  gold  (which 
is  in  the  same  periodic  group  as  the  alkali 
metals)  in  the  known  reaction  Au+Cl  +  Clj 
=  AU  +  +  +CI3.  Again,  it  has  been  advo- 
cated by  Remsen,*  Wells  and  Penfield,* 
McCombe  and  Reade^  (in  February.  1923), 
and  others,  that  one  or  more  of  the  halogen 
atoms  have  a  higher  valence  than  is  true  in 
the  simple  halides.  Several  experimental 
facts  disprove  these  contentions.  Freezing 
point  and  conductivity  exiperiments  show 
that  the  ions  in  a  solution  of  Csl,,  for  ex- 
ample, are  Cs+  and  I3-.  This  means  that 
iM  a  molecule  of  the  trihalido  the  single  pri- 
mary valence  bond  which  holds  cesium  and 
ifnline  together  in  Csl  is  unchanged,  but 
that  the  iodide  ion  is  able  to  associate  with 
itself  two  additional  atoms  of  iodine,  or  a 
halogen  molecule  caipable  of  independent 
existence,  and  form  complexes.  In  solution 
the  equilibriiun  between  I-  +  Ij  and  I.L- 
is  very  definitely  established.  Besides  the 
complex  anions  of  the  half^ens,  those  of 
suliphur,  S.S--.  S,S--,  S,S--,  S,S — , 
and  SjS--,  have  been  identified  by  Kiis- 
t<'r.*  and  those  of  tellurium,  TeTe--  and 
Te,Te--  in  the  beautiful  work  of  Kraus.' 
These  are  all    manifestations  of    secondary 

•  Wells  and  Penfield,  Amer.  J.  Set., 
1892,  XLITL,  2L  475. 

•''  Ephraiw,  Ber.  deut.  chem.  Oes.,  1917, 
L..  1,069. 

•  Rrwf<en,  Amer.  Chem.  J.,  XL,  291. 

''  McComhe  and  Reade,  J.  Chem.  Soc, 
1923.  CXXIIL,  141. 

•  Kiisier,  Zs.  anorg.  Chem.,  1905.  XLITL, 
53;  1905.  XLIV..  431;  1905,  XLVL,  113. 

•  Kraus,  J.    Amer.    Chem.    Soc.    1922, 
XLIV.,  1,216. 


292 


THE  CHEMICAL  NEWS. 


MAY  11,  1923. 


valence  just  as  truly  as  the  combinations  of 
water  with  salts  to  form  hydrates  or  of  am- 
monia to  form  ammines  (cationic  com- 
plexes) are  secondary  valence  iphenomena. 
These  experiments,  however,  cannot  ex- 
plain the  structure  and  the  real  nature  of 
these  complex  groups,  and  they  cannot  be 
interpreted  so  a&  to  give  concrete  know- 
ledge of    secondary    valence.      The    actual 


crystal  structures  give  this  information  un- 
mistakably, and  in  addition  answer  many 
questions  which  are  confronting  chemists, 
such  as  whether  or  not  the  identity  of  the 
single  chemical  molecule  is  retained  in  the 
space  lattice  of  a  solid. 

The  crystal  structures  of  four  alkali  poly- 
halides  have  now  been  more  or  less  com- 
pletely determined.  The  results  are  as 
follows : 


KIg  monoclinic  d^f,^  =  4.10     x   10-^  cm. 

Cslg  orthorhombic  dioo  =  4.49.   Jqio  =  6.43,  d^^^  =  7.02x10-"  cm. 

CsIBr^  rhombohedral  d,^^  =  4.2Q,  ^oio  =  5.91,  r/^^  =  6.90x10-='  cm. 

CsIClj  rhombohedral  hexagonal  d  (Cs  to  1  along  trigonal  axis)  =  6. 102  x  10- 


cm. 


Of  these,  the  first  three  have  been  studied 
by  the  writer^  and  the  last  by  Wyckoff.^". 
In  sipite  of  the  -fact  that  three  crystallo- 
graphic  systems  are  represented,  the  ex- 
ceedingly interesting  result  comes  out  that 
all  four  crystal  structures  present  precisely 
the  same  relative  arrangement  of  atoms  in 
the  unit  paralleloipipeda,  if  these  unit  cells 
are  properly  oriented  so  as  to  include  one 
molecule.  It  is  of  secondary  importance 
for  the  purpose  in  hand  that  the  unit  cell 
planes  may  be  perpendicular  or  inclined  to 
each  other,  or  that  the  axes  may  be  equal  or 
unequal  in  length.  This  arrangement  is 
as  follows  :  metal  atoms  at  the  comers  of 
the  cell,  and  halogen  atoms  inside  the  cell 
in  a  line  on  the  body  diagonal,  with  the 
heaviest  halogen  atom  at  the  centre  and  the 
other  two  on  the  diagonal  on  either  side 
equidistant  from  the  centre  (if  they  are 
alike).  In  Cslg  and  CsIBrg  the  distance 
from  the  centre  along  the  diagonal  of  the 
two  iodine  or  two  bromine  atoms  is  half 
that  from  the  centre  to  the  corner;  hence 
the  co-ordinates  are  (a/'4,  b/4,  c/4)  and 
(-a/4,  -fo/4,  -c/4),  where  a,  h,  and  c  are 
the  edge  lengths  of  the  unit  cell  in  thvoc 
directions  at  right  angles.  In  CsICl,  the 
chlorine  atoms  have  a  parameter  of  0.19  of 
the  total  length  of  the  diagonal  on  either 
side  of  the  central  iodine  atom,  so  that  the 
unit  cell  is  a  rhombohedron  instead  of  a  rec- 
tangular parallelopiped.  It  is  an  interest- 
ing conjecture  whether  the  orthorhombic 
variety  of  CsIClg,  if  it  does  exist,  is  pro- 
duced by  a  displacement  of  the  chlorine 
atoms  farther  along  the  diagonal  from  the 
centre.  The  only  other  possibility  would 
be  that  a  chlorine  atom  occupies  a  central 
position    instead    of    the  iodine,    but    this 


Wyckoff,  Ihid.,  1920,  XLII.,  1,100. 


should  be  very  much  less  stable  than  the 
other  arrangement.  There  is  no  doubt  but 
t'lat  the  normal  tendency  of  the  compound 
is  to  form  the  rhombohedral  hexagonal 
form . 

In  KIg  the  unit  cell  is  a  monoclinic 
prism  which  has  been  formed  by  the  slight 
deformation  of  a  cube.  The  parameter  of 
the  two  non-central  iodine  atoms  on  the 
body  diagonal  is  slightly  less  than  0.25 
(approximately  0.23)  of  the  total  length  of 
the  diagonal. 

Thus  in  every  case  experimentally  ob- 
served the  three  halogen  atoms  are  closely 
associated  together  in  a  line,  and  constitute 
a  singly  '  acting  group  in  the  space  lattice 
just  as  truly  as  they  do  in  the  formation  of 
complex  anions  in  solution,  and  just  as 
truly  as  the  identity  of  the  complex  cation 
I'Ni  (NH)J++  is  perfectly  maintained  in 
the  space  lattice  of  crystals,  as  proven  by 
the  crystal  structures  of  nickel  halide  and 
nitrate  hexammoniates  determined  by 
Wyckoff. ^^  There  is  every  reason  to  believe 
that  the  facts  discovered  for  the  four  typi- 
cal po.l_yhalides  are  also  true  of  all  other 
polyhalides,  since  they  are  so  closely  re- 
lated crystallographically  and  chemically. 
At  least  it  is  practically  certain  that  the 
relative  arrangement  of  atoms  in  the  unit 
cells  is  the  same.  The  experimental  proof 
that  the  heaviest  halogen  atom  is  central 
in  the  halogen  group  is  entirely  compatible 
with  the  facts  also  exiperimentally  observed 
that  salts  containing  iodine  form  one 
stability  and  crystallographic  series  and 
bromine  another.  Differences  in  the  poly- 
halides therefore  arise  only   in  the  size  and 


1,260. 


Wychojf,  Ibid.,  1922,    XLIV.,    1,239, 


MAY  11.  1923. 


THE  CHEMICAL  NEWS. 


293 


shape  of  the  crystal  unit  cell,    and  in  most 
cases  even  the  latter  is  the  same. 

While  it  is  clear  that  the  secondary  val- 
ence group  of  the  pplyhalides,  as  well  as 
those  of  ammines  and  hydrates,  maintains 
its  individuality  in  the  crystal  space  lattice, 
it  is  still  a  question  whether  the  whole 
molecule  of  KI3,  for  example,  exists  ps 
such  in  the  space  lattice.  It  has  been 
clearly  demonstrated  that  the  simplt^ 
chemical  molecule  Na-Cl  as  it  is  found  in 
VBipour  does  not  exist  as  such  in  the  crystal 
lattice,  since  every  sodium  atom  is  sur- 
rounded at  the  comers  of  an  octahedron  by 
chlorine  atoms,  and  every  chlorine  atom 
similarly  by  six  sodium  atoms.  On  the 
other  hand,  Bragg''  has  shown  conclusively 
that  the  single  molecules  of  wganic  sub- 
stances, and  perhaps  of  some  inwganic 
comtpounds,  are  retained  intact  in  the  lat- 
tice, and  that  the  actual  symmetry  of 
single  molecules  is  the  determining  factor 
of  crystallographic  symmetry.  *l'hu8  a 
single  completely  assymetrical  molecule  in 
a  unit  cell  can  produce  only  the  asymmetri- 
cal triclinic  system ;  the  higher  symmetry 
of  the  monoclinic  and  orthwhombic  sys- 
tems is  attained  by  placing  2  or  4  or  8  whole 
asymmetrical  molecules  in  the  unit  coll 
properly  oriented  about  planes  or  centres  of 
symmetry.  As  a  sort  of  middle  ground  be- 
tween the  lattices  of  sodium  chloride  nnfl 
of  organic  compounds,  there  may  bo  citod 
the  examples  of  the  hex.uiimoniatos  of  the 
nickel  halides"  and  thi^  hexahydrato  of 
zinc  bromato."  In  the  single  molecule  of 
Ni(NH,)jClj,  six  molecules  of  ammonia 
arc  bound  to  the  nickel  atom  by  sooondnrv 
valence  forces,  and  the  two  chlorine  atoms 
by  iprimary  valence  bonds.  In  the  crystal 
lattice  each  nickel  atom  is  still  surrounded 
symmetrically  by  six  ammonia  molecules, 
but  there  are  not  two  but  eight  eqin'distant 
chlorine  atoms  in  the  same  way  that  there 
are  six  chlorine  atoms  around  each  swlium 
atom  in  sodium  chloride.  The  compoimd 
Zn(H^()),jBr()3  is  exactly  analogous. 

It  cannot  be  denied  that  the  forces  which 
hold  organic  molecules  fixed  in  crystal  lat- 
tices, or  which  enable  very  long  molecules 
lying  parallel  to  fonn  liquid  crystals,  or 
which  cause  the  molecules  of  almost  all  or- 
ganic substances  to  become  very  definitely 
oriented  in  suraces,    are  the  same    kinrl  of 


'-  Brnrfff,  J.  Cheni.  Snr.  (London).  Drr.. 
1922.  CXXI.,  2,766. 

"  Wyckoff,  Amer.  J.  Sri.,  1922,  IV  .  1R8 


forces  which  hold  electrically  neutral  mole- 
cules of  ammonia  or  water  to  metal  atoms, 
either  in  the  single  molecule  or  in  the  crys- 
tal lattice.  Now  it  has  been  proven  that 
precisely  the  same  thing  is  true  of  the  halo- 
gen grouips  in  polyhaHdes,  even  though  the 
forces  are  holding  together  three  atoms,  or 
even  more,  of  the  same  chemical  nature,  in- 
stead of  grouping  neutral  atoms  or  mole- 
cules around  a  central  atom  of  greatly  dif- 
ferent nature. 

If  planes  are  drawn  through  the  lattices 
of  the  four  experimentally  studied  tri- 
halides  so  as  to  enclose  1/2  instead  of  one 
molecule,  then  the  metal  atoms  and  the 
heaviest  (previously  body-centred)  halogen 
atoms  appear  alternately  at  the  comers  of 
the  new  unit,  while  one*  atom  of  iodine  in 
KI,  or  Cslj,  one  atom  of  bromine  in  CsIBr^ 
or  one  atom  of  chlorine  in  CsICl,  lies  on  the 
body  diagonal  at  0.46  or  0.60  or  0.38  of  its 
length  from  a  corner  iodine  atom.  Hence 
the  structures  are  remarkably  closely  re- 
lated to  the  simple  halide  unit  cubes.  A 
halogen  atom  in  the  latter  case  is  replaced 
by  a  polyhalide  gfoU|p.  Dimensions  are 
changed  and  perfect  cubic  symmetry  de- 
stroyed, but  every  metal  atom  is  sur- 
rounded by  six  complex  halogen  groups, 
each  acting  as  a  single  (>oint  in  the  lattice. 
The  single  primary  valence  bond  of  the 
chemcal  molecule  is  split  in  the  lattice,  but 
the  secondary  valence  group  within  itself  is 
retained  intact. 

It  has  already  been  stated  that  the  sta- 
bility of  the  alkali  polyhalides  deipends 
upon  the  metal — as  a  matter  of  fact  rela- 
tive stabilities  are  directly  proportional  to 
the  atwnic  volumes  of  the  metals.  This  is 
now  easily  explained.  The  size  of  the  metal 
atom  in  the  lattice  determines  the  dimen- 
sions of  the  unit  cell,  or  the  inteiplanar  dis- 
tances, other  things  being  equal.  The 
smaller  the  dimensions  the  more  difficult  it 
is  for  three  halogen  atoms  to  lie  on  a 
straight  line  within  the  cell  with  any  de- 
gree of  stability.  Halides  of  potassium  are 
just  able  to  form  polyhalides;  as  a  matter  of 
fact  only  the  iodide  is  able  to  form  such 
compounds  sufficiently  stable  to  isolate. 
The  size  of  the  potassium  atoms  and  the  in- 
terplanar  distances  are  such  that  upon  the 
formation  of  KTj  the  string  of  iodine  atoms 
predominates,  the  frame-work  of  the  potas- 
sium atoms  is  distorted  unequally  in  differ- 
ent directions,  and  the  resultant  properties 
approximate  those  of  elementary  iodine 
crystals.  The  compound  NaT,  does  not 
exist  because,  even    if  the  I,  grouips    were 


294 


i 


THE  CHEMICAL  NEWS. 


MAY  11.  1923. 


compressed  in  the  lattice,  the  attraction  of 
two  iodine  atoms  under  these  circum- 
stances far  outweighs  the  ability  of  the 
sodium  atom  to  hold  three  iodine  atoms  in 
spatial  distribution.  The  equilibrium  be- 
tween I-  +  I2  and  I. la"  holds  just  as  truly 
in  the  formation  of  soUd  crystal  lattices  as 
it  does  in  ionised  solution.  Hence  even  in 
the  very  stable  Cslg  the  reaction  is  easily 
sent  from  right  to  let  by  the  application  of 
mechanical  comipression  or  by  increasing 
kinetic  energies  of  vibration  by  means  of 
heat. 

The  newly  determined  ciystal  structures 
of  the  trihalides  present  interesting  evi- 
dence bearing  upon  the  general  question  of 
the  additivity  of  atomic  radii.  In  the  case 
of  Cslg,  for  example,  the  diagonal  along 
which  lie  1  atom  of  cesium  and  3  atoms  of 
iodine  has  a  length  of  10.6  x  10-*  cm.  This 
is  appreciably  smaller  than  the  sum  of  1 
cesium  diameter  plus  3  iodine  diameters  as 
evaluated  under  different  assumptions  by 
Bragg,  Richards,  Davey  and  others.  ^^ 
Hence  the  I3  group  must  be  very  consider- 
ably compressed  so  that  the  atoms  may  be 
pictured  as  flattened  in  the  direction  paral- 
lel to  the  crystal  cell  diagonal  into  a  shape 
something  like  that  of  red  blood  corpuscles. 
The  exiperimental  results  are  fui'thor  proof 
of  the  validity  of  the  conception  of  compres- 
sible atoms  so  long  advanced  by  Professor 
T.  W.  Richards  and  of  the  incorrectness  of 
the  hypothesis  of  constant  atomic  radii.'"' 

It  is  interesting  to  note  that  it  is  possible 
to  prepare  Csl^.  Wells  and  Penfield"  claim 
that  the  crystals  are  triclinic.  If  this  is 
true  it  may  be  safely  predicted  upon  the 
basis  of  the  present  analyses,  that  the 
lines  joining  the  two  iodine  atoms  on  each 
side  of  the  centre  to  the  central  iodine 
atom  will  intersect  at  an  angle. 

Finally,  it  may  be  asked  whether  any 
formula  can  express  the  constitution  of  the 
alkali  polyhahdes.  It  is  obvious  that  none 
can  express  all  the  facts.  The  X-ray  data 
gives  the  only  absolute  picture  of  the  con- 


1^  Clark,  Scienee,  1922,  LV.,  401. 

"  Of.  also  Wyckoff,  U.S.  Acad.  Set., 
Feb.,  1923.,  IX.,  33.  The  radius  of  the 
chlorine  atom  calculated  from  CsIClj  is  un- 
usually small,  as  it  should  he,  since  it  is 
measured  along  the  diagonal  in  the  direc- 
tion of  greatest  compressing  forces.  For 
this  reason  the  direct  application  of  this 
dimension  to  other  chlorine  compounds  has 
little  meaning. 


stitution  of  the   solid  state.      The    nearest 
approach    to     a     mechanical     formulation 
would  express  the  empirical  formula  CsICU 
CI 


as  Cs  -  -  -  -  I.     The  dotted  lines  mean  not 


CI 

an  increase  in  the  number  of  primary  val- 
ences for  cesium,  but  a  split  one.  The  ex- 
pression shows  the  halogens  bound  together 
by  secondary  valences,  with  the  heaviest 
halogen  at  the  centre,  so  that  a  singly  act- 
ing unit  is  produced;  and  yet  each  single 
halogen  atom  also  comes  under  the  direct 
influence  of  the  metal  atom.  Otherwise  it 
would  be  difficult  to  explain  the  mechanism 
whereby  CsIClj,  prepared  by  passing  chlor- 
ine into  a  solution  of  Csl,  should  decompose 
into  CsCl  and  ICl.  It  is  of  course  per- 
fectly natural  that  the  strongest  halogen 
should  remain  bound  to  the  metal.  Fur- 
thermore, by  a  simiple  consideration  of  bal- 

Cl 


ance,    the    formula    shows  why    Cs-  -  -  -I 


CI 
should  be,    and  is,  more    stable  even    than 
I 


Cs-  -  -  -I   .       Even  with    these  advantages, 


Br 

however,  the  formula  falls  far  short  of  ex- 
pressing correctly  all  the  facts  which  crys- 
tal structure  determinations  have  revealed. 

— (Froyn    the    Proceedings    of    the    U.S. 
National  Academy  of  Scienees.) 


GENERAL  NOTES. 


CANADIAN  AGRICULTURAL  FAIRS. 
It  is  the  custom  in  Western  Canada  to 
hold,  during  the  summer  months,  at  im- 
portant centres,  a  series  of  agricultural  ex- 
hibitions and  fairs.  At  these  shows,  which 
are  attended  by  the  general  public  as  well 
as  trade  representatives,  and  at  which  all 
classes  of  goods  appealing  to  the_  farming 
community  are  exhibited,    the  majority  of 


MAY  11,  1923. 


THE  CHEMICAL  NEWS 


295 


the  exhibitors  have,  in  the  past,  been 
Canadian  and  American  firms. 

These  exhibitions  should  afford  an  oppor- 
tunity of  familiarising  traders  and  con- 
sumers in  Western  Canada  with  the  pro- 
ductions of  U.K.  firms.  Arrangements 
have  been  made  by  the  Dejpt.  of  Overseas 
Trade  for  participation  by  H.M.  Trade 
Commissioner  in  Western  Canada  in  the 
fairs  to  be  held  at  Brandon,  Edmonton, 
Kegina  and  Vancouver  in  July  and  August. 

At  each  a  Bureau  of  Information  will  be 
maintained  by  H.M.  Trade  Commissioner, 
at  which  it  is  desired  to  display  copies  of 
leading  U.K.  trade  and  technical  journals, 
particularly  those  dealing  with  agricultural 
and  allied  matters.  The  Trade  Commis- 
sioner proposes  not  only  to  display  such 
journals,  but  to  distribute  them  in  suitable 
quarters,  and  would  therefore  be  glad  to 
receive  up  to  50  coipies  each  of  journals 
dealing  with  agricultural  implements  and 
machinery  (including  stationary  engines, 
tractors,  dairy  supplies  and  machinery, 
grinders,  crushers  and  feed  cutters,  resi- 
dential electric  lighting  plants,  etc.),  min- 
ing, engineering  (including  wire  rope,  pul- 
leys, etc.),  telephones,  mechanics'  tools  for 
farm  and  work.S'hop,  numici)pal  equipment, 
ships'  fittings  and  ship  chandlery,  and 
marine  engines;  and  about  20  copies  of 
other  trade  journals. 

CZECHO-SLOVAKIAS    EXPORTS  FOK 
THE  FIRST  QUARTER  OF  1923. 

Following  are  the  values  exported  ac- 
cording to  class  of  goods  during  the  period 
January  to  March  :  — 

Millions 

Wood,  coal  and  fuel  ..ilHK. 495 

Sugar          352 

Cotton,    yams,   etc 344 

Wool  and  woollen  goods  246 

Glass  and  glassware  191 

Iron  and  ironware  143 

Corn,   flour,   malt  130 

Leather  and  leather  goods  03 

Flax,   jute,   hemp   57 

Paper  and  paper  goods  54 

Ready-made  clothes      51 

Earthenware           44 

Chemicals  and  chemical  products  32 

Machines  and   apparatus   28 

Minerals           30 

Wmnlen  ware       23 

Imitation      stones      and      goods 

thereof          28 


The  greatest  increase  took  place  in  the 
export  of  wood  and  coal,  which  in  March 
reached  a  total  value  of  187  million  crowns. 
The  textile  industry  also  had  a  favourable 
month;  cotton  products  of  a  value  of  98 
millions,  and  woollen  goods  of  a  value  of  81 
millions  were  exported.  In  spite  of  the  diffi- 
cult situation  prevailing  in  the  glass  indus- 
try, the  latter  was  able  to  export  glassware 
to  a  value  of  64  million  crowns.  The  ex- 
port of  iron  has  been  steadily  increasing 
since  the  beginning  of  the  year,  and  in 
January  the  export  of  iron  and  iron  goods 
amounted  to  34  million  crowns;  in  Feb- 
ruary the  export  rose  to  50  million  crowns, 
and  in  March  a  further  increase  of  59  mil- 
lions took  place. 

Germany  and  Austria  again  take  first 
place  as  purchasers  of  Czech  goods ;  no  less 
than  40  per  cent,  of  the  total  exports  going 
to  these  countries  in  the  first  quarter  of 
this  year.  England  occupies  third  place 
with  a  total  of  282  million  crowns. 


TOWN  REFUSE  AS  MANURE. 

The  Ministry  of  Agriculture  and  Fisheries 
has  just  issued  a  leaflet  drawing  the  atten- 
tion of  farmers  ««id  others  to  substitutes 
few  stable  manure,  which  is  now  becoming 
very  scarce.  Amonc  the  various  possibili- 
ties is  to  be  reckoned  ashpit  refuse,  which 
is  available  in  large  quantities  but  is  at  pre- 
sent used  to  a  very  limited  extent.  Town 
autliOTities  an-  now  disiposing  of  their  re- 
fuse in  a  better  way,  and  some  are  adding 
other  wastes  and  crushing  the  whole  for 
use  as  a  fertiliser. 

The  amounts  of  ashpit  refuse  available 
over  the  country  are  very  large.  It  is  esti- 
mated that  no  fewer  than  10,000,000  tons 
per  annum  arc  produced  in  England  and 
Wales,  while  in  London  alone  the  produc- 
tion is  estimated  at  1,500,000  tons  per 
annum.  Broadly  speaking,  town  refuse 
has  given  successful  results  in  two  cases:  — 

(a)  On  heavy-land  farms  or  allotments, 
where  it  is  used  for  root  crops,  cabbages, 
&c. ; 

(b)  For  raising  the  level  of  low-lving  wet 
ground  and  forming  new  land  which  can  be 
used  for  allotment^. 

Considerable  quantities  of  town  refuse 
have  been  used  by  farmers  on  the  heavy 
London  clay  soils  of  the  Home  Counties. 
About  10  tons  per  acre  is  a  usual  dressing: 
it  should  be  spread  before  the  winter 
ploughing    begins    so  that    it  can    be    well 


296 


THE  CHEMICAL  WEWS. 


MAY  11,  1923. 


worked  into  the  soil.  It  then  lightens  the 
stiff  soil  and  facilitates  cultivation  gener- 
ally, and  good  root  and  other  crops  are  usu- 
ally obtained.  Farmers  round  some  of  the 
larger  Scottish  towns,  e.g.,  Glasgow,  Dun- 
dee, Perth,  and  Aberdeen,  use  consider- 
able amounts,  probably  even  more  than 
those  round  London.  Uncrushed  refuse  is 
sold  from  Dundee,  where  the  deinand  is 
stated  to  be  greater  than  the  supply :  the 
1921  deliveries  are  said  to  have  been  39,00i) 
tons. 

There  are  six  types  of  refuse  sent  out 
from  towns :  — 

1.  "Dry"  refuse:  the  contents  of  refuse 
bins  and  "dry"  ashpits. 

2.  Separated  dust :  finely  divided 
material  separated  mechanically  from  the 
dry  refuse  through  a  |  in.  or  5/16ths  in. 
sieve. 

3.  "Mixed"  refuse:  the  contents  of 
privy  middens  and  ash  closets. 

4.  Night  soil :  the  contents  of  pails  con- 
taining crude  fsecal  matter  only;  this  is 
produced  in  towns  where  the  pail  system  is 
used.  When  dried  and  granulated  it  con- 
tains some  5|  per  cent,  nitrogen,  5 J  per 
cent,  phosphates,  and  2^  per  cent,  potash. 

5.  Mixed  night  soil. 

Market  and  slaughter-house  refuse  are 
sometimes  mixed  with  1,  2,  3  and  5. 

6.  Street  sweepings  and  other  wastes. 
Of  these,   street  sweepings  and  unmixed 

night  soils  are  well  known  to  farmers,  and 
are  often  easily  disposed  of.  One  large 
London  district  disposes  of  its  street  sweep- 
ings at  10s.  per  ton.  Night  soil  in  the  dry 
form,  unmixed  with  ashes,  is  now  sold  by  a 
few  corporations  at  about  £7  per  ton.  If 
the  methods  used  in  these  places  were 
generally  gupplicable  to  town  and  city  con- 
ditions the  problems  arising  out  of  the 
waste  of  sewage  would  be  solved,  and  the 
shortage  of  organic  manures  on  the  farm 
would  be  greatly  relieved. 

In  its  crude  form,  ashpit  refuse  contains 
a  small  percentage  of  cans,  bottles,  &c.,  of 
no  use  on  the  farm  but  indeed  constituting 
a  nuisance.  In  the  more  progressive  towns 
metals,  cinders  and  bottles,  for  all  of  which 
a  use  or  market  can  be  found,  are  removed. 

The  material  can  be  offered  to  farmers  as 
it  stands.  Its  composition,  however,  is  not 
particularly  good  in  spite  of  its  smell.  Im- 
provement is  effected  by  enriching  with  a 
certain  amount  of  other  waste  matter,  such 
aR  street  sweepings,  slaughterhouse  refuse, 
and  stable  manure.  Analysis  indicates  that 
these  manures  have  the  following  approxi- 
mate composition:  — 


Per  cent. 

Organic  matter   25 — 40 

Nitrogen  0.4—0.6 

Phosphoric  acid  (PaOJ  0.3—0.5 

Equivalent       to      tricalcium 

phosphate,   Ca3(P0j2   0.7—1.1 

Potash  (K2O)      0.3—0.5 

In  some  northern  towns  it  is  found  pos- 
sible to  add  a  considerable  proportion  of 
night  soil  in  addition  to  street  sweepings, 
cattle  market  manure,  slaughterhouse  re- 
fuse and  stable  manure.  An  excellent  fer- 
tiliser is  thus  obtained,  containing  one  or 
more  per  cent,  of  nitrogen. 

The  enrichment  of  the  refuse  is  shown  by 
the  fact  that  the  nitrogen  content  runs  as 
high  as  1  per  cent.,  whilst  the  samples  of 
unfortified  town  refuse  contain  only  about 
0.5  per  cent. 

It  has  been  proiposed  to  add  soot  to  the 
town  refuse,  but  this  would  not  be  a  sound 
procedure. 

These  modern  prepared    wastes  are  well 

worth  attention  by  farmers,    and  trial    lots 

may  usefully    be  put  on    the  root  and    cab- 

'  bage  land,   and  possibly  also    used  for  hay 

on  stiff  clay  soils. 

EEPAEATION    DYESTUFFS. 

The  Board  of  Trade  desire  to  draw  atten- 
tion to  the  fact  that  under  the  Beparation 
Clauses  of  the  Peace  Treaty  requisitions 
are  made  periodically  for  the  delivery  of 
certain  German  dyestuffs  on  reparation  ac- 
count. Information  as  to  the  requirements 
of  colour  users  for  dyestuffs  which  cannot 
be  obtained  from  British  manufacturers  is 
collected  by  the  Colour  Users'  Association 
and  furnished  periodically  to  the  Board  of 
Trade. 

In  order  that  this  information  may  be  as 
complete  as  possible,  the  Board  would  be 
glad  if  all  users — whether  members  of  the 
Association  or  not — would  furnish  particu- 
lars of  their  estimated  requirements  for 
German  dyestuffs,  say  once  every  three 
months,  to  the  Secretary,  Colour  Users' 
Association,  Cromwell  Buildings,  Black- 
friars  Street,  Manchester. 


"The  Inventions  Development  (1923)  Co., 
of  Belfast,  has  been  reorganised.  It  will 
continue  to  carry  on  its  usual  business  and 
develop  ideas  and  processes  commercially. 

The  Federation  of  British  Industries  has 
sent  a  letter  to  H.M.  Government    on  the 
question  of  Inter-Imperial  Trade,    and  urg- 
ing the  early  passage  of  the  Empire  Cotton 
Bill,  which  has  been  promoted  with  the  in- 
tention of  safeguarding  the  cotton  industry. 


MAY  11,  1923. 


tse  chemical  news. 


297 


NEW  CHILEAN  LAW  REGAKDING 

THE  SIZE  OF  JUTE  SACKS  USED 

IN  THAT  COUNTRY. 

H.M.  Charge  d'Aftaires  at  Santiago, 
Chile,  has  reported  to  the  Dept.  of  Over- 
seas Trade  that  a  law  was  passed  by  Con- 
gress and  approved  by  the  Council  of  State 
on  the  9th  February,  lifiting  the  size  of  jute 
sacks  to  be  used  in  transiport  by  human 
labour. 

A  translation  of  the  law  reads  as  follows : 

Article  1. — The  weight  of  any  sack  con- 
taining any  class  of  product  which  has  to  be 
carried  by  human  labour  (man  handled) 
shall  not  exceed  80  kilogrammes.  The  con- 
travention of  this  law  shall  be  punished  by 
a  fine  of  20  pesos  for  each  infraction.  This 
law  will  come  into  forcti  180  days  after  the 
date  of  its  publication  in  the  Diario  Ofpcial. 

Transitory  Article. — The  dispositions  of 
this  law  will  not  afitect  articles  which  ar<' 
already  packed  on  the  date  on  which  it 
comes  into  force. 

The  measure  wjis  introduced  into  Con- 
gi'ess  with  the  object  of  protecting  the 
workers  in  the  nitrate  industry,  where  the 
weight  of  a  full  sack  of  nitrate  has  been  92 
kilos. 

The  importance  of  the  new  law  lies  in  the 
fact  that  Jute  nitrate  bags  form  the  chief 
article  of  importation  into  Chile,  both  as 
regards  quantity  and  value.  Unless  it  is 
found  commercially  possible  to  utilise  thi' 
old  92  kilogramme  sacks,  the  new  law  will 
therefore  presumably  result  in  oixlers  for 
new  jute  sacks. 


Messrs.  Muiiphy  &  Sons,  Bureau  of  Bio- 
Technology,  have  issued  their  Bulletin  No. 
9,  Vol.  II.  (March),  containing  ccmtribu- 
tions  on  the  following:  — 

The  "Biotec"  Comparator. 

The  Destruction    of  Structural  Timber: 
its  causes  and  prevention. 
.     The    Suppression    of  Insect    Pests    and 
Fungoid    Diseases.        The    Fumigation    of 
Commercial  Glasshouses. 

Nicotine  Petroleum  Emulsion. 

Micro  Organisms  in  the  Leather  Indus- 
tries. 


The  May  issue  of  Current  Opinion  con- 
tains a  short  but  important  article  upon 
The  Need  for  Knowledge.  It  is  pointed  out 
that  very  few  peQple  could  pass  a  test  in 
any  subject  outside  their  own  calling,  and 
indeed,  few  are  familiar  with  the  wider 
aspects  of  their  particular  industry  or 
branch. 


DRUGS  AND  CHEMICALS  FOR 
ROUMANIA. 

Mr.  Szana,  British  Vice-Consul  at  Timi- 
soara,  reports  that  a  local  firm  is  desirous 
of  purchasing  drugs  and  chemicals  from 
British  sources. 

The  name  and  address  of  the  firm,  to- 
gether with  further  particulars,  may  be  ob- 
tained by  British  firms  upon  applics^tion  to 
the  Dept.  of  Overseas  Trade. 


WEATHER  FORECASTS. 

The  Postmaster-General  announces  that 
arrangements  have  been  made. in  conjunc- 
tion with  the  Meteorological  Department  of 
the  Air  Ministry  for  weather  forecasts  to  be 
distributed  each  afternoon  to  telephcHie  ex- 
changes. The  forecasts  will  cover  the 
period  from  6  p.m.  on  the  day  of  issue  till 
6  p.m.  on  the  following  day.  These  ar- 
rangements came  into  Qperation  on  May  1. 
The  forecasts  will  be  available  between  5 
p.m.  and  midnight  each  dav  on  demand  by 
telephone  subscribers,  ana  should  be  of 
especial  benefit  to  farmers  and  other  resi- 
dents in  rural  areas. 

Subscribers  on  rural  party  lines  will  re- 
ceive the  information  free  of  charge,  a  local 
call  fee  being  charged  in  the  case  of  other 
subscribers.  The  forecasts  may  also  be  ob- 
tained by  enquirers  at  call  offices  on  pay- 
ment of  the  usual  call  (^ce  fee. 


In  the  April  number  of  The  Journal  of 
the  Chemical  Sccicty,  pp.  881-884,  Dr. 
Alexander  Scott  contributes  a  ipafper  en- 
titled Isolation  of  the  Oxide  of  a  New  Ele- 
ment A  Correction.  Dr.  Scott  states  that 
he  submitted  the  sample  of  his  pale  buff- 
coloured  powder  ("  New  Oxide,"  as  de- 
scribed in  his  communication  to  the  Chemi- 
cal Society  on  February  1,  an  account 
of  which  appeared  in  The  Chemical  Netva, 
Feb.  9.  p.  81,  to  Drs.  Coeter  and  Hevesy  for 
examination  by  X-ray  spectral  analysis. 
These  "authorities  have  failed  to  find  any 
Hafniiim  lines  in  the  oxide  and  in  the  ori- 
ginal New  Zealand  sand  from  which  Dr. 
Scott  prepared  the  oxide. 
The  eonstituenCs  appear  to  be    oxides  of 

iron,  titanium,    and  traces  of  other  metals 

all  pn-viously  known. 
Dr.  Scott  has  unravelled  the  mystery  of 

his  results  by  further  analyses,  which  seen^ 


298 


THE  CHEMICAL  NEWS. 


MAY  II,  1923. 


to  indicate  that  lie  was  dealing  with  a  mix- 
ture of  K/riFfi  and  other  double  fluorides, 
which  would  yield  a  mixture  of  oxides  on 
ignition  by  his  analytical  procedure. 


FROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 

At  the  Ordinary  Meeting  on  Thursday, 
May  3,  the  following  papers  were  read:  — 

Leonard  Hill  and  A.  Eidinow.  The  In- 
fluence of  Temperature  on  the  Biological 
Action  of  Light. 

The  biological  action  of  light  is  acceler- 
ated by  warmth,  retarded  by  cold.  This  is 
true  for  bacteria,  infusoria  and  human 
skin.  The  temperature  coefficient  for  in- 
fusoria, between  1°  and  20°  C,  is  about 
3.0.  By  adequate  exposure  to  cool  air 
over-action  of  the  sun  on  the  skin  can  be 
prevented. 

F.  A.  E.  Crew.  Studies  in  Intersexual- 
ity.  I. — A  Peculiar  Type  of  Developmental 
Intersexuality  in  the  Male  of  the  Domesti- 
cated Mammals.  Communicated  by  Prof. 
R.  C.  Punnett,  F.R.S. 

Papers  read  in  title  only :  — 

E.  J.  Morgan  and  J.  H.  Quastel.  The 
Reduction  of  Methylene  Blue  by  Iron  Com- 
pounds. Communicated  by  Prof.  F.  G. 
Hopkins,  F.R.S.     ' 

1.  The  restoration  of  the  power  to  reduce 
methylene  blue  to  boiled  milk  by  means  of 
ferrous  sulphate  solution  is  shown  to  be 
due  to  the  inorganic  constituents  of  the 
milk. 

2.  It  is  shown  that  methylene  blue  is 
reduced  by  ferrous  sulphate  solution  in  the 
presence  of  sodium  hydroxide,  carbonate, 
bicarbonate  or  phosphate  and  of  the  sodium 
salts,  such  as  acetic,  tartaric  or  citric.  Fer- 
rous sulphate  solution  alone  will  not  effect 
any  perceptible  reduction. 

3.  The  reduction  has  been  followed  quan- 
titatively with  the  result  that  it  is  clear 
that  two  ferrous  molecules  always  react 
with  one  of  methylene  blue. 

4.  The  mechanism  of  the  reduction  has 
been  studied  with  a  view  to  throwing  light 
on  the  biological  hydrolytic  oxidation-re- 
duction system.  It  is  suggested  that  the 
clearest  light    is  afforded  by  the  considera- 


tion of  the  relative  affinities  of  the  oxygen 
acceptor  for  the  hydroxyl  ion  and  of  the  hy- 
drogen acceptor  for  the  hydrogen  ion. 

C.  F,  Cooper.  The  Skull  and  Dentition 
of  Paraceratherium  bugtiense.  a  Genus 
of  Aberrant  Rhinoceroses  from  the  Loiver 
Miocene  Deposits  of  Dera  Btigti.  Commu- 
nicated by  Dr.  A.  Smith  Woodward, 
F.R.S. 

W.  L.  Balls.  The  Determiners  of  Cel- 
lulose Structure  as  seen  in  the  Cell  Walls  of 
Cotton  Hairs.  Communicated  by  Dr.  F.  F. 
Blackman,  F.R.S. 

The  use  of  plane  and  circularly  polarised 
light  and  of  immature  hairs  has  enabled 
further  observations  to  be  made  more  easily. 
The  reversals  of  the  spiral  fibrillar  struc- 
ture show  their  full  number,  as  soon  as  the 
secondary  wall  is  visible,  indicating  prede- 
termination thereof  during  growth  in 
length.  Thus  far,  however,  the  primary 
wall  cannot  be  made  to  demonstrate  such 
reversals  visually;  but  on  development  of 
the  pre-cellulose  it  shows  instead  a  pair  c.f 
opposed  spirals  whose  pitch  corresponds  to 
that  of  the  shp  sipirals  of  the  secondary 
wall.  These  slip  spirals  are  now  found  to 
be  structurally  connected  with  the  quicker 
pit  sipirals  and  invariably  opposed  to  the 
latter  in  direction;  the  tangents  of  their 
angles  happen  to  stand  in  the  ratio  of  4:1, 
which  suggests  polymerisation  from  the 
pre-cellulose  of  the  primary  wall.  The  ro- 
tation of  the  plane  of  polarisation  by  a  sin- 
gle layer  of  secondary  cell-wall  is  inverted 
on  opposite  sides  of  a  reversal  point;  thus 
the  molecular  structures  of  the  right-hand 
and  left-hand  areas  would  seem  to  be 
mirror-images. 

Attention  is  called  to  the  low  specific 
gravity  of  the  cell-wall,  explicable  as  a  con- 
sequence of  its  sipongy  structure,  and  to  the 
uncertainty  of  any  existing  deter-minations 
thereof.  It  is  also  pointed  out  that  coiTect 
microscopic  definition  can  only  be  obtained 
by  the  use  of  an  analyser  in  the  eye-piece. 

Some  tentative  conclusions  can  be  drawn, 
pending  X-ray  analysis,  as  to  the  probable 
space-lattice  conformation  of  cotton  and 
other  celluloses,  which  bring  one  effectively 
to  a  modernised  re-statement  of  Nageli's 
micellar  theory. 

I.  de  B.  Daly.  The  Infln.ence  of  Mech- 
anical Conditions  of  the  Circulation  on  the 
Electro-cardiogram.  Communicated  bv_ 
Prof.  E.  H.  Starling,  F.R.S. 


MAY  11,  1923. 


■rHE  CHEMICAL  NEWS 


299 


Thursday,  May  10, 

Papers  read :  — 

Prof.  A.  Fowler,  F.K.S.  The  Seriea 
Spectrum  of  Trebly-ioniaed  Silicon.  (Si  IV). 

Sir  Robert  Robertson,  F.R.S.,  and  W. 
E.  Garner.  Calorimetry  uf  High  Explo- 
sives. 

H.  S.  Hole  Shaw,  F.R.S.  Stream  line 
Filter. 

F.  W.  Aston,  F.R.S.  A  Critical  Search 
for  a  Heavier  Constituent  of  the  Atmos- 
phere by  means  of  the  Mass-spectrograph. 

Papers  read  in  title  only :  — 

Prof.  H.  E.  Armstrong,  F.R.S.  Elec- 
trolytic Conduction:  Sequel  to  an  attemi>( 
( IWijC)  to  apply  a  I'heory  of  Residual  Afpn- 
ity. 

Prof.  H.  E.  Armstrong,  F.R.S.  The 
Origin  of  Osmotic  Effects.  IV. — Hydrono- 
dynamic  Change  in  Aqueous  Solutions. 

R.  W.  Wood,  For.  Mem.  R.S.,  and  A. 
Ellett.  On  the  Influence  of  Magnetic 
Fields  on  the  Polarisation  of  Resonance 
Radiation. 

W.  G.  Palmer.  A  Study  of  the  Oxidation 
of  Copper  and  the  Reduction  of  Copper 
Oxide  by  a  New  Method.  Comiuunicati.>d 
by  Sir  Williain  Pope,  F.R.S. 

E.  A.  Fisher.  Some  Moisture  Relations 
of  Colloids.  II. — Further  Observations  on 
the  Evaporation  of  Water  from  Clay  and 
Wool.  Communicated  by  Prof.  A.  Smith- 
ells,  F.R.S. 


THE  CHEMICAL  SOCIETY. 

At  the  meeting  on  Thursday,  May  10,  the 
Baeyer  Memorial  Lecture  was  delivered  bv 
Professor  W.  H.  Perkin,  LL.D.,  F.R.S.'. 
in  the  Lecture  Hall  of  the  Institution  cf 
Mechanical   Engineers,    Westminster. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

Ordinary  Meeting. 
Mr.  P.    A.  Ellis  Richard,    President, 
the  chair. 


m 


A  Certificate  was  read  for  the  second 
time  in  favour  of  Mr.  Robert  C.  Grimwood, 
A.C.G.F.C,  D.I.C.,  A.I.C. 

The  following  were  elected  Members  of 
the  Society:  Messrs.  John  Myers,  F.I.C., 
John  Loudon  Buchanan,  F.I.C. 

The  following  papers  were  read:  — 

The  Quantitative  Determination  of  Hemp 
and  Wood  in  Papers  containing  these  two 
Fibres,  by  William  Dickson,  F.I.C. 

The  author  considers  that  in  the  micro- 
scopical determination  of  hemp  fibres  in 
the  presence  of  wood,  examination  altt>r- 
nately  by  ordinary  and  polarised  light  en- 
ables one  to  readily  distinguish  the  mocro- 
structure  of  the  different  fibres.  He  has 
devised  a  method  tot  quantitative  work 
utilising  the  counting  method  of  Spence 
and  Krauss  World's  Peaper  Trade  Review, 
18th  Dec,  1917. 

The  paper  is  disintegrated  by  boiling  with 
dilute  caustic  soda  and  the  ipu^p  churned 
up  with  an  egg  switch.  The  fibre  is  then 
stained  by  Cross  and  Bevan's  double  mala- 
chite green  and  congo  red  method,  well 
spread  out  on  the  cover  slip  and  mounted 
in  the  usual  way.  The  counting  is  done  by 
Spence  and  Krauss 's  method,  but  no  cor- 
rection factor  is  required  to  convert  pro- 
porti(xi8  by  dinmcter  into  proportions  by 
dry  weight  of  furnish. 

The  Estimation  of  Fat,  Lactose,  and 
Moisture  in  Dried  Milks,  by  H.  Jephcott, 
M.Sc,  F.I.C. 

As  a  result  of  examining  over  25,000 
samiples  of  dried  milk,  it  is  contended  that 
(1)  Moisture  is  host  determined  by  drying 
at  102-108"  C.  for  1  to  2  hours;  (2)  Fat  can 
most  satisfactorily  be  determined  by  a  care- 
ful use  of  the  Werner-Schmidt  method.  .V 
modified  Gerber  method  gives  less  accurate 
but  cMicordtuit  results  for  rough  routine 
■purposes;  (8)  The  polarimetric  determina- 
tion of  lactose  in  milk  powders,  whilst  offer- 
ing certain  advantages,  should  not  be  used 
where  great  accuracy  is  desired.  In  such 
cases  a  gravimetric  process,  based  upon  tlio 
modified  Fehling's  method  of  Quisumbin;^ 
and  Thomas,  is  recommended. 

The  Determination  of  Lactose  by  the 
Polarimetric  and  Gravimetric  Method,  by 
.\.  L.  Bacharach,  B.A.,  A.I.C. 

Pure    a- lactose    mono-hydrate    was    pre- 
pared by  careful  recrystallisation    and  dry- 
ing.    It  was  shown    to  have  the  value    for 


300 


THE  CHEMICAL  NEWS. 


May  11,  1925. 


[a]/°    of  52.42,    agreeing    with    the    most 
trustworthy  recorded  figure. 

The  reducing  power  of  pure  a-]actose 
monohjdrate  was  also  determined  bj  the 
modification  of  the  Fehling  method  due  to 
Quisumbing  and  Thomas.  The  accuracy  of 
this  method  claimed  by  these  authors  was 
confirmed,  but  the  reducing  power  obtained 
was  somewhat  higher,  0.1000  gm.  of  lac- 
tose hydrate  giving  0.1565  grm.  of  cupric 
oxide. 

The  Meltmg  Point  and  Iodine  Value  of 
Refined  Natural  D-Camphpr,  by  Maurice 
S.  Salamon,  B.Sc. 

The  iodine  value  and  melting  point  of 
specially  purified  d-camphor  have  been  re- 
determined, and  it  is  shown  that  the  usu- 
ally accepted  value  is  too  high,  and  that 
that  the  usually  published  melting  point  is 
too  low.  The  iodine  value  of  the  specially 
refined  d-camphor  is  found  to  be  0.1,  and 
the  melting  point  179°  C.  It  is  concluded 
that  the  majority  of  previous  determina- 
tions must  have  been  made  on  d-camphor 
that  was  slightly  impure. 

The  iodine  value  of  oil  of  camphor  has 
also  been  redetermined,  and  examples  are 
given  of  how  this  value,  together  with  the 
melting  point  and  iodine  value  of  d-c;im- 
phor  can  be  used  to  indicate  the  percentage 
of  camphor  present  in  a  sample  of  refined 
d-camphor.  This  suggested  that  refined  d- 
camphor  for  pharmaceutical  purposes 
should  have  a  melting  point  not  lower  than 
176°  C.  and  an  iodine  value  of  not  more 
than  0.7. 

The  Presence  of  Barium  and  Strontium 
in  Natural  Brines,  by  A.  G.  Francis,  B.Sc, 
F.I.C. 

The  results  of  the  analysis  of  7  samples 
of  brines  from  deep  boreholes  in  Derby- 
shire, Staffordshire,  and  Scotland  are  re- 
corded together  with  a  brief  account  of  the 
method  of  analysis  adopted.  The  maxi- 
mum quantities  of  barium  and  strontium 
chlorides  found  were  178.2  and  169.4  parts 
per  100,000  respectively. 

An  explanation  based  upon  the  "permu- 
tit"  reaction  is  put  forward  to  account  for 
the  presence  of  chlorides  of  barium  and 
strontium  in  natural  brines,  and  it  is  shown 
that  there  is  a  gradation  in  the  strengths  of 
sodium  chloride  solutions  necessary  com- 
pletely to  remove  calcium,  strontium  anrl 
barium  from  a  "permutif-  filter  charged 
with  these  elements. 


THE  GEOLOGICAL  SOCIETY. 

At  tile  meeting  on  April  18,  1923,  Prof. 
A.  C.  Seward,  Sc.D.,  F.E.S.,  President, 
and,  afterwards,  Dr.  Herbert  H.  Thomas, 
M.A.,  Vice-President,  in  the  chair,  the  list 
of  donations  to  the  library  was  read;  it  in- 
cluded, among  others,  the  following  works : 
Imperial  Institute,  Monographs  on  Mineral 
Kesources,  with  special  reference  to  the 
British  Empire:  Copper-Ores,  by  Kobert 
Allen,  1923;  Mercury-Ores,  by  Edward 
Halse,  1923;  Memoes  of  the  Geological 
Survey  of  England  and  Wales,  Explanation 
of  Sheet  169— The  Geology  of  the  Country 
around  Coventry,  including  an  account  of 
the  Carboniferous  Rocks  of  the  Warwick- 
shire Coalfield,  by  T.  Eastwood,  W.  Gibson 
and  others,  1923;  and  Memoirs  of  the  Geo- 
logical Survey,  Special  Reiports  on  the 
Mineral  Kesources  of  Great  Britain — Vol. 
XXV.  :  Lead-  and  Zinc-Ores  of  Northum- 
berland and  Alston  Moor,  by  Stanlev 
Smith.  1923;  and  Vol.  XXVI.:  Lead-  and 
Zinc- Ores  of  Durham,  Yorkshire,  and 
Derbyshire,  with  Notes  on  the  Isle  of  Man, 
by  R.  G.  Carruthers  and  Sir  Aubrey  Stra- 
han,  1923. 

The  following  communication  was  read: 
The    Structure    of   the     Bowmore-Portas- 

kaiy  District  of  Islay,    by  John  Frederick 

Norman  Green,  B.A.,  F.G.S. 

Microscope-sections    and    rock-specimens 

from  the    Bowmore-Portaskaig    district    of 

Islay  were  exhibited  in  illustration  of  this 

paper. 

At  the  meeting  held  on  Wednesday,  May 
2,  a  lecture  was  delivered  by  Prof.  John 
JoLY,  D.Sr.,  F.R.S.,  F.G.S. ,  on  The  Bear- 
ing of  some  Recent  Advances  in  Physical 
Science  upon  Geology. 


ROYAL  SOCIETY  OF  ARTS. 

On  Wednesday,  May  9,  at  the  Ordinary 
Meeting,  a  lecture  entitled  Surface  Com- 
bustion— ivith  special  reference  to  Recent 
Developments  in  Radiophragm  Heating, 
was  delivered  by  William  Arthur  Bone, 
D.Sc,  Ph.D.,  F.R.S.,  Professor  of  Chemi- 
cal Technology,  Imperial  College  of  Science 
and  Technology,  South  Kensington,  Mr. 
D.  Milne  Watson,  M.A.,  LL.B.  (Gas  Light 
and  Coke  Company)  presided. 

An  experimental  demonstration  of 
"Radiophragm"  TToating  was  given  by  Mr. 
F.  J.  Cox,  M.Inst.M.E. 


MAY  11.  1923. 


THE  CHEMICAL  NEWS. 


301 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 

At  the  Ordinary  Meeting  in  the  Lecture 
Theatre,  on  Thursday,  May  10,  the  Fara- 
day Medal  was  presented  to  the  Hmi,  Sir 
Charles  A.  Parsons. 

The  fourteenth  Kelvin  lecture,  entitled 
Problems  in  Telephony,  Solved  and  Un- 
solved, was  delivered  by  Dr.  J.  A.  Fleming, 
F.R.S.,  Honorary  Member. 


INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

The  seventy-first  general  meeting  was 
held  at  the  house  of  The  Royal  Society  of 
Arts  on  Tuesday,  May  8.  A  patper  entitled 
Heavy  Grade  Egyptian  Crude  Petroleum. 
was  read  for  W.  A.  Guthrie,  F.I.C, 
F.R.S.E.,  M.Inst.P.T.,  &c.  H.  Barrin- 
ger,  M.Inst.C.E.,  M.I.Moch.E.,  M.I.N. A., 
M. Inst. Mar. Eng.,  presided. 


THE  INSTITUTE  OF  CHEMISTRY 
OF  GREAT  BRITAIN  AND  IRELAND. 

Pass  List  for  the  April  Ex\M!NATtnv« 
1928. 

The  following  Associate  has  passed  the 
examination  for  the  Fellowship:  — 

In  branch  G :  Chemical  Engineering  : 
Grisenthwaite,  Arthur  Turner,  A.C.G.F.C.. 
B.Sc.  (Lond.). 

The  following  candidates  have  passed  the 
examination  for  the  Associateship : — 

In  General  Chemistry :  Brady,  Peter 
Joseph,  East  London  College;  Grayson. 
Harold  John,  University  College,  London  : 
Gregory,  Louis  Wilfred,  University  College. 
Nottingham;  Loasby,  Geoffrey.  B.Sc.  (Bir- 
mingham), Birmingham  University;  Mar- 
rison,  Leslie  William,  East  London  Col- 
lege ;  Player,  Harold  William  Victor. 
King's  College,  London;  Smith,  Daniel 
Agnew,  University  College,  Nottingham ; 
Vineall,  George  John  Charles,  B.Sc. 
(Lond.),  University  College,   Southampton 

Seven  candidates  failed  to  satisfy  the 
examiners. 


THE  INSTITUTE  OF  METALS. 
The  thirteenth  annual    May  Lecture    of 
the  Institute    of  Metals    was  delivered    on 


Wednesday,  May  2.  at  Storey's  Gate, 
Westminster,  by  Dr.  W.  Rosenhain, 
F.R.S.,  of  the  National  Physical  Labora- 
tory, who  chose  as  his  subject,  The  Struc- 
ture of  Alloys. 

Referring  to    the  great  accumulation    of 
facts  in  regard  to  the  properties  and  micro- 
structure  of  alloys    which  have  been  forth- 
coming in  recent  years,    the  lecturer    said 
that  the  time  had  arrived  when  it  was  most 
desirable  that  there  should  be  found  a  key 
to  this  maze  of  knowledge  in  the  form  of  a 
general  theory  that  would  link  together  the 
mass  of  facts   "into  a  homogeneous    whole. 
Such  a  theory  he  atteni^pted  to  put  forward, 
basing  it  upon  the  intimate    knowledge  of 
crystal   structure  which  had  recently   been 
acquired  by  means  of  tKe  application  of  X- 
rays  to  the  study    of  the    arrangement    cf 
atoms  in  crystals.      The  crystal  stnictures 
found  in  pure    metals  became  modified  in 
the  case    of  alloys,    particularly    in    those 
called  solid  solutions,  where  a  second  kind 
of  atom,  the  atom  of  the  alloying  element, 
entered    into  the  structure    of  the    crystal 
and  produced  in  it  tcrtain  minute  changes. 
With  regard  to  such  changes    the  lecturer 
put  forward  two  simple  princi^ples,  and  was 
then  able  to  show  a  striking  series  of  infer- 
ences    from  his  thiory,     which     accorded 
closely  with  a  large  number  of  experimental 
facts.     Connections   between  various  series 
of    properties  in    metals    and    their    alloys 
wore  established    which  had  not    formerly 
been  recognised,    such  as  the  relation    be- 
tween hardness  and  alloying  power.     Espe- 
eially  imtportant  is  the  connection  between 
the    minute  distortion    of  crystal  structure 
which  occurs  in  alloys  and  their  behaviour 
on  melting  and  freezing,  while  such  pheno- 
mena as  plasticity,  diffusion  and  others  fell 
easily  into  line  with  the  same    tj'pe  of  ex- 
planation.    Most  important  of  all,  perhaps, 
is  the  fact  that  this    new  theory    of    alloy 
structure  affords  a  ready  explanation  of  the 
electrical  properties    of  metals    and    alloys 
and  the  changes  of    those  properties  when 
the  metal  is  heated    or  cooled.      These  ex- 
planations cover  the  mysterious  phenomena 
of  super-conductivity  found  in  many  metals 
when  cooled  nearly  to  the  absolute  zero  of 
temperature. 


ROYAL    INSTITUTION. 

On  Tuesday,  May  8,    Professor    A.  C. 

Srwaro  began  a  course  of  two  lectures  on 

Ice  and    Flowers    of    Greenland,     and  on 


302 


THE  CHEMICAL  NEWS. 


MAY  11,  1923. 


Thursday,  May  17,  Puofessor  Cokbr  de- 
livers the  first  of  two  lectures  on  Engineer- 
ing Problems  solved  hy  Photoelastic 
Methods. 

The  Friday  Evening  Discourse  on  May 
11  will  be  given  by  Professor  W.  A,  Bo:^e 
on  Gascons  Combustion  at  High  Presstircs. 
and  on  the  18th  by  Mr.  W.  M.  Mordey  on 
Studies  in  Alternating  Magnetism. 

Sir  Ernest  Ruthehford's  postponed 
discourse  will  be  given  on  Friday  evening, 
June  15,  and  his  concluding  lecture  on 
Atomic  Projectiles  on  Saturday  afternoon, 
hine  16. 

The  Annual  Meeting  of  the  members  of 
the  Royal  Institution  was  held  on  Tuesday 
afternoon,  May  1,  Sir  James  Crichton 
Brown,  Treasurer  and  Vice-President,  in 
the  chair.  The  Annual  Report  of  the  Com- 
mittee of  Visitors  for  the  year  1922,  testify- 
ing to  the  continued  prosperity  and  efficient 
management  of  the  Institution,  was  read 
and  adopted.  The  Report  of  the  Davy 
Faraday  Research  Laboratory  Committee 
was  read.  Sixty  new  members  were  elected 
in  1922,  and  63  lectures  and  19  evening 
discourses  were  delivered.  The  books  and 
pamphlets  presented  amounted  to  about 
162  volumes,  making,  with  426  volumes 
(including  periodicals  bound)  purchased  by 
the  Managers,  a  total  of  588  volumes  added 
to  the  library  in  the  year.  Thanks  were 
voted  to  the  President,  Treasurer  and  Sec- 
retary, to  the  Committees  of  Managers  and 
Visitors,  and  to  the  Professors,  for  their 
valuable  services  to  the  Institution  during 
the  past  year.  The  following  were  unani- 
mously elected  as  officers  for  the  ensuing 
year : — 

President,  The  Duke  of  Northumberland. 
Treasurer,    Sir  James  Crichton-Browne. 
Secretary,  Sir  Arthur  Keith. 
Managers,  Sidney  G.  Brown,    John  Mit- 
chell Bruce,    Sir  Dugald  Clerk,    John  Am- 
brose   Fleming,     Sir    Richard    Glazebrook, 
Earl  Iveagh,     Sir  Alexander  C.  Mackenzie, 
Robert  Mond,  Sir  Edward  Pollock,    Alfred 
W.     Porter,    Lord    Rothschild,    Sir    David 
Salomons,   WiHiam  Stone,   Sir  Alfred  Yar- 
row, the  Right  Hon.  Ijord  Justice  Younger. 
Visitors,  Sir  Harry  Baldwin,  William  A. 
Bone,    Alfred    Carpmael,     Ernest    Clarke, 
Edward  Dent,  Thomas  W.  Dewar,    George 
H.  Griffin,  W.  E.  Lawson  Johnston,  Colo- 
nel   F.  K.  McClean,    Sir  Malcolm    Morris, 
W.     Rushton     Parker,     Walter     Peacock, 
Major    C.    E.     S.    Phillips,    Hugh    Munro 
Ross,  Sidney  Skinner. 


Future    Lectures. 

Friday  Evening  Discourses,  addressed  to 
members  and  their  friends  at  9  p.m. 

May  11:  William  Arthur  Bone,  D.Sc, 
F.R.S.,  M.R.I.,  Prof,  of  Chemical  Tech- 
nology, Imperial  College,  Gaseous  Combus- 
tion at  High  Pressures  (New  Experiments). 

May  18 :  William  Morris  Mordey, 
Past  Pres.I.E.E.,  M.Inst.C.E.,  M.R.I. , 
Recent  Studies  in  Alternating  Magnetism 
{ivith  Experiments). 

May  25:  Sir  Aston  Webb,  K.C.V.O., 
C.B.,  President  of  the  Royal  Academy, 
The  Development  of  London. 

June  1 :  Prof.  Hendrik  Antoon 
Lorentz,  Hon.F.R.S.,  Hon.M.R.L,  Ph.D. 
Haarlem  University,  The  Radiation  of 
Ught. 

Jvme  8:  Miss  Joan  Evans,  B.Litt. 
(OxoN.),  F.R.I. ,  Member  of  Council,  St. 
Hugh's  College,  Oxford  ("  Magical 
Jewels,"  Clarendon  Press),  Jewels  of  the 
Renaissance. 

Tuesdays,  May  22,  29,  June  5:  Dis- 
coveries in  Eqypt,  by  W.  M.  Flinders 
Petrie,  D.C."L.,  Litt.D.,  F.R.S.,  etc., 
Prof,  of  Egyptology,  University  of  London. 

Thursdays,  May  17,  24 :  Engineering 
Problems  Solved  by  Photoelastic  Methods; 
1  (1)  Improvement  in  Apparatus,  (2)  Con- 
fact  Pressures  and  Stresses;  2  (1)  The  Test- 
ing of  Materials,  (2)  The  Action  of  Cutting 
Tools.  By  E.  G.  Coker,  D.Sc,  F.R.S.', 
M.Inst.C.E.,  M.R.I. ,  Prof,  of  Engineer- 
ing, University  of  London. 

Thursdays,  May  31,  June  7:  The  Nature 
of  Enzyme  Action,  by  Sir  William  M. 
Bayliss,  LL.D.,  D.Sc,  F.R.S. ,  Prof,  of 
General  Physiology,  University  College, 
London. 

Saturdays,  June  2,  9 :  1,  The  Vegetation 
of  the  Andes;  2,  The  New  Zealand  Flora, 
by  Arthur  W.  Hill,  ScD.,  F.R.S.,  Direc- 
tor of  the  Royal  Botanic  Gardens,  Kew. 


CORRESPONDENCE 

MAKING  COLOUR  MAKERS. 

To  the  Editor  of  The  Chemical  News. 

Sir, — Professor  Perkin,  of  Leeds  Univer- 
sity has  just  announced  that  no  fewer  than 
forty-seven  students  have  gone  out  this 
year  from  the  Departments  of  Colour 
Chemistry  and  Dyeing,  of  which  he  is  the 
head,  to  take  up  positions  with  colour 
makers,  wool  dyers,  cotton  dyers,  calico 
printers,   artificial  silk  manufacturers,     and 


MAY  11,  1923. 


THE  CHEMICAL  NEWS. 


303 


in  other  industries.  It  is  heartening  news 
to  those  who  beUeve,  as  I  do,  that  British, 
industry  depends  to-day,  and  is  in  thf 
future  going  to  depend  more  and  more, 
upon  the  pooling  of  scientific  knowledge 
won  at  our  universities  and  the  technical 
ability  which  can  be  acquired  only  iron 
large-scale  (production. 

In  these  circumstances  it  is  not  quite 
clear  on  what  Professor  Perkin  bases  his 
fear  that,  even  yet,  the  artificial  dyestuffs 
industry  might  one  day  become  "  mori- 
bund "  in  this  country.  At  the  present 
moment  both  colour  makers  and  colour 
users  are  practically  unanimous  in  cheir  de- 
termination that  a  national  dyestuffs  indus- 
try shall  be  maintained  and  developed  in 
Great  Britain;  differences  between  them 
there  are,  but  they  are  differencves  regarding 
not  the  end  to  be  attained,  but  the  means 
to  attain  it. 

There  has  been  a  considerable  amount  of 
prejudice  to  be  overcome  in  securing  the 
widest  use  of  British  made  dyes;  but  that  is 
an  inherent  tendency  which  is  grndually 
and  succi'ssfully  being  lived  down  by  Biitish. 
makers.  Makers  and  users  realise  that  they 
must  work  hand  in  hand,  and  it  is  an  ex- 
cellent augury  for  a  continuance  of  amic- 
able feeling  that  during  the  liuhr  crisis  no 
attempt  has  been  made  to  increase  price<?. 
Before  the  war  we  depended  on  German^' 
for  I'ighty  per  cent,  of  our  dyestuffs;  to-day 
we  can  supply  more  than  eighty  per  cent. 
f>f  the  dyes  required  by  British  colour  users. 
It  is  a  considerable  achievement,  and  it 
gives  promise  in  the  future  of  offering  many 
more  than  Professor  Perkin 's  estimate  of 
twenty  openings  a  year  to  students  quali- 
fied in  colour  chemistry. 

I  am,  Yours,  etc., 

W.    J.    U.    WOOLCOCK, 

The     sAssociation     of     British     Chemical 
Manufacturers,  166,  Piccadilly, 
London,  W.l. 

21th  April,  1923. 


POTASSIUM  PERMANGANATE 
APPTJCATIONS  TO  EXC OECARIA 

AGALLOCHA. 
Two  bleach  methwis  have  been  tried  with 
evident  success,  both  of  which  call  for  the 
('<>-Oiperation  of  sulphurous  acid  as  a  do- 
cf>lori8er.  The  first  methml  produced  a 
wockI  almost  of  pure  whiteness ;  the  second 
howod  a  slight  brownish  tinge  not  alto- 
i,'»'ther  out  of  keeping  with  modem  match 
iruinufacture. 

The  usage  of  neutral  potassium  perman- 
ganate constitutes  the  first  process.  The 
ijangwa  is  chipped    into  sticks  4.5  cms.    in 


length,  having  an  aipproximate  cross-sec- 
tional area  of  4  sq.  mm.,  and  dropped  into  a 
solution  of  potassium  permanganate  (1 :40). 
The  chips  immediately  comence  to  decom- 
,pose  the  solution  and  manganese  dioxide  is 
deposited  upon  them,  as  the  following 
equation  shows:  — 

2KMnO,  =  2:\InO,  +  K^O,. 
The  chips,  after  being  allowed  to  blacken 
thoroughly,  are  removed,  washed,  and 
placed  in  a  solution  of  sulphurous  acid.  The 
liberated  hydrogen  turned  inwards  and  at- 
tacked the  colouring  matter  contained  in  the 
wood,  producing  a  superficial  bleach. 

Commercially,  tliis  method  is  quite  work- 
able for  the  adaption  of  a  cheap  and  plenti- 
ful material,  as  the  actual  steepings  do  not 
last  for  more  than  three  hours  or  so,  al- 
though better  results  would  be  obtained  by 
sipreading  the  two  stages  over  a  coutple  of 
days.  More  rapid  changes  occur  if  the  per- 
manganate be  slightly  acidulated;  this  pro- 
cess is  discussed  ui  infra. 

The  neutral -solution  method  is  productive 
of  an  excellent  whiteness,  far  superseding 
the  grade  of  the  average  white  pine  so 
largely  in  use,  while  combustibility  does  not 
depreciate  in  the  least.  On  the  contrary,  it 
is  improve<l  by  the  part-extraction  of  the 
aromatio  substances  contained  therein, 
figures  based  Ujpon  calorific  values  having 
been  obtained. 

The  estimate*  is  based  upon  recent  obser- 
vations by  J^atta  and  Boeu,  expanded  by 
the  present  writer.  The  yanywa  com- 
menced to  rot  after  3  days,  and  repigmenta- 
tion  t(x>k  place.  Twenty-four  hours  is  a  con- 
venient period. 

In  the  case  where  the  permanganate  solu- 
tion is  acidulated  with  sulphuric  acid,  no 
l>eneficial  results  can  be  obtained.  If,  how- 
ever, a  mixture  of  sulphuric  acid  and  potas- 
sium oxalate  be  used,  satisfactory  results 
are  obtained.  Hot-chamber  drying  should 
be  replaced  by  centrifugal  drying  in  this 
case,  eliminating  the  tendency  of  the  splints 
to  char. 

Here,  only  one  stage  is  necessary,  and  the 
treatment  isan  be  performed  in  an  hour. 
The  bleach  is  not  so  good,  and  may  he  pro- 
vocative of  popular  prejudice,  but  the  pro- 
cess is  chea,p  and  in  no  way  impairs  com- 
bustibility. It  is  certainly  a  debatable 
point  if  the  cheapness  of  the  (jniujwa  wood, 
plus  cost  of  transport,  plus  cost  of  treat- 
ment, would  compare  with  the  prices  paid 
for  the  best  white  pine ;  but  if  manufac- 
turers contem,plate  the  experiment,  enor- 
mous supplies  of  the  wood  are  available  in 
tropical  and  sub-tropical  locaUties. 

J.M. 


304 


THE  CHEMICAL  NEWS. 


MAY  11,  1923. 


BOOKS  RECEIVED. 

Canada  To-day,  Edited  by  Eobert  J.  Ar- 
NOTT.  Pp.  204.  1923.  The  Canada  News- 
paper Co.,  Ltd.,  110,  St.  Martin's  Lane, 
W.C.2.     2s.  6d. 

The  Manufacture  of  Hydrochloric  Acid 
and  Saltcake,  bj  Alexander  Charles  Cum- 
MiNG,  O.B.E.,  D.Sc,  F.I.C.  Pp  XV.  + 
423.  Vol.  V.  1923.  Messrs.  Gurney  & 
Jackson,  33,  Paternoster  Row,  E.C.4. 
31s.  6d.  net. 

Raio  Materials  for  the  Manufacture  of 
Sulphuric  Acid  and.  the  Manufacture  of  Sul- 
phur Dioa-ide,  by  Wilfrid  Wyld.  Pp,  XIII. 
+  558.  Vol.  I.  1923.  Messrs.  Gurney  & 
Jackson,  33,  Paternoster  Row,  E.C.4.  36s. 
net. 


PUBLICATIONS    RECEIVED. 

The  British  Association  for  the  Advance- 
ment of  Science  has  just  issued  as  a  reprint 
entitled  The  Nitrogen  Industry,  a  report  of 
the  discussion  in  the  Chemical  Section  of 
the  British  Association  at  the  Hull  meet- 
ing last  year. 

The  discussion  was  opened    by  Dr.  J.  A. 

Harker,  F.R.S.,    who  gave  an  account  of 

the  post-war    progress  in    the  Fixation  of 
Nitrogen  in  England  and  Abroad. 

Mr.  J.  H.  West  contributed  a  paper  en- 
titled :  Raw  Materials  for  Synthetic  Ammo- 
nia :  The  Manufacture  of  Hydrogen  and 
Nitrogen. 

Mr.  C.  J.  Goodwin  gave  a  paper  on  The 
Hdusser  Process  of  Nitrogen  Fixation,  and 
Dr.  E.  B.  Maxted  one  entitled  Some  As- 
pects of  the  Relation  between  Water 
Power  and  Nitrogen  Fixation. 

The  reprint,  price  9d.,  is  published  by  the 
Association  at  Burlington  House,  W.l. 

The  Department  of  Overseas  Trade  has 
just  issued  a  report  on  the  Economic  and 
Financial  Conditions  in  Switzerland,  Dec, 
1922,  by  Mr.  E.  C.  D.  Rawlins,  Commer- 
cial Secretary  to  H.M.  Legation,  Berne; 
pp.  77.     Price  2s.  6d. 

This  report  is  a  valuable  resume  of  the 
finance,  legislation,  trade  industries,  trans- 
port and  social  matters  during  the  year. 


iHis  lisl  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent   Applications. 

9900— Elektrizitatswerk  Louza.— Process  for  pre- 
paration of  urea  salts  from  cyanamide. 
April  11. 

10133— Franek,     W.~Manufacture      of     sulphuric 

acid.    April  13. 
9779— Thermal   Industrial     &     Chemical     (T.I.C.) 
Research   Co.,   Ltd.— Dehydration     and   dis- 
tillation of  tar  or  oils.    April  10. 

10003~TyreT,     D.— Manufacture     of     phenol     and 
phenolic  bodies.    April  12. 

Abstract  Published  this  Week. 

193722— Synthetic  Tanning  Agents.— Moeller,  W., 
20,  Billhorner  Canalstrasse,  Hamburg, 
Germany. 

Coal-tar  oils  of  high  boiling  point  or  the  liydro- 
carbons  contained  therein  are  subjected  to  treat- 
ment with  finely  divided  sulphur,  and  the  pro- 
duets  sulphonated  with  ordinary  or  fuming  sul- 
phflrio  acid;  the  soluble  sulphonated  products 
are  tanning  agents,  but  may  also  be  used  for  the 
same  purposes  as  the  non-sulphonated  products, 
for  example,  as  impregnating  agents  or  lubri- 
cants. In  an  example,  an  anthracine  oil  of  boil- 
ing point  aJxjve  200°  C.  is  heated  witli  powdered 
sulphur  at  100-150°  C,  and  air  blown  through  to 
remove  sulphuretted  hydrogen;  sulphuric  acid  is 
then  added  and  heating  continued  until  the  pro- 
duct is  soluble  in  water;  after  dilution,  neutrali- 
sation with  alkalis,  alkaline  earths,  or  oxides  or 
hydroxides  of  the  light  metals,  the  siilphates  may 
be  removed  by  filtration  or  crystallisation  and 
the  remaining  solution  used  directly  for  tanning. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  piiblished  Specification,  and  forward  on 
post  free  for  the  price  of  Is.  6d.  each. 


PAMPHLETS. 

Science  by  Definition  Series. 

By  F.  H.  Loring. 


DEFINITION  OF  RELATIVITY. 
DEFINITION  OF  THE  AETHER. 
DEFINITION  OF  EQUIVALENCE. 
DEFINITION  OF  ISOTOPES. 

(Others  in  progress). 
Price  Is.  each  net.     Postage,  British  Isles 
Id.  each. 
"  A  little  series  called    '  Science  by  Defi- 
nition,' in  which    the  author  relies    on  the 
writers  o  recognised  authority." 

Times  Literary  Supplement. 
H.  0.  LLOYD  &  Co.,  Ltd., 

327,  Uppor  Street,  London,  N.l. 


m 


MAY  18.  1923. 


THE  CHEMICAL  NEWS. 


805 


THE  CHEMICAL  NEWS, 

VOL.  CXXVII.      No.  3291. 


BRITISH  EMPIRE  EXHIBITION. 

Science  and  Scientific  Instruments. 

Spucial  efforts  are  being  made  by  the 
British  Empire  Exhibition  authorities  to 
have  all  branches  of  science  adequately  re- 
presented at  Wembley  next  year,  not  only  in 
the  organised  exhibits,  but  by  means  of  con- 
ferences and  discussions  on  scientific  sub- 
jects. The  main  objects  of  the  Exhibition 
are  to  demonstrate  the  great  resources  of 
the  British  Empire  in  raw  materials  and 
the  capacity  and  skill  of  our  manufacturers 
in  producing  the  highest  class  of  goods  in 
every  branch  of  industry.  The  Exhibition 
will  also  show  the  high  position  we  have 
attained  in  music,  literaturt-.  painting  and 
the  arts.  Husbandry,  the  cultivation  of 
gardens,  and  all  the  amenities  of  life  will  be 
illustrated.  There  will  bo  lectures,  e»>n- 
ferences  and  cinemas  dealiiijj  with  all  phases 
of  our  national  life. 

-An  irnprcssion  got  abroad  at  one  time  that 
thi'  Exhibition  would  be  visited  mainly  by 
millions  of  people  inlerestcd  in  sport  and 
amusements.  It  is  important  that  this  im- 
pression should  be  corrected,  and  that  thf 
pubHc  should  realise  that  the  outstandinji 
feature  of  the  Exhibition  will  be  its  educa- 
tional purpose  in  relation  to  science,  art. 
commerce  and  industry.  Scientific  instru- 
ments, for  instance,  will  form  a  notable 
feature  of  the  Exhibition.  It  is  hoped  to 
include  representative  surgical,  optical, 
meteorological  and  photon:r.'iphic  appliances. 

The  latest  inventions  and  the  most  up-to- 
date  tools  of  the  workshops  of  science  will 
be  brought,  by  means  of  this  Exhibition,  to 
the  noti<'e  of  a  wider  public,  and  new  appf>r- 
tunities  will  be  created  for  the  development 
of  trade  in  those  industries. 


THE  ])ECOMPOSITTON  OF  THE 

AMINOBENZOIC  ACIDS  BY 

BOILING  WATER. 

Bv  L.  McMaster  and  R.  L.  Shriner. 

(Cotitrihufion  from  the  Chemical  Lahora- 

fonj  of  Washington  Tlnivemity.) 

Tht>  decomposition  of  nnthranilic  acid, 
when  heated  above  its  melting  point,  into 
carbon  dioxide    and  analine  is  well    known. 


Fritzsche*  identified  the  gas  evolved  as  car- 
bon dioxide,  and  Liebig*  showed  that  the 
oily  distillate  obtained  was  aniline.  Pow- 
lewski^  studied  this  decomposition  and 
found  it  to  be  complete  when  the  acid  was 
heated  for  1  hour  at  205-210°. 

The  m-aminobenzoic  acid  yields  carbon 
dioxide,  aniline  and  ammonia  on  treatment 
with  caustic  potash*,  and  the  p-aminoben- 
/.oic  acid  gives  aniline  and  carbon  dioxide 
when  treated  with  cone,  hydrochloric  acid.^ 
However,  no  mention  is  made  of  the  effect 
of  heating  aquemis  soluticms  of  these  acids. 

The  object  of  this  investigation  was  to 
study  not  only  the  decomposition  of  the 
aminobenzoic  acids  by  boiling  water  but 
also  to  determine  the  rate  of  decomposition 
and  the  volatility  of  the  acids  with  steam. 

EXPRRI.MKNTAL  PART. 

Products  of  Decomposition.  —  The  pre- 
sence or  absence  of  smiline  and  carbon  di- 
oxide as  products  of  the  decomposition  was 
ascertained  by  boiling  6g,  samples  of  the 
pure  acids'  with  water  under  a  short  reflux 
condenser  for  3  hours,  the  gases  evolved 
being  led  into  a  tube  of  lime-water  pro- 
tected by  a  tube  of  soda  lime.  The  solutions 
were  then  neutralised  with  sodium  hydrox- 
ide, extracted  with  ether,  and  the  ether  ex- 
tracts teste<l  for  aniline.  It  was  found  that 
the  ortho  and  para  acids  gave  aniline  and 
carbon  dioxide  while  the  meta  acid  did  not. 

Hate  of  Decomposition.  —  Weighed 
samples  of  the  acids  were  placed  in  Erlen- 
meyer  flasks  and  distilled  water  was  added. 
The  flasks  were  heated  just  to  boiling  over 
the  Bunsen  flame,  and  then  transferred  to 
an  electric  hot  piato,  where  gentle  boiling 
was  maintained  for  the  desired  length  of 
time.  During  this  period  the  carbon  di- 
oxide and  aniline  escaped  from  the  flasks 
along  with  the  steam.  The  quantity  of  solu- 
tion was  kept  constant  by  the  frequent  ad- 
dition of  hot  water  during  the  boiling  period. 
The  flasks  were  then  removed  from  the  hot 
•plate  and    the    undecomposed    acid    deter- 


'  Fritzsche,  Ann.,  1841,  XXXIX..  86. 

'  Liehiq,  ihid..  1041.  XXXIX..  94. 

•■•  Powieu-shi,  Her.,  1904,  XXXVII..  592. 

*  Beilsiein.  "  JJandbuch  dcr  Orgatiischen 
Chemic,"  Voss.  1896,  IL,  1,256. 

^  Weiih,  Ber..  1879,  I.,  105. 

•  We  wish  to  thank  the  Monsanto  Chemi- 
cal Works  of  St.  Louis  for  the  anthranilic 
acid  ichich  was  prepared  and  purified  by 
them  for  ub. 


306 


THE  CHEMICAL  NEWS. 


mined  by  titration  with  standard  sodium 
hydroxide,  using  phenolphthalein  as  indi- 
cator. The  amount  of  acid  decomposed  was 
obtained  by  subtracting  this  value  from  the 
weight  of  the  sample.  Since  the  amount 
obtained  by  this  method  would  also  include 
the  acid  volatilised  with  the  steam,  a  correc- 
tion was  made  in  order  to  obtain  the  true 
decomposition.  The  average  rate  of  evapora- 
tion of  water  from  the  flasks ,  was  found  to 
be  100  cc.  per  hour ;  so  for  each  hour  of 
boihng   the  amount    of  acid  per    100  cc.    of 


MAY  18,  1923. 


water,  as  determined  by  the  distillation  with 
steam,  was  subtracted  from  the  total 
weight  of  the  acid  lost. 

The  steam  distillations  were  carried  out  in 
the  usual  manner  using  a  Claisen  flask.  The 
weight  of  the  acid  per  100  cc.  of  distillate 
was  determined  by  titration  with  standard 
alkali.  It  was  found  that  100  cc.  of  the 
distillate  contained  0.016  g.  of  the  oriho 
acid  and  0.0056  g.  of  the  yara  acid.  The 
meta  acid  is  not  volatile  with  steam. 

The  following  data  were  obtained:  — 


2  g.  m 
Boiling     Acid 
time   deconnp. 
Hours       G. 


0.0672 
0.1429 
0.1870 
0.3072 
0.3422 
0.3768 
0.4052 


150  cc.  water 

Acid  decomp. 
Apparent    True 


% 

3.36 

7.15 

9.35 

15.36 

17.11 

18.84 

20.26 


% 

2.56 

5.65 

6.95 

11.66 

13.11 

14.04 

15.46 


Table  I. 
Anthrayiilic  Acid. 

Acid 
decomp. 
K  G. 

0.027  0.0921 
0.029  0.1857 
0.025  0.3132 
0.031  0.4446 
0.027  0.5592 
0.025  0.6006 
0.025         0.6948 


in  200  cc.  water 
Acid  decomp. 
Apparent     True 

% 


3.07 
6.19 
10.44 
14.82 
18.64 
20.02 
23.16 


% 

2.54 

5.13 

8.84 

12.69 

15.97 

16.82 

19.43 


K 

0.028 
0.028 
0.031 
0.033 
0.033 
0.030 
0.028 


Table  II. 
Para-Aminohenzvic  Acid. 


2g. 
Boiling     Acid 
time    decomp 


Hours 
1 
2 
3 
4 
5 
6 


in  200  cc.  water. 
Acid  decomp. 
Apparent    True 


G.  %  % 

0.0370  1.85         1.57 

0.0640  3.20        2.64 

0.0852  4.26        3.52 

0.1326  6.63        5.51 

0.1754  8.77         7.37 

0.2025         10.13         9.55 
Discussion. 
By  substituting  the  decomposition  values 
in  the    expression    for    a    unimolecular    re- 


K 
0.015 
0.014 
0.013 
0.014 
0.015 
0.017 


action,  K  = 


0.4343  t 


log 


a-x 


,  where  a  is 


the  initial  concentration,  x  the  amount  of 
acid  decomposed,  and  t  the  time  in  hours, 
the  values  for  the  velocity  constants  were 
obtained. 

In  the  case  of  anthranilic  acid  the  values 
of  K  for  the  initial  concentration  of  3  g.  are 
greater  than  in  the  case  of  the  2g,  sample, 
apparently  indicating  an  increase  in  decom- 
position with  increasing  size  of  samiple. 
However,    the    increase     is     comparatively 


small  and  is  due  partly  to  the  fact  that  the 
correction  for  vofctility  with  steam  and  the 
error  due  to  mechanical  losses  uuring  boil- 
nig  form  a  smaller  percentage  of  the  acid  in 
the  case  of  the  3g.  sample  than  in  the  case 
of  the  2g.  sample. 

It  is  interesting  to  note  that  only  the  o- 
and  p-aminobenzoic  acids  decompose  into 
aniline  and  carbon  dioxide  and  that  the  para 
acid  decomposes  only  half  as  fast  as  does 
the  ortho.  A  possible  explanation  of  these 
facts  may  be  due  to  the  formation  of  the 
inner  salt  and  the  subsequent  decomposition 
of  this  salt. 

The  para  acid  also  forms  this  inner  salt 
but  to  a  much  less  extent  than  anthranilic 
acid,  while  the  tn-aminobenzoic  acid  does 
not  form  such  a  salt  at  all,  and  hence  does 
not  give  aniline  and  carbon  dioxide. 

Summary. 

1.  The  anthranilic  acid  and  p-aminoben- 
zoic  acid  are  decomposed  by  boiling  water 
into  aniline  and  carbon  dioxide,  but  the  m- 
aminobenzoic  acid  is  not. 

2.  l3otli  anthranilic  acid  and  />-amino- 
benzoie  acid  are  slightly  volatile  with 
steam,  while  m-aminobenzoio  acid  is  not 


■ 


MAY  18,  1923. 


THE  CHEMICAL  NEWS. 


807 


3.  The  rate  of  these  deconi^positions  has 
been  studied  and  the  reaction  found  to  be 
monomolecular.  The  para  acid  decomposes 
half  as  fast  as  does  the  ortho. 

St.  Louis,  Missouri. 

[Reprinted    from     the    Journal    of    the 


American    Chemical    Society,    Vol 
No.  3.     March.       .  •. ' 


XLV. 


AKKESTING  DECAY  IN  BUILDING 
STONES. 

The  question  of  the  deterioraticai  of  stone- 
work in  buildings  is  a  matter  of  general 
economic  iniiportance.  But  in  the  cases  of 
our  historic  buildings  and  ancient  mtmu- 
ments  prevention  of  the  serious  decay  and 
gradual  demolition  of  tooled  surfaces  and 
main  structures  constitutes  a  special  prob- 
lem which  has  engaged  attention  of  many 
investigators  for  a  considerable  time  with- 
out, however,  finding  any  generally  satis- 
factory solution. 


IS  THEKE  AN  ELEMENT  OF  ZERO 

ATOMIC   NUMBER? 

By  F.  H.  Lorino. 

The  subject  of  atomic  numbers  is  of  great 
interest,  and  the  existence  of  an  element,  if 
it  mav  be-  so  called,  of  zero  number  may  be 
consiaered  in  this  connection.  To  discuss 
this  possibility  one  must  have  scHne  basis  fcx* 
the  argument. 


The  investigation  involved  is  very  com- 
plex, and  needs  to  be  approached  from  dif- 
ferent augles  with  the  help  of  wide  scienti- 
fic knowledge. 

Accordingly,  it  has  been  decided  to  set 
uip  under  the  Department  of  Scientific  and 
Industrial  Research  a  sipecial  committee  of 
the  Building  Research  Board  to  report  on 
the  best  methods  by  which  decay  in  build- 
ing stones,  especially  in  ancient '^structures, 
may  be  prevented  oi-  arrested. 

The  Chairman  of  the  Committee  will  be 
Sir  Aston  Webb,  K.C.V.O.,  P.R.A.,  and 
the  other  members  will  be  : — Mr.  R,  J.  Alli- 
son, C.B.E.,  F.R.I.B.A.,  Professor  C.  H 
Desch,  F.R.S.,  Mr.  A.  W.  Heasman, 
O.B.E.,  Mr.  J.  A.  Howe,  O.B.E.,  Sir  Her- 
bert Jackson,  K.B.E.,  F.R.S.,  Dr.  Alexan- 
der Scott,  F.R.S.,  and  Mr.  H.  0.  Weller, 
M.I.C.E.,  Hon.  A.R.I.B.A. 

All  communications  should  be  addressed 
to  the  Secretary,  Department  of  Scientific 
and  Industrial  Research,  16,  Old  Queen 
Street,  S.W.I. 


The  following  scheme,  in  the  writer's 
opinion,  is  suggestive,  and  while  the 
figured  values  follow  in  general  of  necessity 
when  usin^  Rydbcrg's  numbers,  it  shows 
that  an  initial  element  of  zero  atomic  num- 
l)er  could  be  introduced  so  as  to  give  a  series 
0,  1,2,  8,  4,  6,  as  shown,  completed  to  its 
origin. 


Scheme. 


Act.  Elmts.  preceding  He=  2 

Ne=  2+  7=  9. 
Ar=  9+  7  =  16. 
Kr  =  16+17  =  38. 
Xc  =  33+17  =  50. 
Rn*  =  50+31  =81. 


At.  No.  He=  2. 
No  =  10. 
Ar=18. 
Kr  =  36. 
Xe  =  54. 


2-  2  =  0. 
10-  9  =  1. 
18-16  =  2. 
36-33  =  3. 
54-60=4. 


Rn*  =  86.       86-81=5. 


Abbreviations:  Act  =  active.  Elmts  =  elements.     .Vt.  No.  =atoniic  number. 
*  also  Tn  and  An  (Emanations)  which  occupy  the  same  atomic-number  place. 


The  term  element  repre.sonts  some  places 
or  lacunas  which  may  never  be  properly 
filled  ;  but  this  observation  does  not  atpply  to 
the  elements  below  scandium  according  to 
the  writer's  studies  (this  Journal,  Vol. 
CXXV.,  Nov.  24,  1922,  p.  309). 

Considering,  therefore,  the  existence  of  an 
element  preceding  hydroppn,  it  would  find 
a  place  in  many  periodic  schemes ;  tor  ex- 
ample, the  one  devised  by  the  writer  (Wedge 


type)  and  published  in  this  Journal,  Vol. 
CXXV..  p.  386.  In  this  case  the  series  2, 
6,  10,  14  will  be  completed  to  its  origin  by 
introducing  this  hypothetical  member. 

In  Bohr's  recently-published  book,  Theory 
of  Spectra  and  Atomic  Constitution,  page 
70,  a  pyramid  type  of  periodic  table  is  shown 
which  appears  to  be  a  development  of  one 
due  to  T.  Bayley  (1882),  reiprodnced  in  Mel- 
lor's  Inorganic  Chemistry,  page  810.     Bohr 


ao8 


THE  CHEMICAL  NEWS. 


UAt  18,  1923. 


says:  "Compared  with  usual  representa- 
tions of  the  periodic  system,  this  method, 
proposed  more  than  twenty  years  ago  by 
Juhus  Thomsen,  of  indicating  the  periodic 
variations  in  the  properties  of  the  elements, 
is  more  suited  for  comiparison  with  theories 
of  atomic  constitution."  In  this  type  of 
tabb  the  element  in  question  could  stand  at 
the  apex  of  the  pyramid.  Whether  the 
table  is  a  "wedge"  or  a  "pyramid"  seems 
to  make  no  difference,  but  in  the  former 
type  a  numerical  rule  may  be  used  as  an 
argument  in  favour  of  an  element  preceding 
hydrogen,  that  is  to  say  the  displacements 
occasioned  by  the  wedge  arrangement  lends 
itself  to  this  treatment.  It  may  be  men- 
tioned in  this  connection,  that  the  object  of 
the  Wedge  scheme  was  to  correlate  the 
chemical  properties  of  the  elements  whilst 
giving  the  expansions  obtained  in  the  pyra- 
mid type  of  table,  particularly  on  account  of 
the  rare-earth  elements. 

Now  a  certain  peculiarity  arises  from  the 
introduction  of  a  new  member  at  the  begin- 
ning of  the  series.  In  the  writer's  table 
(loc.  cit.,  p.  387)  this  element  would  fall 
into  the  zero  group,  yet  it  could  not  be  in- 
active according  to  the  above  rule.  Further- 
more, an  element  before  hydrogen  of  atomic 
weight  1.008  would  presumably  have  to  be  a 
fraction.  One  must  proceed  cautiously  in 
advancing  new  ideas,  and  it  can  probably  be 
shown  that  there  are  just  as  many  argu- 
ments for  as  against  the  existence  of  such 
an  element;  and,  therefore,  no  probable  de- 
cision can  be  arrived  at.  The  subject  is, 
however,  a  very  interesting  one,  and  some 
further  views  will  be  given. 

Notes.' 

The  above  exipression,  "  Rydberg  num- 
bers," refers  to  the  atomic  numbers  of  the 
inert  gases  which  may  be  calculated  by  the 
well  known  equation  due  to  Rydberg.  The 
expression,  "  pyramid  table,"  is  not  to  be 
taken  in  the  solid -figure  sense.  It  merely 
means  that  the  table,  as  drawn,  is  sugges- 
tive of  a  pyramid,  but  perhaps  a  better 
name  could  be  found.  It  is  convenient  to 
have  names  for  the  purpose  of  identification 
though  they  may  not  be  scrupulously 
accurate  when  aipplied  to  more  or  less  elastic 
schemes  such  as  periodic  tables. 

London,  S.WA. 
Mmj  12,  1923. 


PRESERVATION  AND  USE  OF 
ARTICLES  MADE  OF  RUBBER. 

By  a.  Pfestorf. 

When  not  in  actual  use,  rubber  goods 
should  be  well  wrapiped  in  pamper  to  hinder 
the  access  of  air  and  light.  They  should  be 
kept  in  a  cool  place,  preferably  at  a  tem- 
perature of  10-12°  C.  Sunlight  has  a  dele- 
terious effect  on  rubber. 

In  order  to  attach  rubber  tubing  to  glass 
or  metal,  it  is  usual  to  damp  the  inside  of 
the  rubber  with  water  or  glycerine.  Both 
these  methods  possess  disadvantages,  since, 
in  time,  the  rubber  adheres  so  firmly  to  the 
glass  or  metal,  and  can  only  be  removed  by 
cutting.  This  difhculty  is  overcome  if  a 
ipaste  made  of  a  mixture  of  glycerine  with 
one-third  of  its  weight  of  talc  is  used.  In 
this  case,  when  the  glycerine  is  absorbed 
the  talc  remains  and  continues  to  function 
as  a  lubricant. 

The  exterior  diameter  of  the  glass  or  metal 
tube  should  not  be  much  larger  than  the  in- 
terior diameter  of  the  rubber. 

When  used  with  a  metal  clip,  only  rubber 
tubing  of  good  quality  should  be  used,  since 
tills  is  less  likely  to  adhere  by  its  inner 
walls  when  these  are  pressed  in  contact  for 
some  time.  The  walls  of  such  rubber  should 
also  be  thick,  so  that  it  may  remain  supple 
for  a  considerable  time. — (From  Chcmiker 
Zeitung,  1923,  XL VII.,  72.) 


BRITISH  INDUSTRY  AND  THE 
EUROPEAN    SITUATION. 

Sir  Eric  Geddes  delivered  a  speech  on  the 
industrial  situation  at  the  seventy-fifth 
annual  meeting  of  the  Association  of  Trade 
Protection  Societies  of  the  United  King- 
dom, at  the  Hotel  Cecil,  on  Thursday,  May 

Sir  Eric  reviewed  the  position  of  British 
industry  at  the  present  time,  and  stressed 
the  difficulties  of  providing  work  for  the 
large  body  of  unemiployed  in  the  face  of  the 
collapse  of  the  European  markets. 

Special  emphasis  was  laid  upon  the  very 
adverse  effects  on  U.K.  trade  by  the  con- 
tinued occupation  of  the  Ruhr. 


MAY  18,  1923. 


THE  CHEMICAL  NEWS. 


809 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  May  10. 
Papers  read :  — 

A.  Fowler,  F.R.S.  The  Series  Spec- 
trum of  Trebly-ionised  Silicon  {Si  IV). 

Numerous  new  lines  of  silicon  have  been 
observed  and  have  been  classified  in  four 
groups,  in  extension  of  the  groupings  made 
by  Lockyer  in  connection  with  stellar  S(pec- 
tra.  The  four  groups  represent  successive 
stages  of  ionisation,  and  have  been  desig- 
nated Si  I,  Si  II,  Si  III,  and  Si  IV.  The 
Sipectra  consist  alternately  of  triplets  and 
doublets,  and  the  series  constant  has  suc- 
cessive values  N,  4N,  9N,  and  16N. 

The  present  paper  deals  with  the  series  of 
Si  IV,  for  which  the  new  data  have  fully 
established  16N  as  the  stries  constant.  The 
spectrum  is  similar  to  that  of  neutral 
sodium,  Na  I,  but  the  main  series  which 
correspond  with  the  familiar  series  of  Na  I 
are  in  the  extreme  ultra-violet,  while  the 
second  series,  which  partially  fall  within  the 
ordinary  range  of  observation,  ccxrespond 
with  series  which  occur  in  the  infra-red  in 
Na  I. 

Including  Paschen's  recent  work  on  Al 
III.  and  the  author's  previous  work  on  Mg 
II,  which  also  have  spectra  similar  to  that 
of  Nu  I,  data  are  thus  available  for  the  com- 
parison of  the  spectra  given  by  four  simi- 
larly constituted  atoms,  which  differ  mainly 
in  the  charge  of  the  nucleus.  The  douTilet 
separations  and  the  series  terms  show 
greater  regularity  than  those  for  elements 
of  the  same  chemical  group. 

The  highest  limit  of  the  Si  IV  system  is 
304,117,  corresponding  to  an  icmisat-ion 
potential  of  40.6  volts. 

Sir  R.  Robertson,  F.R.S.,  and  W.  E.. 
Garner.     Calorimetry  of  High  Explosives. 

The  object  of  this  investigation  was  to 
determine  the  quantities  of  heat  and  volume 
of  gases  produced  when  high  explosives  are 
detonated  under  standard  conditions  of  con- 
finement and  compression,  in  order  to  ob- 
tain a  measure  of  energy  developed,  and  to 
investigate  nat\ire  and  reactions  of  gases 
evolved. 

A  calorimetric  bomb  was  devised  in 
which  high    exiplosives  could  be  Brought  to 


true  detonation  under  comparable  condi- 
tions as  regards  density  of  loading  and  con- 
finement, without  using  a  large  quantity  of 
explosive.  The  methods  of  initiating  de- 
tonation of  the  explosive,  of  determining  its 
heat  value,  and  of  measuring  gases  evolved, 
are  described. 

Results  are  given  fca:  some  high  explo- 
sives; and  in  the  case  of  an  exiplosive 
balanced  in  respect  to  total  combustion, 
where  it  is  possible  to  calculate  values  for 
heat  of  detonation  and  volume  of  gases,  the 
results  are  shown  to  be  in  agreement  with 
these. 

The  influence  of  the  higher  heat  of  for- 
mation of  phenol  witB  respect  to  toluene  is 
shown  to  be  reflected  in  the  similar  values 
for  heat  of  detcMiation  of  trinitrophenol  and 
of  trinitrotoluene,  although  the  latter  has 
much  less  oxygen  for  its  combustion. 

The  paper  discusses  causes  which  in- 
fluence the  nature  of  the  products,  and  the 
effect  of  conditions  under  which  detonation 
is  carried  out  on  heat  generated,  and  gaseous 
reactions  involved,  chiefly  with  regard  to 
liberated  carbon.  The  results  afforded  by 
imperfect  detonation  are  also  quoted. 

H.  S.  Hble-Shaw,  F.R.S.  Stream-Line 
Filter. 

The  author  ipoints  out  that  in  recent  ex- 
periments he  had  found  very  thin  films  of 
coloured  liquid,  or  liquid  containing  matter 
in  very  fine  suspension,  either  lose  their 
colour  in  the  one  case,  at  become  deprived 
of  their  suspended  matter  in  the  other,  on 
entering  such  thin  films. 

The  ipaper  describes  a  new  form  of  filter, 
in  which  sheets  of  paper  made  impervious 
to  the  fluid  containing  the  sustpended  mat- 
ter are  arranged  in  a  pack.  By  perforating 
the  pack  with  a  large  number  of  holes  it  is 
poHsible  to  get  the  equivalent  of  a  number 
of  sources  and  sinks.  This  was  obtained  by 
using  high  pressures,  so  as  to  force  the  mat- 
ter from  one  row  of  holes,  acting  as  sources 
between  the  interstices  of  the  (paper,  to  an- 
other row  of  holes,  each  hole  in  the  latter 
acting  as  a  sink. 

The  use  of  such  a  filter  enables  what 
would  otherwise  be  a  very  slow  rate  £>f  fil- 
tration to  be  made  sufficiently  rapid  for 
actual  use,  and  the  paper  gives  a  description 
of  a  laboratory  filter  constructed  on  this 
principle,  in  which  the  colouring  matter  of 
various  dyes,  from  what  were  apparently 
complete  solutions,  has  been  removed,  wTiile 
substances  like  ipoat  water  have  been  ren- 
dered clear  and  colourless. 


aio 


THE  CHEMICAL  NEWS. 


MAY  18,  1023. 


F.  W.  Aston,  F.E.S.  A  Critical  Search 
for  a  Heavier  Constituent  of  the  Atmos- 
phere hy  means  of  the  Mass-spectrograph . 

A  critical  search  for  a  gaseous  inert  ele- 
ment, heavier  than  xenon,  is  described,  in 
which  the  residues  absorbed  in  charcoal 
from  over  400  tons  of  air  are  dealt  with. 

The  final  analysis  is  made  by  means  of 
the  mass-spectrograph.  The  result  is  nega- 
tive and  indicates  that  such  an  element  cer- 
tainly does  not  exist  to  the  extent  of  1  part 
in  10^^  of  air,  and  probably  not  to  the  ex- 
tent of  1  part  in  2  X  10"  parts  of  air  by 
volume. 

Faint  bands  observed  in  the  region  corres- 
ponding to  masses  150  and  260  are  described 
and  their  origin  discussed.  The  first  of 
these  is  shown  to  be  due  to  a  complex  mole- 
cule of  mercury  with  a  multiple  charge,  but 
no  conclusion  is  reached  in  the  case  of  the 
other. 

The  results  of  the  experiments  are  not  in 
accordance  with  the  presence  of  molecular 
krypton  and  xenon  in  the  air,  recently  sug- 
gested. 

Papers  read  in  title  only  :  — 

H.  E.  Armstrong,  F.E.S.  Electrolytic 
Conduction :  Sequel  to  an  Attempt  (1886) 
to  Apply  a  Theory  of  Residual  Affinity. 

Referring  to  the  distinction  which  he 
drew  in  1886  between  simple  and  composite 
electrolytes — the  former  being  electrolytes 
per  se,  the  latter  solutfons  of  "salts" — the 
author  calls  attention  to  the  diverse  be- 
haviour of  the  silver  and  lead  haloids  on 
electrolysis;  the  current  being  carried,  as 
it  were,  by  the  metallic  ion  of  the  silver  and 
by  the  halogen  of  the  lead  compound.  The 
conclusion  is  drawn  that  the  salts  of  the 
two  metals  differ  in  structure — perhaps  thus 


S.g    Ag    Ag 

—  I  — I 

1               t 

G\,      Gl      CI, 

Pb  _  Pb"—  Pb 

1                      1 

1               I 
—  I  — I 

ig    Ag    Ag 

Pb  —  Pb  —  Pb 

CU     CI2     cu 

The  assumption  is  made  that  the  primar- 
ily active  unit  is  the  fundamental  molecule, 
and  that  the  circuit  is  formed'by  these  mole- 
cules being  coupled  with  the  electrode  face 
and  with  the  complex  molecules. 

A  similar  interpretation  is  applied  to 
aqueous  solutions. 

H.  E.  Armstrong,  F.E.S.  The  Origin  of 
Osmotic  Effects.  IV.—Hydrono-dynawic 
Chhnge  in  Aqueous  Solutions. 


The    conclusions     arrived    at    are     sum- 
marised in  the  following  propositions:  — 

1.  "Water"  is  a  complex  saturated  with 
the  gas  Hy  drone,  OH2.  Primarily  hydrone 
is  the  sole  potentially  "active"  constituent, 
but  it  becomes  actually  active  only  under 
conditions  which  suffice  to  determine  elec- 
trolytic change. 

2.  The  vapour  pressure  of  water,  or  of  a 
solution,  is  the  measure  of  the  proportion  of 
free  hydrone  molecules  present  in  the 
liquid. 

3.  Although  the  vajpour  pressure  is 
lowered  in  presence  of  any  solute,  the  solu- 
tion acquires  attractive  properties.  The  in- 
ternal activity  is  increased  whilst  external 
activity  is  diminished. 

4.  The  effect  produced  may  be  ascribed  to 
an  interaction  of  molecules  of  the  solute  and 
those  of  hydrone.  From  non-electrolytes 
(under  the  influence  of  conducting  impurity) 


a  simple  hydrol  is  formed  M 


H 


OH 


only 


a  single  molecule  of  hydrone  being  "  distri- 
buted "  upon  the  molecule  of  the  solute, 
whatever  its  magnitude, 

5,  In  the  case  of  potential  electrolytes,  a 
reciiprocal  interchange  of  radicles  of  salt 
and  hydrone  is  to  be  postulated.  Not  only 
is  the  solute  hydrolated,  but  it  is  distributed 
upon  hydrone,  the  salt  X'E'  giving  rise 
initially  to  the  reciprocal  systems 


EX 


H 

/ 

\ 

OH 


and 


H,o; 


E 


X 


6.  As  the  concentration  is  lowered,  under 
the    influence    of    hydrone,     the     complex 


EX/ 


H 


OH 


is   more    and    more  converted 


into     hydronol,     HgO 


OH 


H 


Ultimately 


MAY  18.  1923. 


THE  CHEMICAL  NEWS 


the  solution  contains  the  solute  only  in  the 

R 
form    HjOs  together    with    an    equal 


\ 


X 


number  of  molecules  of  hydronol. 

7.  The  "distributed"  reciprocal  com- 
plexes, including  hydronol,  are  the  electro- 
chemical agents  in  a  solution.  The  negative 
radicle  in  such  complexes  has  greater  re- 
sidual affinity  than  it  has  in  the  original 
simiple  molecules. 

8.  The  osmotic  pressure  manifest  in  an 
aqueous  solution  is  the  pressure  exercised 
by  molecules  of  hydrone  acting  as  though 
they  were  present  in  the  gaseous  state.  In 
short,  osmotic  pressure  developed  within  an 
aqueous  solution,  whatever  the  solute,  has 
origin  in  one  and  the  same  cause,  and  is 
properly  spoken  of  as  hydrono-dynamic — if 
the  word  be  permissible :  indeed,  this  term 
may  be  used  as  expressive  of  the  general 
activity  of  water,  electro-chemical  and 
osmotit. 

R.  W.  Wood,  For.  Mem.  R.8.,  and  A. 
Ellett.  On  the  Injiuenre  of  Magnetic 
Field H  on  the  Polarisation  of  Resonance 
Radiation. 

It  is  shown  that  in  the  case  of  the  reson- 
ance radiation  of  mercury  and  sodium 
vapour  strong  polarisation  of  the  light  can 
be  produced  by  weak  magnetic  fields  pro- 
perly oriontatea,  and  the  polarisation  of  the 
light  normally  present  can  be  destroyed  by 
n  magnetic  field  in  a  certain  <Mientatian. 
The  field  strength  necessary  for.  the  destruc- 
tion of  the  mercury  vapour  polarisation  is 
less  than  one  Gauss. 

W.  G.  Palmer.  A  Study  of  the  Oxida- 
tion of  Copper  and  the  Reduction  of  Copper 
Oxide  by  a  New  Method.  Cwnmunicated 
by  Sir  William  Pope,  F.R.S. 

A  film  of  copper  about  1  1000  mm.  thick 
is  prepared  by  chemical  means  on  a  china- 
clay  rod,  which  is  then  clamped  in  a  circuit 
carrying  a  small  current  at  constant 
E.M.F.  The  film  is  oxidised  at  temipera- 
tures  130°-210*'  C.  with  gaseous  oxygen  at 
various  pressures  Uip  to  1  atmosiphere,  and 
the  rate  of  oxidation  determined  by  measure- 
ments of  the  resistance  of  the  film. 

The  rnt<^  of  oxidation  is  proportional  to 
the  second  power  of  the  amount  of  metnl  in 
the  film,  and,  for  pressures  up  to  800  mm., 


311 


to  the  square  root  of  the  oxygen  pressure 
Between  170°  and  190°  C.  the  temperature- 
ooeffioient  of  the  oxidation  a^ppears  to  be 
negative  owing  to  the  simultaneous  oxida- 
tion of  cuprous  oxide  first  formed,  some 
oxygen  in  the  adsorbed  film  being  thus  de- 
viated from  the  metal. 

When  hydrogen  or  carbon  monoxide  is 
inixed  with  the  oxygen  the  rate  of  oxidation 
IS  greatly  enhanced  after  a  short  initial 
period,  during  which  the  rate  of  oxidation  is 
only  slightly  less  than  with  oxygen  alone. 
The  rate  of  reduction  of  copper  oxide  by 
hydrogen  and  by  carbon  monoxide  was 
studied  by  similar  means.  Both  gases  are 
adsorbed  on  the  metal  present  and  reduce 
adjacent  oxide,  but  with  hydrogen  the  water 
formed  also  adheres  to  the  metal. 

The  rate  of  reductiMi  in  both  cases  is 
directly  proportional  to  the  amount  of  metal 
present,  an  additional  term  in  the  case  of 
hydrogen  representing  the  action  of  the 
water. 

E.  A.  Fisher.  Some  Moisture  Relations 
of  Colloids.  II.— Further  Observations  on 
the  Evaporation  of  Water  from  Clay  and 
Wool.  Communicated  by  Prof.  A.  Smith- 
oils.  F.R.S. 

The  study  of  the  evaporation  of  water 
from  certain  colloid  materials  described  in  a 
former  paper  has  been  extended  to  some 
other  materials,  notably  to  kaolin  and  a  ball 
clay. 

The  curvature  (xxjurring  in  the  evapora- 
tion cunes  of  clay  soils,  which  was  formerly 
attributed  to  shrinkage,  is  not  found  in  the 
curves  obtained  with  ball  clay,  although  this 
substance  also  shrinks  on  drying.  The  par- 
ticular type  of  curvature  appears  to  be 
found  only  in  the  evaiporation  curves  of  such 
materials  as  soils,  which  are  mixtures  of 
colloidal  and  non-colloidal  substances,  and 
is  due  to  the  simultaneous  evaporation  of 
imbibitional  water  held  by  the  colloid  and 
of  interstitial  water  held  as  water-wedges 
between  the  soil  grains.  The  former  water 
evaporates  at  a  practically'  constant  rate, 
while  the  latter  evaporates  at  a  rapidly 
diminishing  rate,  curvature  in  the  evapora- 
tion curve  resulting. 

The  bearing  of  these  results  on  the  eva- 
poration of  water  from  wool  fabrics  is  dis- 
cussed, and  it  is  concluded  that  the  linear 
rate-curve  of  wool  is  not  inconsistent  with 
a  real  shrinkage  occurring,  although  so  far 
such  a  shrinka;,'e  has  not  been  demonstrated. 

The  work  is  being  continued. 


8ia 


THE  CHEMICAL  T^EWS. 


MAY  18.  1923. 


Thursday,  May  17. 

Papers  read :  — 

A.  E.  H.  TuTTON,  F.K.S.  (1)  A  Universal 
Interferometer.  (2)  A  Wave-length  Torso- 
meter  and  its  Use  with  the  Universal  Inter- 
ferometer, 

Pbof.  L.  N.  G.  Filon,  F.R.S.,  and  F.  C. 
Harris.  On  the  Diphasic  Nature  of  Gloss 
as  shown  by  Photo-elastic  Observations. 

Prof.  C.  E.  Inglis.  Stress  Distribution 
in  a  Rectangular  Plate  having  two  Oppos- 
ing Edges  sheared  in  opposite  Directions. 
Communicated  by  Prof.  E.  G.  Coker, 
F.R.S. 

Papers  read  in  title  only :  — 

Prof.  T.  H.  Havelock,  F.R.S.  Studies 
in  Wave  Resistance — Influence  of  the  Fodii 
of  the  Water-plane  Section  of  the  Ship. 

W.  M.  H.  Greaves.    On  a  certain  Family 
of  Periodic  Solutions  of    Differential  Equa- 
tions,   with    an  application    to  the    Triodc 
Oscillator.      Communicated  by  Prof.  H    F 
Baker,  F.R.S. 


ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

The  Friday  evening  discourse  on  May  18, 
at  9  o'clock,  will  be  delivered  by  William 
Morris  Mordey,  Past  Pres.  I.E.E.,  M.- 
Inst.C.E.,  M.R.I.  The  subject  is  Recent 
Studies  in  Alternating  Magnetism  (with 
experiments). 

On  Tuesday,  May  15,  Prof.  A.  C.  Sew- 
ard, Sc.D.,  F.R.S.,  gave  a  lecture  on  Arctic 
Vegetation  of  Past  Ages. 

On  Thursday,  May  17,  Prof.  E.  G.  Coker, 
D.Sc.,  F.R.S.,  M.R.L,  dehvered  a  |pa^per  on 
Engineering  Problems  solved  by  Photo- 
elastic  Methods. 

The  General  Monthly  Meeting  of  tho 
members  of  the  Royal  Institution  was  held 
on  May  7,  the  Duke  of  Northumberland, 
President,  in  the  chair. 

Sir  J.  J.  Thomson  was  elected  Honorary 
Professor  of  Natural  Philosophy,  and  Sir 
Ernest  Rutherford  Professor  of  Natural 
Philosophy. 

It  was  announced  that  the  Duke  of  Nor- 
thumberland, President,  had  nominated  the 
following  gentlemen  as  Vice-Presidents  for 
the  ensuing  year:  Dr.  Mitchell  Bruce,  Lord 
Iveagh,  Sir  Edward  Pollock,  Lord  Roths- 
child, Sir  Alfred  Yarrow,  the  Rt.  Hon.  Lord 


•Justice  Younger,  Sir  Jam»s  Crichton- 
Browne,  treasurer,  and  Sir  Arthur  Keith, 
secretary. 

Dr.  P.  J.  Le  Riche  and  Dr.  Liebert  were 
elected  members. 


THE  CHEMICAL  SOCIETY. 

An  informal  meeting  was  held  on  Thurs- 
day, May  17,  1923,  after  the  conclusion  of 
the  formal  business  of  the  Ordinary  Scien- 
tific Meeting. 


ROYAL  SOCIETY  OF  ARTS. 

On  Monday,  May  14,  the  third  Howard 
lecture,  entitled  The  Development  of  the 
Steam,  Turbine,  was  delivered  by  Stanley 
S.  Cook,  B.A.  (Cantab.),  M.I.N.A.,  M.I.M. 
(of  Parsons  Marine  Steam  Turbine  Co.). 

On  Wednesday,  May  16,  at  the  Ordinary 
Meeting,  Mr.  Leon  Gaster,  F.J.I. ,  Editor 
of  The  Illuminating  Engineer,  read  a  paper 
entitled  Industrial  Lighting  and  the  Preven- 
tion of  Accidents.  Sir  Malcolm  Delevingne, 
K.C.B.,  Assistant  Under-Secretary  of  State, 
Home  Office,  presided. 


SOCIETY  OF  GLASS  TECHNOLOGY. 

A  meeting  of  the  Society  was  held  in  the 
Physical  Chemistry  Theatre,  University 
College,  Gower  Street,  London,  W.C.I,  on 
Wednesday,  May  16. 

The  following  papers  were  received  and 
discussed  :  — 

On  the  Refractive  Index  Changes  in  Opti- 
cal Glass  occasioned  by  Chilling  and  Tem- 
pering, by  F.  Twyman,  F.Inst. P.,  and  F. 
Simeon,  B.Sc,  F.Inst. P. 

Notes  on  Burettes,  by  Verney  Stott, 
B.A.,  F.Inst.P. 

A  New  Method  of  Glass  Melting,  by  A. 
Ferguson. 

The  Drying  out  and  Warm-ing  Up  of  Tank 
Furnaces,  by  C.  Saxton,  A.M.I.E.E. 

Notes  on  the  Design  of  Pot  Arches,  by  Th. 
Teisen,  B.Sc,  C.E. 

Works  Visit. 

By  the  courtesy  of  the  Directors,  a  visit 
was  arranged  on  the  morning  of  Thursday, 
May  17,  to  the  new  works  of  Messrs.  James 
PoweU  &  Sons  (Whitefriars),  Ltd.,  Weald- 
stone,  Harrow. 


MAY  18,  1923. 


THE  CHEMICAL  NEWS. 


313 


THE  OPTICAL  SOCIETY. 

A  meeting  was  held  at  the  Imperial  Col- 
Jege,  Imperial  Institute  Road,  South  Ken- 
sington, on  Thursday,  May  10,  when  a 
paper  on  Stereoscopy  Re-stated,  by  Dr.  J. 
\V.  Frexch.  F.Inst. p.,  whs  read  and  dis- 
cussed. 


THE  FARADAY  SOCIETY. 

Papers  read  on  M'ay  14 :  — 

Some  Not^s  on  the  Etching  Properties  of 
the  a  and  ft  Forms  of  Tri-carhide  of  Iron,  by 
Frank  Charles  Tho.mfsun,  J). Met.,  B.Sc, 
and  Edwin  Whitehead. 

In  the  course  of  some  work  on  the  etching 
properties  of  the  carbides  in  alloy  steels  it 
was  noticed  that  a  dilute  solution  of  am- 
monium oxalate,  which  according  to  Mat- 
wieff  stains  cementite  red,  did  not  produce 
this  effect.  In  a  tungsten  steel  one  of  tht! 
constituents  of  which  was  a  carbide  which 
had  shown  tho  etching  characteristics  of 
cementite,  it  was  found  that  with  the  Mat- 
wieff  reagent  a  deep  reddish  colMratimi  was 
produced. 

It  was  believed  that  a  small  amount  of 
tungsten  in  the  carbide  might  cause  the  re- 
tention of  that  form  which  is  ncwrmally 
stable  only  above  200"  C.  The  change 
commences  at  160*  C,  and  is  comiplete 
about  200°  C.  At  even  lower  temperatures 
than  160°  there  may  be  some  modification 
of  cementite.  Further,  if  a  white  cast  iron, 
or  a  high  carbon  steel  is  (juenched  at  280" 
C.  so  that  the  high  temipernture,  or  /9  form, 
of  carbide  is  retained  down  to  normal  tem- 
peratures, the  electrical  resistance  under- 
goes a  gradual  fall.  This  means  that  the 
cementite  in  the  ft  form  is  tempered  nt 
room  temperatures  and  slowly  reverts  to  the 
a  state. 

The  instability  of  ft  cementite  has  ren- 
dered it  difficult  to  obtain  sharp  differences 
in  etching  properties.  Further,  the  differ- 
ences which  are  fairly  clearly  shown  imme- 
diately after  the  quenching  soon  cease  and 
indistinct  structures  are  obtained. 

The  heatings  were  effected  in  an  oil  bath, 
and  duplicate  sipecimens  were  quenched 
from  270°  C,  and  slowly  cooled  in  the  oil 
respectively.  In  the  case  of  the  Swedish 
white  iron  a  third  samiple  was  cooled  from 
190°  C,  a  temperature  at  which  some,  but 
not  nil,  of  the  changes  have  occurred.  At 
each  temperature  the  samples  were  allowed 


to  remain  for  a  period  of  on«  hour  b»for9 
they  were  cooled. 

It  is  of  interest  that  the  authors  have 
been  unable  to  obtain  a  suitable  etching 
with  ammonium  oxalate  of  cementite  in 
cither  form.  At  times  a  very  faint  pink 
coloration  was  observed,  which  was  insuffi- 
ciently pronounced  to  be  of  value. 

It  is  also  remarkable  that  desjpite  the  well- 
known  fact  that  a  hot  solution  of  alkaline 
sodium  picrate  will  darken  carbide  of  iron, 
neither  the  sodium  picrate  nor  the  caustic 
soda  will  effect  this  by  themselves. 

The  reagents  which  darkened  cementite 
are :  — 

(1)  Alkaline  sodium  picrate; 

(2)  Alkaline  sodium  benzoate,  6,3  grams 
benzoic  anhydride,  20  grams  caustic  soda, 
and  100  oc.  water,  used  hot  for  30  minutes. 

(3)  Alkaline  potassium  ferricyanide, 
Murakami's  reagent — 4  minutes  at  100°  C. 

(4)  Le  Chatelier's  reagent,  viz.,  a  boiling 
soluti(Mi  of  10  per  cent,  lead  nitrate  with  an 
equal  volume  of  50  per  cent,  caustic  soda, 
etches  in  5  minutes. 

(5)  A  boiling  solution  of  alkaline  copper 
potassium  cyanide. 

(6J  A  10  per  cent,  solution  in  water  of 
ammonium  molybdat^.  Etches  the  carbide 
in  the  cold  in  18  hours. 

(7)  An  alkaline  solution  of  ammonium 
molybdate  aided  by  a  small  electric  current. 
Etches  ctinentite  in  a  few  minutes. 

No  acid  solution  will  darken  cementite, 
and,  with  the  i-jcception  of  the  ammonium 
molybdate  solution,  and  that  very  slowly, 
no  neutral  solution  was  discovered  which 
will  do  this.  None  of  the  reagents  possess 
any  marked  advantage  over  the  standard  al- 
kaline sodium  picrate,  though  some  act  a 
little  more  quickly.  Murakami's  reagent, 
aided  by  a  small  electric  current,  is  qiiite 
useful  and  possesses  potentialities  as  a 
means  of  differentiating  between  the  two 
forms  of  carbide. 

An  Example  of  Polymorphism  in  an  Inter- 
Metallic  Compound,  by  David  Stockdale, 
B.A. 

The  authw  has  recently  determined  the 
liquidus  of  the  copper  ricn  aluminium-cop- 
per alloys,  using  sensitive  apparatus  for 
measuring  temperatures. 

Between  0  and  18  per  cent,  by  weight  of 
aluminium,  this  liquidus  is  a  smooth  curve 
which  is  described  in  a  remarkable  manner 
by  the  equation — 

T  =   -  x'  +  25x  -^  891, 
where    T  is  temperature  in  degrees    Centi- 


314 


THE  CHEMICAL  NEWS. 


MAY  18,  1923. 


grade,  and  a;  is  the  percentage  of  aluminium 
bj  weight,  the  origin  being  (T  =  0°  C,  x 
=  0  per  cent,  aluminium). 

Between  18  and  22  per  cent,  the  equa- 
tion— 

T  =    -  2.8x=^  +  97.4a;  +  169 
agrees  closely  with  observed  values. 

A  compound  having  the  formula  CU2AI 
would  contain  17.6  per  cent,  of  aluminium. 
The  two  equations  which  describe  the  ex- 
perimental results  so  well  would  show  that 
the  compound  CU2AI  does  exist,  but  that  it 
is  imstable  above  1,015°  C. 

If  the  compound  is  formed  at  1,015°  C.  it 
is  to  be  expected  that  cooling-curves  of 
alloys  between,  say,  16  per  cent,  and  18  per 
cent.,  would  show  thermal  arrest  points  at 
that  temjperature,  due  to  the  heat  of  forma- 
tion of  the  compound  CujAI.  Experiment- 
ally, this  is  found  to  be  the  case,  though,  as 
the  evolution  of  heat  is  small,  the  tempera- 
tures are  difficult  to  measure  with  accuracy. 
The  16.5  per  cent,  alloy  shows  a  point  at 
1,015°  C,  the  17  per  cent,  at  1,016°  C,  and 
the  17.5  per  cent,  at  1.017°  C.  The  18  per 
cent,  also  probably  shows  an  evolution  of 
heat,  but  it  is. merged  in  the  large  quantity 
of  heat  evolved  as  the  alloy  first  freezes. 
.  Further  evidence  for  the  existence  of 
CU2AI  lies  in  the  fact  that  the  nearer  the 
composition  approximates  to  17.6  per  cent, 
of  aluminium  the  harder  is  the  alloy  to  etch. 
A  body  of  the  above  composition  is  ex- 
tremely resistant  to  acids. 

The  Elasticity  of  Organogels  of  CeJhilosc 
Acetate,  by  Ernest  Walter  John  Mardles, 
M.Sc.  (LoND.),  F.I.C. 

The  determination  of  the  elasticity  of  a 
gel  is  complicated  by  the  persistence  of 
strain  after  removal  of  stress,  so  that  the 
elasticity  is  perfect  only  for  small  stresses 
apphed  for  a  short  time.  The  phenomenon 
of  plastic  strain  has  been  studied  with  dif- 
ferent materials,  and  the  general  conclu- 
sions are  applicable  to  the  elastic  properties 
of  jellies.  Various  workers  have  distin- 
guished between  (a)  the  instantaneous  elas- 
tic deformation  which  disappears  simul- 
taneously with  the  suppression  of  the  stress 
(primary  or  erastic  strain),  (b)  the  reversible 
deformation  which  is  a  function  of  time 
(secondary  strain,  subpermanent  deforma- 
tion, or  reactivity),  and  (c)  viscous  or  plas- 
tic flow,  which  is  irreversible  with  time  and 
produced  at  constant  rate. 

Hatschek  observed  that  optical  anis- 
trophy,  caused  by  straining  prisms  of  gela- 
tine gel    (10  per  cent,),    did    not    disappear 


with  the  removal  of  stress.  The  experi- 
ments, repeated  with  gels  of  cellulose  ace- 
tate in  benzyl  alcohol,  gave  similar  results, 
the  period  of  observation  extending  over 
several  weeks. 

The  materials  used  were  the  same  as 
those  employed  for  the  other  exiperiments  on 
the  reversible  sol-gel  transition.  Young's 
modulus  was  measured  by  observing  the  ex- 
tension of  rods  or  strips  on  loading,  by 
means  of  a  travelling  microscope.  The 
sipecimens  were  contained  in  a  constant 
temperature  and  humidity  chamber,  whilst 
under  examination,  since  the  modulus  is 
considerably  affected  by  temperature 
changes,  also  by  humidity  changes  on  ac- 
count of  the  hygroscopic  nature  of  the  cellu- 
lose derivative.  The  relative  modulus  of 
rigidity  of  the  oi'ganogels  was  determined  by 
a  method  similar  to  that  used  by  Rankine, 
viz.,  allowing  about  100  grams  of  the  sol  to 
set  between  two  coaxial  cylinders,  the  dia- 
meter of  the  outer  being  4.5  cm.  whilst  the 
diameter  of  the  inner  was  varied  at  will, 
according  to  the  degree  of  rigidity  of  the  gel 
under  examination.  The  outer  cylinder  was 
fixed  and  a  known  weight  acting  over  a  light 
pulley  tended  to  rotate  the  inner.  The 
angles  of  twist  produced  by  small  loads  were 
observed  by  means  of  a  scale  fixed  at  a 
distance  of  about  50  cm.,  a  small  correction 
being  a^pplied  for  the  friction  of  the  pulley. 

The  relation  between  the  modulus  of 
elasticity  and  concentration  for  the  organo- 
gels of  cellulose  acetate  is  not  expressed  by 
any  simple  formula.  The  expression  E  = 
feC"  represents  the  relation  approximately 
at  higher  concentrations  over  limited 
ranges.  The  value  of  n  decreases  with  fall 
in  temperature.  The  relation  between  log 
E  and  temperature  is  approximately  rectili- 
near over  the  range  of  temperature  ex- 
amined. The  physical  significance  of  these 
relations  is  discussed. 

Addition  of  substances  to  the  gel  mainly 
affects  the  modulus  in  proportion  to  the 
change  in  the  number  of  particles  which 
aggregate. 

The  changes,  with  time,  in  the  modulus 
of  rigidity  of  the  gels,  associated  with  the 
reversible  sol  to  gel  transition,  have  been 
studied.  The  significance  of  the  shape  of 
the  curves  relating  elasticity  and  time,  has 
been  discussed. 

The  Vapour  Pressures  of  Concentrated 
Cane  Siigar  Solutions,  by  Edgar  Philip 
Perman  and  Horace  Leonard  Saunders. 

Many  measurements  have  been  made  of 
the  vapour  pressures  of  dilute  solutions,  but 


MAY  18,  1923. 


THE  CHEMICAL  NEWS 


315 


comparatively  little  has  been  done  on  those 
of  higher  concentrations  except  at  low  tem- 
peratures. 

The  experiments  in  this  investigation 
have  been  confined  to  cane  sugar,  and  ob- 
servations have  been  made  with  concentra- 
tions from  10  per  cent,  to  saturation ;  in  a 
few  cases  it  has  been  possible  to  use  a 
solution  which  was  supersaturated.  The 
measurement  of  the  vapour  pressure  is  a 
direct  one,  the  actual  pressure  of  the  vapour 
being  balanced  against  a  column  of  mer- 
cury. It  was  found  that  Babo's  Law  held 
for  sugar  solutions. 

Some  Experiments  on  the  Hardness  and 
Spontaneous  Annealing  of  Lead,  by  A.  1j. 
NORBURY,  M.Sc 

Part  I. — Description  of  an  adaiptation 
used  for  making  Low  Load  Brinell  Impres- 
sions with  a  Lever  Tensile  Machine. 

Part  II. — Brinell  Hardness  Tests  on  Lend 
using  various  Loads  maintained  or  Various 
Lengths  of  time.      Results  interpreted    ac 
cording  to  Meyer's  Formula  :  L  =  ad° 

Part  III. — Effect  of  Cold-Hammering  on 
the  Hardness  of  Lead.  Results  showing  (ni 
Increase  in  Hardness,  and  (b)  Spontaneous 
Annealing. 

I. — Brinell  hardness  tests  on  lead  showed 
that  the  time  during  which  the  loarl  was 
maintained  was  an  important  variable.  Dif- 
ferences of  seconds  had  a^ppreciable  effect*, 
on  the  diameters  of  the  Brinell  impressions 
produced.  To  make  tests  on  lead  it  was 
necessary  to  use  a  machine  in  which  the 
load  could  be  applied  and  removed  almost 
instantaneously.  Moreover,  owing  to  tht 
fact  that  lead  is  such  a  soft  metal,  onl.\ 
loads  up  to  about  30()  kg.  can  be  used  witli 
a  10  mm.  ball. 

The  lever  tensile  machine  used  was  nn 
adapted  10  ton  Buckton,  and  it  fulfilled  th< 
requirements, 

IT. — The  specimens  of  lead  tested  were 
cut  from  an  ingot  of  Cookson's  chemically 
pure  lead  (99.99  per  cent.  Ph.). 

The  surfaces  on  which  the  Brinell  tesfs 
were  made  were  filed  and  emery  papered 
down  to  O  emery,  and  were  then  annealr<l 
at  100°  for  1  hour  to  remove  any  surface 
hardtming  effects. 

The  time  of  maintaining  the  load  is  a  verv 
importsmt  variable  which  must  be  accu- 
rately determined  when  measuring  the 
Brinell  hardness  of  lead.  It  is  also  obviously 
necessary  to  make  each  impression  on  a 
fresh  surface — as  distinct  from  the  method 
of  making  c/>ncentric  impres.sions  which  is 
pennissible  in  the  case  of  harder  metals. 


III. — The  time  tak&n  to  reduce  a  lead 
specimen  to  a  given  thickness  varied  be- 
tween about  1  and  8  seconds.  The  speci- 
men was  then  rapidly  transferred  to  the 
testing  machine,  and  the  first  Brinell  im- 
pression made  20  seconds  after  completion 
of  hammering.  Further  iniipressions  were 
made  at  intervals.  It  was  dithcult  to  con- 
trol the  conditions  of  hammering  very 
exactly  and  there  are  certain  obvious  vari- 
ables. 

Lead  is  hardened  by  oold-work,  and  it  was 
shown  that,  within  certain  limits,  the 
greater  lue  amount  of  cold-work  the  greater 
the  hardening.  It  is  ^ontaneously  annealed 
at  room  temperature  (16**  to  18°).  The  rate 
of  annealing  increases  with  the  amount  of 
deformation,  and  this  intro<luces  an  inter- 
esting result  in  that  lead  which  has  been 
very  severely  hammered  shows  no  increase 
in  hardness.  The  severe  deformation  in 
this  latter  case  has  caused  such  rapid  an- 
nealing that  the  lead  is  dead  soft  20  seconds 
after  hammering. 


THE  GEOLOGICAL  SOCIETY. 

At  the  meeting  on  May  2,  Prof.  A.  C. 
Seward,  Sc.D.,  F.R.S.,  President,  in  the 
chair,  Prof.  John  Joly,  D.Sc,  F.R.S.,  de- 
livered a  lecture  on  The  Bearing  of  some 
Recent  Advances  in  Physical  Science  on 
(Seology. 

After  referring  to  the  discovery  by  the 
present  Lord  Rayleigh  of  the  general  distri- 
bution of  radioactive  materials  and  to  the 
earlier  but  more  recently  developed  dis- 
covery of  isostasy,  the  lecturer  observed 
that,  assuming  that  the  dense  layer  upon 
which,  according  to  the  theory  of  isostasy, 
the  continents  float,  is  composed  of  basalt 
possessing  the  average  radioactivity  of 
liasalts,  it  may  be  calculated  that  if  this 
substratum  is  now  solid  (as  appears  from 
both  tidal  and  seismological  evidence),  it 
will  have  acquired  sufficient  radioactive  heat 
to  become  fluid  in  about  30  million  years. 

The  change  of  density  then  occurring  will 
cause  a  downward  motion  of  the  continents 
relative  to  the  ocean,  and  transgressionnl 
seas  will  result.  After  a  long  period,  dur- 
ing which  the  liquid  magma  (under  tidal 
forces)  circulates  from  beneath  the  conti- 
nents (which,  owing  to  their  own  radioactiv- 
ity, act  as  an  adiatherminous  covering)  to 
subooeanic  regions,  the  accumulated  heat  is 
given  up  to  the  ocean.  Re-solidificntion  of 
the  magma  ensues,    and  the  restoration  of 


316 


THE  CHEMICAL  NEWS. 


MAY  18,  1923. 


the  former  higher  density  causes  the  conti- 
nents to  rise  relatively  to  the  oceans,  and 
brings  about  the  retreat  of  transgreHsional 
seas.  In  this  manner,  the  coini:)Iete  cycle 
of  a  revolution  finds  explanation. 

Mountain-building  forces  arising  during 
the  climax  of  revolution  originate  from  two 
sources: — (a)  the  effects  of  the  horizontal 
tide-generating  force  and  of  precessional 
force  which,  although  probably  consider- 
able, have  not  yet  been  evaluated ;  (h)  the 
effects  of  the  changing  area  of  the  ocean- 
floor  attending  the  expansion  and  contrac- 
tion of  the  basaltic  layer,  whereby  the 
oceanic  area  becomes  alternately  increased 
and  diminished.  Upon  shrinkage  the  en- 
larged ocean-floor  bears  against  the  conti- 
nents. Hence  "  the  highest  mountains 
confront  the  widest  oceans." 

Mountain-building  is  due  much  more  to 
vertical  than  to  horizontal  forces.  The 
mountains  are  not  pushed  up  by  lateral 
forces :  these  forces  act  uipon  the  subsidis- 
ing geosyncline  to  produce  deformation  of 
the  semi-plastic  materials.  The  mountains 
are  elevated  long  after  by  the  isostatic 
forces,  the  energy  being  traceable  to  the 
stored  radioactive  heat  of  prior  ages. 

Inter-revolutionary  events  consist  of 
"preparatory"  disturbances,  due  to  local  in- 
crease of  liquefaction  of  the  magma :  also  of 
"sequential"  disturbances,  due  to  relief  of 
strain  accumulated  during  revolution,  and 
to  the  restoration  of  isostatic  equilibrium. 

The  conditions  now  prevailing  beneath  the 
continents  preclude  the  establishment  of  a 
steady  state  (that  is,  of  thermal  equilibrium) 
and  in  the  past  always  must  have  done  so. 

The  cyclical  events  outlined  in  the  theory 
here  adduced  appear  to  be  inevitable  as  a 
consequence  of  radioactivity  and  isostasy. 
Cyclical  disturbances  alone  can  explain  the 
past  history  of  the  Earth's  surface. 

At  the  meeting  held  on  Wednesday,  May 
16,  the  following  communications  were 
read :  — 

The  Upper  Ordovician  Bocks  of  the  South- 
Western  Benvyn  Hills,  by  W.  B.  R.  King, 
O.B.E.,  M.A.,  F.G.S. 

The  Geology  of  the  District  around  Corris 
and  Aherllefenni  (Merioneth),  by  Prof.  W. 
J.  PuGH,  O.B.E.,  B.A.,  F.G.S. 

A  lecture  on  the  Geology  of  Novaya 
Zemlya  was  delivered  by  Dr.  Olaf  Holte- 
dahl,  on  Thursday,  May  17,  in  the  Geologi- 
cal Department,  Imperial  College  of  Science 
and  Technology,  Prince  Consort  Road, 
S.W.7.  Prof.  W.  W.  Watts,  Sc.D., 
F.R^S.,  presided. 


ROYAL   AGRICULTURAL  SOCIETY 

OF  ENGLAND. 

prooeedings  at  monthly  council,  held  on 

Wednesday,  May  2,  Lieut. -Col.  E.  W, 

Stanyforth  (President)  in  the  Chair. 

Among  other  business,  the  following  re- 
ports were  presented :  — 

Chemical. 
Mr.  Luddington  reported  that  the  Con- 
sulting Chemist  had  presented  the  list  of 
samples  analysed  by  him  for  members  dur- 
ing the  past  month,  and  had  submitted  vari- 
ous matters  arising  out  of  his  correspond- 
ence. 

Research. 
Mr.  Adeane,  in  the  absence  of  the  Duke 
of  Devonshire,  reported  that  statements  had 
been  received  as  to  the  progress  of  the  fol- 
lowing experiments  which  were  being  car- 
ried on  for  the  Society  :  — 

(1)  Norfolk  Agricultural  Station  (barley 
and  other  cereals). 

(2)  National  Institute  of  Agricultural 
Botany  (oat  trials). 

(3)  Mr.  Arthur  Amos  (silage). 

(4)  Mr.  Thomas  Hacking  (grassland  im- 
provement— Leicestershire). 

(5)  Professor  Seton  (grassland  improve- 
ment— Yorkshire). 

Wtih  regard  to  the  republication  of  the 
results  of  past  experimental  work  of  the 
Society,  it  had  been  resolved  that  Dr.  Voel- 
cker  and  Sir  John  Russel  be  asked  to  pro- 
ceed at  once  with  the  collation  of  the 
material  relating  to  cereals  in  the  past  vol- 
umes of  the  Society's  Journal,  as  well  as 
similar  material  available  at  Rothamsted, 
but  that  Lord  Bledisloe  and  Mr.  Orwin  be 
consulted  prior  to  the  publication  of  the 
work  or  its  reproduction  in  the  Society*8 
Journal. 

It  had  been  finally  determined  with  re- 
gard to  the  yield  trials  of  oats  being  con- 
ducted for  the  Society  by  the  National  In- 
stitute of  Agricultural  Botany  that  the  con- 
tribution from  the  Society  was  not  to  exceed 
£816  for  the  two  years. 

Mr.  Adeane  moved  the  adoption  of  this 
i-eport.  As  two  of  the  experiments — one  on 
pig  feeding  by  Professor  Wood  and  the  other 
on  silage  by  Mr.  Amos — were  being  carried 
out  at  Cambridge,  he  suggested  that  if  pos- 
sible arrangements  should  be  made  so  that 
members  of  Council  who  wished  to  do  so 
could  go  to  Cambridge  after  the  Council 
Meeting  on  August  1.       He  proposed    that 


MAY  18,  1923 


ME  CHEMICAL  NiiWS. 


31? 


the  Council  Meeting  on  that  day  should  be 
held  at  10  o'clock,  in  order  that  those  who 
wished  to  take  part  in  the  visit  could  catch 
an  early  train. 

Mr.  Dampier  Whetham  safd  that  al- 
though he  had  no  ofl&cial  connection  with 
the  School  of  Agriculture,  he  knew  the 
views  of  Professor  Wood  and  others  con- 
cerned at  Cambridge,  and  waa  able  to  sup- 
port very  warmly  Mr.  Adeane's  suggestion. 

The  President  asked  if  it  was  the  wish  of 
the  Council,  after  hearing  what  Mr.  Adeane 
had  said,  that  they  should  hold  their  meet- 
ing at  10  o'clock  on  August  1. 

This  was  agreed. 

Other  business  having  been  transacted, 
the  Council  adjourned  until  Wednesday, 
June  6  (Derby  Day),  at  10  a.m. 


THE    INSTITUTION   OF   PETROLEUM 
TECHNOLOGISTS. 

Heavy  Grade  Eyyptian  Crude  Petroleum , 
by  W.  A.  Guthrie,  F.l.C,  F.R.S.E.,  etc. 

(Owing  to  Mr.  Guthrie's  absence  in 
Egypt,  this  paper  was  read  by  Professor  J. 
S.  S.  Brame,  F.I.C.,  F.C.S.) 

Accwding  to  Hume,    seepages    of  oil    at 
Zeitia,  Gemsah  and  Gebel  Tanka,  the  latter 
on  the   coast    of   West    Sinai,    led    to   the 
Egyptian  borings  for  oil.      Important  sup- 
plies were  first  obtained  at  Gemsah  in  19(^. 
where  the  petroleum  was  present  in  porous 
dolomitic  limestMie    associated    with    }.;yp- 
suni,    of    Miocene    age.      Subsequently    in 
1913  borings  were  connnenced  at  Hurghada. 
These  traversed  the  typical  Miocene  succes- 
cessiou  as  developed    on  the  surface    in  the 
Zeit  Hills — viz.,    below    a    tliick    series    of 
gypsum  followed  dolomitic  limestone  or  the 
characteristic  Globigerina  Marl.    Below  this 
stratum  is  a  series  of  sands  and  shales  (in- 
cluding carbonaceous    varieties),    in    which 
the  main  oil  is  present.      A  third  small  oil- 
field is  the  Abu  Durba,  on  the  west  coast  of 
Sinai,  where  there    are    indicaticms    of    the 
former  presence    of  oil  in  the  Nubian  Sand- 
stone.    Borings  have  shown  that  petroleum 
js  present  in  gravels  of  igneous  rocks  occur- 
ring   between    the  outcrop    of  the    Nubian 
sandstone  amd  the  shore.     Whether  the  r>il 
is  present  in  deeper  seated  strata  has  still  to 
be  shown. 

The  heavy  grade  crude  petroleum  is  founrl 
at  Hurghada  fRargadn),  200  milps  S.E.  of 
Suez.  From  the  striking  f>f  oil  in  the  firsl 
well  in  October.  1014,  until  the  beginning  of 
the  present  year,  1,201,868  metric  tons  have 
been  won.    The  present  production  averages 


3,500  tons  per  week.  A  proiportion  of  the 
production  of  the  field  is  "wet" — i.e.,  con- 
tains about  30  per  cent,  of  salt  water  as  a 
very  refractory  brine  emulsion,  difficult  to 
de-emulsify. 

In  1918  the  author  carried  out  experi- 
ments confirming  that  these  emulsions  were 
amenable  to  the  electrical  dehydrating 
treatment. 

The  oil  is  a  mixture  of  paraffin  base  and 
asphaltic  base  petroleum;  it  has  quite  a 
pleasant  smell,  des(pite  its  sulphur  content, 
and  when  seen  in  a  thin  film  is  brownish- 
black  in  colour,  while  the  calorific  value  is 
just  under  19,000  B.T.U.s  per  pound.  It 
contains  traces  of  Vanadium  and  Nickel. 
The  ultimate  analysis  is:  carbon,  85.15  per 
cent.;  hydrogen,  11.71  per  cent.;  sulphur, 
2.25  per  cent. ;  oxygen  and  nitrogen  (by  dif- 
ference), 0.89  per  cent. 

Although  much  study  has  been  expended 
on  chemical  examination,  this  is  still  incom- 
plete. The  only  practical  method  of 
separating  the  constituents  is  fractional 
distillation,  which,  at  atmospheric  pressure, 
alters  the  composition  of  the  fractions.  In 
order  to  obtain  fractions  having  a  closer  re- 
lati<Hiship  to  the  original  crude  oil,  distilla- 
tions were  conducted  right  down  to  coke, 
under  a  vacuum  of  28  inches,  using  liberal 
supplies  of  steam.  The  final  temperature 
of  the  vapour  was  228"  C.  In  the  earlier 
fractions  from  these  vacuum  distillations, 
very  little,  if  any,  bromine  was  absorbed;  in 
the  earlier  fractions  from  an  atmosipheric 
distillation  3  to  10  per  cent,  unsaturated 
hydrocarbons  occur.  Moreover,  in  the  later 
fractions  from  an  atmoepheric  distillation  as 
nmch  as  40  per  cent,  of  unsaturates  have 
been  found,  while  in  the  same  fractions, 
frcMn  a  vacuum  distillation,  these  were  from 
10  to  20  per  cent. 

The  oil,  when  distilled  in  the  ordinary 
way  for  oonmiercial  products,  yields  6  to  8 
{)er  cent,  benzine  boiling  below  150°  C,  and 
14  to  15  per  cent,  kerosine,  boiling  between 
150  and  290°  C. 

The  benzine  and  kerosine  fractions  can  be 
refined  to  first-class  products.  The  benzine 
is  not  entirely  free  from  sulphur  compounds 
but  these  are  not  present  in  an  objectionable 
form. 

The  kerosine  (specific  gravity,  0.820  at 
15.5"  C.)  can  be  refined  to  a  water  white 
kerosine  of  high  illuminating  value,  by 
treatment  with  2  percent,  of  sulphuric  acid, 
finishing  with  fuller's  earth  or  florida  clay 
treatment. 


3ia 


THE  CHEMICAL  NEWS. 


MAY  18,  1923. 


The  residue  is  ver;y  thick  and  viscous,  be- 
coming semi- solid  at  temperature  slightly 
below  15.5°  C,  and  having  a  viscosity  at 
100°  F.  in  Kedwood's  No.  1  Viscometer  oi 
anything  from  5,000  to  7,500  sees.  The  vis- 
cosity cannot  be  determined  at  all  in  the  No. 
2  Viscometer  at  32°  F.,  or  even  at  60°  F. 
The  high  viscosity  is,  of  course,  due  to  the 
asphalt  and  parafl&n  wax  content,  which 
amounts  to  15.25  per  cent,  of  the  former, 
and  10.35  per  cent,  of  the  latter.  The 
calorific  value  of  the  residue  is  18,370 
B.T.U.s. 

On  analysis  a  tyipical  sample  of  the  still 
coke  gave:  Carbon,  96.76  per  cent. ;  sul- 
phur, 2.96  per  cent. ;  ash,  0.28  per  cent. 


"  THE  PHYSICAL  CHEMISTRY  OF 
THE  PHOTOGRAPHIC  PROCESS." 
The  Society  will  hold  a  general  discussion 
on  this  subject  on  Monday,  May  28  next,  in 
the  Hall  of  the  Institution  of  Electrical 
Engineers,  Victoria  Embankment,  W.C.2. 
Professor  W.  D.  Bancroft,  of  Cornell  Uni- 
versity, will  open  the  proceedings  at  3  p.m. 
with  an  Introductory  Address  on  The  Theory 
of  Photography.  This  wiTi  be  followed  by 
detailed  consideration  of  the  subject,  sub- 
divided as  follows : — 

I.  "  The  Physical  Chemistry  of  the  Ve- 
hicle and  of  the  Emulsion." 

II.  "  Reactions  in  the  Plate  durmg  Ex- 

III. '"  Development  and  Characteristics 
of  the  Developed  Plate."  ^ 

IV.  "  Adsorption  Reactions  m  Photo- 
graphic Films."  ^        .,  ,         _, 

Each  Section  will  be  introduced  by  a  Pre- 
liminary Address  and  followed  by  general 
discussion.  Among  those  wUo  will  read 
papers  are  Dr.  T.  Slater  Price  Dr.  F.  C. 
Toy  Mr.  Olaf  Bloch,  Mr.  T.  Thome  Baker, 
M  Clerc,  Prof.  Luther,  and  Prof.  Gold- 
berg Several  communications  will  be  made 
from  Mr.  S.  E.  Sheppard  and  other  mem- 
bers of  the  staff  of  the  Eastman  Kodak 
Comipany,  and  papers  are  also  expected  from 
Dr.  Chr.  Winther,  Dr.  Luppo  Cramer,  and 
Prof.  L.  Plotnikov. 

Between  the  afternoon  and  evening  ses- 
sions a  comphmentary  dinner  will  be  given 
at  the  Hotel  Cecil  to  Prof.  Bancroft  and  the 

other  guests.  ,  o.     •  j. 

Members  of  the  Chemical  Society  are  m- 
vited  to  attend  this  meeting  Full  particu- 
lars may  be  obtained  from  the  Becret^y  of 
the  Famday  Society,  10.  Essex  Street, 
London,  W.C.2. 


GENERAL  NOTES. 


SANITARY  INSPECTION  OF  ARGEN- 
TINE AGRICULTURAL  EXPORTS. 
A  recently  issued  Presidential  Decree, 
which  is  to  come  into  force  in  July  next, 
lays  down  regulations  for  the  sanitary  in- 
spection of  agricultural  products  exported 
from  the  Argentine  Republic. 

The  Minister  of  Agriculture  is  to  organise 
in  the  ipoits  of  Buenos  Aires,  La  Plata, 
Bahia  Blanca,  Rosario,  in  the  city  of  Men- 
doza  (and  in  other  ports  when  convenient) 
an  inspection  service  for  plants,  shoots, 
tubers,  bulbs,  seeds  and  grain,  fresh  fruits 
and  vegetables  destined  for  export,  in  order 
to  ascertain  their  sanitary  state,  conditions 
of  packing  and  shipment. 

Exporters  are  required  to  apply  to  the 
Minister  of  Agriculture,  in  the  iprescribed 
form,  for  ipermission  to  export  each  consign- 
ment. 

Detailed  instructions  respecting  the 
nature  of  the  inspection,  analysis,  or  clean- 
ing necessary  for  each  category  or  class  of 
produce  are  specified  in  the  Decree,  which 
provides  for  the  issue  of  certificates  if  the 
goods  are  recognised  as  suitable  for  export. 
A  copy  of  the  Decree  in  Spanish  may  be 
seen  by  persons  interested  on  aipplication  to 
the  Tariff  Section  of  the  Department  of 
Overseas  Trade,  35,  Old  Queen  Street, 
London,  S.W.I. 


FOREIGN  SAMPLES  EXHIBITION 
AT  WALSALL. 

An  exhibition  of  foreign  samples  and  cata- 
logues held  at  the  offices  of  the  Walsall 
Chamber  of  Commerce  on  May  3  and  4 
proved  one  of  the  most  successful  displays 
yet  held  at  that  centre. 

The  samples  exhibited,  particulars  of 
♦which  appeared  in  the  Board  of  Trade  Jour- 
nal of  April  26  (page  501)  proved  of  excep- 
tional interest  to  the  manufacturers  of  Wal- 
sall and  district,  who  expressed  their  ability 
to  compete  with  the  foreign-made  article. 
'  A  full  attendance  was  recorded,  whilst 
124  samples  and  150  catalogues  were  bor- 
rowed by  firms  who  desired  to  consider 
carefully  the  question  of  export  of  similar 
goods.  The  fact  that  over  40  definite  en- 
quiries were  received  for  names  of  buyers 
and  information  res^pecting  export  matters 
indicates  that  Walsall  firms  intend  to  make 
practical    use  of  the    lessons  of  the    exhibi- 


tion. 


m 


MAY  18,  1923. 


THE  CHEMICAL  NEWS. 


3ld 


LJUBLJANA  TRADE  FAIR. 

The  Department  of  Overseas  Trade  is  in- 
formed that  the  Third  Ljubljana  (Laibach) 
International  Trade  Fair  wiTTbe  held  from 
September  1  to  10. 

There  is  a  market  in  Jugo-Slavia  for 
automobiles,  parts  and  accessories;  metal 
goods;  celluloid  products;  chemical  and 
pharmaceutical  products;  electro- technical 
and  other  machinery ;  bicycles  and  acces- 
sories ;  typewriting  machines  and  ribbois ; 
office  equipment;  iperfumery;  optical  instru- 
ments; sports  equipment;  watches  and 
clocks;  jewellery  and  fancy  goods. 

Stand  prices  vary  from  60  to  160  dinars 
per  square  metre,  according  to  the  position 
of  the  stand. 

A  booklet  and  specimen  application  form 
(in  French)  may  be  seen  on  a4pplication  to 
the  Department  of  Overseas  Trade,  35,  0I<1 
Queen  Street,  London,  S.W.I. — (From  the 
"  Board  of  Trade  Journal,"  May  10.) 


I 


DYESTUFFS  (IMPORT  REGULATION) 
ACT. 

Applications  for  Licenses  in  April. 

The  following  statement  relating  to  appli- 
cations for  licences  under  the  Dyestuffs  (Im- 
port Regulation)  Act,  1920,  made  during 
April  has  been  furnished  to  the  Board  of 
Trade  by  the  DyestufiEs  Advisory  Licensing 
Committee. 

The  total  number  of  applications  re- 
ceived during  the  month  was  512,  of  which 
430  were  from  merchants  and  dealers.  To 
these  should  be  added  the  22  cases  out- 
standing on  April  1,  making  a  total  f<x  the 
month  of  534,  These  were  dealt  with  as 
follows :  — 

Granted— 331  (of  which  318  were  dealt 
with  within  seven  days  of  receipt). 

Referred  to  British  makers  of  similar  pro- 
ducts— 130  (of  which  121  were  dealt  with 
within  sevtn  days  of  receipt). 

lieferred  to  Reparation  Supplies  avail- 
able— 56  (all  dealt  with  within  two  days  of 
receipt). 

Outstanding  on  April  30 — 17. 

Of  the  total  number,  534,  of  applieatiotis 
received.  479,  or  90  per  cent.,  were  dealt 
with  within  four  days  of  receiipt. 

UNIVERSITY  OF  LONDON, 
UNIVERSITY  COLLEGE. 
On  Friday,    May  11,    the    Rt.    Hon.    thr 
Viscount  Chelmsford,  G.C.S.I.,  G.C.M.O.. 


G.C.I.E.,  G.B.E.,  Chairman  of  the  College 
Committee,  unveiled  the  tablet  commemor- 
ating the  munificent  gifts  for  the  new  chem- 
istry building  made  by  Sir  Ralph  FcH-ster, 
Bt.,  J.P. 

The  chemistry  laboratories    were  open  to 
inspection  after  the  ceremony. 


NOTICES  OF  BOOKS. 
Einfuhrung    in  die  Kolloidchemie,    von 

Prof.  Dr.  Viktor  Poschl.     Sechste  ver- 

besserte  Auflage.     Pp.  158.     Dresden  and 

Leipzig:    Verlag  von  Theodor  Steinkopff. 

1923.     Price  3s.  Id. 

The  appearance  of  the  sixth  edition  of  this 
very  clearly  written  Introduction  shows  how 
widely  Prof.  Poschl 's  little  volume  is  used 
for  the  study  of  Colloid  Chemistry.  It  will 
certainly  continue  to  fulfil  the  author's  in- 
tentions, as  exipressed  in  the  preface,  as  a 
text-book  by  those  who  wish  to  gain  a  clear 
conception  of  the  phenomena  in  this  branch 
►f  natural  science. 

His  endeavours  to  establish  coll<Md  chem- 
istry as  an  exact  science  will  meet  with 
general  approval. 

The  book  constitutes  an  interesting  sur- 
\  ey  of  the  subject  and  gives  a  clear  concep- 
tion of  various  colloidal  phenomena.  It  also 
point*  to  the  ways  in  which  a  knowledge  of 
these  phonomcna  can  be  utilised  in  dealing 
with  other  chemical  and  technical  problems. 

The  advi'nt  of  this  edition  is  opportune 
since  the  elementary  study  of  colloids  will 
l>e  included  more  and  more  in  science  cur- 
ricula. Prof.  Poschl's  book  will  therefore 
be  found  very  valuable  for  students,  since  it 
is  sound  and  precise ,  and  will  leave  a  correct 
improKsion  in  the  students'  mind,       V.K. 


Synthetic     Inorganic     Chemistry,      by 
Arthur    A.    Blanchard,      Pn.D..      and 
Joseph  W.  Phelan,  S.B.     Third  edition, 
entirely  rewritten    and  greatly    enlarged. 
Pp.  XIV.  +  321.    London:  Messrs.  Chap- 
man &  Hall.  Ltd..    11,    Henrietta  Street, 
W.C.     1922.     Price  15s.  net. 
Thf  authors  of  this  volume    on  practical 
inorganic  chemistry  rightly  commence  with 
an  introduction  on  manipulation  and  general 
laboratory  processes.       Early    chapters    are 
devoted    to    the    (|uantitative     asipects    of 
chemistry,  solution,    and  experiments  illus- 
trating the  thef>ry  of  lonisation. 

Subsequent  chapters  give  numerous 
methods  of  pr<^!parfitions  of  compoimds, 
grouped  according  to  the  Periewlir  Clnssifica- 
tion  of  the  eletrjents.  The  prc'pnrations  are 
followed  by  further  illustrative  cxiperiments 


320 


THE  CHEMICAL  NETVS. 


MAY  18,  1923. 


and  each  chapter  concludes  with  a  set  of 
questions  designed  to  test  how  far  the  stu- 
dent has  grasped  the  subject  matter. 

The  volume  abounds  in  exiplanatory  de- 
tails, and  has  evidently  been  revised  in  ac- 
cordance with  the  latest  knowledge,  al- 
though in  the  case  of  the  appendix  on  the 
Periodic  Classification  of  the  Elements  ac- 
cording to  their  Atoviic  Numbers  and  the 
Arrangement  of  their  Electrons,  this  seems 
to  have  been  done  rather  hurriedly.  The 
outstanding  advantages  outweigh  any  minor 
defects  of  this  nature,  which  can  be 
remedied  in  the  next  edition. 

The  practical  exercises  are  arranged  to 
follow  lecture  work.  Practically  every  type 
of  chemical  reaction  is  exemplified  in  the 
course  outlined.  This  is  done  in  such  a  man- 
ner as  to  preclude  the  operations  being  con- 
ducted in  a  mechanical  manner. 

These  are  among  the  many  good  points  to 
be  noticed  in  a  perusal  of  this  work. 

BOOKS  RECEIVED. 
The  Examination  of  Hydrocarbon  Oils 
and  of  Saponifiablc  Fats  and  Waxes,  by 
Prof.  Dr.  D.  Holde.  Pp.  XIX.  +  572. 
Second  Edition.  1922.  Messrs.  Chapman 
&  Hall,  11,  Henrietta  Street,  Covent  Gar- 
den, W.C.2.    3as.  net. 

Thermodtfyiamics  and  the  Free  Energy  of 
Chemical  Substances,  by  Gilukkt  Newton 
Lewis  and  Merle  Randall.  Pp.  XXIII. 
+  651.  First  Edition.  1923.  Messrs.  Mc- 
Graw  Hiii  Publishing  Co.,  Ltd.,  6  &  8, 
Bouverie  Street,  E.C.4.    25s.  net. 

Synthetic  Inorganic  Chemistry,  by  Ar- 
thur A.  Blanciiard,  Ph.D.,  and  Joseph  W. 
Phelan,  S.B.  Pp.  XIV.  +  321.  Third 
Edition.  1922.  Messrs.  Chapman  &  Hall, 
Ltd.,  11,  Henrietta  Street,  Strand,  W.C.2. 
15s.  net. 

Practical  Chemistry,  by  E.  J.  Holmyard, 
MA  Pp  XVI  +  264.  1923.  Messrs.  G. 
Bell  &  Sons,  Ltd.,  York  House,  Portugal 
Street,  W.C.     4s.  net. 

The  Chemistry  of  Urea,  by  Emil  A.  Wer- 
ner, M.A.,  Sc.D.,  F.I.C.  Pp.  X.  +  212. 
1923.  INIessrs.  Longmans,  Green  &  Uo.,  6\), 
Paternoster  Row,  P].C.4.     Ms.  net. 


PUBLICATIONS    RECEIVED. 
The  Board  of    Agriculture  and    Fisheries 
has  issued  a  leaflet.  No.  246,    entitled    Pre- 
vention   of  Damage    to  Hides,    Shns,    and 

Wool.  ,      .    T         i.     1 

Among    the    most    important    live    stock 

products,  after  the  meat  itself,  are  the  hides 


of  cattle  and  the  wool  and  skin  of  sheep. 
These  are,  it  is  true,  bye-products  in  the 
sense  that  the  animals  are  primarily  grown 
for  meat  and  not  for  their  hides  or  skins,  but 
they  are  bye-products  of  very  considerable 
value,  and  as  such  deserve  more  attention 
at  the  hands  of  farmers  and  others  in- 
terested in  the  live-stock  industry  than  they 
commonly  receive. 

The  value  of  these  bye-products  is  fre- 
quently depreciated  by  causes  which  arc  re- 
cognised as  injurious  in  other  ways,  but 
which  are  not  usually  regarded  as  neces- 
saril}-  affecting  the  price  which  the  farmer 
receives  for  his  stock  and  produce.  The  loss 
in  value  thus  caused  is  a  serious  matter. 

Leaflet  No.  242,  "Stripe"  Disease  of 
Tomatoes,  is  abridged  from  an  important 
article  by  S.  G.  Paine  and  W.  F.  Bewley  in 
the  Journal  of  the  Ministry  of  Agriculture. 
Januarv.  1920. 


iHis  list  is  specially  compiled  for    The  Chemical 
News,  by  Messrs.  Bayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chance 'y  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trada  Marks, 
and  Designs  can  be  obtained  gratuitously. 
Latest  Patent  Applications. 
10583— Badisehe     Anilin  &     Soda-Fabrik.— Produc- 
tion of  tanning  materials.     April  18. 
10804— Cheraische  Fabrik     Anf  Aktien     vorm,     E. 
Schering.— Manufacture     of    vaccines  from 
bacteria.    April  20. 
10592— Kuhn,   A.— Apparatus    for  extraction     and 
removal  of     resin  from     solution  in     acid. 

^^P"l  18.  „     .  ^      , 

10883— Voeal,  H.— Process  for  manufacture  of  col- 
loidal sulphur.     April  21. 
Specifications  Published  this   Week. 
195710— Zahm,  E.— Process  and  apparatus  for  con- 
centrating liquids.  . 
195753— Soc.     of  Chemical     Industry     m     Basle.— 
Manufacture  of  vat  dyestuffs  derived  from 
anthraquinone.                          ,,,,,«    -r. 
195798— West.  J.  H.,    Jaques,     A.,    Tully,  C.  B.— 
Manufacture  of  liydrogen  or  gases  rich  m 
hydrogen.                     ,       .    „,    , 
Abstract  Published  this  Week. 
194244--Dyeing   cellulose     acetate.— British     Cellu- 
lose &  Chemical  Manufacturing  Co.,  Ltd  , 
8,  Waterloo  Place,  London,  and  Bader,  W  . 
vS'pondon,  near  Derby. 
Tlie  partial   alkaline   saponification  of  cellulose 
acetate  threads,  films,  or  fabrics,  to  facilitate  dye- 
ing  is  carried  out  by  first  treating  the  goods  with 
a  hot  or  cold  salt  solution,    and  then  saponifying 
with  substantially  cold  caustic  alkali.    If  desired, 
a  little  alkali  or  alkaline-earth  hydroxide  may  be 
added  to  the  salt  bath,     to  prime  the   subsequent 
saponification.       Sodium,   calcium,   or   magnesium 
chloride  are     suitable  salts  for  the    pretreatnient 
bath.    Mixed    goods  containing    cellulose    acetate 
and  cellulose  threads  may  be  treated  by  the  pro- 

'''^M^srs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  Si>ecification3,  and  forward  on 
post  free  for  the  price  of  Is.  6d.  each. 


MAY  25,  1923. 


THE  CHEMICAL  NEWS. 


321 


THE   CHEMICAL  NEWS, 

VOL.  CXXVII.     No.  3293. 


AN  EXPLANATION  OF  THE. THEORY 

OF  THE  ROTATION  OF  THE  ATOMIC 

NUCLEUS. 

Part  II. 

By  Herbert  Hen  stock. 

Before  proceeding  to  apply  the  theory  to 
sipecific  cases  there  is  one  concepticm  of  a 
gemTiil  nature,  which  srhould  be  realised  in 
order  fully  to  appreciate  the  workings  of 
the  nucleus.  Let  us  consider  two  neigh- 
bouring atoms  of  a  chain,  the  one  positive, 
the  other  negative.  The  nucleus  of  the 
negative  atom  is  using  a  considerable 
amount  of  its  force  in  holding  together  the 
electrons  of  the  unions  of  the  chain,  so  that 
its  power  uipon  the  side  bonds  is  weakened, 
and  therefore  the  atoms  or  groups  attached 
to  it  are  less  strongly  held,  hence  the 
greater  ease  with  which  such  side  atoms  or 
groups  are  usually  substituted.  On  the 
other  hand,  the  nucleus  of  the  positive 
atom,  being  reipelled  by  that  of  the  nega- 
tive, does  not  exert  so  much  of  its  force 
upon  the  electrons  of  the  chain  unions,  with 
the  consequence  that  its  positive  force 
shrinks  away  from  these  bonds  and  is 
exerted  chiefly  upon  the  side  bonds,  which 
accounts  for  the  greater  difficulty  in  ref>lac- 
ing  atoms  or  groups  attached  by  these 
bfmds:  circumstances  in  many  cases  may, 
of  course,  modify  these  actions,  but  this  is 
the  genernl  tendency  in  most  cases. 


'  In  all  following  demonstrationH  where 
any  haliden,  nlhal!  metals,  hydrogen  or  the 
OH  group  come  into  a  compound  their  oc- 
tets mil  he  omitted  and  inntrad  their  nym- 
hoh  tviU  be  given  tvith  an  arrow  showing 
I  heir  point  of  union. 

'  Refers  to  the  groups  of  the  periodic 
table. 

•"'  All  inner  electrons  have  been  omitted. 


Some  Applications  of  the  Theory  to 

Inorganic  Chemistry. 
In  aippraising  the  value  of  a  theory  it  is 
natural  to  consider  the  more  difl&cult  cases, 
and  especially  those  where  the  difficulties 
have  so  far  been  unexplained,  as  being  the 
more  important  or  more  interesting;  but  of 
necessity  a  theory  must  conform  to  the 
common  cases  as  well  as  the  extraordinary 
ones:  a  short  general  survey  will  therefore 
be  given,  which  will  include  some  of  these 
interesting  problems  in  their  due  order. 

Hydrides,  Halides  and  Hydroxides.' 
Groups  I.,  Including  Hydrogen. 
General  types'    of  the  alkali  halides    and 
hvdrogen  halides,  I'ig.  1;    Alkaline  hydrox- 
ides. Fig.  2. 


niouLcuJ 


oi'uZaA. 


<n 


'^fvu^cOuKxtAn. 


Fc'ol, 


cncAj^ae/n. 


<^c^^2%.<rp^^ 


322 


THE  CHEMICAL  NEWS. 


MAY  25.  1923. 


In  electrolytes  the  electron  of  the  posi- 
tive atom  will  pass  over  to  the  negative 
octet.  For  reasons,  see  The  Chemical 
News,  1923,  GXXVI.,  133. 

The  hydrogen  is  united  to  oxygen,  in  the 
-OH  group,  by  a  co-valence  bond,  since 
oxygen  is  not  strong  enough  in  permanent 
ipolarity  to  wholly  take  over  its  electron; 
this  co-valence  permits  the  group  to  act  as 
an  entity;  the  permanent  polarity  of  the 
oxygen  is,  however,  thereby  strengthened, 
and  it  can  then  take  over  the  electron  of  a 
metal  and  form  an  electrovalence  bond  with 
it. 

Tri  atomic  hydrogen  will  presumably  be 
linked  by  partial  valencies  and  will  have  the 
form,  Fig.  3. 


N_^ 


'3 


3. 


The  nuclei  are  only  partially  rotated, 
and  there  are  three  line&  of  force  from  each 
nucleus,  where  normally  there  should  bo 
but  two,  hence  the  three  are  considerably 
weakened,  and  the  whole  molecule  will  be 
very  unstable. 


Cl.-etc 


Fi^^. 


Group  II. 

General  types  of  the  halogen  compounds 
BeCl^,  etc.,  Fig.  I;  hydroxides  CaCOH),, 
etc.,  Fig.  5. 


-    -f 

0-H 


€ 

^ 

■»/v 

a 

< — 

-f-     - 

^A 

^KJ^ 

^--^ 

H  -0 > 

f 

V 

ip 

Those  present  little  diflBculty. 

Group  III. 

General  types  of  the  halogen  compounds 
as  BCI3,  AICI3.  Fig.  6. 


^3 


6. 


The  hydroxides  are  foi'med  on  the  same 
plan  by  substituting  -OH  groups  for  halo- 
gens. 

In  this  class,  Boron  forms  several  hy- 
drides, notably  BjHj„  and  BgH^,;  accord- 
ing to  Stock  (Ber.,  1912,  XLV.,  3539)  the 
former,  on  heating  to  100°,  forms  BjHg, 
which  is  a  gas,  and  this,  when  heated  at 
115°  for  some  time,  forms  Bj^Hj^;  he  ex- 
presses surprise  that  these  are  formed'  and 
not  BH, :  but  according  to  this  theory  these 
compounds  are  just  what  might  be  ex- 
pected. Boron  evidently  has  a  tendency  to 
unite  with  itself  like  carbon,  therefore  BH, 
is  not  formed.  B^Hj^  will  have  the  compo- 
sition aa  indicated  in  Fig.  7,  the  cubes  re- 
presenting the  boron  atoms.  It  apipears  as 
an  open  chain. 


MAY  25,  1923. 


THE  CHEMICAL  NEWS. 


323 


4    '! 

H 


<rt 


BHf  any  BH-BH^ 


Teg/. 
B,H,2  will  appear  as  a  ring,    Fig.  8.    all    the  bonds  being  single  ones. 


r  s 


ot. 


H 

/%3 

3H, 

F  <■  g 


^, 


li,„li,^  is  a    ring    compound    containing  three  double  bonds.       A    double  bond  be- 
tween two  atoms  of  this  element    (see  Fifr.  9), 


it 


THE  CHEMICAL  NEWS. 


MAY  25,  1923. 


Co  'nj.aaJAA^i. 


leaves  two  negative  bonds  in  the  po?;itive 
atom,  but  none  in  the  negative  atom;  also 
from  Fig.  8  it  will  be  seen  that  in  two 
atoms  united  by  a  single  bond,  the  positive 


atom  has  throe  sipare  negative  valencies  and 
the  negative  atom  only  one;  we  can  then 
write  the  formula — 


4- 


--f-        -+-       +       -+        - 


3/y^=  3- 23 A/^=B-iSH3-0  H-aH^  =  0 -0//3-iS//-| 


<n 


B  -  6.^ 


H  S 


^      \ 


/ 


6 
I 

B  H^ 
I 

BH 


in  which  it  will  be  seen  that  the  boron 
atoms  are  alternately  tri  and  penta  valent. 
It  must  be  conceded  that  boron  may  be 
penta  valent,  otherwise  these  formulae  can- 
not be  constructed :  it  is  impossible  to  con- 
struct any  on  a  purely  tri  valent  basis. 


The  above  formula    can    be    seen    more 
clearly  on  drawing  out  the    octets  and  put- 
ting   in  the    lines  of  force,    which    was  the 
method  by  which  the  author  arrived  at  it. 
B„H.  is  as  follows:  — 


MAY  25,  1923. 


THE  CHEMICAL  NEWS. 


325 


ric  /o. 


It  may  be  written  BHj-BH^. 

In  all  these  boron  hydrides  it  will  be 
noticed  that  both  positive  and  negative 
bonds  come  into  play  in  the  same  atoms 
they  are  therefore  unstable  (see  rule  2)* 

Group  IV. 

Geni'ral  types,  as  CH^,  SiH^,  etc.,  Fig. 
11;  CC1„  SiCl^,  etc.,  Fig.  12. 


FJo  II, 

{To  be  Continued.) 


*  For  rules  $ee  Part  I.  of  this  nerics  {The 
Chemical  News,  1923,  CXXVI.,  263). 


IS  THERE  AN  ELEMENT  OF  ZERO 
ATOMIC  NUMBER? 

II. 
By  F.  H.  LoRiNG. 

lu  this  Journal,  May  18th,  the  subject  of 
the  above  title  was  discussed.  It  was  as- 
sumed that  wueu  dealing  with  series  num- 
bers, they  should,  if  possible,  be  completed 
to  tueir  origins.  Two  series  were  given, 
and  in  each  case  when  they  were  completed 
as  far  as  possible  to  then*  origins,  i.e.,  with- 
out passing  into  negative  values,  they 
seemed  to  iniiply  that  an  element  should 
exist  with  zero  alomio  number;  but  there 
were  other  reasons  given  for  doubting  this 
possibility.  The  subject,  however,  merits 
iurthur  treatment. 

It  IS  of  interest  to  consider  this  problem 
in  its  more  realistic  asj)ect.  JN  umbers 
alone  will  not  curry  the  argument  very  far. 
ilic  figures  shown  in  the  scheme  on  page 
307  had  in  themselves  no  remarkable  signi- 
iicance;  indeed,  other  numerical  sets  could 
be  given,  but  the  point  made  was  that  if 
there  were  two  active  elements  preceding 
helium — hydrogen  and  one  other — then  the 
series  as  constructed  ran  0,  1,  2,  3,  etc.,  in- 
stead of  1,  2,  3,  etc.,  as  would  be  the  case  if 
there  was  oa\y  one  preceding  element. 

Atomic  numbers,  as  is  well  known,  are 
intimately  bound  up  with  the  net  nuclear 
charge  of  the  atom,  and  since  this  is  posi- 
tive the  number  is  thus  associated  with  a 
eliarge  oipposite  to  that  of  an  electron.  This 
being  so,  the  question  arises — Where  does 
the  unit  prxiitive  charge  representing  unit 
atomic  number  reside?  According  to 
inodern  views  bused  largely  on  the  work  of 
Rutherford,  this  unit  would  be  the  proton, 
and  it  resides  in,  or  is,  the  hydrogen  atom 
apart  from  its  single  electron  exteriority 
situated.  Since  the  hydrogen  atom  can 
now  be  placed  in  the  periodic  table  (see 
references  in  previous  ipa<per)  and  it  is  pos- 
sible to  remove  from  it  its  single  electron, 
it  is  not  stretching  matters  to  regard  the 
protMi  as  properly  classified,  especially 
since  thu  atomic  numbers  are  nuclear  mag- 
nitudes. The  electron  belonging  to  hydro- 
gen can  thus  bo  ignored  in  the  placing  of 
the  nuclear  magnitude,  the  proton. 

The  electron,  however,  is  not  as  yet 
placed,  and  since  it  cannot  function  by  it- 
self us  a  positive  entity,  like  hydrogen 
minus  its  electron,  it  is  natural  to  conclude 
that  it  cannot  ipossess  a  normal  atomic 
number,  though  it  may  enter  into  the  nuclei 


326 


THE  CHEMICAL  KEWS. 


May  25,  1923 


of  atoms  and  condition    them  in    terms    of 
atom.ic  number. 

It  may  be  jumping  to  a  wrong  conclu- 
sion to  give  t-he  electron  a  zero  number,  but 
it  is  quite  as  reasonable  a  proposition  as 
the  assigning  of  its  opposite  type,  the  pro- 
ton, to  the  hydrogen  place,  for  in  the  latter 
case  the  hydrogen  atom  normally  takes 
with  it  an  electron.  It  might  also  be 
argued  that  since  the  atomic  numbers  are 
essentially  positive  electrically,  the  elec- 
tron, it  placed  in  any  scheme,  should  have 
a  negative  place  and  not  a  neutral  one,  as 
represented  by  a  zero  number. 

As  a  further  consideration  it  is  well  to 
remember  that  the  net  nuclear  charges  of 
the  atoms  are  to  all  practical  intents  and 
purposes  their  atomic  numbers;  and,  there- 
fore, the  periodic  scheme  is  one  involving 
the  classification  of  atomic  nuclei.  The 
nucleus  is  in  fact  the  predominant  condi- 
tioning or" controlling  factor  in  the  atom; 
and  the  properties  of  all  atoms  seem  to  rest 
uipon  this  nuclear  magnitude  as  the  sort  of 
foundation  on  which  the  superstructure  of 
the  atom  is  built.  The  atomic  numbers  are 
magnitudes  which  govern  the  number  and 
disposition  of  the  external  electrons  that 
function  in  valency  phenomena. 

Another  point  to  be  considered  is  that  in 
all  the  relations  studied  which  involve  pro- 
tons and  electrons  there  appears  to  be  only 
one  foundation,  as  it  were,  in  the  structural 
characteristics  of  matter,  and  all  variations 
are  due  to  those  relative  to  that  foundation. 
There  are  not  two  distinct  electricities,  but 
only  one  by  comparison  which  may  vary 
from  zero  to  a  maximum  value  representing 
positiveness,  the  electron  being  the  agent  of 
entity  which  brings  about  this  change.  If 
this  is  so,  there  can  be  no  such  thing  as  a 
negative  atomic  number,  for  the  asymp- 
totic limit,  so  to  speak,  is  zero.  The  elec- 
tric agent  which  brings  about  this  change, 
the  electron,  cannot  do  more  than  neutral- 
ise a  positive  charge  until  it  is  practically 
zero.  Since  the  relations  studied  are  rela- 
tive, this  dual  oneness  of  affairs  is  difficult 
to  understand,  and  what  appears  to  be  a 
negative  charge  pure  and  simple  must  per- 
haips  be  judged  in  its  relative  aspect. 

It  is  not  possible  to  pass  through  zero 
with  atomic  numbers,  but  the  negative  elec- 
tron may  be  given  the  zero  place  in  the 
system  of  representation,  inasmuch  as  it 
can,  in  its  most  advantageous  position,  only 
neutralise  a  single  unit  positive  charge  to 
zero.  It  is  true  that  the  picture  can  be  re- 
presented in  the  reverse  way,    making  the 


electron  the  main  factor,  but  this  does  not 
harmonise  with  the  atomic  number  concep- 
tion based  upon  the  positive  charge  of  the 
nucleus  of  the  atom  which  is  fundamentally 
associated  with  its  mass;  or,  at  least,  the 
discussion,  to  be  consistent,  must  be  from 
the  standpoint  of  atomic  numbers.  There- 
fore, from  the  relative  view  given,  there  can 
be  no  negative  atomic  number,  but  it  might 
represent  zero  charge,  in  which  case  the 
electron  could  be  taken  as  a  zero-produciny 
quantity  so  far  as  atomic  numbers  are  con- 
cerned. 

It  must  be  remembered  that  the  series 
given  on  page  307  implies  that  the  zero- 
atomic-number  element  is  active  yet  with- 
out a  positive  charge.  The  electron  is  cer- 
tainly active  in  the  chemical  sense,  as  it 
serves  as  a  bond  of  union  in  chemical  com- 
binations, and  it  is  without  a  positive 
charge — it  is  relatively  negative  in  fact,  for 
its  addition  to  a  positive  nucleus  reduces 
the  charge  as  already  discussed. 

The  conventions  of  language  involving 
terms  denoting  ppposites  should  be  used 
cautiously,  as  it  is  the  phenomena  which 
should  be  pictured  rather  than  the  descrip- 
tive words  as  such  (see  notes  below). 

There  is  another  development  in  this 
connection  as  discussed  by  Eutherford  and 
by  Eddington,  affording  a  further  view 
which  will  be  developed  in  the  next  section. 

Notes. — It  should  be  aippreciated  that  the 
process  of  electrification  consists  in  trans- 
ferring electrons  from  one  body  to 
another.  An  electric  current  is  a 
flow  or  drift  of  electrons.  The  posi- 
tive charge  appears  always  to  be 
associated  with  matter  in  that  the  charge 
appears  in  proportion  as  electrons  are 
separated  from  matter,  the  term  matter 
here  referring  to  the  protonic  structure  in 
which  the  main  mass  resides. 


DISINFECTANT  FLUID,    TALLOW 

AND  LINSEED  OIL  REQUIRED 

IN  SOUTH  AFRICA. 

Mr.  W.  G.  Wickham,  H.M.  Senior 
Trade  Commissioner  in  South  Africa,  re- 
ports that  the  South  African  Railways  and 
Harbours  Administration,  Johannesburg, 
are  calling  for  tenders  to  be  presented  bv 
Monday,  May  28,  1923,  for  the  supply  of 
disinfectant  fluid  during  the  period  1  July, 
1923,  to  31  December,  1923  (Tender  No. 
441). 


MAY  25,  1923. 


THE  CHEMICAL  NEWS 


327 


A  copy  of  the  tender  form,  specification 
and  conditions  of  tendei',  can  be  inspected 
by  British  firms  at  the  Department  of 
Overseas  Trade  (Boom  52),  35,  Old  Queen 
Street,  Westminster,  London,  S.W.I. 

The  same  Administration  are  calling  for 
tenders,  to  be  presented  by  Monday,  June 
4,  1928,  for  the  supply  of  tallow,  and  also 
anti-friction  grease,  during  the  period  July 
1,  T923.  to  June  30,  1924  (Tender  No.  448). 

A  cfipy  of  the  specification,  etc.,  may  be 
seen  at  the  Dept.  of  Overseas  Trade  (Room 
53). 

The  South  African  Railways  and  Har- 
bours Tender  Board  are  calling  for  tenders, 
to  be  presented  by  Monday,  May  28.  for 
the  supply  of  raw  and  double  boiled  Tmscod 
oil  for  the  six  months  ending  December  31. 
1923  (Tender  439). 

A  copy  of  the  specification,  general  con- 
ditions of  tender,  etc.,  may  be  seen  at  tJie 
Oept.  of  Overseaa  Trade  (Room  53). 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE    ROYAL    SOCIETY 
CONVERSAZIONE. 

The  following  exhibits  were  shown  on  the 
oocasion  of  the  annual  conversazicMie,  held 
on  May  10  :  — 

Db.  Hele-Suaw,  F.R.S.  :  Stream  Line 
Filter. 

The  Stream  Line  Filter,  as  its  name  in- 
dicates, causes  the  fluid  which  has  to  be  fil- 
tered to  flow  with  stream  line  motion.  This 
is  done  by  forcing  the  fluid  between  parallel 
sheets  in  a  pack  of  such  sheets  made  of 
material  impervious  to  the  fluid  itself. 

The  space  between  the  sheets  can  be  re- 
gulated at  will  in  such  a  way  as  to  obtain 
films  so  attenuated  that  the  matter  in  sus- 
pension, however  minute,  can  be  prevented 
from  entering  the  interstices  between  the 
sheets. 

The  sheets  may  have  a  matted,  or  more 
or  less  rough,  surface,  but  if  the  sheets  an* 
smooth  a  stream  line  pattern  may  be  em- 
bossed on  them  either  by  dies  or  surface 
printintr.  The  employment  of  sheets  of  a 
suitable  kind  of  paper  gives  a  sample  and 
inexp«nsiv('  filter  for  laboratory  and  other 
work,  the  filtrate  being  drawn  from  one  tap 
and  the  residuum  from  another.  The  filter 
can  be  wasEed  out  without  opening  it. 


The  Government  Laboratory  (Dr.  Fox) : 
Nephelometer  with  Observation  Tubes  of 
Fixed  Height. 

Two  tubes  of  the  same  dimensions,  con- 
taining the  turbid  liquids  to  be  compared 
are  placed  in  the  path  of  a  beam  of  hght. 
Over  the  tubes  and  at  right  angles  to  the 
direction  of  the  light  are  two  Nicol  prisms 
which  can  be  rotated  to  adjust  the  zero. 
The  polarised  beams  of  light  pass  into 
separate  total  reflecting  prisms  arranged  to 
reflect  the  light  into  planes  perpendicular 
to  each  other.  The  beams  then  traverse  a 
Lunmier-Brodhun  cube,  and  are  brought 
into  a  rotatable  Niool  prism  through  which 
the  emergent  beam  enters  the  observation 
tube. 

Prof.  J.  T.  MacGreqor-Morris  and 
Prof.  E.  Mallett:  Sand  Figures  showing 
the  numerous  resonant  modes  of  Vibration 
of  Telephone  Receiver  Diaphragms. 

A  telephone  receiver  whose  diaphragm  is 
arranged  in  a  horizontal  plane  is  excited 
with  alternating  current  supplied  by  a  ther- 
mionic valve  oscillator. 

Sand  is  sprinkled  on  the  diaphragm,  and, 
as  the  frequency  of  the  alternating  current 
is  progressively  raised,  the  various  modes 
of  mechanical  resonance  a(ppear  with  great 
sharpness.     (Chladni's  figures.) 

At  least  seven  modes  of  vibration  are 
shown  within  the  limits  of  audition.  The 
frequencies  of  these  have  been  compared 
with  those  obtained  from  both  the  mem- 
brane and  the  plate  the<Mies,  and  a  graph  is 
shown  of  the  results. 

Sir  William  Braoo,  F.R.S. :  (1)  Models 
showing  Structure  of  Tartaric  and  Rarrviic 
Arid  (Mr.  W.  T.  Astbury).  (2)  Model  show- 
ing arrangement  of  Molecules  in  Basic 
Beryllium  Acetate. 

Mr.  E.  E.  Brooks  :  Photographs  of  Lines 
of  Electric  Force. 

Certain  of  the  aniline  dyes  suspended  in  a 
dielectric  liquid  such  as  tunpentine  are 
found  to  give  a  very  fair  map  of  the  elec- 
tric field.  The  photographs  shown  deal 
with  the  more  important  special  cases. 

The  Royal  Society:  (1)  Centenary  of 
Death  of  Dr.  Edward  Jenner. 

Cortificate  of  candidature  of  Dr.  Edward 
Jenner,  elected  a  Fellow  of  the  Roval  So- 
ciety, 1789.  ^ 


328 


THE  CHEMICAL  T^EWb. 


MAY  26.  1923. 


(2)  Early  Meeting  Places  of  the  Societfy. 

Photographs  of  Engravings  showing  the 
earher  meeting  places  of  the  Royal  Society, 
namely,  Gresham  College  (1660-1666  and 
1673-1710),  Arundet  House,  Strand  (1666- 
1673),  Crane  Court,  Fleet  Street  (1710- 
1780),  Somerset  House  (1780-1857),  Old 
Burlington  House  (1857-1873). 

Prof.  H.  C.  H.  Carpenter,  F.R.S.  : 
Large  Aluminium  Crystals. 

Test  pieces  prepared  from  sheets  and 
round  bars,  consisting  of  minute  crystals — 
about  3,500,000  per  cubic  inch — have  been 
converted  into  single  crystals  over  the  para- 
llel portion  of  the  test  piece  by  a  combina- 
tion of  mechanical  strain  and  thermal 
treatment.  When  subjected  to  tensile 
stress  these  crystals  become  deformed  in  a 
peculiar  way  which  depends,  in  the  case  of 
the  sheet,  on  the  orientation  of  the  crystal. 
The  round  bars  pull  out  so  as  to  give  a 
double  groove  instead  of  a  cu(p  and  cone 
fracture  as  obtained  from  the  microcrystal- 
line  test  pieces.  Remarkable  twinning 
efEeots  are  also  observed. 

The  Science  Museum:  Copies  of  some 
Early  Scientific  Instruments. 

(1)  The  "Merkhet"  or  instrument  used 
by  the  horoscope  priests  of  Ancient  Egypt 
to  lay  out  temple  axes,  and  to  determine 
the  hours  of  the  night.     Giro.  700  B.C. 

(2)  An  Egyptian  Waterclock  from  Kar- 
nak  for  recording  the  hours  of  the  night  by 
the  fall  of    the  water  surface.       Girc.  1400 

B.C. 

(3)  An  Egyptian  Waterclock  from  Edfu 
for  recording  the  passage  of  the  hours  by 
means  of  a  rising  water  surace.  Ptolemaic 
Period. 

(4)  A  Roman  Groma  constructed  from 
drawings  and  details  suipplied  by  Cav. 
Mateo  Delia  Corte,  Director  of  Excavations 
at  Pompeii. 

International  Western  Electric  Com- 
pany: 

(1)  Watercooled  Vacuum,  Tubes. 

This  vacuum  tube  is  of  the  same  type  as 
those  used  in  the  recent  Transatlantic  tele- 
phony test.  A  special  feature  of  this  tube 
is  the  copper-glass  joint.  Some  parts 
showing  the  construction  of  the  tube  are 
also  exhibited. 

The  photographs  show  a  100  Kw.  tubo 
and  also  some  10  Kw.  tubes  mounted  ready 
for  operation.  Curves  are  also  given  show- 
ing the  relation  between  Transatlantic  sig- 
nal strength  and  interference. 


(2)  A  Low  Voltage  Kathode  Hay  Oscillo- 
graph (in  operation). 

The  instrument  consists  of  a  glass  tube  in 
which  a  kathode  ray  is  generated  between  a 
hot  filament  kathode  and  a  small  tubular 
anode.  The  ray  is  rendered  visible  by  strik- 
ing a  fluorescent  screen  at  the  end  of  the 
tube.  It  is  deflected  with  the  help  of  two 
pairs  of  parallel  plates  set  at  right  angles 
between  which  the  ray  passes.  To  the  two 
pairs  of  plates  two  alternating  potentials  are 
applied :  the  fluorescent  spot  then  traces 
out  a  curve  which  is  a  graph  of  the  relation 
between  the*  two  potentials. 

(3)  Rochelle  Salt  Fiezo-Electric  Crystals. 
A  Rochelle  salt  crystal  suitably  mounted 

is  shown  used  as  a  gramqphone  transmit- 
ter. The  vibrations  on  the  records  are 
transmitted  through  the  needle  and  cause 
deformations  of  the  crystals.  The  deforma- 
tions produce  corresponding  alternating 
differences  of  potential  which,  when  applied 
to  a  telephone  receiver,  will  reproduce  the 
music  very  faithfully.  The  crystal  is  rever- 
sible and  can  be  used  as  a  loud  speaking  re- 
ceiver. If  alternating  differences  of  poten- 
tial are  atpplied  to  the  crystal  the  corres- 
ponding deformations  can  be  made  to  cause 
air  vibrations '  by  suitably  fitting  a  paper 
cone  to  it. 

Mr.  Conrad  Beck  : 

(1)  A  New  Illumi7iator  for  Opaque  Ob- 
jects under  the  Microscope. 

A  development  of  the  principle  of  the 
old  Lieberkuhn,  but  consisting  of  an  aiplana- 
tic  ring  of  glass  silvered  on  back  surface, 
enabling  a  short  focus  reflector  of  great 
light  intensity  to  be  used  with  powers  as 
high  as  4  mm.  (1/6).  The  same  illumina- 
tor can  be  used  on  powers  from  40  mm.  to 
8  mm.,  a  special  type  being  made  for  4  mm. 

The  objects  shown  illustrate  its  use  with 
and  without  polarised  light. 

The  latter  method  removes  the  glare 
caused  by  reflection  at  the  object  and  en- 
ables true  colours  to  be  observed. 

(2)  Illumination  of  Ordinary  Objects  with 
Polarised  Light  under  the  Microscope. 

Amphipleura  Pellucida  resolved  into  dots 
— 1.4  N.A.  Beck  apochromatic  object 
glass — immersion  condenser  full  axial  cone 
of  light  —  crossed  tourmalines  —  approxi- 
mate size  of  dots  1,200,000  inch. 

(a)  Dark  ground,  illustrating  advantacjo 
for  distinguishing  colour  —  method  em- 
ployed by  Sir  Herbert  Jackson,  F.R.S. 

(h)  Without  dark    ground,    for    resolving 
fine  structure. 


May  25,  1928. 


tHE  CSEMICAL  NEWS. 


329 


•  It  was  shown  bj  Sir  Herbert  Jackson 
that  this  method  enables  the  full  resolving 
power  of  the  microscope  to  be  realised. 
Direct  light  is  almost  extinguished,  and  ad- 
vantage is  taken  of  the  elipticallj  polarised 
light  reflected  from  fine  elements  of  struc- 
ture, thus  eliminating  all  glare,  which  has 
been  demonstrated  b^  Mr.  Conrad  Beck  to 
be  mainly  due  to  reflections  from  the  glass 
and  slip. 

The  Cambridge  and  Paul  Instrument 
Co.,  Ltd.  :  A  method  of  Tunning  a  direct- 
current  motor  under  a  variable  load,  or  on  a 
variable  voltage,  in  synchronism,  with  a 
tuning  fork. 

A  phonic  motor,  designed  by  Dr.  A.  B. 
Wood,  which  is  driven  by  a  tuning  fork  (50 
V.D.),  moves  a  contsujt  on  a  circular  rheo- 
stat, the  latter  being  rotated  by  the  motor 
which  it  is  wisheS  to  control.  If  the  latt^T 
gains  or  loses  speed  relatively  to  the  iphonic 
motor,  the  rheostat  is  adjusted  automatic- 
ally to  correct  the  speed  of  the  motor. 

The  mechanism  exhibited  forms  the  driv- 
ing part  of  a  Plotting  Chronograph  designed 
by  Dr.  W.  Rosenhnin,  F.R.S.,  and  is  ex- 
hibited by  the  courtesy  of  the  Director  of 
the  National  Physical  Laboratory. 

National  Institute  of  Industrial  Psy- 
chology (Dr.  C.  S.  Myers,  F.R.S.):  Ex 
amples  of  Research  Work—{l)  Investiga 
tio7i8  in  a  Coal  Mine  (Mr.  Eric  Farmfr)  ; 
(2)  Specimen  Curves  of  Improved  Output 
and  Wastage  (Dr.  G.  H.  Miles  and  Mr. 
Eric  Farmer);  (8)  Intelligence  Tests  CDr. 
Cyril  Burt);  (4)  Vocational  Selerfiim 
Tests  for  Entrants  to  the  Engineerinq 
Trades  (Mr.  M.  H.  Taoo). 

Messrs.  J.  J.  Griffin  &  Sons,  Ltd.  : 

(1)  The  "Boys"  Integrating  and  Record- 
ing Gas  Calorimeter. 

In  this  calorimeter,  which  is  of  tho  water 
flow  type,  tho  water  used  is  iiK^asurod  and 
doled  out  ipoaitively  at  such  a  rate  that  if 
will  be  heated  10°  C.  by  tho  oombustion  of 
half  a  cubic  foot  of  gas  per  hour  if  the  pas  is 
of  tho  "declared"  value,  whatever  that 
value  may  be.  The  gas  is  doled  out  posi- 
tively at  atmospheric  pressure  at  that  rnlo 
corrected  for  temperature,  pressure  and 
contained  water  vapour  accurately  to  one 
part  in  1,000.  The  means  used  for  adjust- 
ing the  rate  are  a  ball-cylindor-disc  integra- 
tor and  oipicyclic  gearing.  eallerT  the  thiiik- 
ing  machine.  A  recording  drum  and  driv- 
ing gear  of  extremely  siniple  CMistruction 
keep  a  record  of  the    ever-chanering  volume 


factor  of  the  gas.  The  heat  interchanger  of 
folded  sheat  lead  autogenously  soldered  is 
also  a  new  construction,  as  is  the  method 
used  for  the  soldering.  The  operative  ther- 
mometers are  brass  boxes  with  elastic  ac- 
cordion tops  filled  with  amyl  alcohol.  These 
through  a  lever  system  working  in  three 
dimensions  of  space,  operate  a  pen  moving 
one  inch  for  each  degree  centigrade.  This 
rests  on  the  middle  line  of  the  chart  if  the 
gas  is  of  its  declared  value,  and  it  moves 
one-tenth  of  an  inch  for  each  1  per  cent,  of 
increase  or  decrease.  An  Amsler  integrat- 
ing wheel  gives  the  average  value  since  it 
was  last  set.  The  pamper  is  ruled  and  marked 
in  half-hours,  days  and  half-days  as  it 
passes  through  the  machine.  Distilled 
water  produced  by  an  automatic  still  only 
is  used,  and  this  is  circulated  and  cooled  by 
the  operation  of  a  small  hot  air  engine. 
The  one-wheel  clock  which  governs  all  the 
lueohanism  is  driven  by  the  waste  water. 

(2)  New  small  "spot  test"  Calorimeter. 

This  is  the  meter  and  interchanger  of  the 
recording  instrument  adapted  for  personal 
observaticm.  The  final  temperature  is 
reached  in  10  minutes  !r(xn  hghting  the  gas, 
and  the  tiresome  meter  proving  operations 
are  not  necessary. 


Mb.  D.  Nohthall-Laurib  :  Photomicro- 
graphs of  Crystals  in  Colour  mounted  to 
show  changing  tints. 

When  crystals  are  examined  under  a  mi- 
croscope with  polarised  light  with  the  addi- 
tion of  a  selenite  plate  out  of  such  thickness 
to  show    a  green  colour    and    a  red    coloiu: 
when  rotated    through  an  angle  of  45°,    the 
predominant  tint    changes  from    green    to 
red.    The  Paget  viewing  screen  used  for  the 
Paget  oolour    photographic    process    being 
oompoeed  of  minute    squares  of  green    and 
red,  neglecting  fw  the  moment  the  smaller 
blue  squares,  enables    it  to  be    possible    by 
changing  the  register  of  the  viewing  screen 
when    combined    with  the  transparency    to 
imitate  on  the  lantern  screen  the  effect  pro- 
duced when  using  polarised  light.       Colour 
photographs    are  taken  of  the  subject    and 
the  slides  are  so  constructed  to  allow  of  the 
viewing  screen  being  slowly  moved   across 
the  transparency.     In  this  manner  tho  tint 
of  the    slide  changes    from    green     through 
various  intermediate  colours  to  red,  depend- 
ing upon  the  relative    position  of  the  slide 
and  screen.     Varirms  slides  of  subjects  suit- 
able for  exhibiting  this  effect  have  been  con- 
structed on  this  principle. 


330 


THE  CHEMICAL  NEWS. 


MAY  25,  1923. 


The  National  Physical  Labroatory: 

(1)  Iron  Mercury  Calorimeter  (Dr.  Ezek 
Griffiths  and  Mr.  F.  H.  Schofield). 

The  caloorimeter  consists  of  a  cylindrical 
block  of  iron  with  a  hole  for  receiving  the 
specimen  and  a  lid  which  serves  also  as  a 
container  of  mercury.  Arrangements  are 
made  for  flooding  the  hot  sipecimen  with 
mercury.  The  apparatus  is  particularly 
useful  for  dealing  with  materials  of  low 
thermal  conductivity  (X  materials  which 
react  with  water. 

(2)  X-liay  Spectra  of  Alloys  (Dr.  E.  A. 
Owen  and  Mr.  G.  D.  Preston). 

Spectrographic  curves  showing  the 
atomic  structure  of  pure  metals  and  alloys. 
The  method  depends  upon  the  ipresence  of  a 
large  number  of  small  crystals  in  plates  of 
the  material.  The  effect  is  enhanced  by 
polishing  and  etching. 

(3)  Photomicrographs  of  Woods  (Dr.  G. 
W.  C.  Kaye  and  Mr.  W.  F.  Higgins). 

Certain  woods  of  low  density,  viz.,  Och- 
roma  lagopus  (Balsa  wood),  Apeiba  tihoiir- 
bou  and  Paulownia  imperialis  (Japanese 
Kiri  wood),  have  been  found  to  possess  very 
low  thennal  conductivities.  Photomicro- 
graphs of  these  are  shown  side  by  side  with 
those  of  pine  and  beech,  and  the  marla-d 
difference  in  the  thickness  of  the  cell  walls 
is  easily  seen. 

Mr.  E.  Hatschek  :  Imitations  of  Organic 
Forms  by  Drops  and  Vortices  of  Gelatin. 

Permanent  "hanging  drop"  and  vortex 
forms  can  be  obtained  by  allowing  gelatin 
sol  to  run  into  suitable  coagulating  solu- 
tions, the  temperatures  and  densities  being 
so  adjusted  that  the  gelatin  sets  when  the 
desired  form  has  developed.  Owing  to 
shrinkage  a  number  of  features,  such  as 
radial  ribs,  undulating  membranes,  stellate 
and  crenated  discs,  etc.,  appear,  which  are 
absent  in  liquid  models.  Further  modifica- 
tions can  be  introduced  by  causing  perme- 
able or  semi-permeable  membranes  to  form 
at  the  proper  time;  models  of  the  red  blood 
corpuscle  and  segmented  forms  are  pro- 
duced by  this  procedure. 

Physical  Department,  Rothamsted  Ex- 
perimental Station,  Harpenden  :  Floccu- 
lation  and  Defjocidation  in  Soils. 

The  phenomena  of  flocculation  and  de- 
flocculation  are  of  great  importance  in  soils, 
as  they  are  associated  with  the  formation  of 


tilth.  The  experiments  include  iiica«ure- 
meuts  of  tJie  volume  changes  of  soil  result- 
ing trom  alterations  in  its  moisture  content, 
and  a  demonstration  of  the  influence  of  lime 
on  the  flocculation  of  soil  samples  taken 
li'om  successive  depths  of  an  experimental 
plot.  The  automatic  electrical  balance,  de- 
vised by  Prof.  Oden  and  Dr.  Keen,  furnishes 
a  continuous  time  record  of  the  accumulat- 
ing weight  of  deposit  from  a  soil  suspen- 
sion. Analysis  of  the  time-weight  curve 
tiius  obtamed,  leads  to  a  distribution  curve 
showing  the  relation  between  the  weight  (or 
number)  of  particles  and  the  effective  radii ; 
the  shape  of  the  curve  varies  according  to 
the  degree  of  dispersion  of  the  soil  suspen- 
sion. 

Certain  practical  consequences  are  illus- 
trated by  means  of  dynamometer  reoord- 
chai'ts  of  di-aught  of  ploughs  under  difleient 
conditions. 

[iShown  by  Dr.  B.  A.  Keen,  with  Mr.  E. 
M.  Crowther  and  Mr.  "vV.  B.  Haines.] 

Mr.  F.  Harrison  Glew  :  A  Levitating 
Magnet. 

This  exiperiment  shows  a  bar  magnet  of 
cobalt  steel,  floating  by  repulsion  above  the 
opposed  poles  of  a  fixed  magnet,  at  a  verti- 
cal distance  of  half-an-inch,  or  more,  ac- 
cording to  the  strength  of  the  magnetic 
field. 

The  floating  magnet  is  free  to  move  verti- 
cally and  may  be  made  to  oscillate  up  and 
down  in  its  glass  enclosure.  The  experi- 
ment fails  with  ordinary  magnet  steel,  as 
reversal  of  polarity  takes  place  in  the  in- 
tense magnetic  field  necessary  for  flotation. 

National  Institute  for  Medical  Re- 
search (Dr.  Leonard  Hill,  F.R.S.,  and 
Dr.  a.  Eidinow)  :  Effect  of  Temperature 
on  the  Biological  Action  of  Light. 

Dr.  W.  Lawrence  Balls,  F.R.S.  :  Mir- 
ror-hnage  Structures  in  Cell-walls  of  Cotton 
Hairs. 

The  cotton  hair  has  a  characteristic  con- 
voluted form;  these  convolutions  have  long 
been  known  to  be  both  right  and  left-handed 
in  any  one  hair.  Such  reversals  of  the  ex- 
ternal spiral  are  primarily  due  to  reversals 
of  a  spiro-fibrillar  internal  structure  in  the 
cellulose  wall,  these  in  their  turn  being  due 
to  growth-causes  as  yet  unknown. 

The  preparation  is  a  longitudinal  section 
of  a  cotton  hair,  through  a  reversal.  The 
single  layer  of  wall  thus  observed    between 


MAY  25,  1923. 


THE  CHEMICAL  NEWS 


381 


crossed  nicols,  with  light  eliiptica%  polar- 
ised through  quartz  plates,  shows  the 
structural  reversal  clearly  by  a  change  in 
the  interference  colours.  If  now  the  circu- 
lar stage  of  the  microscope  be  rotated,  it 
will  be  found  that  the  ipositions  of  maxi- 
mum extinction  are  also  reversed  on  either 
side  of  the  micro  structural  reversal,  the 
optical  axes  being  thus  related  to  the  spiral- 
fibril  axes,  and  not  to  the  cell-axis.  This 
indicates  the  existence  of  a  definite  pseudo- 
crystalline  space-lattice  structure. 

National  Institute  for  Medical  Ke- 
SEARCH  (Dr.  E.  H.  J.  Schuster):  A  New 
liecurding  Kata-T hermo meter. 

Mr.  E.  13.  Moullin:  A  Direct  Reading 
Thermionie  Voltmeter. 

The  voltmeter  employs  the  rectifying  pro- 
perty of  the  Thermionic  Vacuum  tube.  If 
an  alternating  IM).,  whose  itieaa  value  is 
zero,  is  applied  between  grid  and  filament, 
a  current  is  iproduced  in  the  anode  circuit 
whose  mean  valut  is  not  zero.  The  value  of 
the  current  so  produced  is  used  as  a  measure 
of  the  alternating  P.D.  applied  to  the  in- 
strument. The  exact  conditions  obtaining 
at  the  time  of  calibration  are  readily  repro- 
duced in  a  simple  manner. 

The  readings  of  the  instrument  are  un- 
affected by  the  frequency  of  the  applied  al- 
ternating P.D.,  and  experiment  shows  that 
if  this  frequency  is  changed  from  10  ipir 
second  to  a  million  per  second,  the  error 
produced  is  less  than  2  per  cent. 

The  electrostatic  capacity  of  the  volt- 
meter is  of  the  order  of  20  oms  and  the 
power  it  absorbs  at  full  scale  ie  about  50 
ergs  per  second. 

Mr.  George  H.  Gabb  :  Bust  of  Galileo, 
carved  in  pear  wood.  Probably  a  work  of 
about  1650-70. 

This  bust,  formerly  in  the  Methuen  Col- 
lection, is  rather  larger  than  life  size,  and 
stands  39  inches  high. 

The  socle  consists  of  a  grouip  of  astrono- 
mical emblems,  carved  in  high  relief;  sur- 
mounted by  a  globe,  around  which,  in  a 
belt,  ore  carved  the  Signs  of  the  Zodiac. 

At  the  back  of  the  bust,  in  a  circular 
glazed  recess,  is  preserved  a  relic  of  Galileo; 
a  piece  of  crimson  velvet,  with  silk  fringe, 
possibly  a  piece  of  the  covering  of  his 
academic  chair. 

This  has  been  romovod  care  .illy,  and  was 
shown  in  the  small  glass  case. 


Mr.  Walter  Heape,  F.R.S.  :  Exhibition 
of  three  series  of  photographs  illustrative  of 
the  following:  — 

{1)  Heape  and  Grill's  rapid  cinema 
machine  designed  to  take  photographs  at 
rates  from  500  to  5,000  per  second.  (This 
machine  is  now  in  use  at  Shoeburyness  for 
recording  the  results  of  gunnery  experi- 
ments.) 

(2)  111m  photographs  taken  at  the  rate  of 
2,500  per  second  of  a  15  in.  glass  vacuum 
globe  (Osram)  broken  by  a  hammer.  (This 
shows  what  occurs  during  the  coniiplete 
break  up  of  the  globe  in  about  one-twentieth 
oi  a  second.) 

(3)  Film  photographs  taken  at  the  rate  of 
2,000  per  second  of  a  5  in.  solid  rubber  ball 
weighing  2i  lb.  shot  from  the  mouth  of  a 
2  l/16th  in.  diameter  gun  against  a  steel 
target. 

They  show  the  extraordinary  contortions 
of  the  ball  from  the  instant  when  it  is  shot 
off  a  tee  by  the  head  of  a  tompion  fixed  in 
the  mouth  of  a  gun  until  it  rebounds  from 
the  target — that  is,  a  flight  of  about  l/40th 
of  a  second. 

Mr.  H.  J.  Buchanan-Wollaston  :  On 
the  Value  of  Markings  on  Herring- Scales  as 
a  Means  for  Estimating  Age  and  Growth 
Hate  of  the  Fish. 

Mr.  Percy  B.  Lowb:  Variation  in  licd- 
Legged  Partridges  {Alectoris  rufa). 

Mr.  H.  Graham  Cannon  :  Beetles  show- 
ing transplanted  heads. 

Prof.  J.  W.  Gregory,  F.R.S.,  and  Mr. 
C.  J.  Gregory:  Fossils  from  the  Devonian, 
Carwoniferoua  and  Triaasio  Rocks  of  Chin- 
ese Tibet. 

The  collections  were  made  by  Prof.  Gre- 
gory and  Mr.  Gregory  during  the  Sladen 
Trust  Expedition,  1922. 

Department  of  Zoology,  British 
Museum  (Natural  History)  (Mr.  C.  Tate 
Ueoan,  F.R.S.,  and  Mr.  M.  A.  C.  Hinton). 

(1)  Deep-sea  Cables  Damaged  by  Shark 
Bites;  (2)  Contents  of  a  Crocodile's 
Stomach;  (3)  Modifications  of  the  dentition 
in  some  African  Vertebrates. 

Botany  School.  Cambridge  (Mr.  John 
Walton)  :  A  Nciv  Method  of  isolating  Mum- 
mified Fossil  Plants  for  purposes  of  Micro- 
scopical Examination. 


332 


THE  CHEMICAL  NEWS. 


MAY  25,  1923. 


The  Director,  Eoyal  Botanic  Gardens, 
Kew  : 

(1)  Efwatakala  Grass — Melinis  minuti- 
flora  P.  Beauv. 

(2)  Rubiaceous  Plants  with  Bacterial 
Nodules  in  the  Leaves. 

Mr.  H.  Taverner  :  Stereo-pJioto  Micro- 
graphs of  Hydracarina  (Water  Mites)  in 
Natural  Colours. 

Eesearch  Department,  Woolwich  :  (1) 
Detection  of  Feeble  X-ray  beams  by  Smoke 
Clouds. 

In  this  method  a  smoke  cloud,  having  a 
flat  top,  is  produced  in  a  small  clfkmber, 
and  above  this  cloud  is  placed  an  electrode 
maintained  at  a  potential  about  400  volts 
above  earth.  The  cloud  is  then  interposed 
in  the  path  of  an  X-ray  beam,  and  some  of 
the  ions  thus  produced  attach  themselves  to 
the  smoke  particles,  which  are  then  drawai 
up  from  the  top  of  the  cloud  under  the  in- 
fluence of  the  electro-static  field. 

The  movement  of  these  particles  is  ob- 
served by  an  ultra  microscope.  The  ex- 
hibit illustrates  the  application  of  the 
method  to  the  detection  of  feeble  X-ray 
beams  refected  from  crystals. 

(2)  Chronograph,  for  use  with  a  pliofo- 
graphic  Recorder. 

(3)  Autographic  Recording  of  Dilation  of 
Solids  at  High  Temperatures. 

Mr.  S.  G.  Brown,  F.R.S.  :  The  Freno- 
phone. 

Messrs.  Adam  Hilger,  Ltd.  :  Optical 
Apparatus  for  Research. 

(1)  Vacuum  Grating  Spectrogi-aph  for 
photography  of  the  Schumann  and  Lyman 
^Regions. 

(2)  Diffraction  Gratings  ruled  at  the 
National  Physical  Laboratory, 

(3)  Interferometer  for  measuring  the 
aberrations  of  lens  systems. 

(4)  Lummer  Gehrcke  Parallel  Plate  with 
resolving  power  of  850,000.  Made  for  the 
Physical  Laboratory  of  the  University  of 
Toronto. 

(Shown  by  kind  permission  of  Prof.  J.  C. 
McLennan,   F.R.S.) 

National  Institute  for  Medical  Re- 
search (Mr.  J.  E.  Barnard,  Mr.  John 
Smiles  and  Mr.  F.  Welch)  : 

(1)  Iw.provew.ents  in  the  w,ethod  of  Mi- 


croscopical Observation  known  as    "  Dark- 
ground  Illuw,ination." 

(2)  An  Expermental  Demonstration  with 
the  Microscopic  Interferometer. 

The  Microscopic  Interferometer  is  in- 
tended for  the  double  purpose  of  testing 
microscope  objectives  and  similar  optical 
combinations,  and  for  use  as  a  microscoipe 
of  high  accuracy. 

The  experiments  shown  indicate  the 
effect  of  alteration  of  tube-lengths  on  the 
zonal  corrections  of  an  objective.  As  the 
illuminant  used  in  this  case  is  a  mercury 
vapour  lamp,  the  demonstration  is  confined 
to  the  three  brightest  colours  emitted  by 
mercury  va^pour. 

When  used  as  a  microscope  the  accuracy 
of  the  fine- adjustment  motion  is  some  ten 
times  greater  than  in  any  ordinary  micro- 
scope. Thus,  if  ultra-violet  light  is  the 
illuminant,  successive  images  in  any  single 
wave-length  can  be  obtained  with  precision. 

Dr.  Irvine  Masson  :  Apparatus  for 
Measuring  the  Compressibility  of  Oases. 

The  body  contains  four  holes,  communi- 
cating with  each  other  and  with  a  space  in 
which  a  plunger  works  through  a  special 
gland.  The  cavity  is  full  of  mercury;  in 
each  hole  is  set  a  glass  tube  filled  with 
about  15  cc.  of  gas.  By  screwing  in  the 
plunger  the  mercury  forces  the  gases  into 
the  visible  capillary  portions  of  the  tubes 
where  their  volumes  are  measured,  the 
capillaries  having  previously  been  cali- 
brated. One  tube  contains  a  standard  gas 
and  thus  serves  as  an  accurate  pressure- 
gauge. 

The  advantages  of  this  form  of  Andrews' 
original  pattern  lie  chiefly  in  its  freedom 
from  leakage  at  high  pressures  and  in  its 
capacity  for  four  samples  at  once.  It  has 
been  used  at  450  atmospheres'  pressure, 

Anglo-Persian  Oil  Co.,  Ltd.  :  Lubricat- 
ing Oils  under  Electrostatic  Stress. 

The  Electrostatic  Stress  is  applied  by 
means  of  a  disc  of  brass  resting  on  the 
smooth  surface  of  a  piece  of  lithographic 
stone,   commonly  called  printer's  stone. 

The  metallic  disc  is  connected  to  a  nega- 
tive source  of  saipply  of  105  volts  whilst  the 
stone  is  connected  by  a  copper  plate  (on 
v/hich  it  rests)  to  the  opposite  pole  of  the 
supply. 

Under  these  conditions,  it  can  be  shown 
by  a  balance  system  of  suspension  that  the 


MAY  25,  1923. 


THE  CHEMICAL  NEWS. 


333 


electrostatic  stress  is  capable  of  supporting 
a  considerable  weigat. 

If  the  smooth  surface  of  the  stone  is 
covered  with  a  thin  film  of  lubricating  oil, 
and  the  potential  difference  applied  as  be- 
fore, a  decrease  in  the  electrostatic  pull  is 
observed;  this  pull  varies  with  different 
oils. 

Sir  Richard  Paget,  Bart.,  gave  a  de- 
monstration on  The  Nature  and  Reproduc- 
tion of  Vowel  Sounds.  Mr.  Walter  Heape. 
F.R.S.,  also  gave  a  demonstration  on 
Cinematograph  Exhibition.  A  series  of 
films,  the  photographs  of  which  were  taken 
at  rates  varying  from  2,000  to  3.000  per 
second. 


THE  ROYAL  SOCIETY. 
Thursday,  May  17. 
Papers  read :  — 

A.  E.  H.  Tutton,  F.R.S.  (1)  A  Univtr 
aal  Interferometer.  (2)  A  Wave-length  Tor- 
aometer,  and  its  Use  with  the  Universal  In- 
terferometer. 

(1)  The  instrument  is  an  interferomet^^r  of 
general  application,  for  the  nieasnremont 
of  very  short  distances,  small  deformationv; 
or  changes  of  dimensions,  or  minuti 
amounts  of  motion,  by  the  interferonco- 
band  scale  of  half  wave-lengths  of  light.  Tf 
was  suggested  by  the  success  attained  with 
the  comparator  for  standards  of  length,  de- 
signed for  the  Standards  Department  of  the 
Board  of  Trade,  and  described  to  the  Roval 
Society  in  1009. 

Its  essential  feature  is  a  travelling  micro 
scope  driven  by  a  specially  constructed  finr 
screw  along  a  very  tr\ie  V-nnd-pIane  guid- 
ing bed,  so  steadily  that  one  of  the  two 
^Inss  reflecting  surfaces  concerned  in  (pro- 
ducing the  interfering  monochromatie 
light  rays  is  actually  carried  rigidly  with  it. 
so  that  the  amount  of  its  motion  i< 
measured  directly  in  interference  bnnd«. 
The  microscope  and  its  moimtings.  th*^ 
large  driving  wheel  which  works  tho  {\r\r 
screw  by  means  of  a  connoctine  flexible 
shaft,  endless  screw  and  worm-wheel,  a'o 
similar  to  the  pair  of  microscopes  carried  bv 
the  standards  comparator,  btit  the  one 
microscope  is  more  conveniently  arranged 
for  the  special  purpose  in  view,  and  has 
several  minor  improvements,  includinnr  hot- 
ter    rRsohition    of    Grayson -ruling    fiducial 


marks,  combined  with  greater  w'orking  dis- 
tance, and  more  convenient  lighting  of  these 
40,000  to  the  inch  rulings. 

The  interference  aipparatus  is  practically 
identical  with  that  of  the  coiuiparator,  con- 
sisting of  the  same  type  of  autocollimating 
telescope  with  micrometer  eyepiece,  and 
vacuum  tube  on  the  elbow  tube,  a  constant 
deviation  prism  for  the  selection  of  the 
monochrocatio  radiation  to  be  used,  and 
large  truly  worked  glass  interference  discs. 
The  telescope  is  mounted  to  the  right,  and 
the  driving  wheel  to  the  left,  and  the  30- 
inch  long  V-and-plane  bed,  in  its  rigid  carry- 
ing plinth-bed,  is  supported  on  pillars  at 
the  Airy  positions  for  no  flexure,  the  whole 
being  counted  on  a  heavy  solid  rectangular 
base.  The  large  middle  space  on  the  latter, 
and  that  underneath  the  arch,  are  available 
for  the  accommodation  of  whatever  object, 
or  apparatus  carrying  the  object  and  pos- 
sibly causing  its  motion,  is  brought  to 
measurement.  A  large  circular  work-table, 
provided  with  every  possible  requirement  of 
adjustment,  is  suipplied  in  this  clear  middle 
space,  for  the  convenience  of  the  support  of 
the  object  or  its  manipulating  apparatus. 

(2)  This  \&  a  refinement    of  the  Voigt  in- 
strument fw  determining  the  torsion    con- 
stants of  miniature    bars    of    crystals    and 
other  small  bodies.       The    essential    differ- 
ence is  that  the  two  optical  levers  of  Voigt 
are  replaced  by  radials  which  move  the  two 
sliders      carrying     Grayson-ruling      fiducial 
marks,  referred  to  in  the  preceding  commu- 
nication.    The  new  torsometer  Is  essentially 
comiposed  of  a  miniature  lathe-bed.    carry- 
ing   two    similar     but     mutually    reversed 
wheel-and-chuck    fittings,    the    chucks    for 
gripping    the    object    bar   ends,     and    the 
wheels,     which     move     solidly     with     the 
chucks,  for  delivering    the  force-couple    at 
one  end  and  holding    it  firmly  at  the  othor, 
the  two  ends  being  interchangeable,    either 
wheel  being  capable  of  lockinc:  fixation  or  of 
driving  by  a  power  band.     The  band  passes 
round  the  lower  half  of  that    pulley-wheel 
on  a  standard.     The  end  depending  from  in 
front  of  the  latter    terminates  in  a  loop  of 
the  cord-band,    into  which  the  hook  carried 
by  the  weight  can  be  allowed  slowly  to  fall, 
until  the  whole  weight  is  acting  in  twisting 
the  object  bar.    The  apparatus  of  Voigt  foi- 
bringing  the  weight    into  action  is  replaeod 
by  the  far  more  delicate    one  belonging  to 
the  elasmometer,   the  interference    appara- 
tus described  by  the  author  in  1004  for  de- 
termining Young's  modulus  by  the  bending 


334 


THE  CHEMICAL  NEWS. 


MAY  25,  1928. 


of  bars  or  plates.  The  weight  can  be  de- 
livered by  this  apparatus  by  either  a  coarse 
or  a  very  line  movement,  as  required  or  de- 
sired. 

When  in  use  the  torsometer  is  supported 
on  the  work-table  of  the  universal  inter- 
ferometer, described  in  the  preceding  com- 
munication, where  it  can  be  rigidlj^  clamiped 
and  delicately  adjusted,  so  that  the  two 
aluminium  radials  carried  by  the  object  bar 
near  its  two  ends,  just  clear  of  the  chuck- 
grippers,  are  in  contact  near  their  upper 
terminations  with  the  blunt  knife-edge  ends 
of  the  two  sliders.  The  table  adjustments 
permit  matters  to  be  aiTanged  so  that  the 
Grayson-ruling  signal  is  centred  under  the 
microscope  when  the  radial  under  observa- 
tion is  just  in  complete  contact  with  the 
sUder.  On  delivering  the  weight  and  effect- 
ing the  twist,  the  slide  and  signal  move, 
and  the  movement  is  followed  by  driving 
the  microscope  by  the  big  wheel  of  the  in- 
terferometer until  the  signal  mark  is  again 
centred,  the  number  of  interference  bands 
effecting  their  transit  the  while  being  care- 
fully counted. 

L.  N.  G.  FiLON,  F.E.S.,  and  F.  C.  Har- 
ris. On  the  Diphasic  Nature  of  Glass  as 
shown  by  Photo-elastic  Observations. 

A  block  of  Hint  glass  was  heated  to  about 
400°  C,  when  it  showed  some  signs  of 
softening;  it  was  then  allowed  to  cool  under 
longitudinal  pressure .  On  removing  the 
pressure  it  was  found  to  have  become  per- 
manently doubly-refracting.  The  residual 
stress  which  should  produce  the  observed 
amount  of  double-refraction  is  calculaterl 
by  a  new  method,  and  the  result  shows  that 
this  residual  stress  does  not  balance  accord- 
ing to  the  laws  of  statics.  It  is  deduced 
that  a  "crypto- stress"  exists,  which  does 
not  manifest  itself  Qptically. 

This  leads  to  the  conclusion  that  the  glass 
is  not  hoinogeneous,  but  behaves  as  a  mix- 
ture of  two  components  or  phases.  A  pos- 
sible interpretation  of  the  results  on  this 
hypothesis  is  put  forward. 

Papers  read  in  title  only  :  — 

C.  E.  Inglis.  Stress  Distribution  in  a 
Rectangular  Plate  having  Two  Opposing 
Edges  sheared  in  Opposite  Directions. 
Communicated  by  Prof.  E.  G.  Coker 
F.R.S. 

The  type  of  deformation  dealt  with  in  this 
paper  may  be  termed  a  pure  mechanical 
shear,  in  contradistinction  to  pure  shear  as 


usually  understood  in  stress  analysis.     The 
deformation  is  produced  as  follows: 

Imagine  a  thin  rectangular  plate  bounded 
by  two  horizontal  lines  AB  CD  and  two 
vertical  lines  AD  BC.  The  two  horizontal 
edges  while  remaining  straight  and  un- 
changed in  length  and  in  distance  from  one 
another  are  displaced  longitudinally  in 
opposite  directions,  the  vertical  edges  being 
kept  free  from  applied  stress.  The  plate 
being  thin,  the  distribution  of  stress  conse- 
quent on  this  deformation  is  regarded  as 
two-dimensional  and  the  stress  components 
are  obtained  via  solutions'  of  V  *  V  =  0. 
Two  different  sets  of  functions  satisfying 
this  equation  are  evolved,  and  by  methods 
of  Harmonic  Analysis  they  are  combined  to 
satisfy  the  prescribed  boundary  conditions 
to  a  high  degree  of  approximation. 

Particular  attention  is  given  to  the  stress 
distribution  along  the  horizontal  centre 
line.  This  stress  starting  from  Zero  at  the 
free  edge  mounts  up  rapidly,  and  for  a  plate 
in  which  the  length  is  considerable  com- 
pared with  the  depth,  the  stress  soon  as- 
sumes a  constant  value ;  but  before  doing 
so,  it  overshoots  this  value,  and  the  curve 
of  stress  distribution  in  consequence  de- 
velops humps  near  the  free  vertical  edges. 
If  the  length — breadth  ratio  of  the  plate  is 
2  to  1  these  humps  combine  to  give  a  flat- 
topped  curve.  If  the  plate  is  square  the 
coincidence  of  the  humps  makes  the  curve 
approximate  to  a  parabola. 

These  characteristics  were  first  brought 
to  light  by  Prof.  Coker,  who  examined  this 
particular  stress  distribution  by  Optical 
methods.  The  results  obtained  in  this 
paper  are  in  close  agreement  with  his  deter- 
minations. This  investigation  reveals  the 
existence  of  large  stresses  at  the  corners  of 
the  plate,  a  state  of  affairs  confirmed  bv 
reference  to  Prof.  Coker's  original  coloured 
photographs. 

T.  H.  Havelock,  F.B.S.  Studies  in 
Wave  Resistance — Influence  of  ihe  Form 
of  the  Water-plane  Section  of  the  Ship. 

In  these  calculations  the  ship  is  repre- 
sented bv  a  vertical  post  of  infinite  donth 
whose  horizontal  section  is  similar  to  the 
water-plane  section  of  a  sTTip.  Exinressions 
for  the  wave  resistance  are  developed  and 
are  evaluated  in  terms  of  Bessel  and  Rtmve 
fnnctinns  of  which  tnbles  are  nvnilahlo.  Tho 
level  lines  of  the  model  are  varied  whilp  thp 
displacement  is  kept  constant;  and  in  thic 
manner    a  comparative    s^udy    is  made    nf 


MAY  25,  1923. 


THE  CHEMICAL  NEWS. 


335 


such  problems  in  ship  resistance  as  the 
effect  of  finer  lines  and  greater  beam,  and 
of  the  difference  between  straight  and  hol- 
low lines.  Numerical  calculations  are 
made  for  four  models,  and  the  results  are 
shown  graphically  and  analysed  in  relation 
to  exiperimental  data. 

W.  M.  H.  Greaves.  On  a  certain  Fam- 
ily of  Periodic  Solutions  of  Differential 
Equations,  with  an  Application  to  the 
Triode  OsciUalor.  Communicated  by  Prof. 
H.  F.  Baker,  F.R.S. 

An  application  is'  made  to  the  equation 
of  Applefcon  and  Van  der  Pol  for  the  Triodo 
oscillator.  It  is  shown  that  this  equation 
can  be  reduced  to  a  particular  case  of  the 
above  equations,  and  that  the  series  for  the 
periodic  solutions  which  were  obtfuned  in  a 
purely  formal  manner  by  Dr.  Appleton  and 
the  writer  in  a  recent  issue  of  the  Philoso- 
phical Magazine  are  cMivergent  for  suffi- 
ciently small  valuer  of  some  of  the  quanti- 
ties involved. 


ROYAL    INSTITUTION. 

On  Tuesday,  May  22,  Professor  Fltx- 
DRRS  Prtrie  began  a  course  of  three  lor- 
tures  at  the  Royal  Instittition,  on  DIr 
coveries  in  Egypt;  on  Thursday,  May  31. 
Sir  William  Bayliss  will  deliver  the  fir^st 
of  two  lectures  on  The  Nature  of  Enzyme 
Action;  and  on  Saturday,  .Tune  2.  Dr.  A. 
W.  Hill  the  first  of  two  on  The  Veqetatwn 
of  the  Anden  and  the  New  Zealand  Flora. 

The  PVidav  evening  discourse  on  May 
25  will  be  given  by  Sir  Aston  Webb  on  The 
Development  of  London,  and  on  Juno  1  Rv 
Professor  H.  A.  Lorentz  on  The  Tlndin- 
tion  of  TJfjht,  and  on  Tune  R  by  Mis.s  Joan 
PjVANS  on  Jeu^eh  of  the  Renaissance. 


THE  CHEMICAL  SOCIETY  OF  JAPAN. 
Papers  communicated  :  — 

The  Influence  of  the  Temperature  upon 
the  Action  of  Tnvertase.  and  a  Theorif  on  the 
"Mechanism  of  the  Action  of  Invertasr,  bv 
Br^NSTTKi  Suzuki. 

Chemical  Investigation  on  Japanese 
Minerals  containing  Rarer  Elements.  Pari 
Y.  Analysis  of  Beryl  from  Tshilfairn. 
Jwahi,  by  Taku  Uykmura. 


On  the  Preparation  of  fi-Oxymethylamine 
and  its  Salts,  by  Sin-iti  Kawai. 

The  Constitution  of  Pyrethronic  Acid,  by 
Kvo  Yamamoto. 


NOTICES  OF  BOOKS. 
Practical  Chemistry,    by  E.  J.  Holm- 
yard,  B.A.     Pp.  XVI.  +  267.     London: 
G.  Bell  &  Sons,    Ltd.,    Portugal  Street, 
W.C.     1923.     Price  48.  net. 
The  author    has  divided    his    laboratory 
textbook    in    two    parts.      The    elementary 
portion  includes  a  wide  range  of  simple  and 
very     suitable     experiments,       introducing 
young  students  to  chemical  principles  and 
laws.      These  experiments  have    evidently 
been  so  chosen  that  general  chemical  mani- 
pulation   and  different  types  of    operations 
will    all    be    carried    out    in  the    practical 
study    of  such  matt<^rs    as  the  simple  laws, 
equivalence,     the     common     gases,'    acids, 
bases  and  salts. 

The  second  part  contains  sections  on 
more  advanced  experiments  in  inorganic 
chemistry,  such  as  the  more  diflfioult  pre- 
parations, and  the  general  reactions  of  the 
motsls.  There  is  a  lengthy  section  on 
Volumetirio  Analysis.  ;ind  n  few  gravimetric 
exercises  are  given. 

An  excellent  feature  of  this  practical 
volume,  primarily  intended  for  use  in 
schools,  is  the  inclusion  of  n  series  of  ex- 
periments in  Physical  Chemistry.  These, 
like  the  others,  and  the  twenty  or  so  Or- 
ganic Preparations  given  in  the  final  sec- 
tion, are  (described  with  adequate  detail,  so 
that  the  students  may  be  largely  left  to 
themselves  to  arrange  the  apnarattis  and 
conduct  the  experiments  with  the  minimum 
of  help. 

However  j?ood  a  Inboratorv  manual  mnv 
be,  it  cannol  completely  supersede  personal 
supervision  in  practical  work,  btit  Mr. 
Holm  yard's  textbook  should  prove  of  the 
greatest  value  in  the  teaching  of  nractienl 
chemistrv.  J.G.F.D. 


BOOKS  RECEIVED. 
Qualitative  Organic  Analysis :  An  Ele- 
mentary Course  in  the  Identification  of  Or- 
qanic  Compounds,  by  Oliver  Kamm.  Pp. 
VII.  +  260.  First  Edition.  1923.  Tion- 
don  :  Messrs.  Chapman  k  Hall.  Ltd.,  11. 
Henrietta  Street,  Covent  Onrden,  W.C. 2. 
12s.  6d.  net. 


336 


THE  CHEMICAL  NEWS. 


MAY  25,  1923. 


The  Phase  Rule  and  the  Study  of  Hetero- 
geneous Equilibria:  An  Introductory  Study, 
by  A.  C.  D.  KivETT,  M.A.,  B.Sc.  (Oxon.), 
D.Sc.  (Melb.).  Pp.  204.  1923.  Oxford: 
The  Clarendon  Press.     10s.  6d.  net. 

The  Chemistry  of  the  Inorganic  Complex 
Com'pounds :  An  Introduction  to  Werner's 
Co-ordination  Theory,  by  Dr.  Robert 
ScHWARZ.  Authorised  Translation  by  Law- 
rence W.  Bass,  Ph.D.  Pp.  X.  +  82.  1923. 
London:  Messrs.  Chapman  S;  Hall,  Ltd., 
11,  Henrietta  Street,  Covent  Garden, 
W.C.2.     8s.  6d.  net. 


The  U.S.  Deipt.  of  Agriculture  have  just 
issued  a  bulletin.  No.  1,146,  The  Infltience 
of  Copper  Sprays  on  the  Yield  and  Compo- 
sition of  Irish  Potato  Tubers,  by  F.  C. 
Cook, 

Tubers  from  copper-sprayed  potato  plants 
at  the  time  they  were  large  enough  for  ana- 
lysis, usually  contained  more  solids,  starch, 
and  nitrogen  than  the  tubers  from  un- 
sprayed  vines.  The  starch  content  increased 
approximately  50  per  cent,  as  the  tubers 
matured,  while  dextrose  disappeared  and 
sucrose  was  materially  reduced.  Early 
varieties  of  potatoes  showed  a  decrease  in 
their  sugar  content  accompanying,  an  in- 
creased starch  content  in  the  copper-sprayed 
tubers  during  the  early  stages  of  develop- 
ment. The  proportion  of  insoluble  ash  de- 
creased during  the  growth  of  the  tubers,  al- 
though the  total  ash  content  remained  con- 
stant. Total  nitrogen  increased.  The 
figures  for  soluble,  coagulable,  and  particu- 
larly the  monoamino  and  amide  nitrogen  in- 
creased as  the  tubers  matured. 

The  proportion  of  tubers  to  green  vines 
appeared  to  be  higher  for  the  copper- 
sprayed  than  for  the  unsprayed  plants. 

Average  data  for  seven  States  in  1919 
showed  the  food  value  of  an  acre  of  copper- 
sprayed  potatoes  to  be  839  pounds  more 
than  that  for  an  acre  of  non copper-sprayed 
potatoes.  Two  factors,  increased  yield  (48 
bushels  an  acre)  and  an  increase  of  solids 
(5.6  per  cent.),  are  involved. 

Tubers  from  several  varieties  of  potatoes 
from  a  northern  State  were  higher  in  solids 
than  tubers  of  the  same  varieties  grown  in 
a  southern  State. 

A  larger  yield  of  potatoes  was  secured 
from  copper-sprayed  than  from  cheeky  or 
noncopper-sprayed  vines.  Late  bliofht 
(Phytophthora  infestans)  is  eliminated  as  a 
necessary  factor  in  the  case. 

When  a  lime  spray  containing  no  copper 
was    used  on    one  occasion,    the    yields    of 


tubers  were  decreased.  Pickering- lime- 
-water spray  and  a  barium-water  spray  gave 
practically  the  same  increase  in  yield  and 
in  solids  of  the  tubers  as  a  Bordeaux  spray. 
The  copper  in  the  spray  seems  to  be  the 
essential  factor. 


The  Forty-seventh  Annual  Report  of 
H.M.  Inspectors  of  Explosives  (1922)  has 
been  issued  for  the  Home  Office  by  H.M. 
Stationery  Office,  Price  6d.     Pp.  36. 

This  report  deals  with  matters  arising  out 
of  the  oiperation  of  the  Explosives  Act, 
1875.  These  include  Inspection,  Accidents, 
Accounts,  and  comments  on  Accidents 
abroad.  Experiments,  Use  of  Explosives  in 
Coal  Mines,  Petroleum  and  Carbide  of  Cal- 
cium. An  appendix  classifies  the  accidents 
for  the  period. 


xHis  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chanoe-y  Lane.  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  cnn  be  obtained  gratuitously. 

Latest   Patent   Applications. 
11003 — Agricultural    Developments    Co.    (Pyrford), 
Ltd. — Manufacture   of   nitrogenous     fertili- 
sers.   April  23. 
11082 — Borchers,  W. — Process     for  refining    crude 

chromium  alloys.     April  24. 
11389 — Borchers,   W. — Ferrous  alloys.     April   27. 
11110 — Carbide  &  Carbon  Chemicals     Corporation. 

— Process  of  oxidising  dibenzyl.     April  24. 
11000 — Cbristensen,     C.   P. — Manufacture     of     cal- 
careous and  nitrogenous  fertilisers.     April 
23. 
11526— Evans,  E.  V. — Treating  gases  for  removing 
carbon   disulphide.      April    28. 
Specifications   Published   this    Week. 
195998 — Bnchner,  Dr.  M. — Production  of  pure  alu- 
mina. 
198002    dimming,     A.  C,     and  Klarit.     Ltd.-De- 
colorisation   and  clarification  of  fnts,   oils, 
sugars,  and  other  liquids,     and  adsorptive 
materials  for  use  therein. 
196012— Vielle,  J.  A. — Process  for  the  manufacture 
of  insecticidal  and  fungicidal  preparations. 
196115  -Pli ill ipson,   G.   A. — Process   and    apparatus 
for    drying   and      neutralising   sulphate    of 
anjmonia. 

Abstract  Published  this  Week. 
1942/)8 — Phosphatic   fertilisers. — Soe.      Anon.     Pro- 
ducts Chimiques  et  Engrais  L.,     Bernard. 
Mesvin,   Cipley,   Belgium. 
Calcium  phosphate. — A   fertiliser  is  obtained  by 
heating  together     a  homogeneous     mixture  of     a 
phosphate   rook,     blast-furnace   slag     or   feldspar, 
and  bye-products  containing  alkalies  such  a«  resi- 
dues   from  sugar  mills    or  distilleries,     or     wool 
grease.      The  residue  containing  alkalies  may  be 
employed  as  such     or  may  be  first  calcined     and 
ground.      The  mixture  of  the  materials     may  be 
effected     wet  or  dry  and    the  heating  may    be  at 

^f^^-r,3m°  c. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  Specifications,  and  forward  on 
poet  free  for  the  price  of  Is.  6d.  each. 


JUNE  1.  1923. 


THE  CHEMICAL  NEWS. 


33'; 


THE  CHEMICAL  NEWS, 

VOL.  CXXVI.       No.  3294. 


AN  EXPLANATION  OF  THE  THEORY 

OF  THE  ROTATION  OF  THE  ATOMIC 

NUCLEUS. 

Part  II. 

By  Herbert  Hen  stock. 

{Continued  from  Page  325.) 

Carbon  has  been  included  in  order  not  to 
spoil  the  sequence  of  the  elomonts,  but  it  is 
proposed  to  discuss  organic  iproblcms 
separately. 

The  case  of  stannous  chloride  is  also  post- 
poned until  those  cases  where  distortion  of 
the  octet  is  considered. 

(7roup  V. 

General  types,  as  NHj,  PH,,  AsH,,  etc., 
Fig.  13. 


0^ 


Fc'j  13. 


In  these  compounds  the  stability  de- 
creases with  increase  of  atomic  weight,  that 
is  to  say,  the  negative  bonds  are  weakened 
or  the  octet  electrons  arc  not  so  strongly 
held  by  reason  of  the  successive  layers  of 
inner  electrons.  One  result  of  this  is  that 
the  negative  bond  a-b  (Fig.  13)  in  nitrogen 
is  stronger  than  those  in  phosphorus  or  ar- 
senic, with  the  consequence  tbat  nitrogen  is 
more  l)asic  iind  so  will  form  more  stable 
compounds  liy  means  of  that  bond. 

Such  nitrogen  compounds  as  NH^Cl, 
NH^NOj,  etc.,  will  be  formed  on  the  f^enr- 
ral  equation  expressed  in  Fig.  14. 


ri^  /« 


The  electrolyte  HCl  unites  with  ammonia 
by  the  negative  bond  a  -  b :  the  nitrogen  in 
ammonia  is  negative  in  alternate  polarity 
and  is  trivalent.  It  is  a  general  rule,  put 
forward  by  Lowry  (lecture  before  the  Fara- 
day Society,  Nov.  20,  1922),  and  also  by 
Sidgwick  (lecture  before  the  Cheniical  So- 
ciety, March  1,  1023),  that  when  an  atom 
shares  two  electrons  with  another,  both 
electrons  being  supplied  by  one  atom,  then 
that  atom  acquires  a  positive  charge;  that 
is  to  say  it  loses  part  of  its  octet ,  and  so  the 
nucleus  gains  more  power  over  the  re- 
mainder. The  atom  which  supplies  no 
electrons  acquires  a  negative  charge,  due  to 
the  extra  electrons  in  its  octet.  This  means 
that  each  atom  slightly  alters  its  pemianent 
polarity,  and  this  acts  upon  the  nucleus  of 
each  and  revolves  it,  making  the  alternate 
polarities  chan;?!"  their  signs.  The  consti- 
tution of  ammonium  chloride  will  then  be 
represented  bv  Fig.  16. 

K3\ 


Tl^JS^ 


338 


THE  CHEMICAL  NEWS. 


JUN 


1Q9,a 


The  key  atom  is  the  nitrogen,  and  the  un- 
doubted cause  of  its  being  so  is  the  partial 
loss  of  the  two  electrons  of  the  bond  a-b, 
which  slightly  alters  the  permanent  polar- 
ity causing  the  nucleus  to  revolve  and  the 
valency  of  the  nitrogen  to  be  raised.  The 
bond  a-b  becomes  positive  and  so  also  do 
those  bonds  uniting  the  three  hydrogen 
atoms  of  the  ammonia,  whose  nuclei  re- 
volve, making  them  negative  in  alternate 
polarity  only :  the  nucleus  of  the  fourt.h 
hydrogen  atom  also  revolves,  and  it  be- 
comes negative,  but  in  permanent  as  well 
as  alternate  polarity,  hence  the  difference 
between  the  action  of  this  and  the  other 
three.  This  fourth  hydrogen  atom  unites 
with  the  chlorine,  in  the  electrovalenoe 
bond,  by  one  of  its  ipositive  edges,  but  since 
it  is  united  to  the  nitrogen  by  a  normal  edqo 
therefore  this  union  is  stronger  than  the 
electrovalence  bond,  so  that  the  A^hole  of 
the  NH^  isi  a  fairly  stable  entity  and  can  act 
as  a  group. 

Ammonium  hydroxide  will  be  repre- 
sented by  Fig.  16. 


H 

H 
h 


N 


H 

5 
I 

H  + 


'CUCCAA) 


V, 


oJjl/^ 


au 


the  extreme  instability  of  which  is  apparent. 


The  fact  that  ammonium  hydroxide  is 
not  so  strong  a  base  as  the  alkali  metal  hy- 
droxides is  due  to  the  intervening  fourth 
hydrogen  atom  with  its  inherent  weakness 
where  positive  and  negative  edges  both 
come  into  play  (see  rule  2).  Organic  tetra 
alkyl  ammonium  bases  are  as  strong  as  the 
metallic  alkalis,  but  the  very  simple  ex- 
planation of  this  will  be  included  amongst 
the  organic  comipounds. 

Those  hydrides  of  the  types  NH2-NH2  or 
PH., -PH,  will  have  the  general  formula  ns 
in  Fig.  17. 


+  H, 

H  \ 


1^ 

jv     /     TV 

f 
A 

A 

—  jj 

i 

t-1 — 

^oT- 

^ 
+. 

\qI' 

^ 

I 

.  '■*- 

% 

9 

^H 

f:<^j7- 


In  hydrazine  the  positive  nitrogen  atom 
is  united  to  hydrogen  by  negative  edges, 
which  makes  the  molecule  unstable  (rule  2) 
and  accounts  for  this  com^pound  being  less 
stable  than  those  of  the  NH3  type. 

The  positive  nitrogen  atom  is  an  example 
of  how  one  cannot  strictly  label  all  atoms 
completely  positive  or  negative.     In  writing 


H 
H 


N  - 


N  r  + 


\ 


H 


the  facts  are  not  properly  expressed,  for  no 
wholly  positive  or  wholly  negative  bonds 
ever  unite  two  atoms,  their  alternate  polari- 
ties must  be  opposite.  A  more  explicit 
method  would  be  to  label  the  second  nitro- 
gen thus — 


+  - 
-N 


which  woul3"  show  where 
the  molecule  lay. 


-t- 
H 

H 


the  weakness  of 


The  iphosphonis  hydride  PjaHo  will 
be  found  to  have  the  following  con- 
stitution, if  it  be  worked  out  in  a  simi- 
lar fashion  to  those  already  .  shown  for 
boron.  It  is  a  ring  containing  three  double 
bonds,  in  which  the  phosphorus  is  tri  val- 
ent.     Thus:  — 


JUNE  1.  1923. 


THE  CHEMICAL  NEWS. 


339 


^ 

P- 


H 


H 

P 


\ 


P 


=  P 


7n\ 

+  ? 

~PH 
+    / 
P 

H 


^"'^^ 


/«-• 


The  general    tyipes,    NCI3,    PC1„    AsCl„ 
etc.,  are  represented:  — 


r/^./9. 


The  chlorine,  bromine,  etc.,  are  united  to 
positive  bonds,  but  nitrogen  is  an  element 
fairly  strong  in  negative  permanent  polarity 
and  it  is  only  in  those  compounds  where  the 
electrons  of  the  bond  a-b  (Fig.  13)  are 
shared  with  another  element  that  it  be- 
come*; positiv*'  and  basic,  hence  when  this 
bond  is  unoccuipied  the  nitrogen  atom  tends 
to  unite  along  negative  edges  (as  in  ammo- 
nia, Fig.  13),  in  order  to  form  stable  com- 
pounds. In  the  case  of  these  halogen  cotn- 
ipounds  this  tendency  is  not  fulfilled,  which 
accounts  for  the  extreme  instabilitv  o! 
\CI,,  etc. 

Mono  chlor  amide  will  have  the  oonstitu- 


iion- 


-I- 
H 
+ 
H 


N-ci 


where  the  nitrogen    is  imited    by    negative 


edges  to  the  hydrogen  and  by  a  positive 
edge  to  the  chlorine  :  the  molecule  is  there- 
fore unstable  (rule  2). 

The  general  types,  PCI5,  AsClg,    may  be 
constituted  as  s*hown  in  Fig.  20. 
a 


The  two  chlorine  atoms  in  the  rings  sure 
the  two  extra  ones,  and  they  may  unite 
with  the  i>ositive  bonds  a-b  and  b-c,  but 
both  of  them  will  be  weak  because  there 
will  be  two  electrons  at  each  of  two  cor- 
ners (rule  6).  These  two  bonds  are  the  only 
two  spare  positive  ones,  each  of  the  others 
has  one  of  its  electrons  already  shared  with 
another  chlwine  atom.  In  this  case  the 
nucleus  of  the  phoeiphorus  atom  will  not  re- 
volve since  two  electrons  are  supplied  by 
the  two  extra  chlorine  atoms. 

Holrovd  (Chemistry  and  Industry  Re- 
rictr,  l'023,  XLII.,  348)  suggests  that 
phosphorus  penta  chloride  should  be  con- 
stituted in  an  analogous  fashion  to  ammo- 
nium chloride  and  should  be  an  electrolyte : 
he  proposes  to  carry  out  ex4)eriments  to 
verify  this,  and  should  his  surmise  prove 
correct.  PCI,  will  be  ropresented  by  Fig.  21. 


Cn^u/^AAfXJt, 


cLU 


l/VXJt. 


TcQ,2f. 


340 


THE  CHEMICAL  NEWS. 


JUNE  1.  1923. 


It  will  be  interesting  to  see  which  formu- 
la the  results  of  these  egperiments  will  sub- 
stantiate. 


Hydroxyl amine   will 
tion  shown  in  Fig.  22. 

have 

the     con 

^ 

4 

\,  /. 

f 

H  > 

> 

C 

? 

'  \ 

w 

11, 


Rule  2  makes  this  an  unstable  com- 
pound :  it  decomposes  at  about  15°.  Ac- 
cording to  this  formula  the  hydroxylamates 
are  formed  with  bases.  The  oxonium  salts 
will  be  constituted  similarly  to  the  am- 
monium salts,  but  with  the  OH  group  still 
attached  to  the  nitrogen.  The  bond  a-h 
(Fig.  22)  will  act  with  acids  exactly  as  that 
already  described  for  ammonia  (Figs.  14 
and  16).  The  oxygen  of  the  OH  grouip  may 
form  a  double  bond  with  the  nitrogen  and 
the  hydrogen  go  on  to  the  nitrogen,  but  this 
oxygen  atom  would  not  come  into  the  bond 
a-b  (Fig.  22)  uniting  the  group  to  an  acid, 
so  that  quadrivalent  oxygen  does  not  come 
into  the  question. 

Group  VI. 

General  types,  HjO,  HjS,  are  shown  in 
Fig.  23. 


F^glS. 


HjOj  and  HjSg    will    be  represented    by 
Fig.  24. 


In  the  positive  atom,  both  positive  and 
negative  bonds  come  into  play  (rules  1  and 
2),  which  accounts  for  the  instability  of  the 
molecules'.  The  remainder  of  the  polysul- 
phides  of  hydrogen  may  be  represented 
somewhat  similarly,  and  the  same  may  be 
said  f;>r  sulphur  chloride,  SoClj,  but  each 
chlorine  atom  will  be  united  to  a  p' sitive 
bond  in  both  atoms  of  sulphur. 

Group  VII. 

General  types,  HP,  HCl,  etc.,  see  Fig.  1. 

Group  VIII. 

General  types,  FeClg,  CoCla,  etc.,  will 
have  a  structure  similar  to  Fig.  4,  and 
types  FeClg,  C0CI3,  etc.,  similar  to  Fig.  6. 

One  difference  between  these  elements 
and  those  of  groups  II.  and  III,  is  that 
these  may  have  varying  numbers  of  elec- 
trons in  their  octets.  (See  Bury,  J.  Avier. 
Chem.  800.,  1921,  XLIII.,  1602).  This  fact 
makes  the  whole  group  very  complieat(^d  : 
each  series  of  compounds  of  this  group 
should  be  worked  out  seiparately. 

Chemical  Research   Laboratory, 
School  Gardens, 
Shrewsbury . 


GENERAL  NOTES. 


The  Department  of  Overseas  Trade  has 
issued  a  Report  on  the  Economic  and 
Financial  Conditions  in  Germany,  to 
March,  1923,  by  J.  W.  F.  Thelwall,  Com- 
mercial Secretary  to  H.M.  Embassy,  Ber- 
lin, assisted  by  C.  J.  Kavanagh,  Commer- 
cial   Secretary,     Oceuipied    Territory,    etc., 


JUNE  1,  1923. 


t^E  CfiEMICAL  NiiWS. 


641 


Col(^ne.  rp.  158.  Price  4s.,  or  jpost  free 
48.  2^d. 

The  report  contains  much  valuable  infor- 
mation regarding  the  internal  and  foreign 
trade  of  Germany  for  the  year  under  re- 
view. The  conditions  prevailing  in  the 
various  industries  are  given,  and  the  effect 
of  the  continued  occupation  of  the  Ruhr  is 
also  indicated. 

The  supplementary  statistics  occupy  17 
apipeudices. 


MARKET     FOK     SURGICAL     INSTRU- 
MENTS, NEEDLES,  AND  RUBBER 
GOODS  IN  SPAIN. 

Cajptain  U.  de  B.  Charles,  Commercial 
Secretary  at  Madrid,  reports  that  a  demand 
exists  in  Spain  for  surgical  instruments, 
needles  and  rubber  goods,  and  that  the 
moment  is  favourable  for  the  introduction 
of  British  made  articles.  German  manu- 
facturers have  hitherto  had  a  practical 
monopoly  of  the  trade,  but  the  surtax  on 
depreciated  currency,  which  increases  the 
duty  by  about  80  per  cent.,  together  with 
the  high  prices  fixed  in  pesetas,  make  sales 
almost  iiii|K  ssible,  and  supplies  from  Ger- 
many are  now  running  short. 

Opportunities  of  entering  the  Spanish 
market  will  be  greatly  enhanced  if  cwres- 
pondence  is  conducted  in  Spanish. 

The  Department  of  Overseas  Trade  will 
supply  British  firms  lists  of  likely  impor- 
ters and  dealers  in  these  articles. 

The  following  headings  of  the  Sipanish 
Customs  Tariff  relating  to  surgical  articles 
are  quoted  for  information : 

Articles  of  rubber  for  hygiene,  <M^hopaBdie 
or  medical  purposes,  without  admixture  of 
other  materials — 6  pesetas  per  kilog. 

Medical  and  surgical  apparatus  and  in- 
struments :  (1)  of  metal — 10  pesetas  iper 
kilog;  (2)  of  other  materials — 5  pesetas  per 
kilog. 

Orthopaedic  apparatus — 3  pesetas  per 
kilog. 

The  above  duties  are  quoted  in  gold 
pesetas.  When  the  amount  of  duties  is 
tendered  in  notes  of  the  Bank  of  Sipain  or 
Spanish  silver  coins,  a  surcharge  is  im- 
posed. This  varies  monthly,  and  for  May 
is  fixed  at  25.61  iper  cent. 


GERMANY'S  TRADE    AND  INDUSTRY 
IN  APRIL. 

Mr.  H.  N.  Sturrock,  the  Commercin! 
Secretary  at  Berlin,  has  forwarded  to  the 
Dept.  of    Overseas  Trade    a  report  on  Ger- 


man trade  and  indust'-v  durin?  April. 

There  has  been  no  important  chani::^  in 
the  economic  situation  during  April.  Busi- 
ness continued  quiet  in  the  first  half  of  the 
month.  On' the  18th,  however,  in  conse- 
quence of  the  renewed  fall  of  the  mark,  a 
small  revival  of  trade  took  place.  On  this 
day  the  Reichsbank  were  unable  any  longer 
to  hold  the  mark,  which  had  remained 
^  V  since  the  end  of  January. 
In  the  retail  trade,  disinclination  to  buy 
l)egan  gradually  to  disappear;  there  was 
oven  a  lively  demand  from  the  18th  to  the 
20th. 

In  occupied  territory,  the  French  suc- 
ceeded in  increasing  the  desipatch  of  coal 
and  coke.  The  quantities  transported  did 
not,  however,  amount  to  one-sixth  of  the 
deliveries  under  the  Reparations  pro- 
gramme. 

Mining. 
Coal. — The  pit-coal  production  in  Upper 
Silesia  proceeded  without  disturbance,  and 
is  estimated  at  about  760,000  tons.  The 
demand  for  Upper  Silesian  large  coke  con- 
tinued. The  large  iniipcMi*  of  British  ooal 
led  to  the  accumulation  of  stocks,  and  any 
palpable  improvement  on  the  coal  market 
cannot  be  expected  until  a  change  in  the 
general  situation  or  an  increase  in  exports 
takes  place.  Stagnation  also  occurred  in 
the  Central  German  brown  coal  district. 

Potash. — The  unfavourable  development 
of  market  conditions  continued.  There  was 
also  no  improvement  in  foreign  sales  of  pot- 
ash products. 

The  sales  of  chemical  bye-products  of 
the  potash  industry  improved  with  the  rise 
in  foreign  bills  towards  the  end  of  the 
month.  Bye-products  obtained  by  electro- 
chemical process  found  a  good  market  dur- 
ing the  whole  month,  particularly  abroad. 
Electro-Teciinical  Industry. 
In  the  electro- technical  industry  a  fur- 
ther decline  of  business  activity  was  re- 
corded. The  difficulties  in  the  way  of 
obtaining  ooal  and  semi-manufactures 
owing  to  the  occupation  of  the  Ruhr  were 
overcome,  but  delivery  contracts  were  de- 
layed by  transport  difficulties. 
Chemical  Industry. 
The  falling  off  in  the  demand  for  chemi- 
cal preparations  and  ceramic  chemicals, 
which  became  noticeable  immediately  after 
the  unexpected  rise  of  the  mark,  gave  place 
at  the  beginning  of  April  to  a  brief  revival. 
The  world's  market  price  has,  in  part,  been 
reached  and.  in  part,  exceeded.  In  parti- 
cular, German  prices  for  chemicals  are 
higher  than  those  of  America,  especially  as 


342 


THE  CHEMICAL  NEWS. 


JUNE  1.  1923. 


that  country,  unlike  Germany,  enjoys  very- 
favourable  Customs  treatment,  not  only  by 
Entente  countries,  but  also  by  Czecho- 
slovakia and  Poland.  It  is,  therefore,  ur- 
gently desired  that  the  exiport  duty  for 
laboratory  chemicals  and  ceramic  chemicals 
be  soon  still  further  reduced  in  view  of  the 
enormous  foreign  competition. 
Glass  Industry. 

In  the  sheet  glass  industry,  raw  material 
deliveries  were  satisfactory.  There  was 
scarcely  any  inland  demand,  and  exports 
decreased  by  a  third  as  compared  with 
March,  as  it  was  not  possible  to  compete 
with  Belgian  and  Czecho- Slovak  prices. 
The  Export  Association  of  German  Sheet 
Glass  Factories  have  issued  new  offers,  tak- 
ing into  consideration  the  reduction  of  the 
export  duty  to  1  ipcr  cent. 

In  the  hollow  glass  industry  the  supply 
of  raw  materials  and  coal  was  satisfactory. 
Owing  to  the  high  costs  of  production  in- 
land business  fell  off  considerably.  Eestric- 
tions  of  operations  occurred  on  a  large 
scale,  and  a  number  of  furnaces  were  iput 
out. 

Leather  Industry. 

Only  urgent  requirements  were  covered 
at  the  beginning  of  April.  Later,  as  in  the 
case  of  raw  hides  and  skins,  business 
improved. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 

Thursday,  May  31,  1923. 

Papers  read :  — 

E.  Griffiths,  D.Sc,  and  G.  W.  C. 
Kaye,  D.Sc. — The  Measurement  of  Ther- 
mal Conductivity,  No.  1.  Communicated 
by  Sir  Joseph  Petavel,  F.R.S. 

G.  W.  C.  Kaye,  D.Sc,  and  J.  K.  Rob- 
erts. —  The  Thermal  Conductivities  of 
Metal  Crystals.  I.  :  Bismuth.  Communi- 
cated by  Sir  Joseph  Petavel,  F.R.S. 

C.  V.  Drysdale  and  S.  Butterworth. — 
The  Distribution  of  the  Magnetic  Field  and 
return  Current  round  a  Submarine  Cable 
carrying  Alternating  Current.  Communi- 
cated by  F.  E.  Smith,  F.R.S. 


Sidney  Russ,  D.Sc— T7ie  Effect  of  X- 
rays  of  different  Wave-Lengths  upon  som,e 
Aniynal  Tissues.  Communicated  by  Prof. 
A.  W.  Porter,  F.R.S. 

Papers  read  in  title  only:  — 

E.  F.  Armstrong,  F.R.S.,  and  T.  P.  Hil- 
ditch,  D.Sc. — A  Study  of  Catalytic  Actions 
at  Solid  Surfaces.  Part  XL  :  The  Action  of 
Alainina  and  certain  other  Oxides  in  pro- 
moting the  Activity  of  Nickel  Catalyst. 

N.  K.  Adam. — The  Structure  of  Thin 
Films.  Part  IV.  :  Benzene  Derivatives.  A 
Condition  of  Stability  in  Monomole&idar 
Films.  Communicated  by  W.  B.  Hardy, 
Sec.  R.S. 

N.  K.    Adam.— T/ic    Structure     of     Thin 
Films.     Part  V.     Communicated  by  W.  B 
Hardy,  Sec.  R.S. 

W.  B.  RiMMER. — The  Spectrum  of  Am- 
monia. Communicated  by  Prof.  A.  Fowler, 
F.R.S. 


ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

The  Friday  evening  discourse  on  June  1, 
at  9  o'clock,  will  be  delivered  by  Prof.  H. 
A.  Lorentz,  Hon.  F.R.S.,  Hon.  M.R.I. , 
Haarlem  University.  The  subject  is  The 
Radiation  of  Light. 

On  Thursday,  May  31,  Sir  William  M. 
Bayliss,  LL.D.,  D.Sc,  F.R.S.,  gave  his 
first  lecture  on  The  Nature  of  Enzyme 
Action. 

On  Saturday,  June  2,  Arthur  W.  Hill, 
ScD.,  F.R.S.,  Director,  Royal  Botanic 
Gardens,  Kew,  will  lecture  on  The  Vegeta- 
tion of  the  Andes. 

On  Friday  evening,  June  15,  Sir  Ernest 
Rutherford  will  give  his  postponed  dis- 
course on  Life  History  of  an  Alpha  Particle 
of  Radium,  and  his  concluding  lecture  on 
Atomic  Projectiles  on  Saturday  afternoon, 
June  16. 


PHYSICAL  SOCIETY  OF  LONDON. 

A  meeting  was  held  on  Friday,  May  25, 
at  the  Imperial  College  of  Science,  South 
Kensington,  S.W. 


JUNE  1.  1923. 


THE  CHEMICAL  NEWS 


843 


The  following  papere  were  read:  — 

The  Effect  of  Torsion  pn  the  Thermal  and 
Electrical  Conductivities  of  Metals,  by 
Pkof.  C.  H.  Lees,  D.Sc,  F.R.S.,  and  J. 
E.  Calthrop,  B.A.,  B.Sc. 

The  Use  of  the  Wien  Bridge  for  the 
Measurement  of  the  Losses  in  Dielectrics  at 
High  Voltages,  with  Special  Reference  to 
Electric  Cables,  by  A.  Rosen,  B.Sc, 
A.M.I.E.E. 

A  Demonstration  of  an  "  Experiment  ou 
the  Production  of  an  Intermittent  Pressure 
by  Boiling  Water  "  was  shown  by  0.  R. 
Darling,  F.I.C,  F.Inst.P. 

A  Demonstration  of  "A  Novel  Instru- 
ment for  Recording  Wireless  Signals  "  was 
given  by  N.  W.  McLachlan,  D.Sc. 
M.I.E.E. 

Pbocbedings  at  the  Meeting  held  on  May 

11,  1923,  AT  the  Imperial  College  of 
Science,  Alexander  Russell,  M.A.,  D.Sc, 
IN  THE  (Jhaik.  ' 

The  Duddell  Medal. 

Sir  William  Bragg,  F.H.S.,  Chairman  of 
the  Duddell  Memorial  Committee,  handor? 
oyer  to  the  President  of  the  Physical  So- 
ciety a  copy  of  the  Memorial  Medal,  to- 
gether with  the  dies  and  n  certificate  for  the 
unexpended  balance  of  the  memorial  fund. 
In  the  cr)ur8e  of  his  remarks  Sir  William 
Jiragg  said  that  the  committee  had  been 
formed  in  response  to  a  widely  felt  wish 
that  the  work  of  this  distinguished  scientist 
should  be  commemorated  in  a  suitable 
manner.  \  sum  of  no  loss  than  £70()  had 
been  subscribed,  thanks  in  the  main  to  the 
energy  of  Mr.  R.  S.  Whipple,  secretary-  to 
the  committee.  As  regards  t^e  design  of 
the  medal,  very  great  pains  had  been  taken 
to  ensure  that  it  should  bo  worthy  of  the 
memory  of  the  dead  and  of  the  art  of  the 
nation  to  which  he  belonged.  The  work 
had  been  entrusted  to  Mrs.  Mary  Gillick, 
and  tho  oommittee  felt  that  their  choice 
had  been  very  fully  justified  by  the  result. 
Mrs.  Gillick  had  devoted  immense  trouble 
and  care  to  her  task,  and  the  medal  she  had 
produced  was  one  of  which  the  Society 
might  be  prrmd. 

Photo<,'rnphic  slides  of  the  medal  were  ex- 
hibilcrl.  On  the  obverse  is  a  miniature  of 
Mr.  Duddell;    and  on    the  reverse    a  figure 


symbolical  of  Science  examining  the  world 
as  she  finds  it,  with  legends  "  The  Physical 
Society  of  London  "  and  "Rerum  Naturavi 
Expandere." 

Dr.  Alexander  Russell,  President,  in 
accepting  the  medal  on  behalf  of  the 
Society,  said  that  he  did  so  with  gratitude 
to  all  who  had  combined  to  make  this 
memorial  possible,  and  particularly  to  Sir 
William  Bragg  and  Mr.  R.  S.  Whipple, 
whose  initiative  had  set  the  undertaking  on 
foot,  while  their  perseverance  had  carried 
it  to  such  a  successful  issue.  He  had  been 
associated  with  Mr.  Duddell  at  the  City  and 
Guilds  Technical  College  and  in  other  con- 
nections. He  ha<f  always  marvelled  at  the 
encyclopaedic  character  of  Mr.  Duddell's 
technical  knowledge,  which,  couipled  with 
his  mechanical  skill  and  inventive  ingenu- 
ity, had  enabled  him  to  make  so  many  con- 
tributions of  permanent  importance  to  the 
progress  of  science  and  of  industry.  He 
had  been  Treasurer,  Member  of  Council, 
ind  Vice-President  of  the  Physical  Society, 
and  President  of  the  Institute  of  Electrical 
Engineers. 

Sir  Richard  Glazebrook  said  that  it  gave 
him  great  pleasure  to  express  his  warm  and 
intense  admiration  for  Mr.  Duddell.  The 
latter  had  been  a  owdial  helper  of  the 
National  Physical  Laboratory,  especially 
during  the  war,  and  had  always  been  ready 
fo  give  generously  from  his  great  store  of 
Ijnowledge  and  of  scientific  resource.  His 
memwy  would  be  kept  alive  not  only  by  his 
own  work,  but  bjr  the  admirable  medal 
which  had  been  designed ;  and  it  was  to  be 
hoped  that  the  latter  would  encourage 
others  to  follow  his  examtple  and  to  engage 
in  the  field  of  .scientific  enterprise  in  which 
Duddell  had  been  such  a  prominent  worker. 
Terms  of  Awards  of  the  Duddell  Medal. 

The  following  resolution  was  adopted  by 
the  Council  on  May  11,  1923:  — 

Duddell  Memorial  Medal. 
Resolution.— Th&t  the  £400  War  Loan  5 
per  cent.  1929/47  Inscribed  Stock  be  ac- 
cepted in  trust  from  the  Duddell  Memorial 
Fund  Committee,  and  that  the  income 
therefrom  be  expended  in  accordance  with 
the  following  regulation:  — 

A  brotfze  medal  shall  bo  awarded  by  the 
Council  not  moro  frequently  than  once  a 
year  to  persons  who  have  contributed  to  the 
iidvancoment  of  knowledge  by  tho  inven- 
tion or  design  of  scientific  instruments  or 
by  the  discovery    of  materials  used  in  their 


344 


TME  CaEMlCAL  KliVViS. 


JUNE  i,  i923. 


oonstruction.  The  award  shall  be  made 
without  restriction  as  to  nationality^  or  Fel- 
lowship of  the  Society.  A  parchment  Cer- 
tificate of  Award  and  a  sum  of  money  may 
aooomjpany  the  medal. 

Should  more  than  one  person  be  con- 
nected with  the  invention  or  discovery  for 
which  the  award  is  made,  the  Council  may, 
at  its  discretion,  present  more  than  one 
medal  and  apportion  the  money  accord- 
ingly- 

The  terms  of  awards  shall  not  be  varied 
except  by  Sipeoial  Kesolution  passed  by  the 
Society  at  a  General  Meeting  and  confirmed 
at  a  subsequent  meeting. 

The  Eighth  Guthrie  Lecture  was  de- 
livered by  J.  H.  Jeans,  D.Sc,  LL.D., 
F.E.S,,  who  took  as  his  subject  The  Pre- 
sent Position  of  the  Radiation  Problem. 

Since  about  1900  it  has  been  obvious  that 
classical  dynamics    are  in  conflict    with  ex- 
perience in  certain  respects,     and    particu- 
larly with  respect  to  the  radiation  problem. 
The  observed  discrepancies  suggest  that  the 
laws  of  nature  must  in  some  way  be  discon- 
tinuous.    To  explain  the  observed  nature  of 
black-body    radiation    Planck    propounded 
the  quantum  theory;  in  the  hands  of  Bohr 
it  soon  became  apparent  that  the  quantum 
theory  contained    also  the  clue    to  the    line 
spectrum.     Hence  arose  hopes  of  rapid  de- 
velopment which  should    explain  the  whole 
of  the  radiation    problem  and  reduce  mole- 
cular physics  to  order.     Progress,  however, 
has  been  slow  and  difficult,    and  what  pro- 
gress there  has  been    is  concerned  with  the 
structure  of  matter  and  not  with  radiation. 
Einstein's  hypothesis    of  light  quanta  ap- 
peared to  possess  obvious  advantages,    but 
has  had  to  give  way    before  the  destructive 
criticism  of  Lorentz    and    others,    and    the 
direct  experimental  test  of  G.  I.  Taylor. 

The  different  methods  of  interchange  of 
energy  between  matter  and  ether  or  radia- 
tion may  be  classified  as  sub-atomic, 
atomic,  and  mass  transfers.  Typical  of  the 
first  is  the  emission  or  absorption  of  radia- 
tion by  a  Bohr  atom ;  of  the  second  the 
motion  constituting  heat  in  a  solid;  and  of 
the  third  the  transmission  of  momentum 
occurring  when  a  beam  of  radiation  falls 
upon  the  surface  of  a  perfect  reflector.  An 
examination  of  these  leads  to  a  consistent 
view,  namely,  that  physical  and  chemical 
transfers  take  place  by  quanta,  while 
mechanical  transfers  ta.ke  place  according 
to  the  classical  laws. 

As  an  example  of  the  application  of 
general  principles  to  a  special  problem,  the 


case  of  the  exchange  of  energy  between  a 
free  electron  e  and  a  field  of  radiation  X  may 
be  considered.  It  appears  probable  that  in 
such  a  field  the  mechanical  force  on  the 
electron  is  not  represented  by  the  expression 
eX.  The  interchange  of  energy  cannot  be 
covered  by  the  classical  laws ;  neither  can  it 
take  place  by  quanta.  It  thus  seems  prob- 
able that  no  exchange  of  energy  at  all  can 
occur  between  a  free  electron  and  a  field  of 
radiation.  A  conception  in  regard  to  this 
which  was  used  by  Einstein  in  1917  ap- 
pears difficult  to  interipret  except  on  the 
fiew  that  electric  forces  are  a  manifestation 
of  a  sub-universe  more  fine-grained  than 
anything  we  have  yet  imagined.  Many  pos- 
sibilities must  be  explored  before  we  are 
driven  to  believe  in  a  sub-universe  of  this 
kind. 

Discussion. 

Sir  Oliver  Lodge  said  he  shared  the  en- 
thusiastic admiration  which  the  audience 
had  manifested  for  the  lecturer's  work.  He 
would  seize  the  opportunity  of  asking  him 
one  or  two  questions,  and  particulai'ly,  how 
•  he  would  define  the  temperature  of  radia- 
tion in  a  vacuum.  As  regards  the  stability 
of  the  orbits  in  an  atom,  how  would  Dr. 
Jeans  view  the  suggestion  that  circular  or- 
bits, which  are  free  from  tangential  accele- 
ration, are  stable;  and  that  when  disturbed 
an  electron  spirals  down  to  a  successive  cir- 
cular orbit,  radiation  taking  place  since  now 
the  speed  is  varying?  Such  a  change 
would  be  of  finite  duration,  not  instan- 
taneous. 

Dr.  Jeans  replied  that  by  the  tempera- 
ture of  radiation  in  a  vacuum  he  meant  the 
temperature  of  matter  which  could  be  in 
equilibrium  with  space  containing  that 
radiation.  The  word  stability  denoted  a 
conception  that  had  been  left  behind  by  the 
quantum  theory,  which  only  thinks  of 
states.  The  notion  of  asymptotic  sipirals 
seems  open  to  the  fatal  objection  that  each 
circular  orbit  must  be  quitted  determinately 
for  the  nearest  orbit,  whereas  in  reality 
each  orbit  may  be  quitted  for  any  one  of  a 
number  of  possible  orbits.  The  passage 
from  orbit  to  orbit  may  be  supposed  to 
occupy  a  time  equal  to  some  1,000,000 
light  periods. 

A  hearty  vote  of  thanks    to  the    lecturer 
was  moved    by  Dr.  C.  Chree,    seconded  by 
the  Lord  Rayleigh,  and  carried  by  acclama- 
tion. 


JUNE  1,  19-26. 


THE  CHEMICAL  NEWS. 


345 


THE  OPTICAL  SOCIETY. 

A  meeting  of  the  Optical  Society  was  held 
at  the  Imperial  College,  Im^perial  Institute 
Koad,  on  Thursday,  24  May,  when  the  sixth 
of  the  series  of  lectures  deaUng  with  the 
evolution  and  development  of  optical  in- 
struments was  delivered.  It  was  entitled : 
Telescopes  before  the  early  part  of  the 
Sincteenth  Century,  and  the  lectui'er  was 
Mk.  David  Baxandall,  A.K.C.S. 

It  was  illustrated  by  exhibits  from  the 
collection  in  the  Science  Museum. 


THE  INSTITUTION  OF  MINING 
ENGINEEKS. 

NoTICii   AND    AgKNDA-PruGRAMME   OF 

Gknkkal  Mejsting,  at  Glasgow,  un 
June  12tu,  13tu,  and  14th,  1923. 

As  previously  announced,  the  seveuty- 
uiuth  general  meeting  ol  tj^ie  Institution  of 
Mining  Engineers  will  be  held  at  Glasgow, 
by  invitation  of  the  President  and  Council 
of  the  Mining  Institute  of  Scotland,  on 
Tuesday,  Wednesday,  and  Thursday,  June 
I2lh,  iOLU,  and  14tti,  1'j23. 

Tueuday,  June  12. 
General  meeting  at    the  Uoyal  Technical 
College,  George   btreet,   Glasgow,     by  kind 
permission  of  the  lioaid  of  Governors. 

The  following  pampers  will  be  read  (or 
taken  as  read)  and  submitted  for  discus- 
sion :  — 

Coal-duat  as  an  Explosive  Ayent  (with 
special  reference  to  the  experimental  work 
of  the  United  States  Bureau  of  Mines),  by 
George  S.  Kice. 

Summary  of  Kesearth  Work  carried  out 
fur  the  Committee  on  "The  Control  of  At- 
muspheric  Conditions  in  Hot  and  Deep 
Mines." 

The  Recent  Search  for  Oil  in  Great 
Britain,  by  H.  P.  Giffard,  M.A.,  B.Sc. 

.4  Volcano  in  the  Bathgate  Coalfield  of 
West  Lothian,  by  H.  M.  Cadbll,  B.Sc, 
F.H.S.E. 

The  Hurlet  Sequence  in  Renfrewshire  and 
Dumharfonnhire,  and  the  Evidence  of  the 
Basin  Structure  in  the  Coalfields  of  Scot- 
land, by  David  Ferguson. 


Excursions,  to  which  ladies  are  also  in- 
vited, fo  the  Royal  Technical  College, 
Messrs.  Mavor  &  Coulson's  Works,  and  the 
colheries  of  the  Fife  Coal  Co.,  have  also 
been  arranged. 


THE  INSTITUTION  OF  ELECTRICAL 

ENGINEERS. 

A  Wireless  Section  meeting    will  be  held 

on  Wednesday,  June  6,  when  a  lecture  en- 

litled    Wireless   Direction-Finding   in     Steel 

Ships  will  be  given  by  C.  E.  Horton. 

ROYAL  SOCIETY  OF  ARTS. 
On  Friday,  June  1,  at  4.30  p.m.,  there 
will  be  a  lecture  before  the  Indian  Section, 
entitled  The  Participation  of  India  and 
Burma  in  the  British  Empire  Exhibition, 
1U24,  by  Austin  Kendall,  I.C.S.,  retd.. 
Secretary,  Indian  Advisory  Committee. 
Sir  Charles  Campbell  McLeod,  Member, 
Board  of  the  British  Emipire  Exhibition, 
will  preside. 


THE  FARADAY  SOCIETY. 

The  Electronic  Theory  of  Valency. 

A  general  discussicm  on  the  above  subject 
is  being  arranged  by    the  Faraday  Society, 
to  be  held  at  Cambridge    on  July  13th  and 
14th  next.     Prof.  G.  N.  Lewis  will  open  the 
proceedings  on  the  Friday  afternoon  with  a 
general    Introductory  Address,    and  he  will 
ppobablv  be  followed  by  Mr.  R.  H.  Fowler, 
who    will  contribute    a  paiper    intended    to 
open    discussion    on  the    physical  and    in- 
organic side  of  the  subject.      Among  those 
expected    to  speak  are    Sir  J.J.  Thomson, 
who  will  be  in  the  chair,  Sir  Ernest  Ruther- 
f<M'd,    Sir  Wm.  Bragg,    and  Prof.    W.    L. 
Bragg.     The  Saturday  morning  session  will 
be    devoted  chiefly    to  applications    of  the 
theory  in  organic  chemistry.       Sir  Robert 
Robertson,   President  of  the   Society,     will 
(preside,  and  opening  papers  will  be  given  by 
Prof.  T.  M.  Lowry  and    Dr.    N.  V.    Sidg- 
wick.     Among  those  expected  to  speak  are 
Prof.  W.  A.  Noyes,  Sir  Wm.  Pope,  Prof.  A. 
Lapworth,  Prof.  I.  N.  Heilbron,  Dr.  W.  H. 
Mills.    Prof.  J.  F.  Thorpe,    and    Prof.    R. 
Robinson.     On    the  Friday  evening  a  com- 
plimentary   dinner  will    be  given    to  Profs. 
Lewis  and  Noye*;  and  other  guests,  at  Trin- 
ity Hall.     Arrangements  are  being  made  to 
accommodate   those  attending  the  meeting 
in  one  or  other  of  the  colleges,  and  it  will  be 
possible  to  include  a  limited  number  of  non- 
members  of  the  Society.       Particulars  may 
be  had  from    the  Secretary  of  the  Farnday 
Scxjiety,  10,  Essex  Street,  London,  W.C.2. 


346 


THE  CHEMICAL  NEWS. 


JUNE  1,  1923. 


THE    FARADAY    SOCIETY. 

General  Discussion  on  the  Physical 
Chemistry  of  the  Photographic  Process. 
At  the  meetings  on  Maj  28. 

2'he  Physical  Chemistry  of  the  Vehicle 
and  of  the  Emulsion,  by  T.  Slater  Price, 
O.B.E.,  D.Sc,  F.I.C. 

Of  the  substances  which  were  early  used 
in  making  photograiphic  emulsions,  gelatin 
and  the  silver  haloids  are  still  thos^  which 
give  the  best  results.  Even  at  the  present 
day  we  do  not  know  what  causes  the  sensi- 
tivity of  an  emulsion,  or  if  the  manufac- 
turer has  obtained  this  information,  he  has 
not  published  it.  If  the  same  gelatin  is 
sent  to  two  different  firms,  the  one  may  re- 
ject it  as  unsuitable  whilst  the  other  is  just 
as  likely  to  say  that  it  is  eminently  satisfac- 
tory. One  cannot  deduce  from  this  that  if 
the  acception  or  rejection  is  based  on  tests 
other  than  the  making  erf  an  emulsion,  the 
two  firms  have  come  to  different  conclu- 
sions as  to  the  causes  of  sensitivity,  since 
the  methods  used  in  making  emulsions  vary 
considerably. 

In  discussing  the  properties  of  gelatin  it 
may  be  of  advantage  to  contrast  them  with 
those  of  collodion,  the  other  medium  largely 
used  for  photographic  emulsions.  Collodion 
differs  from  gelatin  in  that  it  is  insoluble  in 
water,  a  mixture  of  alcohol  and  ether  being 
generally  used  as  the  solvent.  This  fact  at 
once  limits  its  applicability.  The  influence 
of  temperature  on  the  viscosity  is  also  very 
different  with  gelatin  and  collodion.  Gela- 
tin sols  have  the  advantage  that  at  the  tem- 
peratures at  which  emulsions  are  made  they 
are  quite  fluid,  whereas  at  lower  tempera- 
tures their  viscosity  increases  enormously 
and  at  ordinary  temperatures  they  set  to  a 
stiff  gel,  no  evaporation  of  the  solvent  being 
necessary  before  setting  takes  place.  Be- 
cause of  this,  as  soon  as  an  emulsion  has 
been  made,  it  can  be  "set"  quite  readily. 
In  addition  to  this  influence  of  the  hydrion 
concentration  there  is  also  the  effect  of  the 
degradation  products  which  arc  always  pre- 
sent in  gelatin.  Hitherto  no  suitable 
method  has  been  devised  of  estimating  the 
amount  and  effect  of  these  degradation  pro- 
ducts, but  it  may  be  mentioned  that  con- 
siderable progress  has  been  made  towards 
obtaining  a  gelatin  which  may  be  classed  as 
a  unitary  product. 

The  readiness  with  which  a  gelatin  gel 
swells  in  water  is  an  important  factor,  both 
in  the  preparation  of    the  emulsion  and  in 


development  and  fixing.  Swelling  is  very 
sensitive  to  the  influence  of  various  salts, 
and  especially  to  that  of  acid  or  alkali. 
During  the  manufacture  the  "set"  emul- 
sion is  shredded  and  washed  to  remove 
soluble  salts;  the  washing  is  generally  done 
with  tap  or  with  spring  water,  both  of  which 
contain  calcium  and  magnesium  salts, 
which  repress  swelling,  and  consequently 
the  gel  does  not  increase  in  volume  to  un- 
desirable proportions.  If  distilled  water 
were  used,  it  would  not  only  be  very  costly, 
but  also  the  emulsion  would  swell  so  con- 
siderably that  not  only  would  the  charac- 
teristics of  the  emulsion  produced  be  al- 
tered, but  the  succeeding  operations  would 
have  to  be  modified. 

As  compared  with  collodion,  the  dried 
film  of  gelatin,  as  found  on  photographic 
plates  or  papers,  offers  many  advantages. 
When  a  collodion  film  dries  there  is  a  ten- 
dency for  it  to  become  horny  on  the  surface, 
and  since  it  is  insoluble  in  water  hindrance 
is  thereby  offered  to  the  penetration  of  de- 
veloping and  fi«ng  solutions.  The  gelatin 
film,  however,  readily  swells  in  the  de- 
veloper solution,  which  then  diffuses  into  it 
almost  as  readily  as  it  would  do  into  pure 
water,  and  hence  reaction  with  the  silver 
haloid  readily  takes  place.  Since  the  gela- 
tin is  attached  to  a  rigid  support  it  does  not 
swell  equally  in  'all  directions,  effective 
swelling  takes  place  only  in  a  direction  nor- 
mal to  the  surface.  The  amount  of  swell- 
ing will,  of  course,  depend  on  the  salts, 
etc.,  present  in  the  developer  solution  and 
also  on  the  temperature.  Solutions  of  the 
ordinary  developers  are  alkaline,  and  alka- 
linity increases  the  swelling  of  gelatin  to 
such  an  extent  that  very  undesirable  results 
would  accrue  were  no  other  substances  pre- 
sent to  check  the  swelling.  Carbonates  and 
sulphites  are  present,  however,  and  when 
present  in  concentrations  greater  than  5 
iper  cent,  they  depress  the  swelling  in  the 
alkaline  solution  to  a  value  below  that 
which  obtains  in  water.  The  depressing 
effect  increases  rapidly  with  the  concentra- 
tions of  the  salts,  a  fact  which  is  taken  ad- 
vantage of  in  preiparing  developing  solutions 
for  use  at  high  temperatures,  as  in  the 
tropics. 

Another  method  of  preventing  the  swell- 
ing which  takes  place  at  the  high  temipera- 
tures  of  the  tropics,  is  to  harden  the  film 
before  development.  This  may  be  done,  for 
example,  by  the  use  of  a  formaldehyde 
solution  containing  a  salt  such  as  sodium 
citrate,  sodium  sulphate,  sodium  phosphate, 


JUNE  1.  1923. 


THfi  CHEMICAL  NEWS 


347 


Another  factor  which  is  influenced  by  the 
swelling  is  the  time  of  fixation.  The  more 
swollen  the  gelatin  the  more  readily  does 
the  thiosuiphate  diSuse  into  it;  also  the 
greater  the  concentration  of  the  thiosui- 
phate the  quicker  will  be  its  solvent  action 
on  the  silver  haJoid.  Increase  in  concentra- 
tion of  the  thiosuljphate  tends,  however,  to 
decrease  the  swelling  of  the  gelatin,  and 
there  will  come  a  point  when  this  decrease 
more  than  counterbalances  the  influence  of 
mass  action.  There  will  thus  be  a  mini- 
mu  mtime  of  fixation,  and  this  is  at  a  o<mi- 
centration  of  about  40  per  cent,  thiosui- 
phate; above  and  below  this  concentration, 
the  time  of  fixation  increases. 

SwelUng  also  has  an  influence  on  the 
washing  of  the  fixed  negative  (c/.  recent 
papers  of  Hickman  and  tSheppard).  Affect- 
ing both  the  washing  and  the  fixing  of  the 
negative  is  the  use  of  hardening  agents, 
such  as  potash  alum,  formaldehyde,  ctt'.. 
in  that  these  have  an  anti-swelling  effect. 

Another  advantt^ge  of  gelatin  over  collo- 
dion is  that  it  permits  the  growth  and  ri)peu- 
ing  of  crystals.  Since  the  highly  sensitive 
emulsions  contain  large-sized  crystals,  it 
has  often  been  assumed  that  ripening  con- 
sists in  the  growth  of  large  crystals  at  the 
expense  of  smaller  ones,  acccM^ing  to  the 
Ostwald  princitple.  This  is  not  necessarily 
the  case,  since  a  high-speed  emulsion  is  pre- 
pared in  a  different  way  from  a  low-speed 
emulsion.  The  increase  in  size  may  only 
be  a  concomitant  factor  to  the  one  which 
produces  speed  in  the  grain,  that  is  to  say, 
in  the  methcxis  used  for  producing  high  sen- 
sitivity it  so  happens  that  increase  in  «ze  of 
the  grain  takes  place  at  the  same  time  as 
production  of  speed. 

As  to  what  it  is  which  makes  gelatin  so 
valuable  as  a  sensitising  material,  we  are 
still  in  the  dark. 

The  Solubility  of  Silver  Bromide  in  Ani- 
nioyiium-Bromide  and  Gelatin,  by  Chr. 
WiNTiiER,  Copenhagen. 

In  some  theories  of  the  latent  image  and 
development  it  is  assumed  that  the  silver 
bromide  grain  of  the  plate  is  more  soluble 
in  potassium  bromide  solutions,  and  esipe- 
cially  gelatin,  than  in  pure  water.  These 
Hssertion  ■;  may  not  hold  for  very  dilute  solu- 
tions of  ipotassium  bromide,  since  according 
to  the  law  of  mass  action,  the  silver  bro- 
mide must  be  less  soluble  in  the  said  solu- 
tions than  in  pure  water.  In  concentrated 
solutions  there    is  the  possibility    of  com- 


plex ions  being  formed,  the  solubility  of  sil- 
ver bromide  then  being  increased  in  propor- 
tion to  the  concentration  of  these  ions. 
From  Hellwig's  measurements  the  complex 
ion  must  have  the  oomipoeition  AgBr-*,  the 
complexity  constant  being  equal  to  1.2  x 
10«. 

I  have  measured  the  solubility  of  silver 
bromide  in  solutions  of  ammonium  bro- 
mide and  of  gelatin.  In  some  of  the  experi- 
ments I  added  known  quantities  of  ammo- 
nia, ammonium  iodide,  ammonium  chloride 
and  erythosine. 

Experiments. 
The  investigation  was    made  by  measur- 
ing the  electromotive  force  of  a  series  of  ele- 
ments of  the  type  :  — 


Ag     0.1-H  AgNO, 


XI  Ao 


NH^NO, 

10  per  cent,  soln 

where  X  is  a  mixture  of  silver  bromide,  and 
of  that  solution,  in  which  its  solubility  has 
to  be  measured.  For  each  solution  two 
identical  elements  were  measured.  The 
potential  n  very  soon  attained  a  constant 
value,  which  remained  unaltered  for  many 
hours. 

The  experiments  showed  that  the  law  of 
mass  action  is  valid  for  an  excess  of  bro- 
mide of  betwt(>n  the  limits  of  concentration 
used.  With  one  exception,  the  solubility 
product  obtained  had  the  same  value.  This 
was  also  the  case  when  gelatin,  and  small 
amounts  of  ammonia,  erythrosine,  ammo- 
nium iodide  and  ammonium  chloride  were 
added,  using  concentrations  of  these  sub- 
stances of  the  same  order  as  employed  in 
emulsion  making. 

When  both  the  ammonium  iodide  and  the 
ammonium  chloride  are  reckoned  as  bro- 
mide, we  get  the  solubility  products  which 
are  seen  to  be  of  the  same  magnitude  as  in 
the  other  series. 

Thus,  the  solubility  of  silver  bromide  in 
water  is  not  altered  by  the  addition  of  gela- 
tin, erythrosine,  and  small  amounts  of 
anmionium  iodide  or  ammonium  chloride. 
By  the^  addition  of  bromide,  the  solubility 
is  decreased  in  accordance  with  the  law  of 
mass  action. 

Notes  on  the  l^hoiographic  Gheviistry  of 
Gelatin,  by  S.  E.  Sheppard,  F.  A.  Elliott 
and  S.  S.  Swkkt. 

The  properties  of  gelatin  as  a  protective 
colloid  (largely  associated  with  its  viscosity) 


348 


THE  CHEMICAL  NEWS. 


JUNE  1,  1923. 


are  of  importance    in  photographic  chemis- 
try—    • 

(a)  For  the  formation  of  the  emulsion  as 
a  ipoly  disperse  system  of  silver  haloid 
grains. 

(b)  For  the  inhibition  of  reduction  in  ab- 
sence of  exposure,  and  the  regulation  of  re- 
actions of  reduction,  etc. 

(c)  In  its  function  as  a  reversible  water 
swelling  hydrogel,  permitting  free  diffusion 
of  crystalloids  (salts,  etc.). 

These  functions  of  gelatin  are  largely 
physico-chemical,  i.e.,  they  are  determined 
by  the  equilibrium  of  the  gelatin :  water  as 
a  function  of  concentration,  temperature, 
hydrogen  ion,  etc.  There  probably  are  fac- 
tors in  emulsion  making  which  have  little 
or  nothing  to  do  with  these  physico-chemi- 
cal conditions. 

While  the  iphysical  chemistry  of  the 
vehicle  has  much  to  do  A\'ith  the  structure 
of  the  emulsion  as  an  aggregate  of  grains  of 
various  siges,  shapes,  etc.,  it  has  very  little 
to  do  with  the  structure  and  sensitivity  of 
the  grains  themselves. 

Gelatin  Protective  Action. — The  general 
character  of  colloid  protective  action,  as  in- 
hibition of  precipitation,  coagulation,  and 
crystallisation  —  in  short,  aggregation 
changes,  is  not  clear.  Although  viscf  sity 
plays  some  part,  there  is  evidence  that  more 
specific  factors  are  dominant.  In  the  pre- 
cipitation of  silver  haloids  in  gelatin,  it  is 
obviously  inviting  to  connect  the  protective 
action  with  both  the  polar  character  of  the 
silver  haloid  and  of  the  gelatin. 

Results  with  ash-free  gelatin  were  con- 
firmatory. While  the  direct  solutions  show 
some  difference  in  plasticity  (slightly  lower) 
from  the  diluted  ones,  in  all  cases  their  mo- 
bility was  greater.  These  differences  indi- 
cate, like  the  difference  in  gold  number 
observed  by  Sheppard  and  Elliott  under 
similar  conditions,  a  structure  in  the  sol 
which  depends  to  some  extent  on  its  mode 
of  prciparation. 

For  the  practice  of  the  photographic  pro- 
cess, the  iphysical  chemistry  of  the  jelly  is 
important.  Some  evidence,  and  consider- 
able argument,  has  been  brought  in  favour 
of  various  theories  of  gelatin  jelly  structure. 

The  "skin"  effect  might  explain  this. 
Cortner  finds  that  if  jellies  of  different  initial 
concentration  are  dried,  then  ground  up, 
and  swollen  in  water  again,  that  the  swell- 
ing limit  still  aippears  to  depend  upon  the 
initial  concentration.  We  have  made  some 
experiments  on    the  anisotropy    of    drying 


and  swelling  of  gelatin  jellies  which  bear  on 
this  structure  problem.  Gelatin  jellies  on 
rigid  supports  tend  to  dry  down  and  swell 
up  normally  to  the  surface.  This  is  not 
absolute,  as  shown  by  stripping,  frilling, 
reticulation  troubles.  We  have  tried  to 
compare  the  relative  contractility  of  differ- 
ent gelatins.  By  contractility  we  mean  the 
relative  extent  to  which  a  reduction  in  unit 
area  of  a  drying  sheet  of  gelatin  takes  place, 
compared  with  reduction  in  thickness. 

Contraction  varies  with  the  origin  of  the 
gelatin.  The  low  value  for  the  sizing  gela- 
tin, which  undoubtedly  contained  much 
liydrolysed  material,  would  suggest  that 
this  plays  a  part.  De-ashing  removes  the 
greater  part  ot  these.  Persistent  differences 
exist  in  gelatins  of  different  origins.  That 
hydrolytic  factors  do  play  a  part  is  shown 
by  results  with  jellies  at  different  initial  p^ 
adjustment. 

Anisotropy  of  Swelling. — Ten  per  cent. 
jellies  were  dried  down  under  identical  con- 
ditions and  stripped  from  glass.  The  sheets 
were  then  swollen  in  water,  and  the  area, 
•Lveiyht,  and  thickness  measured.  The 
direct  measurements  of  thickness  were  not 
very  accurate  in  this  case,  owing  to  the 
weakness  of  the  jellies,  but  volumes  were 
calculated  from  the  weights,  using  the 
specific  gravities  corresponding  to  each 
stage. 

Figures  did  not  show  any  unequivocal  re- 
lation between  the  contractility  and  the 
lateral  swelling  or  expansion.  The  highest 
relative  expansion  is  actually  given  by  the 
poorest  grade  of  gelatin.  They  point  to  the 
existence  of  individual  structural  differences 
in  gelatins,  depending  not  simiply  on  actual 
physico-chemical  conditions,  but  on  origin 
and  previous  history. 

While  the  total  volume  swelling 
diminishes  as  the  concentration  of  formal- 
dehyde is  increased,  the  lateral  swelling  is 
only  slightly  reduced,  on  a  relative  basis  of 
500  per  cent,  volume  increase,  the  lateral 
expansion  of  the  formaldehyde  treated 
material  appears  to  be  nearly  twice  that  of 
the  untreated,  and  fairly  constant.  In  these 
experiments  the  CH,0  is  based  on  dry 
weight  of  gelatin,  and  was  mixed  with  the 
solution  before  coating  and  drying. 

An  equilibrium  or  limited  swelling  ap- 
pears to  be  essential  to  the  Proctor- Wilson- 
Loeb  theory.  Swelling  reaches  a  condition 
of  negligible  increase  in  reasonable  times, 
but  all  factors  which  decrease  swelling 
tend  to  make  limited  sicelling  more  appar- 
ent, while  conversely  those  which  increase 


JUNE  1.  1923. 


THE  CHEMICAL  NEWS. 


349 


swelling  tend  to  make  the  swelling  un- 
limited. It  is  obvious  that  this  makes  f(n- 
difficulty  in  respect  of  assertions  as  to 
"  swelling  limits,"  However,  most  photo- 
graiphically  operative  solutions  tend  to  dis- 
Cf>urage  rather  than  encourage  swelling, 
relative  to  water  at  the  same  temperature, 
so  that  it  is  (possible  to  obtain  some  fairly 
definite  evidence  on  the  rate  and  limits  of 
swelling  in  these.  In  our  work  we  have 
used  two  methods,  rne  by  tceighing,  th*' 
other  by  measuring  the  thickness.  Th( 
weighing  method  is  only  partially  satisfac- 
tory for  solutions.  To  find  the  volume  of 
jelly  from  the  weight  it  is  necessary  to 
know  the  composition  and  specific  gravitv 
of  the  solution  which  has  entered  the  film, 
and  which  may  vary  with  the  progress  of 
swelling. 

With  solutions  of  moderate  ooncentratif>n 
there  is  not  a  great  difference  between  thiit 
absorbed  and  that  remaining,  and  the  in- 
crease in  volume  can  be  calculated. 

The  Mechanism  of  Ike  Latent  hun,i' 
Formation,  by  F.  C.  Toy,  D.Sc,  F.Inst. P. 

The  problem  of  the  rcjictions  which  take 
place  in  a  photographic  j)!ate  on  exposure  is 
of  primary  importance  foi-  knowledge  of  the 
complete  process.  A  t^'ieat  advance  has 
been  made  in  the  last  few  years,  due  to  the 
realisation  of  the  fact  (hat  the  single  silver 
haloid  crystal  of  an  emulsion  is  the  funda- 
mental unit,  and  a  complete  theory  of  (he 
photographic  process  can  only  be  built  uip 
on  a  knowledge  of  the  behaviour  of  these 
individual  crystals  in  relation    to  exposure. 

Thefe  is  something  even  more  fundamen- 
tal than  the  grains  themselves,  viz.,  the 
"  centres,"  the  points  in  the  grains  from 
which  develoipment  starts. 

The  main  facts  in  regard  to  the  localisa- 
tion and  distribution  of  the  centres  are:  — 

1.  They  are  distributed  amongst  the 
grains  haphazard. 

2.  On  the  average  they  are  distributed 
equally  over  the  surface  of  spherical  grains, 
and  are  concentrat-ed  mostly  on  the  edges 
if  the  grains  are  flat  plates. 

The  centres  from  which  development 
commences  are  the  actual  points  where  the 
grain  has  been  changed,  and  therefore  indi- 
cate the  actual  distribution  of  the  material 
of  the  latent  image. 

There  is  a  controversy  ae  to  how  these 
centres  ore  formed.  Thp  different  views 
may  be  sunmiarised  as  follows : — 

1.    They    are    formed    in     homogeneous 


grains  entirely  by  the  light  which  is  inci- 
dent at  points  ou  the  plate  in  finite  discrete 
quantities. 

2.  They  are  pre-existent  in  the  grains 
before  exiposure  as  chemically  different  sub- 
stance, the  function  of  the  light  being  to 
change  their  condition  in  such  a  way  that 
they  become  capable  of  acting  as  reaction 
centres. 

3.  A  combination  of  (1)  and  (2).  Hetero- 
geneous radiation  incident  on  grains  con- 
taining specially  light  sensitive  points. 

The  recent  work  of  Whittaker  is  an  indi- 
cation that  the  reconciliation  of  tliese 
theories  may  be  accomplished  at  no  great 
distant  date. 


Exposure  Theories,  by  S.  E.  Sheppard, 
A.  P.  H.  Trivelli,  and  E.  P.  Wightman. 

Exposure  theM-ies  of  photographic  de- 
veloipability  deal  with  the  quantitative 
growth  of  di'velopability  with  exposure,  and 
with  the  nature  of  sensitivity  of  the  photo- 
graphic material.  They  may  also  consider 
the  nature  of  the  latent  image. 

The  salient  features  of  early  theories  were 
the  assumptions  (1)  of  homogem  ity  and 
continuity  of  the  sensitive  emulsion,  (2)  of 
a  like  condition  of  the  incident  radiation, 
and  (8)  of  the  same  for  the  developed 
image. 

The  essential  characteristics  of  later 
views  are,  ( 1 )  the  full  recognition  of  the 
microscopically  and  submicroscopicaily  dis- 
perse character  of  the  emulsion,  and  (2)  the 
assuniiptions  (a)  that  the  light  may  be 
heterogeneous,  i.e.,  radiated  and  absorbed 
in  discrete  quanta,  (h)  that  the  grains  of 
the  emulsion  may  be  inherently  heterogene- 
ous as  to  their  sensitivity,  and  (c)  that  (a) 
and  (/>)  may  both  have  to  be  taken  into 
account. 

Absorption  of  Light'and    Photocatahjsis. 

Any  formula  based  on  the  older  theories 
must  b(»  deduced  on  the  further  assumption 
that  the  rate  of  change  is  proiportional  to 
the  light  absorbed  by  the  sensitive  material. 

Hurtt^r  and  Priffield  postulated  :  (1)  only 
the  energy  absorbed  by  unchanged  silver 
haloid  is  effective  in  producing  latent 
image ;  (2)  the  absorption  coefficient  of  the 
changed  silver  haloid  is  the  same  as  that  of 
the  unchanged.  It  is  difficult  to  attribute 
a  physical  and  chemical  meaning  to  this, 
and.  as  shown  by  Ross,  leads  to  a  mathe- 
matical contradiction. 


350 


THE  CHEMICAL  NEWS. 


JUNE  1,  192a. 


Equations  for  rate  of  photochemical 
change  allowing  for  iphotocatalysis  have 
been  developed  by  Plotnlkoff,  but  are  too 
unrelated  to  experimental  facts  to  be  of 
much  assistance.  Before  any  such  mathe- 
matical excursions  are  attemipted,  there  are 
other  possible  assumptions  which  should  be 
examined. 

Newer  theories  recognise  the  disperse 
character  of  the  emulsion  as  fundamental. 
Thanks  to  the  investigations  of  Slade  and 
Higson,  Svedberg,  and  others,  it  is  recog- 
nised that  not  only  do  the  grains,  although 
crystals  of  one  system  and  class,  differ  in 
size  and  shape,  but  they  differ  in  sensitivity. 

A  grain,  however  small  the  exposure, 
might  have  its  developability  changed,  that 
is,  its  rate  of  reduction  by  a  developer  in- 
crease with  exposure.  An  emulsion  of 
equal-sized,  equally  sensitive  grains,  would 
then  still  give  gradation  under  differential 
exposure,  within  limits.  The  less  exposed 
grains  would,  for  a  given  stage  of  develop- 
ment, give  a  smaller  portion  of  developed 
silver  than  the  more  exposed. 

But  from  microscopic  examination,  it  ap- 
pears (1)  generally,  with  normal  developers 
and  exposures,  that  a  grain  which  hav^; 
started  to  develop  becomes  entirely  re- 
duced, without  reference  to  the  exposure, 
and  (2)  that  a  grain  is  either  wholly  de- 
velopable, or  not  at  all. 

These  statements  require  some  qualifica- 
tions, and  a  more  rigorous  experimental 
verification.  It  has  not  yet  been  conclu- 
sively shown  that  the  above  statements 
hold  for  developers  of  low  reduction  poten- 
tials, although  there  are  indications  that 
not  all  of  the  grains  are  completely  de- 
veloped in  the  same  way  as  with  high  re- 
duction potential  develoipers.  Again,  it  ap- 
pears that  as  reduction  potential  is  lowered 
by  bromide,  the  developability  is  progres- 
sively affected,  this  influence  becoming  less 
with  increasing  exposure. 

Not  the  ultimate  size  of  developed  grains 
is  affected  by  exposure,  but  the  number 
only. 

Sufficient  evidence  has  been  brought  to 
show  that  in  many  emulsions  "clumps"  ol 
contiguous  grains  are  formed  which  develop 
as  a  unit  when  only  one  grain  of  the  clump 
is  light-affected.  At  the  same  time,  there 
are  cases  of  apparent  "  clumps,"  not  defi- 
nitely distinguishable  from  the  others. 
which  do  not  develop  as  units. 

Since,  on  the  quantum  radiation  theory. 
a  "clump"  may  act  as  a  "target"  of  size 
equal  to  its  projective  area,  and  since  it  is 


not  easy  to  see  how  a  simple  nucleus  theory 
of  sensitivity,  without  "quantum  radia- 
tion," can  give  the  same  chance  of  develoip- 
ment  to  "clumps"  as  the  former  theory,  the 
settlement  of  this  disputed  point  is  of  great 
importance  to  exposure  theories.  The  sen- 
sitivity of  a  clump  is  that  of  its  most  sensi- 
tive gLain,  or,  according  to  Svedberg,  to  the 
number  per  unit  area  of  grain.  On  the  for- 
mer, it  is  purely  a  function  of  the  projective 
area  of  the  "  clump." 

Not  only  does  sensitivity  of  grain  increase 
with  area,  because  of  number  of  nuclei,  but 
also  that  nucleus  sensitivity  increases  with 
grain  size.  This  is  in  agreement  with  emul- 
sion practice. 

Results  of  treatment  with  CrOg  and  other 
oxidisers  also  indicate  that  the  alteration  of 
the  sensitivity  by  the  desensitising  agent  is 
a  function  of  the  grain  size,  i.e.,  the  ratio  of 
percentage  develoipable  grains  between  the 
treated  and  the  untreated  grains  is  de- 
creased markedly  with  increasing  grain  size, 
the  smaller  grains  apparently  being  much 
more  affected  by  the  desensitising  treat- 
ment than  the  larger  grains. 

It  is  possible  that  the  average  area  of  the 
spots  (=  w)  increases  with  grain  size  and 
that  either  (1)  ttie  spots  become  more  re- 
sistant to  the  chromic  acid  treatment  with 
their  increase  in  size,  or  (2)  that  sufficient 
time  is  not  allowed  to  dissolve  the  large 
ones,  the  rate  of  solution  of  all  the  grains 
being  uniform  but  slow.  The  latter  is  hardly 
likely,  since  the  time  is  far  longer  than  is 
required  to  dissolve  any  developed  silver 
image  where  whole  grains  had  been  con- 
verted to  silver.  The  greater  resistance  in 
the  case  of  (1)  might  be  attributed  to  the 
position  of  the  spots  on  the  octahedral  faces 
of  the  larger  fiat  grain,  instead  of  on  the 
cubiea  Isurfaces  of  the  smaller  less  flat  ones. 


Tltc  Sensitiveness  to  Light  of 
Asphalt  as  Function  of  its  Degree  of  Disper- 
sion, by  Jacques  Errera  (Brussels). 

The  name  of  asphalt  is  given  to  a  brown- 
black  inflammable  and  fusible  natural  mix- 
ture. Niepce  showed  asiphalt  is  sentitive  to 
light. 

By  successively  dissolving  asphalt  in  boil- 
ing alcohol,  in  ether,  and  by  submitting  the 
residue  to  the  action  of  chloroform,  Kayser 
isolated  three  components,  which  he  calls, 
a,  /3  and  y  asphalt,  to  which  he  assigns  dif- 
ferent molecular  formulae  with  a  growing 
percentage   of  sulphur:    CgaH^o^.   C^^HygS, 


JUNE  1,  1923. 


THE  CHEMICAL  NEWS. 


351 


Cgalli^Sj.     y  Asphalt    alone  is  really  sensi- 
tive t»  light. 
U  appears : 

1.  That  the  viscosity  of  the  solution  ol 
raw  asiphalt  is  much  less  than  that  of  as- 
phalt after  treatment,  and  that,  of  the  two, 
the  one  which  is  obtained  by  precipitation 
(Farquhar  prrxjess)  is  the  more  viscous. 

2.  The  molecular  weight  of  raw  astphalt 
is  five  times  as  small  as  that  of  Kayser 
asphalt,  the  latter  being  about  half  that  of 
y  asphalt  (Farquhar). 

3.  Submitted  to  ultrafiltratiMi,  the  solu- 
tion of  raw  asphalt  lets  through  into  the 
ultrafiltrate  a  much  greater  quantity  of 
product  than  the  solution  of  asphalt  when 
tn-ated. 

MfKlern  theories  seem  to  admit  in  sensi- 
tive asphalt  the  existence  of  three  sub- 
stances chemically  defined  as  a,  fi  and  y 
asphalt.  When  studying  the  question  from 
a  colloidal  point  of  view,  it  would  appear 
more  correct  to  say  that  asphalt  is  a  "poly- 
dispersoid";  the  sensitive  part  is  the  one 
which  is  found  in  a  state  of  colloidal  disper- 
sion. When  chemically  analysed,  this  col- 
loidal part  proves  to  be  the  richest  in  sul- 
iphui-,  the  valences  of  which  being  a  factor 
of  polymerism.  According  as  their  degree 
of  association  is  greater  or  smaller  we  find 
in  asphalt  the  intermediate  stages  Jbetween 
molecular  and  colloidal  asphalt.  Sunlight 
seems  to  have  a  coagulating  action. 

Tests  of  visooeity,  molecular  weight,  di- 
alysis, and  sensitiveness  to  light  corroborate 
this  view. 

A  new  process  of  sensitisation  of  at^phalt 
was  indioat<'d. 

Plate  Sensitometry ,  by  Olap  Bloch. 
F.I.C.  (Tlford  Research  Laboratory). 

Considerable  advance  has  been  made  in 
iplate  sensitometry  since  the  time  of  Hurtor 
and  Driffield. 

The  complete  analysis  of  the  quality  of 
an  emulsion  is  a  matter  of  some  complexity, 
and  e.ortain  points  which  have  arisen  in  the 
C/ontinuous  endeavour  to  make  testing 
methods  more  accurate  and  keep  them  sim- 
ple seem  of  sufficient  interest  to  record. 

The  so-called  speed  of  a  plat^  is  dediiced 
from  the  straight  lino  portion  of  the  charac- 
teristic curve  of  the  emulsion ;  whilst  this  is 
of  some  value  there  are  many  cases  (por- 
trait emulsions  for  instance)  when  the  under 
exipoRure  curve  comprises  the  most  useful 
portion  of  the  functions  of  the  plate. 
To  be  of  value,  any    system  must    oovci 


the  case  of  all,  emulsions  and  give  useful  in- 
fcjrmation  on  contrast  giving  power,  "  cut," 
character  of  the  under  exposure  portion 
of  the  plate  curve,  nature  of  the  curve  in 
the  region  of  full  exposure,  behaviour  to 
developers  with  regard  to  the  production  of 
veil,  and  some  expression  giving  a  reason- 
able idea  of  speed.  In  special  cases  some 
knowledge  of  resolving  power  and  size  of 
grain  is  also  necessary. 

Fog. — Fog  is  a  variable  so  far  as  the 
image  is  concerned,  since  the  greater  the 
exposure  the  higher  the  local  concentration 
of  soluble  bromide  produced  in  develop- 
ment, and  the  less  the  fog. 

The  dam  in  a  I/iue. — Fairly  good  curves 
can  be  obtained  using  the  H.  and  D.  sector 
wheel,  but  exposures  are  too  widely  apart 
for  reliable  work  with  many  emulsions. 
Good  curves  can  be  obtaine<l  by  using  a 
wedge. 

The  following  method  gives  good  results. 
A  stencil  iplato  is  cut  in  black  cardboard, 
having  four  sets  of  circular  mpenings,  five  in 
each  set;  these  openings  are  of  sufficient 
diameter  to  cover  the  ^eld  of  the  photo- 
meter, and  so  arranged  that  each  exposed 
circle  is  well  surrounded  by  unexposed 
plate.  A  series  of  timed  exposures  is  given 
to  the  plate  placed  in  the  dark  slide  behind 
the  stencil.  For  fast  plates,  exiposures  are 
made  SSO  cms.  from  a  standardised  lamp, 
having  a  small  loop  filament  in  one  plane. 
The  exposures  all  fall  within  the  straight 
line  portion  of  the  plate  curve.  After  ex- 
posure the  backing  is  removed,  and  the 
glaas  is  so  cut  that  each  set  of  exposures  is 
protected  against  trouble  arising  from  the 
develmper  at  the  edges  of  the  plate.  De- 
velopment is  carefully  conducted,  the  dish 
\nAng  regularly  rocked  in  four  directions. 

For  certain  emulsions,  the  gamma  lines 
for  varying  times  of  development  intersect 
above  the  Log  E  axis.  With  a  view  to  get- 
ting further  evidence',  ten  different  emul- 
sions (made  by  five  different  manufacturers) 
were  thoroughly  tested. 

Seven  of  these  had  their  points  of  inter- 
section above  the  TiOg  E  axis  and  comprised 
5  rapid  and  2  mo^lerate  sipeed  plates.  Two 
had  points  of  intersection  on  the  Log  E  axis, 
and  one  (a  fast  panchromatic^^  had  the  point 
below  the  Log  E  axis. 

Temperature. — An  alteration    of  the    de- 
velopment temperature  produces  a  shift  in 
the     gamma    slope,     and     a  corresiponding 
change  in  the  speed  values  as  deduced  from 
the  straight  line  portion  of  the  curve.     The 


352 


THE  CHEMICAL  NEWS. 


JUNE  1,  1923. 


densities  produced  at  the  higher  tempera- 
ture are  uniformly  greater  than  those  pro- 
duced at  a  lower  temperature  for  the  same 
gamma,  but  in  the  under  exposure  curve 
the  same  relationship  does  not  hold  good. 

The  light  source,  the  exposure  distance 
and  times,  the  method  of  making  the  expo- 
sure ,the  composition  of  the  developer  and 
its  temperature,  the  mode  and  duration  nf 
development,  the  question  of  fog,  the 
method  and  apparatus  for  measuring  den- 
sity, and  the  mode  of  expressing  the  re- 
sults, all  require  discussion  and  standardi- 
sation. 

The  Theory  of  Photographic  Dye  Mor- 
danting, bj  E.  E.  Bullock,  B.Sc. 

One  of  the  several  methods  of  converting 
an  ordinary  photographic  image  of  gray  sil- 
ver into  one  of  a  coloured  substance  con- 
sists in  first  changing  the  former  into  an  in- 
termediate image  possessing  a  mordanting 
character  and  then  treating  this  v^'ith  a  solu- 
tion of  a  basic  or  acid  dye.  As  with  all  dye 
mordanting  processes,  so  dye  mordanting  in 
photography  has  not  as  yet  been  found  to 
conform  to  any  simple  theory. 

The  mutual  flocculation  of  the  respective 
colloid  particles  on  mixing  two  colloidal 
solutions  of  opposite  electrical  character 
was  known  to  Graham.  Biltz  (1904)  enun- 
ciated the  rule  that  colloids  carrying  oppo- 
site charges  always  precipitate  each  other  if 
mixed  in  the  proper  ratio.  On  mixing  solu- 
tions of  silver  nitrate  and  potassium  bro- 
mide, precipitation  of  the  silver  and  bro- 
mide ions  takes  place  not  only  at  the  point 
oorresiponding  to  the  ratio  Ag :  Br,  but  also 
through  a  small  range  on  either  side  owim,' 
to  adsorption.  When  a  silver  iodide  hydro- 
sol  is  added  to  solutions  of  methyl  violet, 
precipitation  occurs  over  a  wide  range,  but 
complete  mutual  precipitation  only  over  a 
narrow  one. 

The  solubility  of  silver  cyanide  in  A/  po- 
tassium cyanide  solution  is  greater  than 
that  of  silver  iodide  in  IV  potassium  iodide, 
this  than  silver  chloride  in  iV  sodium  chlor- 
ide, and  this  again  than  silver  sulphide  in  N 
sodium  sulphide.  As  regards  the  three 
last-named  silver  salts,  as  ordinarily  pre- 
pared as  images  in  gelatine  by  precipitation 
with  an  excess  of  the  oorrespondng  potas- 
sium or  sodium  salt,  this  is  the  order  of 
their  decreasing  mordanting  power  for 
basic  dyes.  In  order  to  test  silver  cyanide, 
a  silver  image  on  film  was  bleached  by  im- 
mersion in  a  solution  of  cyanogen ;    the  re- 


sultiDg  image  of  silver  cyanide  was  found  to 
mordant  basic  dyes,  but  owing  to  the  ab- 
normal opacity  of  the  silver  cyanide  image 
a  direct  comparison  with  silver  iodide  w^is 
not  feasible.  The  sulphides  of  tin,  anti- 
mony-, and  arsenic  are  readily  soluble  in 
sodium  sulphide,  and  are  excellent  mor- 
dants for  basic  dyes.  To  show  this,  the  sil- 
ver image  is  bleached  to  silver  bromide  in  a 
ferricyanide-bromide  bath,  washed,  and  im- 
mersed in  a  freshly  prepared  and  very  dilute 
solution  of  a  salt  of  the  type  of  ammonium 
thiostannate,  etc. 

By  a  series  of  experiments  in  which  alu- 
minium hydroxide  (as  an  example  of  a  posi- 
tive colloid  mordant)  was  precipitated  in 
gelatine,  and  this  system  then  immersed  for 
a  sufficient  time  in  solutions  of  a  number  of 
basic  and  acid  dyes,  and  finally  washed  in 
running  taip  water,  it  was  observed  in  every 
case  that  a  basic  dye  is  retained  longer  by 
plain  gelatine  than  by  gelatine  containing 
aluminium  hydroxide  than  by  plain  gela- 
tine. The  dyes  used  were  acridine  orange, 
brilhant  green,  capri  blue  GON,  crystal 
violet  0,  fuchsine  FCOOB,  methyl  violet, 
methylene  blue  B,  tannin  heliotrope,  acid 
violet  4BS,  anthracene  blue,  complemen- 
tary red  D,  Fuchsine  S,  anthraquinone 
green,  quinoline  yellovi^  and  tartrazine.  On 
substituting,  in  a  few  tests,  chrome  alum 
and  iron  alum  for  aluminium  alum,  the 
same  general  results  were  obtained. 

The  rule  of  mutual  flocculation  of  col- 
loids of  opposite  sign  is  distinctly  service- 
able as  a  simple  qualitative  guiding  prin- 
ciple in  the  study  of  the  subject  of  the  dye 
mordanting  of  photographic  images. 


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tlieir  alkali  salts. 

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JUNE  8.,  1923. 


THE  CHEMICAL  NEWS. 


353 


THE   CHhMICAL  NEWS, 


VOL.  CXXVL       X...  3295. 


ISOTOPES:   RECENT  ADVANCES 
MADE  BY  DR.  F.  \V.  ASTON. 

In  the  current  issue  of  the  PhilosujiJiical 
Ma<j(i>ine  for  May,  Dr.  Aston  records  offi- 
cial l_v  further  results  in  the  mass  sipectra 
work  on  the  chemical  elements,  and  sonie 
negative  experiments  are  given  which  are 
of  interest. 

One  of  the  most  helpful  advances  has 
been  the  use  of  more  sensitive  plates 
termed  Schinnannised  plutt'H,  because  the 
treatment  of  the  plate  is  like  that  of  an 
onlinary  oni-  when  the  gelatine  is  removinl 
as  far  as  possible,  but  in  platis  used  by  7^r. 
Aston  the  dissolving  off  of  the  gelatine,  by 
means  of  dilute  sulphuric  iicid.  is  not  car- 
ried so  far. 

Dealing  now  with  the  tieraents,  etc.. 
given  in  l)r.  .\ston's  pajx'r,  the  main  points 
are  stated  below:  — 

HrJinm. — At  the  suggestion  of  Prof.  Mo 
Lennau,  samples  of  helium  frMn  Canadian 
gas  wells  were  examined  for  isotopes,  but 
none  were  observed.  In  this  connection  it 
may  be  not<>d  that,  should  there  be  any 
He++  atoms  present  during  analysis,  these 
would  register  themselves  on  the  plates  ns 
if  their  mass  was  4.00  2,  which  lines  eould 
be  checked  against  hych-ogen  lines  of  mass 
2.010.  By  this  test  the  decimal  difference 
in  mass  could  be  accurately  determined, 
but  no  He  +  +  lines  could  be  found,  presuni- 
ably  on  account  of  the  high  ionisation 
potential  of  80  volts  which  reduces  to  a 
negligible  figure  their  percentage  numbers 
in  the  mixture. 

Nickel . — Sir.  J.  J.  Thomson  had  em- 
ployed nickel  carbonyl.  but  in  the 
(juantities  then  used  it  decomposed, 
and  tlie  metal  was  deposited  on  the 
walls     of     the      disohai-ge      tube.  Dr. 

Aston  has  overcome  this  difficulty  by 
diluting  the  nickel  carbonyl  with  carbon 
dioxide  and  regulating  the  discharge  cur- 
rent to  a  safe  limit.  The  chemically  deter- 
mined atomic  weight  is  oS.OS.  The  isotopes 
recorded  were  58  and  GO  in  such  proportions 
as  to  give  the  atomic  weight  as  a  mean 
figiu*e. 

Metallic  chlorides.  —  Metallic  chlorides 
ore  particularly  satisfactory  to  handle  in 
thio  vnpmn-  state   mwing  to  their  instability. 


but  these  have  a  violent  action  on  rubber 
and  tap  grease.  The  result,  apart  fiom  un- 
desirable compounds,  is  the  release  of  free 
chkrtine.  Conse(]uf  ntly  there  is  a  "perfect 
maze  of  lines  filling  every  successive  unit 
place  and  effectually  screening  any  clear 
vision  of  the  lines  of  the  element  under 
observation."  Moreover,  chlorine  forms 
hydrogen  addition  products,  chlorine  itself 
having  isotopes,  35  and  37,  and  for  every 
type  of  combining  particle  there  will  be 
lira  lines  for  tliv  uionochloride,  three  for 
the  diehloride.  and  four  for  the  trichloride, 
etc. 

Titanium.— On  account  of  the  foregoing 
difficulty  titanium  chloride  gave  spectra  of 
great  complexity  and  no  proper  identifica- 
tions of  isotopes  could  be  made.  Two  pro- 
mising lines  were  recorded,  but  these  were 
identified  from  previous  exfperiments  as 
being  due  to  tap  grease. 

Chromyl  rhloriilc. — This  chloride  was 
"  even  more  hopeless,  for  its  action  on  tap 
grea.se  and  wax  was  so  rapid  as  to  make  it 
quite  unworkable." 

Lead  ethide  and  zinc  methide. — No  lines 
were  recorded  with  these  compounds,  the 
probable  reason  being  the  abundant  libera- 
tion of  carbon  and  hydrogen  compounds 
from  the  decomposing  ethide  or  methide. 
As  an  instance  of  the  delicacy  of  the 
method,  a  single  iodine  line  127  appeared 
when  using  the  vapour  of  zinc  methide, 
which  was  supposed  to  be  quite  pure,  being 
colourless.  Dempster's  fine  work  on  the 
isotope*  of  zinc  is  referred  to. 

Xenon,  krypton,  etc. — ^This  method  was 
successfully  used  to  verify  the  purity  of  the 
xenon  from  krypton  contamination,  the 
sample  being  one  provided  by  Dr.  R.  B. 
Moore,  as  used  in  his  density  determination, 
thus  rendering  the  density  determi- 
nation fnv  from  any  criticism  on 
the  groun<l  of  krypton  being  pre- 
stmt.  The        value       deduced        from 

this  determination  is  180.2.  Dr.  Aston  con- 
siders it  a  little  on  the  low  side,  but  the 
mean  evaluation  in  the  case  of  isotopes  is 
not  accurate  enough  to  carry  weight  against 
a  good  chemical  or  density  determination. 
Excellent  lines  were  obtained  on  the  Schu- 
mannised  plates,  and  suspected  xenon  lines 
128  and  130  were  confirmed. 

Dr.  Aston  here  refers  to  the  search  for  in- 
ert gases  of  higher  atomic  weight  than 
xenon,  and  mentions  that  in  this  connec- 
tion two  new  components  of  xenon,  124, 
126,  were  discovered. 


354 


THE  CHEMICAL  NEWS. 


JUNE  8.  1023. 


It  will  be  remembered  that  Sir  J.  J. 
Tlioiiisoii  [liuij.  Soi'.  Proc,  11122,  vaL  CT. , 
p.  290)  found  by  his  positive-ray  method 
two  atmospheric  constituents  of  apparent 
masses  163  and  260,  and  suggested  that 
these  might  be  due  to  molecules  Kv^  and 
and  Xe,. 

To  make  this  review  up  to  date  and  fairly 
complete,  the  following  abstract  from  this 
Journal  of  May  18,  1923,  of  Dr.  Aston 's 
paper,  read  before  the  Royal  Society,  en- 
titled A  Critical  Search  for  a  Heavier  Con- 
stitue-nt  of  the  Atmosphere  by  means  of  the 
Mass-spectroqraph,  is  here  reproduced:  — 

"  A  critical  search  for  a  gaseous  inert 
element,  heavier  than  xenon,  is  described, 
in  which  the  residues  absorbed  in  charcoal 
from  over  400  tons  of  air  are  dealt  with. 

The  final  analysis  is  made  by  means  of 
the  mass-spectrograph.  The  result  is  nega- 
tive and  indicates  that  such  an  element 
certainly  does  not  exist  to  the  extent  of  1 
part  in  10^^  of  air,  and  probably  not  to  the 
extent  of  1  part  in  2  x  10*®  parts  of  air  by 
volume. 

Faint  bands  observed  in  the  region  cor- 
responding to  masses  150  and  260  are  de- 
scribed and  their  origin  discussed.  The 
prst  of  these  is  shown  to  be  due  to  a  com- 
plex molecule  of  mercury  with  a  multiple 
charge,  but  no  conclusion  is  reached  in  the 
case  of  the  other. 

"  The  results  of  the  experiments  are  not 
in  accordance  with  the  presence  of  molecu- 
lar krypton  and  xenon  in  the  air,  recently 
suggested."     See  above. 

Tin  and  the  whole-number  rule. — The 
earlier  work  on  the  isotopes  of  tin  is  now 
confirmed,  the  values  being  116.  117,  118. 
119,  120,  121?,  122,  124.  The  intensities 
of  the  lines  are  such  as  to  render  it  improb- 
able that  any  of  the  lines  are  due  to  hydro- 
gen addition  products  except  the  value  121, 
this  being  very  faint  on  the  plate. 

In  this  experiment  tin  tetramethide  was 
used,  which  was  supplied  by  Sir  W.  Pope. 
The  evidence  that  the  above  lines  were  due 
to  tin  isotopes  is  supported  by  the  presence 
of  lines  15,  30  and  45  units  higher  up  in  the 
mass  scale  by  reason  of  compounds  SnCHg, 
SnfCHg)^,  and  Sn(CH3)3.  These  lines 
show  exact  whole-number  differences,  but 
"  when  cormpared  with  other  lines  on  the 
plate  they  give  values  less  than  whole  num- 
bers by  2  to  S  parts  m  1,000."  The  pre- 
sence of  xenon  lines  and  those  of  tin  mono- 
methide  amongst  them  made  it  possible  to 
compare  the  registration  of  the  tin  lines 
with  them.     If  the  xenon  lines,    134,  136, 


represent  whola-number  masses,  then  the 
compound  Sn'^^CHg  should  lie  exactly  mid- 
way if  the  tin  isotope  120  is"  a  whole  num- 
ber, but  it  is  displaced  to  the  left  slightly  so 
as  to  "  coalesce  partly  with  Xe'"'^,"  mak- 
ing this  line  appear  broadened. 

J)r.  Aston  remarks  as  follows  :  "  It  seems 
impossible  to  imagine  any  instrumental  de- 
fect which  could  give  rise  to  this  shift. 
There  a^ppears  therefore  to  be  no  escape 
from  the  conclusion  that  tin  and  xenon 
cannot  both  obey  the  whole-number  rule. 
It  was  realised  and  emphasised  (Phil.  Mag., 
XXXIX.,  p.  624)  that  this  rule  was  not  to 
be  expected  to  hold  with  mathematical 
exactness  owing  to  the  packing  effect,  but  it 
is  very  surprising  that  elements  only  differ- 
ing by  three  units  in  atomic  number  should 
show  so  large  a  divergence.  It  seems  prob- 
able that  the  divergence  from  the  mean 
(()  =  16)  is  greater  in  the  case  of  tin  than  in 
that  of  xenon,  but  since  the  arithmetic 
sum  of  the  two  (supposing  them  to  be  of 
opposite  signs)  is  only  about  three  times 
the  experimental  error,  satisfactory  settle- 
rnent  of  this  point  will  have  to  be  deferred 
till  an  instrument  of  higher  precision  is 
available." 

Iron. — This  element  gives  a  volatile  car- 
bonyl  (prepared  by  W.  H.  Mills),  and  thus 
makes  it  possible  to  obtain  a  record  of  this 
compound  on  the  plate.  A  strong  line  was 
obtained,  indicating  that  an  atom  of  iron 
existed  of  mass  56.  A  fainter  line  giving  a 
value  54  was  also  recorded,  which  may  be 
an  isotope,  but  the  line  is  so  weak  that  iron 
may  be  made  up  entirely  of  atoms  of  mass 
56,  though  the  chemical  atomic  weight  is 
55.84. 

Cadmium. — Cadmium,  though  easily  va- 
pourised,  gives  no  lines  in  the  expected 
region.  In  this  experiment  a  quartz  vessel 
containing  the  cadmium  was  lowered  into 
the  cathode-ray  path  by  means  of  a  winch. 
The  metal  was  vapourised  and  it  condensed 
on  the  walls  of  the  tube,  forming  a  bright 
mirror. 

It  was  noted  that  mercury  was  com- 
pletely eliminated  from  the  discharge  by 
the  presence  of  the  cadmium,  and  it  did 
not  reappear  "  so  long  as  the  cadmium 
mirror  remained  on  the  walls  of  the  dis- 
charge-tube." A  method  of  eliminating 
mercury  is  thus  discovered. 

Thalliu)ii.—As  part  of  the  above  experi- 
ment, this  element  was  tried  without  re- 
sults, and  it  is  probable  that  the  cadmium 
layer  removes  the  thallium  vapour  as  effec- 
tively as  it  does  mercury. 


JUNE  8,  1923. 


THE  CHEMICAL  NEWS. 


355 


Selenium. — The  unsuccessful  use  of 
scknium  hydride  (Phil.  Matj,  XLll..  p. 
140)  led  to  the  volatilising  of  the  element 
itself  with  the  result  that  five  strong  lines 
were  obtained,  viz.  :  76.  77,  78,  80,  82. 
There  is  a  faint  line  at  74.  These  values 
were  confirmed  by  a  set  of  corresponding 
lines  12  units  higher  up  on  the  mass  scale. 
due  to  C  Se;  also  lines  28  units  higher, 
due  to  COSe,  were  obtained,  and  some  faint 
lines  of  CSe^  were  identified.  It  is  to  be 
noted  that  three  selenium  isotopes  have  the 
same  masses  as  some  of  those  of  krypton. 
Thi.^  is  a  case  of  isobaric  helerotopes. 

TcUurium  and  hcnjUiuin.  —  Pure  tel- 
liu'iuin  was  volatilised,  yet  no  lines  were 
obtained,  but  this  failure  is  probably  due  to 
its  high  bf)iling  point  and  consequent  low 
vapour  pressure.  Tellurium  chloride  was 
uscfl  without  success. 

Ikryllium  acetate  was  tried,  hut  its  im- 
mediate decompf>sition  yielding  a  white 
o.\ide  prevented  this  experiment  becoming 
successful.  G.  P.  Thomson's  positive  rny 
analysis  of  this  element,  however,  stands, 
there  being  only  one  value.  0,  which  is  in 
close  agreement  with  Hcinigschmid  and  Bir- 
ckenbach's  value,  9.018. 

.Wuniinium.  —  The  chemical  atomic 
weight  of  this  element  is  now  known  to  be 
2t).9r),  and  it  is  therefore  evident  that  in  nl! 
proliability  it  is  a  simple  element  having 
only  one  mass  value,  27.  Dr.  Aston  re- 
marks that  as  a  rule  odd  atomic-weight  ele- 
ments have  never  more  than  two  isotopes, 
and  the  occasional  appearance  of  the  line 
13.5  is  iprobably  due  to  AI  +  +  from  the  elec- 
trodes. The  line  27  has,  however,  been  ob- 
served. Lines  02  and  97.  also  recorded, 
indicate  mono-  and  dichlorides  of  bodies  of 
masses  27  and  28.  The  latter  may  be  Si" 
or  CO,  but  the  former  is  probably  alu- 
minium, and  Dr.  .\ston  says  "  it  is  there- 
fore reasonably  certain  that  this  element 
consists  mainly  of  atoms  of  mass  27,  and 
since  there  is  no  evidence  of  atoms  of 
lighter  mass,  the  chemical  atomic  weight 
leads  definitely  to  the  conclusion  that  it  is 
simple." 

Chlorine. — In  the  foregoing  experiments 
exceedingly  intense  lines,  35,  36,  37,  38, 
have  been  obtained,  but  no  trace  of  a  line 
at  39,  and  Dr.  Aston  concludes  that  the  hy- 
pothetical isotope  39  does  not  exist. 

Antimony. — Antimony  hydride  proved  of 
no  \ise,  but  antimony  methide.  prepared  bv 
Prof.  O.  T.  Morgan,  when  introduced  with 
COj,  gave  values  121  and  123.  With  s\iffi- 
cient  exposure  similar  lines  appear  15  and 


30  units  higher  u,p  on  the  mass  scale  due  to 
the  mono-  and  dimethide  respectively. 
Faint  companion  lines,  122  and  124,  appear 
to  be  due  to  hydrides  from  their  in-egular 
intensities.  The  antimony  isotopes  seem 
to  be  in  accord  with  the  whole-number  rule. 
The  atomic  weight  as  determined  by  Wil- 
lard  and  McAIpine  is  121.77,  which  agrees 
with  the  mean  estimate  of  the  above  iso- 
topes, judging  from  the  relative  intensities 
of  the  lines. 

Table  of  Isotopes. 
Dr.  Aston  gives  the  table  of  isotopes  as 
appeared  in  this  Journal  March  9,  1923, 
and  he  proposes  to  call  the  integers  mass- 
numhers,  as  it  is  evident  from  the  fore- 
going that  there  are  some  cases  where  the 
deviation  from  whole  numbers,  though 
small,  is  still  appreciable.  The  mass  num- 
bers are  given  in  the  wder  of  the  intensity 
of  the  mass  lines,  and  numbers  in  brackets 
are  provisional. 

Sri'FLK.MKXTARY    XoTES. 

Those  wishing  to  studv  the  literature  ex- 
clusively devott'd  to  the  non-radioactive 
isotfjpes  from  the  experimental  (discovery) 
point  of  view  should  consult  the  following 
iit+'rature:  — 

Aston:  ATaft/rc— Nov.  27,  1919;  Dec.  18. 
1919;  Mar.  4.  1920;  July  1,  1920;  Dec.  9, 
1920;  Mar.  17.  1921;  June  28,  1921;  Se,pt. 
2.  H>22;  Jum-  21.  1922;  Nov.  18.  1922; 
Dec.  2,  1922;  June  2,  1923. 

.\ston  and  Thomson :  Nature — p>b.  24, 
1921. 

Aston  :  PhiloHophical  Magazine — April, 
1920;  May,  1920;  Nov.,  1920;  July,  1921; 
Sept..  1921;  May,  1923. 

G.  P.  Thomson  :  Philogophical  Maqazine 
-Nov..  1921. 

Dempster:  Science — April  15,  1921; 
Dee.  10.  1921. 

Dempster:  Phtjstical  Hrvinr  —  Dec, 
'  '1:  March,  1922;  Dec,  1922. 

The  basic  discovery  that  stimulated  re- 
search in  connection  with  isotopes  of  the 
non-radioactive  class  was  made  by  Sir  J. 
J.  Thomson  when  he  revealed  the  duality 
of  neon.  See  his  book,  "  Rays  of  Positive 
Electricity."  1913,  or  later  edition. 

The  above  list  may  be  extended  to  in- 
clude experiments  made  to  separate  iso- 
topes, their  classification,  those  belonging 
to  the  radio-active  class,  theoretical  views, 
etc. 

.\nnouncements  of  the  discoveries  ap- 
pear in  Nature  and  Science.  For 
fuller  accounts  see  Philoitophical  Magazine 
and  Physical  Review,  ns  listed  above. 


356 


THE  CHEMICAL  NEWS. 


JUNEl  8.  1923. 


A  NOTE  ON  liAFFIE  MELON  OIL, 
^    Analyses  of  Seeds. 

-   By  Chas.  F.  Juritz,  M.A.,  D.Sc, 
F.R.S.E.,  F.R.S.{S.Af.),  F.I.C. 

In  Science  Bulletin  No.  6  of  the  Depart- 
ment of  Agriculture,  I  tabulated  thirty- 
eight  anal^'Ses  o  fthe  ring,  seed,  and  puljp  of 
the  two  well-known  varieties  of  kaflfir  melon 
(Tsamma  and  Monketaan),  made,  in  the 
latter  case,  at  different  stages  of  ripening, 
and  also  gave  a  brief  description  of  the 
melons  and  their  adaptability  as  stock- 
food.  Only  one  analysis  of  tsamma  seed 
was'  made,  and  in  that  case  the  yield  of  fat 
or  oil  from  the  fresh  seed  was  4.64  per 
cent.,  the  corresponding  oil-content  of  fresh 
monketaan  seed  ranging  (according  to  eight 
analyses)  from  20.25  per  cent,  to  23.10  per 
cent. 

The  analyses  above  referred  to  were 
shortly  summarised  by  Professor  M.  Eindl 
in  the  course  of  his  article  on  "  Vegetable 
Oils  and  Fats  "  in  the  December,  1920, 
issue  of  the  South  African  Journal  of  In- 
dustries. 

The  tsamma  analysed  eight  years  ago 
had  grown  in  the  Vryburg  district,  and  the 
monketaans  in  the  Cape  Peninsula.  Early 
in  1920  I  procured,  through  the  Magistrate 
of  Kuruman,  suppUes  of  tsamma  and  mon- 
ketaan seed  from  the  vicinity  of  the  Kala- 
hari Desert. 

These  seeds  (without  further  drying)  were 
analysed,  with  the  following  results:  — 


Tsamma 

Monketaan 

Seed. 

Seed. 

Per  cent. 

Per  cent. 

Water      ... 

6.57 

7.04 

Oil        

12.85 

22.10 

The  oils,  which  were  of  a  paTe-yellnw 
colour,  were  extracted  by  means  of  ether, 
and  showed  the  following  constants: 

Tsamma  Monketaan 

Seed  Oil.  Seed  Oil. 
Specific  gravity  at 

15.5°  C.       0.917  0.930 

Refractive      index 

at  40°  C 1.4684  1.4668 

Iodine   value    131.5  118.8 

Saponification 

value       161.1  187.9 

Acid  value      1.8  5.8 


The  iodine  value  o£  an  oil  indicates  the 
mount  of  oxygen  the  oil  is  capable  of  ab- 
sorbing from  the  air,  and  therefore  of  drying 
to  a  solid  elastic  film  when  exposed  to  the 
air  in  thin  layers.  A  good  drying  vegetable 
oil  usually  shows  an  iodine  value  between 
120  and  200,  whereas  the  iodine  value  of  a 
semi-drying  oil  lies  between  100  and  120, 
and  that  of  a  non-drying  oil  between  80  and 
100.  The  monketaan  oil  examined  seems 
to  be  near  the  border  line,  but  the  tsamma 
oil  is  well  within  the  region  of  flie  drying- 
oils.  The  iodine  value  of  linseed  oil,  how- 
ever, is  much  higher,  and  varies  from  175  to 
200.  Tsamma  oil,  in  this  respect,  more 
nearly  resembles  sunflower  oil  (with  an 
iodine  value  of  about  130)  and  soya  bean  oil 
(with  a  range  between  126  and  135). 

The  saiponitiction  value  of  an  oil  is  an  in- 
dex of  the  proportion  of  alkali  needed  to 
convert  a  certam  quantitj^'  of  the  oil  into 
soap  :  hence  it  indicates  the  amount  of  the 
particular  oil  which,  when  treated  with  al- 
kali, would  be  required  in  order  to  produce 
a  definite  quantity  of  soap.  Waxes,  which 
are  not  cajpable  of  yielding  soap,  have  rela- 
tively low  saponification  values,  which 
rarely  rise  above  140.  Lard  and  tallow,  on 
the  other  hand,  aipproximate  to  200  in  their 
saponification  values,  while  butter-fat  ex- 
ceeds 220.  The  tsamma  oil  shows  one  of 
the  lowest  saponification  values  in  the  re- 
cords of  vegetable  oils,  but  the  monketaan 
oil  is  closer  to  the  usual  average  of  this  typo 
of  oil. 


The  acid  value  shows  the  proportion  of 
free  acids  in  an  oil,  and  is  subject  to  con- 
siderable variation  in  which  the  age  and 
quality  of  the  oil  often  play  a  great  part.  A 
high  acid  value  is  objectionable  in  an  ^il  in 
many  ways  :  if  the  oil  is  intended  for  edible 
purposes,  the  presence  of  much  free  acid 
produces  a  sharp  unpleasant  flavour;  it 
lowers  the  oifs  potential  yield  of  glycerine ; 
it  imparts  corrosive  qualities  to  the  oil  as  a 
lubricant;  the  free  acid  tends  to  cause 
blocking  of  oil-ducts  by  crystallising;  and 
in  medicinal  and  pharmaceutical  prepara- 
tinns  its  action  on  skin  and  raucous  mem- 
brane is  of  an  irritant  nature.  In  neither 
case  quoted  above  is  there  any  objectior? 
against  the  melon  oil. 


JUNE  8,  1923. 


THE  CHEMICAL  NEWS. 


357 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAI;  SOCIETY. 

Thursday,  May  31. 

Papers  read  :  — 

E.  Griffiths,  D.Sc.,  and  G.  W.  C.  Kaye, 
D.Sc.  The  Measurement  of  Thermal  Con- 
ductivity, No.  1.  Communicated  by  vSir 
Joseph  Petavel,  F.R.S. 

Among  the  points  dealt  with  in  the 
paper  were  the  thermal  resistance  at  the 
bounding:  faces  of  a  material,  the  effect  of 
superimposing  layers  of  compressible 
material,  the  measurement  of  the  thickness 
of  compressible  material,  tlie  dependence 
of  the  conductivity  of  timlxr  on  structure 
and  moisture-content,  the  variation  of  the 
conductivity  of  rubber  with  mineral  con- 
tent. 

G.  W.  C.  Kaye,  D.Sc.,  and  J.  K. 
Kdukkts,  Ph.D.  The  Thermal  Conduc- 
liiilics  of  Metal  Crystals.  /. — Bismuth. 
Communicated  by  Sir  Joseph  Petavel, 
K.R.S. 

Previously  all  accurate  measurements  of 
the  tlicrmai  conductivity  of  metals  have 
been  made  on  bars  of  heterogeneous  struc- 
ture. It  was  thought  desirable  to  compare 
the  values  so  obtained  with  the  more  funda- 
mental ones  given  by  single  crystals. 

A  "  plate  "  apparatus  has  been  developed 
which  makes  it  possible  to  measure  thermal 
conductivities  as  high  as  0.02  c.g.s.  with  an 
accuracy  of  about  1  per  cent.,  using  speci- 
mens 2  cms.  by  1  cm.  in  area  and  about  1 
or  2  mm.  in  thickness. 

The  thermal  conductivities  of  single 
crystals  of  metallic  bismuth  have  been 
determined  in  directions  parallel  and  per- 
pendicular to  the  trigonal  axis.  The  values 
found  at  18°  C.  are,  in  c.g.s.  units:  — 
Thermal  conductivity  of  bismuth 

parallel  to  trigonal  a.xis  ...   =0.0159 

Thermal  conductivity  of  bismuth 

|)erpendicular  to  trigonal  axis  =0.0221 
Ratio  of  conductivities     =1.39 

The  mean  value  0.0191  agrees  well  with 
the  figure  0.0193  obtained  on  bars  by 
Jaeger  and  Diesselhorst  in  1899. 

This  agreement  indicates  that  in  the  case 
of  bismuth  metal  in  the  aggregate,  the  dis- 
tiilmtioii  of  the  constituent  small  crystals 
is  random,  and  that  the  effect  on  the 
thermal  conductivity  of  such  inter-crystal- 


line layers  as  may  be  present  is  not  appre- 
ciable. It  is  hoped  to  carry  out  experiments 
on  other  metal  crystals  to  see  whether  this 
result  is  generally  true. 

C.  V.  Drvsdalh  and  S.  Butterworth. 
The  Distribution  of  the  Magnetic  Field  and 
Return  Current  Round  a  Submarine  Cable 
carrying  Alternatimr  Current.  Communi- 
cated by  F.  E.  vSmith,  F.R.S. 

Part  I.     (By  C.  V.  Drysuai.e.) 

The  exijcrimental  results  obtained  con- 
firm the  values  of  the  velocity  of  propaga- 
tion and  attenuation  derived  from  theory, 
and  the  field  distribution  above  the  surface 
agrees  very  fairly  with  the  theory  of  Mr. 
Butterworth  derived  from  consideration  of 
the  water  as  a  conducting  lamina. 

Part  II.    (By  S.  Butterworth.) 

Expressions  for  the  distribution  of  elec- 
tric force  due  to  a  long  cable  carrying 
alternating  currents  and  immersed  in  a  sea 
of  uniform  depth  have  been  obtained  in  the 
torm  of  Fourier  integrals.  From  these  in- 
tegrals formulse  have  been  developed  which 
cover  the  following  cases  :  — 

(1)  Tlie  field  alx)vc  the  surface  of  the  sea 

when  the  depth  of  the  water  is  small. 

(2)  The  field  almvc  the  sea  at  large  dis- 

tances from   the  cable,  there  being 
no  restriction  in  regard  to  depth. 

(3)  The  field  below  the  surface  of  the  sea 

for  i)oints  vertically  alx)ve  the  cable. 

(4)  The  field  below  the  surface  of  the  sea 
at  large  distances  from  the  cable 
when  the  depth  of  the  sea  is  great. 

Sidney  Russ,  D.vSc.  The  Effect  of  X- 
rays  of  Different  Wave-Lengths  upon  Some 
Animal  Tissues.  Communicated  by  Prof. 
A.  W.  Porter,  F.R.S. 

The  experiments  recorded  were  designed 
to  find  whether  a  diflFerential  action  exists 
when  X-rays  of  different  wave-lengths  act 
upon  animal  tissues.  Two  regions  in  the 
X-ray  spectrum  were  selected,  and  it  was 
arranged  that  equal  doses  of  X-ray  energy 
were  absorbed  in  their  passage  through  the 
tissues.  It  was  found  that  under  these  cir- 
cumstances more  profound  effects  were  pro- 
duced by  the  longer  wave-lengths  (0.45  to 
0.30  A.IJ.)  than  by  the  shorter  wave- 
lengths (alx>ut  0.168  A.U.),  both  upon  the 
normal  skin  of  the  rat  and  upon  Jensen's 
rat  sarcoma.  The  degree  of  this  differ- 
ential action  is  more  pronounced  in  the  case 


358 


^     THE  CHEMICAL  NEWS. 


JUNE  8,  1923. 


of  the  skin  than  it  is  for  the  tumour,  the 
numerical  values  being  6  and  2.6  respec- 
tively. It  is  proposed  that  these  numbers 
be  termed  "  therapeutic  factors,"  and  the 
bearing  they  have  in  radio-therapeutics  is 
discussed. 


Papers  read  in  title  only  :  — 

E.  F.  Armstrong,  F.R.S.,  and  T.  P. 
HiLDiTCH,  D.Sc.  A  study  of  Catalytic 
Actions  at  Solid  Surfaces.  Part  XI. — The 
Action  of  Alumina  and  Certain  Other 
Oxides  in  Promoting  the  Aciivity  of  Nickel 
Catalyst. 

In  the  absence  of  any  carrier  for  the 
nickel,  the  presence  of  a  small  proportion 
(up  to  5  per  cent.)  of  an  oxide,  such  as  that 
of  aluminium  or  magnesium,  etc.,  causes 
considerable  increase  in  the  catalytic  acti- 
vity of  the  reduced  metal,  the  mixed 
oxides  being  prepared  by  precipitation  from 
a  solution  of  the  corresponding  mixed  salts. 

When  the  nickel  oxide  is  deposited  on  a 
support,  the  behaviour  is  different.  Thus 
kieselguhr,  from  which  the  metallic  con- 
stituents have  been  extracted,  gives  a  nickel 
catalyst  inferior  to  that  on  natural  kiesel- 
guhr. The  activity  of  the  resulting  cata- 
lyst is  restored  if  alumina  to  the  extent  of 
about  20  per  cent,  of  the  nickel  is  precipi- 
tated with  the  hydroxide  of  the  latter, 
whereas  a  proportion  of  alumina  equal  to 
that  of  the  nickel  depresses  the  catalytic 
activity  of  the  product  again.  If,  however, 
the  latter  proportion  of  alumina  is  first  de- 
posited on  the  acid-extracted  kieselguhr 
and  the  nickel  hydroxide  or  carbonate  then 
precipitated  on  to  this  preparation,  the  cata- 
lytic activity  of  the  product  generally  ex- 
ceeds that  of  nickel  on  the  natural  kiesel- 
guhr. 

All  these  observations  are  explicable  on 
the  hypothesis  that  the  action  of  the  non- 
reducible oxide  is  mainly  mechanical  and 
connected  with  increase  or  diminution  of 
the  surface  area  of  the  exposed  nickel. 

We  have  not  been  able  to  effect  more 
hydrogenation  with  a  given  weight  of  re- 
duced nickel  in  presence  of  these  oxides 
than  with  the  same  weight  of  nickel  de- 
posited in  the  ordinary  way  on  a  suitable 
support  offering  a  maximum  of  surface,  and 
accordingly  we  believe  that  the  "promoter" 
cfifect  observed  is  simply  due  to  their 
influence  on  the  available  surface  of  the 
reduced  nickel. 


N.  K.  Adam.  The  Structure  of  Thin 
Films.  Part  7F. — Benzene  Derivatives. — 
A  Condition  of  Stability  in  Monomolecular 
Films.  Communicated  by  W.  B,  Hardy, 
Sec.  R.S. 

1.  Derivatives  of  benzene,  such  as  hexa- 
decyl  phenol,  containing  one  long  chain 
and  one  polar  group  in  the  para  position, 
orient  on  water  surfaces  like  fatty  acids,  the 
phenol  group  forming  the  head  of  the  mole- 
cule in  contact  with  the  water.  Measure- 
ments of  the  cross-section  of  the  head  by 
the  method  of  Part  II.  of  these  papers  gave 
a  result  in  good  agreement  with  the  corre- 
sponding cross-section  of  the  nuclei  of 
aromatic  compounds,  deduced  from  Bragg's 
measurements  on  crystals.  The  relation  be- 
tween the  films  on  water  and  the  mono- 
molecular  layer,  which  would  be  obtained 
by  repeated  cleavage  of  the  crystal,  is 
explained. 

2.  Films  of  these  compounds  show  the 
usual  phenomena  of  expansion  to  a  two- 
dimensional  vapour,  described  in  Part  III. 

3.  Compounds  such  as  cetyl  palmitate, 
palmitic  anilide,  etc.,  which  contain  one 
polar  group  placed  between  two  chains  or 
one  chain  and  a  ring,  do  not  adhere  to  a 
water  surface  well  enough  to  give  measur- 
able condensed  films,  though  in  the  ex- 
panded state  such  films  are  often  more 
stable. 

4.  The  para  sulphonic  acids  in  hexadecyl 
and  octadecyl  benzene  give  soap-like  solu- 
tions in  water. 

N.  K.  Adam.  The  Structure  of  Thin 
Films.  Part  V.  Communicated  by  W.  B. 
Hardy,  Sec.  R.S. 

1.  Bromine  in  the  a  position  in  the  brorno- 
acids  and  esters,  increases  the  cross-section 
of  the  molecules  in  the  films.  The  heads  of 
bromo-acids  may  pack  in  several  different 
arrangements,  having  areas  from  32.8  A.U. 
to  26  A.U. 

2.  The  bromine  atom  increases  the  solu- 
bility of  films  of  the  higher  fatty  acids.  It 
also  lowers  the  temperature  of  change  from 
condensed  to  expanded  films  ;  byt  it  does 
not  appreciably  affect  the  properties  of  the 
films  when  expanded. 

3.  The  double  linkage  in  the  a  (3  position 
relative  to  the  COOC2H5  group  increases 
the  cross-section  of  the  molecule  in  the 
films,  as  it  does  in  iso-oleic  acid. 

4.  The  transition  betwen  two  forms  of 
condensed  film,  such  as  those  found  with 
the    substituted  areas,    seems  exactly  ana- 


JUNE  8,  1923. 


THE  CHEMICAL  NEWS 


359 


logons  to  that  between  two  polymorphs  or 
allotropic  modifications  of  solid  substances. 
5.  The  law  found  in  Part  III.,  giving  the 
increase  of  the  temperature  of  expansion  of 
the  films  with  increasing  length  of  the 
hydrocarbon  chains,  has  been  confirmed  on 
eight  homologous  series. 

\V.  B.  RiM.MER.  The  Spectrum  of  Am- 
monia. Communicated  by  Prof.  A.  Fowler, 
F.R.S. 

Of  the  three  bands  which  are  associated 
with  the  spectrum  of  anmionia,  the  ultra- 
violet band  has  already  been  investigated  in 
detail  by  P'owler  and  (Gregory,  and  has  been 
found  to  be  represented  in  the  solar  spec- 
trum. In  the  present  investigation  atten- 
tion has  been  specially  directed  to  the 
"Schuster  bands,"  A  5635  and  A  5070,  and 
the  "  a  band  "  of  Eder  and  Valenta. 

The  vSchustcr  bands  have  given  no  sign 
of  resolution  under  high  dispersion,  and  it 
is  probable  that  they  do  not  occur  in  the 
solar  spectruni.  The  a  l)and  is  of  great 
complexity,  consisting  of  alx)Ut  3,000  lines, 
of  which  many  of  the  ])rightest  have  been 
measvred  with  sufficient  accuracy  for  pro- 
per comparison  with  the  solar  spectrum  ; 
there  is,  however,  no  conclusive  evidence 
that  this  band  occurs  either  in  the  solar 
spectrum  or  in  the  spectrum  of  sunsi>ots. 

Observations  under  a  variety  of  experi- 
mental conditions  are  in  accordance  with 
previous  conclusions  that  the  Schuster 
l)ands  have  their  origin  in  the  normal  am- 
monia molecule  ;  while  the  ultra-violet  l>and 
is  probably  due  to  emission  from  a  more 
stable  combination  of  nitrogen  and  hydro- 
gen.    In  addition,  it  is  concluded  that  the 

band  is  associated  with  a  combination  of 
nitrogen  and  hydrogen  of  intermediate 
stability. 

The  occurrence  of  the  ultra-violet  band 
alone  in  the  solar  spectrum  thus  indicates 
that  only  the  most  stable  combination  of 
nitrogen  and  hydrogen  can  exist  under  the 
conditions  that  obtain  in  the  reversing 
layer. 


KOYAL  SOCIETY  OF  ARTS. 
A  lecture  was  given  before  the  Dominions 
and  CoUmics  Section,  on  Tuesday,  June 
5.  entitl('(l  The  Economic  Conference  and 
ihr  Colnniea,  by  Sir  EinvAun  Davson.  His 
Clraoo  the  Dnko  of  D.vonshire,  K.G.. 
(i.C.M.G..  O.C.V.O.,  P.C,  Secretary  of 
Statv  for  the  Colonies,  presided. 


THE    FARADAY    SOCIETY. 

General  Discussion  on  the  Physical 
Chemistry  of  the  Photographic  Process. 

At  the  meetings  on  May  28. 

(Continued  from  Page  352.) 

The  Theory  of  Photography,  by  Wilder 
D.  Bancroft  (Cornell  University,  U.S.A.). 

The  three  fundamental  things  in  photo- 
graphy are  Emulsion,  Latent  Image,  and 
Development.  The  question  of  the  latent 
image  may  be  considered  as  almost  settled. 
I  present  to-day  a  theory  of  development. 
The  theory  of  the  emulsion  is  still  very 
much  up  in  the  air  in  spite  of  the  work  done 
in  the  last  few  years. 

The  Emulsion. 

The  photographic  emulsion  consists  es- 
sentially of  silver  bromide  dispersed  in 
gelatine  and  usually  submitted  to  a  ripen- 
ing process  to  increase  its  sensitiveness. 
Fust  plates  ccmtain  some  silver  iodide,  and 
slow  plates  silver  chlwide.  The  question  of 
ripening  involves  what  Svedberg  called 
plate-sensitiveness,  and  was  studied  by 
Hurtor  and  Driffield.  Since  the  condrtions 
of  emulsion  making  are  keipt  secret  by  the 
makers,  the  development  of  u  theory  of 
emulsion  making  has  been  slow,  and  H  is 
extremelj'  probahlo  that  present  enmlsions 
art'  nothing  like  as  good  as  they  would  have 
IxH-n.  had  the  problem  been  one  which 
could  have  been  studied  by  more  people. 

Plate  Scnsiiivcncaa. — The  ripening  of  an 
emulsion  involves  the  dissolving  and  repre- 
cipitation  of  silver  bromide.  It  has  been 
generally  believed  that  a  coarse  grain  is 
more  sensitive  than  a  fine  one,  but  this  is 
not  always  necessarily  true.  At  present  it 
is  generally  admitted  that  there  is  no  neces- 
sary connection  between  size  of  grain  and 
speed,  although  under  apparently  similar 
conditions  the  plate  with  the  coarser  grains 
is  usually  faster.  Sensitiveness  is  due  to 
differences  in  structure  or  composition  of 
silver  bromide  grains.  The  smallest  grains 
of  the  bromide  are  definitely  crystalline  and 
have  the  same  structure  as  the  larger  ones, 
the  crystalline  form  being  a  cubic  lattice. 
Trivelli  and  Sheppard  have  shown  that  sil- 
ver bromide  crystals  belong  in  the  dynkis- 
dfxlocahedral  class  and  there  is  no  sufficient 
n-ason  for  assuming  the  existence  at  an  or- 
dinary temperntuns  of  a  cfnble  or  metn- 
stabk'  bromide. 


mo 


THE  CHEMICAL  NEWS. 


JUNE  8,  1923. 


Ripening  is  not  due  to  a  reduction,  to  a 
series  of  allotroipic  modifications,  or  to  a 
coarsening  of  the  grain  as  such.  That  eli- 
minates changes  in  the  composition  of  the 
silver  bromide  itself,  changes  in  the  chemi- 
cal state  of  the  silver  bromide,  and 
changes  in  the  physical  state  of  the  silver 
bromide  alone,  which  leaves  us  facing  a 
blank  wall  if  we  postulate  that  the  effec- 
tive grain  is  pure  silver  bromide.  The  only 
aipparent  way  out  of  the  dilftculty  is  to  pos- 
tulate that  the  silver  bromide  grain  is  a 
complex  of  silver  bromide,  gelatine,  and 
water,  and  that  ripening  consists  in  an  un- 
sipecified  change  in  the  relative  proportions 
of  these  three.  Since  this  was  written, 
lleinders  has  shown  that  silver  chloride 
crystals  contain  gelatine  when  they  separ- 
ate from  an  ammoniacal  solution  of  silver 
chloride  to  which  gelatine  has  been  added. 
While  it  is  probable  that  silver  bromide  be- 
haves in  the  same  way,  this  seems  to  have 
been  assumed  rather  than  to  have  been 
shown  experimentally.  Recent  work  on 
catalysis  shows  that  adsorption  and  cataly- 
tic activity  vary  enormously  with  the  struc- 
ture of  the  surface,  and  perhaps  we  are 
dealing  with  gelatine  adsorbed  at  the  sur- 
face of  silver  bromide  crystals  and  not  en- 
tangled in  the  space  lattice.  If  the  action 
of  the  gelatine  is  solely  on  the  surface,  it 
should  be'  possible  to  make  a  fast  plate  by 
precipitating  silver  bromide  under  suitable 
conditions  from  an  aqueous  solution  and 
emulsifying  the  crystals  in  gelatine. 

It  is  possible  to  obtain  a  much  faster 
plate  with  gelatine  than  with  dry  collodion. 

Grain  Sensitiveness. — It  is  admitted  that 
the  silver  bromide  grain  is  the  unit,  though 
the  group  of  grains  may  act  as  a  single 
grain.  We  should  thus  expect  to  get  the 
same  blackening  on  prolonged  development 
for  widely  varying  exposures,  which  is  not 
so.  The  following  hypotheses  may  be 
made  to  account  for  this  :  — 

1.  The  incident  light  may  not  be  homo- 
geneous. 

2.  The  opacity  of  the  silver  may  vary 
with  the  exposure. 

3.  The  grains  in  an  emulsion  may  vary  in 
sensitiveness. 

Silberstein,  who  starts  from  Einstein's 
hypothesis  that  "light  does  not  consist  in  a 
continuous  distribution  of  energy,  as  in  the 
classical  theory,  but  is  entirely  split  up  into 
light  quanta  or  diserele  parcels  of  very  con- 
centrated monochromatic  light,  each  parcel 
containing  a  quantum  of  energy,"  considers 
that  the  broniide  grains  are  bombarded  by 


light-darts  and  that  a  grain  is  made  develop- 
able only  when  the  axis  of  the  dart  hits 
it  in  a  point  not  too  near  the  edge. 

The  bombardment,  without  the  concep- 
tion of  darts,  had  been  suggested  previously 
by  Lowry.  But  Clark  has  made  attem,pts 
to  see  whether  the  development  of  silver 
haloid  grains  after  treatment  with  sodium 
arsenite  proceeded  in  the  same  way  as 
when  light  is  used,  or  X-rays,  for  making 
the  plate  developable.  Single-layer  plates 
were  prepared  from  a  commercial  ultra- 
rapid  plate  in  the  manner  described  by 
Slade  and  Higson.  The  grains  in  the  emul- 
sion were  mostly  fiat  plates.  The  emulsion 
used  was  the  same  as  that  employed  by 
Toy.  The  plate  obtained  as  described  was 
examined  ii  the  microscoipe.  A  few  of  the 
grains  were  observed  to  be  changed  com- 
pletely ;  but  the  majority  showed  centres 
exactly  similar  in  appearance  to  those  ob- 
tained by  Toy  when  exposure  is  to  light. 
These  results  indicate  that  the  reduction 
centres  are  an  essential  part  of  the  grain 
structure,  and  t|^at  they  exist  in  the  grains 
from  the  time  the  emulsion  is  made. 

We  are  forced  to  conclude,  Mees  pointed 
out  (in  1915),  that  grains  in  an  emulsion  are 
of  many  sizes,  and  both  the  sensitiveness 
and  plate  curve  depend  on  the  distribution 
of  the  different  sizes  of  grains.  Svedberg 
showed  later  that  with  grains  of  the  same 
size,  the  same  type  of  curve  is  obtained  as 
with  grains  of  assorted  sizes.  We  may. look 
upon  each  grain  as  either  entirely  develop- 
able or  not  developable  at  all.  The  be- 
haviour of  a  haloid  grain  towards  a  de- 
veloper should  vary  with  exposure  in  a  dis- 
continuous way ;  when  the  exposure  has 
reached  a  certain  minimum  limit  the  grain 
becomes  developable  and  remains  so  until 
the  exposure  has  reached  a  maximum  limit 
— solarisation — when  the  grain  suddenly 
loses  its  reducibility. 

Svedberg  (l;)-j,2)  stated  that  the  substance 
of  the  latent  image  in  the  haloid  grain  con- 
sists of  small  centres  distributed  through  it 
or  its  light-affected  part,  and  these  centres 
are  distributed  by  chance. 

Later,  Svedberg  stated  that  a  statistical 
study  of  the  distribution  of  the  centri^s 
showed  that  within  each  size-class  of  grain 
they  were  distributed  according  to  chance. 

In  the  emulsion  with  nearly  spherical 
grains,  of  narrow  range  of  sizes,  mutual  in- 
fection occurs  little  if  at  all;  while  in  emul- 
sions with  a  wide  range  of  grahi  sizes  and 
having  many  large  polyhedral  tablets, 
mutual  infection  iplays  a  large  role  in  deter- 


■JUNE  8,  1928. 


THE  CHEMICAL  NEWS. 


361 


.  4i 
cining  the  "speed"  and  the  density  per 
unit  exposure  increment.  The  result  is  evi- 
dently of  capital  importance  for  the  thewy 
of  sensitivity  and  exposure ;  for  whether  the 
high  correlation  of  grain  size  with  effective 
sensitivity  is  due  to  a  discrete  structure  of 
radiation,  or  to  a  pre-existing  change  distri- 
bution of  sensitising  nuclei  amongst  grains, 
it  is  evident  that  the  extension  of  the  defini- 
tion of  grain  size  to  clumps,  the  existence 
of  mutual  infection,  is  of  basic  importance 
for  photographic  theory. 

Latent  Itnayc. 
Owing  to  the  very  slight  change  in  silver 
bromide  on  short  exposure,  it  has  always 
been  popular  to  assume  that  the  latent 
image  is  a  physical  or  allotropic  modifica- 
tion. Xamias  assumed  ipolymerisation, 
Hurter  and  Driffield  depolymerisation, 
Bredig  mechanical  disintegratkm,  Chap- 
man Jones  labile  fonn,  and  Bose  a 
mechanical  strain.  All  these  assumptions, 
and  the  further  one  of  von  Tugolessow  that 
the  latent  image  is  an  oxidation  product, 
fail,  since  all  the  phenomena  of  the  latent 
image  can  b(!  duplicated  by  immersing  the 
phit<3  in  a  solution  of  a  weak-reducin}, 
agent,  such  as  sodium  arscnite.  This 
proves  that  the  latent  image  is  a  reduction 
product  of  silver  bromide.  It  oannot  be  a 
single,  definite  subhaloid  because  no  such 
compound  has  been  prepand.  No  satisfac- 
tory chemical  reactions  can  be  assigni-d  to 
it,  and  the  prolonged  action  of  light  (hxs 
not  yield  the  pure  compound,  and  this  hy- 
pothesis cannot  be  reconciled  with  the 
facts  of  Rolarisation. 

Trivclli  at  one  time  postulated  the  exist- 
ence of  green  Ag'Br^  blue  A^''*Br*,  yellow 
Ag^Br",  and  red  Ag»Br* ;  but  he  probably 
docs  not  believe  in  them  now. 

The  latent  image  cannot  be  free  metallic 
silver  (nucleus  theory),  as  it  does  not  show 
the  reactions  of  free  silver,  and  because  the 
hypothesis  cannot  be  reconciled  with  solari- 
sation. 

It  is  due  to  silver  adsorbed  by  the  bro- 
nude  because  it  can  be  prepared  synthetic- 
ally. It  behaves  like  a  phase  of  continu- 
ously varying  composition.  This  hyi)otli( - 
sis  also  accounts  for  all  the  chemical  re- 
actions of  the  latent  imagt>,  and  for  the 
facts  of  solarisation. 

The    Developer. 
The   theory   usually     h«ld   regarding    de- 
velopment of    the  latent,  [wa'j:^    is  that  the 
developer    is  a  reducing    ag<  iil     sufiieiently 
powerful  to  reduce  exposed  silver  bromide 


and  yet  not  powerful  enough  to  reduce  un- 
exposed silver  bromide. 

A  theory  of  photographic  development 
must  account  for  the  following : 

1.  A  developer  must  be  a  fairly  strong 
reducing  agent,  and  yet  it  is  apparently  im- 
possible to  produce  a  satisfactory  negative 
with  stannous  chloride,  m-aminophenol, 
formaldehyde,  or  gallio  acid. 

2.  There  is  no  appreciable  difference  be- 
tween the  electromotive  forces  of  unexposed 
silver  bromide  and  of  that  which  has  re- 
ceived a  short  cxiposure. 

3.  All  developers  develop  gelatine  free 
silver  bromide  readily  even  though  the  sil- 
\  t-r  bromide  has  not  been  exposed  to  light. 

4.  Most  developers  give  negatives  after 
very  short  expoaures  and  positives  after 
very  long  ones. 

u.  Some  developers  give  positives  with 
very  short  exposures. 

•     0.  With  any  one  develqper    the  exposure 

;  necessary  to  cause  a  change  from  negative 
to  positive  varies  w  ith  varying  concentra- 
tion of  the  develoix.'r. 

,.  7.  Very  dilute  developers  act  like  light 
ami  decompose  silver  bromide  without  de- 
veloping it. 

8.   Some    developers    work    rapidly    and 

j  others  slowly;  the  difference    is  not  always 
one  of  reducing  power  as  measured    by  elec- 
tromotive foi'ce,  though  this  is  unquestion- 
ably u  factor, 
y.  Bromide  is  very    effective  with    some 

j  developers  and  less  so  with  others. 
!      The  fact  that  we  get  a  negative  with  one 
^  develeiper    and     a    positive     with     another 
I  shows    that  the  potentials    of  exposed    and 
unexposed  silver  bromides    are  not  the  sole 
factors.        Developers  must  therefore   have 
other     functions    than     those    of    reducing 
agents  of  varying  strengths.     The  sunplest 
assumption  seems  to  be  that  we  have  selec- 
tive adsorption  and  thereby  markedly  vary- 
ing concentration  at  the  surfaces  of  the  sil- 
ver bromide  grains.     If  the  reducing  agent 
is  adsorbed  much  more  strongly  by  exposed 
silver    bromidt;    than  by    unexjposed    silver 
bromide,     the    former    will    develrjp    more 
rapidly  than  thi'    latter  and  we  shall  get    a 
negative.     If  the  reducing  agent  is  adsorbed 
more  strongly  by  the  unexposed  silver  bro- 
mide than  by  the  txpoeed  silver  bromide  we 
shall  get    a  positive.       By    the    adsorpticMi 
theory  we  are    thus  able  to  predict  the;  pos- 
.sible  existence  of  the    three  types  of  fairly 
strong  reducing  agents  that  we  actually  en- 
counter; but  that  does  not  necessarily  mean 


862 


THE  CHEMICAL  NEWS. 


JUNE  8,  1923. 


that  the  develoipers  really  behave  in  this 
way.  Until  some  independent  proof  is  fur- 
nished, the  theory  remains  an  assumption. 
In  Ij-IB  I  discussed  the  theory  of  the  de- 
veloper exclusively  from  the  point  of  view 
of  selective  peptisation.  I  have  now  laid 
stress  on  selective  adsorption  with  selective 
peptisation  as  a  resultant  phenomenon, 
partly  because  it  seems  to  me  a  better  way 
of  presenting  the  subject,  but  also  because 
Dr.  Sheppard  tells  me  that  this  way  of  pre- 
senting the  matter  will  meet  with  less  oppo- 
sition from  those  who  know  about  photo- 
graiphy. 

The  Most    Important    Adsorption    Reac- 
tions   in  the    Photographic    Film,    by    Dr. 
Luppo-Cramer  (Schweinfurt  in  Bayern). 
Adsorption  Phenomena  of  Silver  Haloids. 

Primary  consideration  should  be  given  to 
the  latent  image,  but  I  shall  confine  my 
attention  to  Optical  Sensitising  and  De- 
sensitising. 

In  1873  Vogel  discovered  the  method  of 
optical  sensitisation  by  means  of  dye-stuffs, 
and  it  is  usual  to  date  the  invention  of  or- 
thochromatic  photography  from  that  year. 
But,  immediately  after  the  discovery  of 
the  Daguerreotype  iprocess,  phenomena 
were  obsen^ed,  which  undoubtedly  depend 
on  a  quite  analogous  sensitisation,  described 
first  in  1840  by  E.  Becquerel  on  the  "action 
excitatrice,  continuatrice  et  destructive"  of 
light  rays.  It  was  observed  that  the  latent 
image  could  be  made  directly  visible  on  a 
Daguerreotype  plate  by  yellow,  green  and 
red  light  rays,  and  also  that  an  under- 
exposed image  could  be  intensified  by  sub- 
sequent development  in  mercury  vapour,  if 
the  image  before  development  were  further 
exposed  under  a  yellow  or  red  glass.  In 
these  cases  the  colloidal  silver  formed  in  the 
silver  iodide  by  the  first  exposure  is  an  opti- 
cal sensitiser.  In  fact,  finely  divided  silver 
is  like  an  organic  dye ;  it  dyes  wool  and  silk, 
and  can  be  used  exactly  like  a  dye  to  colour 
silver  haloids,  so  that  Eder,  as  a  result  of 
spectral  analytical  .investigations  of  photo- 
chloride  and  photobromide  gelatin  films, 
which  I  had  prepared,  concluded  that  col- 
loidal silver  is  an  ideal  panchromatic  sensi- 
tiser. 

Dyeing  of  silver  haloid  by  silver  and  dye- 
stuffs  is  in  both  cases  a  characteristic  ab- 
sorption process.  Shortly  after  H.  _  W. 
Vogel's  discovery,  it  was  found  that  silver 
oprically  sensitised,  but  that  this  was  not 
chloride  and  silver  bromide  could  be  easily 


the  case  with  silver  iodide,  which  remained 
practically  indifferent.  This  is  remarkable, 
since  silver  iodide  can  be  easily  dyed.  This 
tendency  for  adsorbing  dyes,  depends  less 
on  the  chemical  nature  of  this  silver  haloid 
than  on  the  fact  that  silver  iodide  has  a  col- 
loidal gel  structure,  and  takes  up  dye  more 
easily  than  the  bromide  or  a  highly  sensi- 
tive plate,  which  from  ripening  grows  into 
the  form  of  more  or  less  compact  large  crys- 
tals. 

Numerous  dye-stuffs  also  act  as  chemical 
sensitisers,  increasing  the  total  sensitivity 
towards  white  light. 

The  sensitivity  of  silver  bromide  is 
diminished  by  certain  dye-stuffs.  It  is  pos- 
sible to  .develQp  even  panchromatic  plates 
in  the  unscreened  light  of  a  candle.  Safra- 
nines  are  especially  suitable  for  this,  and 
there  I  have  called  it  the  Safranine  Process. 
Recently  E.  Konig  and  R.  Schuloff  have  in- 
troduced the  pinakryptoTs,  pinakryptol 
green  being  especially  good. 

Dyeing  by  desensitisers  does  not  appear 
to  differ  from  that  with  sensitisers.  De- 
sensitising appears  to  depend  on  the  oxidis- 
ing action  (by  reason  of  chemical  constitu- 
tion) exerted  on  nascent  silver. 

The  strongest  sensitisers  of  the  cyanine 
group  also  act  as  desensitisers  if  bromine 
salts  are  present  to  support  the  tendency  of 
regression  of  the  silver  bromide. 

It  is  especially  noteworthy  that  basic 
dye-stuffs  coagulate  a  mixture  of  the  sols  of 
silver  bromide  and  silver  with  the  forma- 
tion of  photobromide. 

Adsorption  Phenomena  with  Silver. 

Both  silver  sols  and  also  gels  resulting 
from  them  by  coagulation  adsorb  many 
substances.  The  black  silver  of  the  photo- 
graphic negative  also  shows  a  strong  adsoiip- 
tive  power  for  many  substances,  including 
thiosulphate.  If  normally  developed  nega- 
tives are  hardened  with  chrome  alum  before 
fixation,  and  then  fixed  in  concentrated  bro- 
mide, it  is  possible  to  obtain  the  silver  free 
from  adsorbed  substances.  If  such  a  nega- 
tive is  now  bathed  in  thiosulphate,  washed, 
and  then  the  silver  dissolved  in  chromic 
acid,  nitric  acid,  or  persulphate,  a  residue 
of  silver  sulphide  remains. 

Adsonption  of  thiosulphate  by  silver  is 
really  the  cause  of  the  peculiar  reducing 
action  of  persulphate.  In  the  lesser  ex- 
posed parts,  the  silver  is  more  finely 
divided  than  in  the  high  lights,  which  nro 
more  quickly  attacked  by  the  persulphate. 


JUNE  8,  1923. 


THE  CHEMICAL  NEWS 


363 


SOCIETY   OF  GLASS  TECHNOLOGY. 

The  sixty-second  meeting  of  the  Society 
was  held  in  University  College,  London,  on 
May  16.  The  President,  Prof.  W.  E.  S. 
Turner,  D.Sc,  occupied  the  chair. 

At  the  first  session  two  papers  were  pre- 
sented. The  first  was  entitled  "  On  the 
Refractive  Index  Changes  in  Optical  Glass 
Occasioned  by  Chilling  and  Tempering," 
by  F.  TwYMAN,  F.Inst. P.,  and  F.  Simeons, 
B.vSc.,  F.Inst. P.  Mr.  vSimeon  defined 
"  Chilling  "  as  the  rapid  cooling  from  a 
high  temperature,  as  opposed  to  the  con- 
trolled cooling  from  a  medium  temperature 
known  as  "  annealing."  Considerable 
"  chilling  "  could  be  effected  by  allowing 
glass  to  cool  in  air  from  a  temperature 
within  or  above  the  annealing  range.  The 
process  of  tempering  a  metal  consisted  in 
the  removal  of  a  part  of  the  properties  in- 
troduced in  the  preceding  operation  by 
heating  it  to  a  definite  temperature  con- 
sidera!)ly  lower  than  that  attained  for 
"  chilling,"  and  allowing  it  to  cool  slowly. 
The  term  "  tempering  "  ua.s  applied  to  the 
analogous  partial  recovery  of  the  proi)crtics 
of  glass  in  the  annealed  state  on  heating. 
"  Annealiu''  temperature  "  was  defined  as 
the  temperature  at  which  internal  stresses 
existing  in  a  glass  were  reduced  to  one- 
twentieth  their  original  amount  in  0.26  min. 

The  effect  of  chilling  dense  barium  crown 
and  borosilicate  crown  glasses  might  be  to 
lower  the  refractive  index  by  as  nnich  as 
0.004  and  0.0013  respectively.  Tin's  lower- 
ing was  removable  by  heating  to  a  tem- 
perature and  for  a  time  which  had  been 
ascertained  in  certain  cases.  A  want  of 
homogeneity  could  be  i)roduced  by  mould- 
ing, owing  to  surface  chilling,  which  re- 
quired for  its  removal  a  longer  maintenance 
at  the  high  temperature  than  would  suffice 
to  remove  elastic  stress  from  a  homogeneous 
sample. 

Mr.  V.  vStdtt,  B.A.,  F.Inst. P.,  gave  a 
l)ai)er  entitled  "  Notes  on  Burettes,"  in 
which  he  gave  details  of  measurements  of 
the  amounts  of  liquids  run  from  burettes 
under  various  conditions.  A  burette  which 
empties  rajndly  has  a  high  drainage  factor, 
and  the  draining  from  the  walls  continues 
over  a  very  long  period.  In  fact,  in  a  50- 
c.c.  burette  emptying  in  20  sec,  the  drain- 
age was  not  complete  in  30  minutes.  On 
the  other  hand,  a  burette  which  has  a  long 
emptying  time,  has  a  small  drainage,  which 
is   practically   complete  aft<.r  a  short  time. 


Accurate  readings  can  be  obtained  much 
more  quickly  by  using  a  long  emptying 
time  and  a  short  drainage  than  by  using  a 
short  emi)tying  time  and  a  correspondingly 
longer  drainage  time. 

The  errors  occurring  through  using  a 
burette  calibrated  for  a  certain  delivery  time 
with  a  jet  which  gave  different  delivery 
time  were  dealt  with,  and  in  specified  in- 
stances it  was  shown  that  such  errors  were 
too  large  to  be  negligible. 

At  the  second  session  the  President  re- 
ferred to  the  death  of  Sir  Albert  J.  Hobson, 
one  of  the  first  members  of  the  Society.  He 
also  intimated  that  the  visit  to  Paris  which 
liad  been  ixjstponed  would  take  place  some 
time  in  July. 

Two  pai>ers  were  presented.  (1)  ''  A 
New  Method  of  Glass  Melting,"  by  A. 
Ferguson. 

Tliis  method  claimed  to  melt  and  refine 
tank  bottle  elasses  with  30  tons  of  coal  to 
100  tons  of  glass,  including  a  60  per  cent, 
margin  of  safety.    The  i)rocess  consisted  of 
a  cone  or  column  of  whirling  gases  at  1,800° 
C,  into  the  vortex  of  which  batch  ground 
to  a  60-mesh  standard  was  dribbled  at  the 
rate  of  two  ix)unds  per  second,  the  carbon 
dioxide  of  the  limespar  and  soda  having 
been  first  driven  off  in  a  preheater,  so  that 
the  work  of  the  furnace  was  only  to  raise 
the  temperature  from  850°  to  1,350°.     The 
particles  of  finely-divided  batch  exposed  to 
the  heat  in  a  surface  which  was  over  6,000 
times  that  of  batch  "spread  on,"  and  the 
permeation  of  the  particles  was  2,000  times 
easier.  All  reactions  necessary  to  form  glass 
molecules  took  place  in  a  gas  at  least  two 
million  times  less  viscous  than  tank  metal, 
so   that  affinities  could    reach  each  other, 
collide    and    react    millions    of    times    per 
second,    instead  of   all    the  energy  of   the 
atom  being  required  for  hours  to  find  the 
waiting   affinity    lurking  somewhere    in   a 
tank,  and  when  not  encountered  resulting 
in   seed,   striae  and  unequal   strain   in  the 
glass.     All  preheating  was  done  by  waste 
heat  after  the  duty  of  the  heat  had  been  car- 
ried out.     The  coal  was  retorted,  the  hydro- 
carlx)ns  saved,  air  and  batch  preheated  and 
freed  from  carl)on  dioxide  (which  was  later 
converted  into  carbon  monoxide  in  the  pro- 
ducer).    The    process    was   entirely    auto- 
matic.      The  batch,  instantly  melted  and 
refined,  flowed  through  a  stream  line  tank 
to  a  periphery  gatherer  in  a  fire-hearth. 


364 


TfiB  CHEMICAL  i^EWS. 


JUNE  8,  1923. 


(2)  "  Natural  Sillimanite  as  a  Glass  Re- 
fractory," by  S.  English,  M.Sc.  Results 
of  tests  showed  that  this  material  possessed 
properties  of  value  to  glass  makers.  Test 
pieces  were  made  up  by  mixing  100  parts  of 
sieved  sillimanite  with  10  parts  of  finely- 
ground  clay  ;  such  mixture  could  be  made 
into  slabs  and  pressed  into  crucibles.  These 
slabs  and  crucibles  were  examined  for  the 
properties  which  are  the  chief  causes  of 
trouble  to  glass  makers  when  using  ordin- 
ary clay  refractories,  and  the  results 
showed  :  (I.)  The  drying  and  firing  shrink- 
ages of  the  sillimanite  mixture  were  very 
much  less  than  the  corresponding  contrac- 
tions of  pot  clay  mixtures  ;  in  fact,  when 
the  sillimanite  slabs  were  completely  air 
dried  thev  showed  practically  no  further 
shrinkage' on  firing  to  1,400°.  (II.)  The 
porosity  of  the  fired  sillimanite  slabs  was 
rather  less  than  the  porosity  of  pot  clay 
slabs  fired  to  the  same  temperature.  (III.) 
Sillimanite  crucibles  were  attacked  much 
less  by  molten  glass  at  1,400-1,420°  C  than 
were  similar  sizes  pot  clay  crucibles.  The 
attack  was  measured  by  determining  the 
iron  oxide  and  alumina  content  of  two 
glasses  and  remelting  each  of  them  for  6 
hours  at  1,400-1,420°  C  in  sillimanite  and 
in  clay  crucibles.  The  iron  oxide  and 
alumina  contents  were  again  determined, 
and  comparisons  showed  that  in  each  case 
the  clay  crucibles  were  attacked  three  times 
as  rapidly  as  the  sillimanite  crucibles. 

The  Annual  Dinner  of  the  vSociety  was 
held  in  the  Hotel  Cecil.  The  President  Avas 
in  the  chair.  Among  those  present  were 
Sir  F.  W.  Dyson,  F.R.S.,  Astronomer 
Royal  and  President  of  the  Optical  Society; 
vSir  Lawrence  Weaver,  K.B.E.,  Director, 
United  Kingdom  Exhibits,  British  Empire 
Exhibition  (1924)  ;  H.  J.  C.  Johnston,  Esq., 
President  of  the  Institute  of  Clayworkers  ; 
Frank  Wood,  C.B.E.,  B.Sc.,  and  Dr.  M.  W. 
Travers,  F.R.D.,  Past-Presidents  of  the 
Society;  A.  R.  Upjohn,  Esq.,  LL-B., 
Master  of  the  Glaziers  Company  ;  R.  L. 
Frink,  Director  of  the  Glass  Research  Asso- 
ciation ;  Mons.  Courty,  Paris  ;  J.  Connolly 
(Hon.  Treasurer)  ;  S.  English  (Hon  Secre- 
tary) ;  and  others. 

The  following  day  a  party  from  the 
Society  had  the  privilege  of  visiting  the  new 
works  of  ]\Iessrs.  James  Powell  &  Sons 
(Wliitefriars),  Ltd.,  at  Harrow. 


THE  OPTICAL  SOCIETY. 

Visit  to  Royal  Observatory. 

By  the  courtesy  of  the  Astronomer  Royal, 
a  visit  has  been  arranged  to  the  Royal  Ob- 
servatory, Greenwich,  on  Saturday,  June  9, 
1928,  at  3  ip.m.  Fellows  and  Members  de- 
sirous of  availing  themselves  of  the  oppor- 
tunity of  visiting  the  Observatory  on  this 
date  are  requested  to  send  their  names  to 
the  Honorary  (Business)  Secretary  of  the 
Society  at  the  Imperial  College,  not  later 
than  Thursday,  June  7. 

Ordinary  Meeting. 
A  meeting  of  the  Society  will  be  held  at 
the  Imperial  College,  Imiperial  Institute 
Road,  South  Kensington,  at  7.30  p.m.,  on 
Thursday,  June  14,  1923,  when  the  follow- 
ing paipers  will  be  presented  and  dis- 
cussed :  — 

Levels  and  level  Bubbles,  by  S.  G.  Star- 
ling, A.R.C.Sc,  B.Sc,  F.Inst. P. 

A  new  form  of  Balloon  Theodolite,  by  T. 
F.  Connolly,  M.Sc. 

The  Primary  and  Secondary  Image 
Curves  formed  by  a  Thin  Achromatic  Ob- 
ject Glass  ivith  the  Object  Plane  at  Infin- 
ity, by  E.  Wilfred  Taylor. 


THE  GEOLOGICAL  SOCIETY 
OF    LONDON. 

May  16,  1923— Prof.  W.  W.  Watts, 

Sc.D.,  F.R.S.,  Vice-President,  in 
THE  Chair. 


The 
read  :- 


following       communications      were 


I 


The  Upper  Ordovician  Rocks  of  the 
South-Western  Berwyn  Hills,  by  William 
Bernard  Robinson  King,  O.B.E.,  M.A., 
F.G.S. 

A  new  sipecies  of  Calynicne  was  incident- 
ally described  from  the  upper  part  of  the 
Ashgillian,  where  it  is  taken  as  a  local 
index-fossil. 

Tlie  Geology  of  the  District  around  Corris 
and  Aherlle'fenni  (Merioneth),  by  Prof. 
William  John  Pugh,  O.B.E.,  B.A.,  F.G.S. 


f 


JUNE  8,  1923. 


THE  CHEMICAI.  NEWS. 


365 


ROYAL  MICROSCOPICAL  SOCIETY. 

The  section  of  the  Society/  which  has  bocu 
formed  to  deal  with  the  Industrial  Applica- 
tions of  thu  Microscoipe,  and  to  assist  in  Ihf 
development  of  Industrial  Research  in 
British  Industries,  held  a  meeting  at  20, 
Hanover  Square,  W.l,  on  Wednesday, 
May  30. 

The  demonstrations  and  exhibits  included 
the  following:  — 

Mr.  M.  T.  Denne,  O.B.E.,  F.R.M.S.,  de- 
monstrated an  improved  apparatus  for  the 
production  of  photomicrographs. 

Mr.  C.  A.  Newton  gave  a  demonstration 
of  a  new  form  of  micr<>scoip<'  lamp  for  easy 
<'xchange  of  iparalleliser  and  polariser. 

Mr.  Mansell  P.  Swift  dcmcMistrated  a 
Hutchinson   universal   gonioiiiet<?r. 

The  following  papers  were  read:  — 

On  the  Microscopical  F^xaminafion  ni 
China  Clay,  by  Mr,  Joseph  M.  Coon. 

The  Microscopical  Invcxiujation  of  Haiuh 
for  various  Industrial  I'urposrs,  by  Mh.  H. 

13.    MiLNER. 

Professor  A.  Hut-chinson  ^Pembroke  Col- 
lege, Cy'amhndge)  pn'sidfi 


ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

On  Thursday',  June  7.  Siu    William    M 
Bayliss,  LL.D.,  D.Sc,  F.R.S.,    gave  his 
sex'ond  lecture  on    The  Sature   of   Enzyme 
Action. 


THE  SIXTH    INTERNATIONAL 

MINING  EXHIBITION. 
To  BE  Held  4th  to  8th  June,  1923. 
Papers  to  be  read  at  the  Oil  Cwiferenco  : 

Monday,  June   1. 

The  Riddle  of  the  Carpathians    (Opening 
Address),    bv    E.  H.    Cunningham    Crak; 
B.A..   F.R.S.E..  F.G.S.,  M.Inst.P.T. 

0/7  Deposits  and  the    Tectonics  of    Verti- 
cal Pressure,  by  Dr.  Maxmilian  Kraus. 


Note  on  the  Genesis  of  Hydrocarbons  and 
their  Localisation    in  certain    zones    of  the 
Earth's  Crust,  by  R.  d'Anduimont. 
Tuesday,  June  o. 

OilHeld  Waste,  by  A.  Beefy  Thompson, 
O.B.E.,  M.I.Mech.E.,  M.Inst.M.M., 
M.Inst.P.T.,  F.G.S. 

Thursday,  June  7. 
The  Mode  of  appearance  of  the  Petroleum 
Deposits  in  the  Carpathian  Region,  with 
General  Consideration  on  the  Genesis  of  the 
Petroleum  and  the  source  of  the  Actual 
Deposits,  by  J.  Voitesti,  Professor  Cluj 
University. 

An  Economic  Study  of  Petroleum  Mining 
by  Underground  Drainage,  by  Major  J.  A. 
Lautikr,  M.Inst.P.T. 

Friday,  June  8. 
The  Standardisation  Movement  in 
America  and  its  relation  to  and  application 
totcards  the  Elimination  of  Waste  in  the 
Petroleum  Industry,  by  C.  A.  Young  and  S. 
D.  Tutuill. 

The  Caribbean  Oil  Region,  by  George 
Howell,  F.G.S. ,  F.R.G.S.,  M.Inst.P.T. 


THE  CHEMICAL  SOCIETY. 

Ordinary  Scibntific  Meeting, 

Thursday,  June  7th. 

The  following  papers  were  read  :  — 

Investigations  on  the  dependence  of 
rotatory  power  on  chemical  constitution. 
Part  XX.  The  rational  study  of  optical 
properties  :  Refraction  a  constitutive  pro- 
perty.— H.  Hunter. 

Researches  on  indium.  Part  I.  Diphenyl 
indium  chloride  and  phenvl  indium  oxide. 
—A.  E.  Goddard. 

The  properties  of  ammonium  nitrate. 
Part  VI.  The  reciprocal  salt  pair,  am- 
monium nitrate  and  potassium  sulphate. — 
E.  P.  Pernian  and  \V.  J.  Howells. 

Ring  chain  tautomerisni.  Part  VI.  The 
mechanism  of  the  keto-cyclol  change  in  the 
propane  series. — K.  W.  Lanfear  and  J.  F. 
Thorpe. 

The  reversibility  of  additive  reactions. 
Part  I.  The  aldol  reaction.-  E.  H.  ITshcr- 
wood. 


366 


THE  CHEMICAL  NEWS. 


JUNE  8,  1923. 


Mechanism  of  the  piijacone-pinacoline 
and  WaRner-^Ierrwein  transformations — 
C.  K.  Infold. 

Researches  on  antimony.  Part  I.  Tri- 
m-xylylstibine  and  its  derivatives. — A.  E. 
Goddard. 

GENERAL  NOTES. 


URUGUAY. 
Tenders   Invited  for  General  Stores. 

The  British  Vice-Consul  at  Montevideo 
has  forwarded  particulars  of  the  call  for  ten- 
ders for  the  supply  of  general  store  require- 
ments of  the  State  Electric  Light  Works  of 
Montevideo. 

Tenders  in  sealed  envelopes  are  to  be  pre- 
sented at  the  head  offices  of  the  State 
Electricity  Works  Administration  before  4 
p.m.,  12th  July. 

The  list  of  goods  required  is  extensive, 
including  tools,  nuts,  bolts,  greases,  lamp 
shades,  cord,  files,  saws,  lumber,  stationery, 
waste,  etc.  and  firms  may  tender  for  all  or 
any  part  of  the  requirements. 

The  full  list  (in  Spanish)  and  a  sum- 
marised translation  of  the  general  conditions 
of  tender  can  be  consulted  by  interested 
U.K.  firms  on  application  to  the  Depart- 
ment of  Overseas  Trade  (Room  84) . 


The  Bulgarian  State  Railways  are  de- 
sirous of  receiving  tenders  for  the  supply  of 
hnseed  oil.  A  public  adjudication  of  tenders 
will  be  held  on  the  15th  June. 

U.K.  firms  who  are  desirous  of  receiving 
further  particulars  should  apply  to  the 
Department  of  Overseas  Trade  (Reference 
10754/F.E./C.C./2). 

INTERVIEWS  WITH  THE  COMMER- 
CIAL -SECRETARY  AT  COPENHAGEN, 
DENMARK. 

The  Commercial  Secretary  at  Copen- 
hagen, Mr.  R.  M.  A.  Turner,  will  be  in 
attendance  at  the  Department  of  Overseas 
Trade  from  the  25th  to  30th  June,  inclusive, 
and  will  be  pleased  to  interview,  by  appoint- 
ment. United  Kingdom  manufacturers  and 
merchants  interested  in  export  trade  to 
Denmark. 

Applications  for  interviews  should  be 
addressed,  without  delay,  to  the  Depart- 
ment of  Overseas  Trade,  and  the  reference 
7505  F.R.  should  be  quoted. 


PUBLIC  ANALYST  FOR  GLOUCESTER 
COUNTY  AND  CITY. 
The  Council  of  the  Institute  of  Chemistry 
of  Great  Britain  and  Ireland  advise  any 
Fellow  or  Associate  of  the  Institute  who 
may  contemplate  accepting  appointment  as 
Public  Analyst  for  the  Covnity  of  Gloucester 
or  for  the  City  of  Gloucester  on  the  terms 
recently  advertised  to  communicate  at  once 
with  the  Registrar  of  the  Institute. 


CANADIAN  CHEMICALS  AND  ALLIED 
PRODUCTS,  1919-1920. 
A  special  survey  of  Canada's  chemical  in- 
dustries was  undertaken  by  the  Dominion 
Bureau  of  Statistics  as  a  section  of  the  In- 
dustrial Census  to  provide  a  directory  of 
Canadian  Chemical  Industries  and  their 
products  for  the  use  of  the  trade.  It  also 
served  to  assemble  data  regarding  raw 
materials  used,  products  and  by-products 
manufactured,  imports  and  exports,  etc., 
thus  indicating  not  only  the  importance  of 
the  industry  and  the  progress  which  it  has 
made  in  Canada,  but  also  possible  new  and 
profitable  trade  openings  in  industrial 
chemical  lines. 

The  present  report  is  the  result  of  the  first 
comprehensive  survey  of  the  production  of 
chemicals  and  allied  products  in  Canada. 

Industries  are  grouped  by  classes  accord- 
ing to  the  principal  component  materials  of 
their  products  ;  on  this  principle,  the  pre- 
sent study  was  carried  out  in  ten  main 
groups,  namely  :  Coal  tar  and  its  products  ; 
acids,  alkalies,  salts  and  compressed  gases; 
explosives,  ammunition,  fireworks  and 
matches  ;  fertilisers  ;  medicinal  and  pharma- 
ceutical preparations  ;  pigments,  paints  and 
varnishes  ;  soaps,  perfumery,  cosmetics  and 
other  toilet  preparations  ;  inks,  dyes  and 
colour  compounds  ;  wood  distillates  and  ex- 
tracts ;  miscellaneous  chemical  industries. 
The  industries  coming  under  these  items  in 
1920  comprised  456  establishments,  employ- 
ing more  than  17,000  hands.  A  total  of 
nearly  $120,000,000  was  employed  as 
capital,  and  products  aggregating  nearly 
$122,000,000  in  value  were  made.  Pig- 
ments, paints  and  varnishes  were  easily  the 
leading  group.  Soaps,  perfumery,  cosmetics 
and  other  toilet  preparations  came  second, 
with  acids,  alkalies,  salts  and  compressed 
gases  a  close  third.  Medicinal  and  pharma- 
ceutical preparations  ;  explosives,  ammuni- 
tion,   fireworks    and  matches ;    wood   dis- 


JUNE  8,  1923. 


THE  CHEMICAL  NEWS. 


367 


tillates  and  extracts  ;  fertilisers  ;  inks,  dyes 
and  coliHir  conipoiriids  ;  and  coal  tar  and  its 
distillation  products  followed  in  the  order 
named. 

The  continuous  advance  which  repre- 
sented normal  conditions  before  the  war 
was  much  accentuated  in  the  last  four  war 
years,  and  it  is  encouraging:  to  note  that 
during  the  past  two  fiscal  years  the  export 
trade  has  been  maintained  at  a  level  very 
considerably  above  what  the  normal  pre-war 
rate  of  increase  would  have  produced. 

Progress  in  the  manufacture  of  chemicals 
and  allied  products  in  recent  years  has  been 
rapid  and  the  results  attained  have  more 
than  justified  the  ventures  made.  The  pro- 
fessional chemist  and  the  chemical  manufac- 
turers have  combined  to  advance  the  com- 
mon weal,  and  a  feeling  of  optimism 
dominates  and  leads  the  industry.  Oj^iwr- 
tunities  for  the  development  of  Canadian 
chemical  industries  are  beintj  sought  out  In- 
careful  research,  and  while  Canada  may  not 
lead  the  world,  there  still  are  some  of  the 
chemical  industries  in  which  her  influence 
will  be  strongly  felt. 

CANADIAN  CHKMICAL  EXPORTS. 
1922. 

lixports  of  chemical  products  from 
Canada  during  the  jiast  fiscal  year  amounted 
to  $14,046,940,  as  compared  with  the  1921- 
22  total  of  $9,506,170  ;  and  exports  of 
automobiles  were  more  than  tripled,  ship- 
ments of  trucks  amounting  to  3,720,  worth 
$1,444,549  (1,296,  worth  $611,185,  in  1921- 
22)  ;  of  i)assenger  vehicles  45,108,  worth 
$25,606,359  (13,428,  valued  at  $7,421,619. 
in    1921-22);  and  of  auto  parts  $2,355,066, 

compared  with  $1,151,453  last  year. 


NOTICES  OF  BOOKS. 


PADUA  SAMPLE  FAIR. 

Many  foreign  countries  are  to  exhibit  at 
the  International  vSample  Fair  to  take  place 
in  Padua  (near  Venice)  in  June.  This  Fair 
is  one  of  the  oldest,  if  not  the  oldest,  held  in 
Europe. 

There  is  always  a  good  British  attend- 
ance. Many  tourists  take  the  opportunity 
of  visiting  this  historic  town  to  see  the  fine 
array  of  many  categories  of  products  which 
this  event  brings  together. 

The  London  office  of  the  Italian  State 
Railways  ^:  Tourist  Department  announces 
thst  special  reduced  rate  tickets  will  be 
issued  to  Padua  during  the  period  of  the 
Fair. 


The  Chemistry  of  Urea,    by    Emil    A. 

W'ekxer,  M.A.,  Sc.D.,  F.I.C.     Pp.  XII. 

+  212.     London:     Longmans,    Green    k 

Co.,  39,  Paternoster,  Row,    E.G.      1928. 

Price  14s.  net. 

The  physiological  importance  of  urea  in 
animal  metabolism  is  in  itself  a  sufficient 
reason  for  the  publication  of  this  volume  in 
the  Series  of  Monographs  on  Biochemistry 
under  the  general  ediborshiip  of  Profs.  Plim- 
nier  and  Hopkins.  It  will  be  recalled  that 
urea  was  the  first  organic  compound  to  be 
synthesised  without  the  intervention  of 
"\ital  force"  in  1828  by  Wohlor. 

In  addition,  the  ehemical  history  of  urea 
is  remarkable;  this  substance,  so  well- 
known  and  thoroughly  investigat<?d,  has  had 
the  erroneous  carbamide  formula  ascrihea 
to  it  until  Prof.  Werner's  researches  be- 
came known. 

Soon  after  its  discovery  and  isolation  in 
the  latter  half  of  the  eighteenth  century,  it 
was  found  to  yield  CO,  and  NH,  by  hydro- 
lysis and  by  fermentation.  This  suggested 
the  carbamide  structure  and  received  ap- 
parent confirmation  from  the  various  at- 
tt'mpted  syntheses  of  carbamide,  which  all 
yielded  urea. 

The  general  reactions  and  decompositions 
s<'emcd  to  agree'  well  with  this  formula  and 
et'rtain  anomalous  proiperties  and  the  occur- 
rence of  subsidiary  products  in  the  synthe- 
ses and  decoriipositions  were  overlooked  or 
ingeniously  explained  on  the  basis  of  the 
carbamide  formula,  the  acceptance  of 
which  has  undoubtedly  hindered  advance- 
ment in  the  study  of  urea. 

During  the  la.st  decade  the  author  has 
published  a  number  of  scientific  communi- 
cations, giving  an  account  of  his  own  inves- 
tigations on  the  chemistry  of  urea*and  the 
results  are  incorporated — together  with 
umch  new  matter  —  in  the  monograiph 
under  review. 

It  is  .shown  that  all  the  syntheses  are 
really  similar  to  Wohler's,  involving  the 
union  of  NH,  with  the  keto-form  of  cyanic 
acid.  This  is  clearly  brought  out  by  the 
author's  careful  explanation  of  the 
mechanism  of  these  syntheses,  which  have 
led  to  his  cyclic  formula  being  adoptod  for 
this  compound. 

Further  confirmation  of  this  formula  is 
to  be  found  in  a  study  of  the  reactions  of  the 
substance  with  HNOj  and  NaBrO,  althoiigh 
formerly  these  were  regarded  ns  affording 
proof    of    the    carbamide    structure.       The 


368 


THE  CHEMICAL  NEWS. 


JUNE  8,  1923. 


action  of  hjpohalogenites,  for  example,  on 
urea,  was  regarded  as  in  complete  accord 
with  this,  since  equal  volumes  of  COj  and 
Ng  were  evolved.  The  fact  thai  the  volume 
of  N3  evolved  was  decidedly  below  the 
theoretical  amount  was  ignored,  as  was  the 
presence  of  other  gases,  e.g.,  CO,  N„0,  and 

"The  author  is  easily  able  to  reconcile  this 
behaviour  with  his  formula,  which  also  ac- 
counts for  all  the  "anomalies"  associated 
with  the  reactions  of  urea.  In  the  estima- 
tion of  urea  by  means  of  NaBrO,  no 
method  is  known  whereby  all  the  Nj  can  be 
evolved  in  one  Qperation,  but  the  author 
has  devised  a  very  satisfactory  method  in- 
volving two  simple  operations. 

The  considerable  value  of  this  Monograph 
is  enhanced  by  the  inclusion  of  a  chapter 
on  Simple  Lecture  Experiments  to  demon- 
strate the  prQperties  of  urea.  There  are 
also  two  useful  appendices  and  a  good 
bibhography  and  index.  J.G.F.D. 

Reports  on  the  Progress  of  Applied 
Chemistry,  issued  by  The  Society  of 
Chemical  Industry.  Vol.  VII.  1922. 
Pp.  586. 

The  chemical  and  technical  advances  in 
chemical  industry  during  the  past  year  are 
recorded  in  chapters  written  by  leading 
authorities  in  the  various  branches  of  the 
subject. 

Each  section  is  not  merely  a  summary  of 
the  discoveries  and  inventions  for  the  period 
under  review,  but  is  more  in  the  nature  of 
an  authoritative  discussion  and  statement 
of  the  recent  developments  in  the  inclus- 
tries  concerned. 

Over  twenty  technical  chemists  of  repute 
have  contributed  to  the  Reports. 


•     BOOKS  RECEIVED. 

Annual  Reports  of  the  Society  of  Chemi- 
cal Industry  on  the  Progress  of  Applied 
Chemistry  for  1922  (Vol.  VII.).  Pp.  586. 
1922.  Society  of  Chemical  Industry,  46-7, 
Finsbury  Square,  E.C.2. 

Canada,  Dominion  Bureau  of  Statistics, 
Mining,  Metallurgical  and  Chemical 
Branch.  Chemicals  and  Allied  Products, 
1919  and  1920.  Pp.  150.  1922.  F.  A.  Ac- 
land,  Ottawa,  Canada. 

Theoretical  Chemistry,  from  the  Stand- 
point of  Avagadro's  rule  and  Thermodyna- 
mics by  Prof.  Walter  Nernst,  Ph.D.,  of 
the  University  of  Berlin.  Pp.  XX.  +  992. 
1923.  Messrs.  Macmillan  &  Co.,  Ltd.,  St. 
Martin  Street,  W.C.2.     28s.  net. 


PUBLICATIONS    RECEIVED. 

The  INIinistry  of  Agi-icult-ure  and  Fisheries 
leaflet  No.  300,  The  Breeding  and  Utiliiy  0} 
Pigeons. 


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Latest  Patent  Applications. 

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dialkvlamino  arylpliosphinous  acids.  May 
3. 

11849— Damard  Lticquer  Co.,  Ltd.— Phenolaldehyde 
condensation    products.     May   2. 

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11617 — Imray,  O.  Y. — Maniifacture  of  vat  dyestuffs 
from  anthraquinone.    April  30. 

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Ltd. — Tliermometer  stand.    May  4. 

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of  butyl  chlorides. 

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Aniline-black  and  like  dyeing.— Black  shades  are 
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imptregnating  the  material  with  diphenyl  black 
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mium, and  cupric  chlorides,  and  sodium  chlorate, 
and  developed  in  a  drying  room  at  80°  C. ;  acetate 
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diphenyl  black  base,  acetic  acid,  and  boiled-off 
liquor," and  developed  in  a  bath  of  ammonium  per- 
sulphate; or  oxidising-agents  such  as  hypochlor- 
ate,  chloride  of  lime,  persulphate,  or  perborate, 
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I 


JUNE  15,  1923. 


THE  CHEMICAL  NEWS. 


360 


THE   CHEMICAL  NEWS, 


VOL.  CXXVI. 


3296. 


A  CHEMICAL  BASIS  FOR  THE 
TREATMENT  OF  TUBEHCULOSIS. 

By  Louise  G.  Kobinovitcii,  B.bs.L.,  M.D. 

[A  PreJiniinnry  State ntcnl   uf  Research 

Work  in  the  Chemical  Lahcmtories  of  the 

Colorado  School  of  Mines. \ 

The  main  part  of  tho  tiibcicie  bacillus  is 
generally  regarded  as  consisting  of  waxy 
and  fatty  rnatt^-r,  free  fnliy  acids,  and 
otherothcr  organic  substances.  It  a4ppearB 
that  the  waxy  coating  is  the  main  protec- 
tion to  the  bacillus  and  offei-s  the  greatest 
resistance  to  cheuucal  atiick.  If  this 
waxy  and  fatty  matter  coull  he  chemically 
decomposed  and  destroyed  1>\  agents  not  in- 
jurious to  living  tissue,  it  steins  reasonable 
to  assume  that  a  cure  for  tuberculosis 
should  lie  in  such  a  treatment.  This  ab- 
stract presents  a  brief  outline  ol  the  essen- 
tial features  of  such  a  metli'd  of  nttaek,  de- 
veloix?d  on  the  basis  of  tli<  above  assump- 
tions and  line  of  reasoning. 

The  apparent  success  f>f  this  new  treat- 
ment depends  largely  on  tin  agent  which  I 
have  found  to  be  an  iffecti\i  solvent  for  the 
tubercle  bacillus.  It  consists  of  a  highly 
concentrated,  slightly  alkaline,  glycerol  ex- 
tract of  st<apsin  or  lipase,  and  probably 
insulin  into  which  has  been  incorporated  a 
small  amount  of  chloroform.  The  (pure 
extract  of  insulin  will  proliably  make  it 
possible  to  use  smaller  doses  of  the  fat- 
splitting  agent  more  effeclively.  Potas- 
sium bicarbonate  was  used  to  obtain  the 
desired  alkalinity.  Small  doses  of  bile  salts 
(prepared  from  ox  bile)  administered  orally 
increased  tho  effectiveness  of  the  above 
agent. 

An  important  adjunct  to  the  chemical 
treatment  of  the  disease  is  activated  oxy- 
gen, which  acts  as  does  a  radio-active  ray, 
by  releasing  its  negative  electric  charge. 


HELIUM  AND  ITS  USES. 

The  following  account  of  hcliimi    and  ifn 

uses  is  based  upon  one  issued  by  the 
British  Science  Quild,  by  Prof.  J.  C. 
McLellan,  F.R.S. 

As  is  well  known,    helium  is  one  of  the 

chief  constituents    of  prominences  in  the 


sun  which  shoot  out  from  this  body  a  dis- 
tance of  many  thousand  miles,  as  seen  dur- 
ing its  total  eclipse.  In  1868  Sir  Normau 
Lwkyer  anaomiced  the  discovery  of  this 
element  in  the  sun  by  spectroscopic  obser- 
vation and  named  it  helium.  In  1895  Sir 
Wm.  Ramsay  obtained  helium  fronri  a 
mineral,  clevite,  along  with  argon.  Helium 
occurs  in  radio-active  changes  as  the  alpha 
particle  which  is  ejected  from  the  disinte- 
grating atom  in  some  cases,  and  where  this 
tvpe  of  activity  is  intense,  at  a  velocity  as 
high  as  12.000  miles  per  second.  Sir  E. 
Rutherford  has  made  use  of  the  high 
velocity  of  the  alpha  particle  in  using  it  as 
a  projectile  for  bivaking  up  the  nitrogen 
atom,  but  the  quantities  dealt  with  are  in- 
finitesimal. 

Of  particular  interest  are  the  sources 
from  which  helium  is  now  obtained.  It 
exists  in  the  atomsphere  in  the  proportion 
of  about  four  parts  to  one  million  of  air,  by 
volume;  but  it  exists  in  much  higher  per- 
centages in  natural  gases  reaching  the  (pre- 
sent known  limit  of  1  or  2  per  cent,  therein 
in  the  gas  wells  situated  in  the  western 
States  of  America,  particularly  in  Texas. 

In  FVance,  som«^  springs  yield  as  much  as 
5  per  CA*nt.  It  is  widely  distributed, 
though  in  Great  Britain  the  supply  is  al- 
most negligible,  being  only  one-fifth  per 
cent,  in  the  natural  as  at  Heathfield.  Sus- 
sex. At  King  Spring,  Bath,  one-sixth  per 
cent,  has  been  foimd.  Canada  affords  the 
richest  siipply  so  far  discovered  in  the  Em- 
pire, the  localities  being  Ontario  and  Alber- 
ta, but  the  percentages  are  low,  being  about 
one-third  per  cent,  of  the  natural  gases. 
See  concluding  statement. 

.\ctivity  in  olitaining  helium  has  reached 
a  commercial  staije  in  the  United  States. 
where  from  30,000  to  40,000  cubic  feet  of 
this  gas  are  now  being  extracted  daily,  but 
its  export  is  prohibited  by  Taw.  Sir 
Richard  Threlfall  had  suggested  in  1915  an 
inquiry  into  the  helium  content  of  supplies 
of  natural  gas  within  tho  Empire,  and  the 
United  States  began  developing  tho  indus- 
try two  years  aft(^r  the  war. 

It  is  instnictivt>  to  record  that  this  ele- 
ment was  a  chemical  curiosity  imme- 
fliately  prior  to  1918,  at  which  time  100 
cubic  feet  would  have  cost  about  €301  to 
collect,  and  since  then  nearly  three  million 
cubic  feet  of  this  gas  have  been  extracted 
in  the  United  States  for  use  in  the  Ameri- 
can Army  and  Navy.  It  is  oompressed  and 
stored  in  steel  cylinders  for  use  in  airships 
and  other  purposes. 


370 


THE  CHEMICAL  NEWS. 


JUNE  15,  1023. 


With  regard  to  its  uses,  it  has  just  been 
announeed  that  new    airships  of  the    ri^id 
type     are  approaching    completion  for    fhe 
•   fl  ;  ^"vernnient,  and  that  they  are  being 
inflated  with  helium    instead  of  hydrogen 
the  latter  gas  being,    of  course,    hi ahly  ex- 
plosive  and  inflammable.        Hellurn     being 
non-inflammable     and     non-explosive      and 
giving  a  lifting  power  of  92  per  cent,  of  that 
of  hydrogen,  the  desirability  of  its  use  in  in- 
flating   the  airship  envelopes    is  made  evi- 
dent.     For  this  purpose  hydrogen    can  be 
mixed  with  helium    to  the  extent  of  15  per 
cent,   without    the  mixture    being    inflam- 
mable or  explosive  in  air.     As  a  matter  of 
fact,  the  engines    of  airships  can  be  placed 
within  the    gas  envelope  is  desired,    and  a 
further  advantage  of  helium  over  hydrogen 
is  that  the    buoyancy  can  be  increased  "  at 
will  by  heating  or  cooling    the  gas  by  elec- 
tric heaters    or    other    means.       Moreover 
K    To.  fliffuses       through     the     envelope 
about  30  per  cent,  less  than  hydrogen 

It  IS  stated  that  helium  can  be  used  to 
hll  thermiomc  amplifying  valves  for  use  in 
wireless  telephony,  and  also  used  as  a  filler 
lor  metal  filament  lamps  and  arc  lamps 

Prof.   Onnes,    of  Leyden,    in  1908,     suc- 
ceeded in  liquefying  helium  having  reached 
a  temperature  of  490°  F.    below  the  freez- 
ing point  of  water,    which   is  within  2  or    3 
degrees  of  the  absolute  zero.     Using  Hquid 
helium    as    a  cooling    agent.    Prof.    Onnes 
found    that    a  number    of  metals    became 
practically  perfect  conductors  of  electricity 
when  cooled  down  to  within  a  few  degrees 
of  absolute  zero.       An  electric  current  in- 
duced m  a  closed  conductor  bv  magnetic  in- 
duction continued  to  flow  for^more  than  an 
hour,  in  this  instance  the  metal  being  lead 
Mercury  was  also  used  with    a  similar  re- 
sult     This  IS  called  "  super-conductivitv  " 
tor  the  metal    becomes  many  million  time^ 
more  conducting  at    this   low  temperature 
than  at  room  temperature. 

Under  the   title,     "  Need     for     Develop- 
ment, '  Prof.  McLennan  says:  — 

''From  ten  to  twelve  million  cubic  feet 
ot  hehum  could,  however,  be  obtained  an- 
nually from  natural  gases  in  Canada,  and 
the  gas  has  such  direct  bearing  upon  prob- 
!w^?  "^^^^n^i^c  and  practical  importance 
that  the  Governments  of  Great  Britain  and 
Canada  might,  even  from  the  point  of  view 
of  national  safety,  le.gitimately  be  asked  to 
follow  the  example  of  the  United  States 
and  operate  the  plant  which  was  con- 
structed during  the  late  war  and  was 
erected  and  operated  for  a  time  at  Calcrarv 


With  this  plant    it  was  shown  that  hehum 
nf  high    purity  could    be  produced  at    less 
than  hvepence  a  cubic  foot.      With  sugges- 
tions    received     from       Prof.     Kamerfingh 
Onnes,  of  Leyden,  and  with  financial  assist- 
ance received  from  the  Honorary  Advisory 
Council  for  Scientific    and    Industrial     Re- 
search of  Canada,  the  Carnegie  Foundation 
for  Eesearch  and  the  University  of  Toronto, 
a     magnificent     cryogenic    equipment     has 
been  installed  in  the    Physical  Laboratorv 
of  the  University  of  Toronto.     With  it  large 
supplies  of  hquid  air,   liquid  hydrogen    and 
liquid  helium  can  be  obtained.      This  cryo- 
genic laboratory  was  opened  on  January  10 
last,  and  on  that  occasion    demonstrations 
were  given  of  the  production    of  liquid  air 
hquid  hydrogen,  and  liquid  helium  in  quan- 
tity.    It  is  hoped  that  the  facilities  of  this 
laboratory  will  be    used  by  workers    in  low 
temperature  research    who  may  find    it  in- 
convenient to  go  to  Leyden    to  work  under 
Prof.   Onnes,  the  distinguished  physicist  of 
the  Netherlands." 


ON  7  RAYS  FROM  RADIUM  D  ^NB 

RADIUM  E. 

By  Mlle.  I.  Curie  and  M.  G.  Fournier. 

A  strong  preparation  of  Radium  D  mixed 
with  some  milligrams  of  lead  was  em- 
ployed. The  rays  were  studied  and  charac- 
terised by  their  absorption  in  aluminium. 

Method     of    Procedure— The    measuring 
apparatus  was  a  vertical  cylinder,  of  which 
the  upper  half  contained  a  gold  leaf  electro- 
scope and    the  lower    half    constituted    an 
lonisation  chamber  closed  by  a  thin  leaf  of 
aluminium    5.5    centimetres    in    diameter. 
This  apparatus    was    placed  several    centi- 
metres above  the  poles  of  an  electro-magnet 
giving  a  field  sufficient    to  completely  eli- 
minate the  /5-rays.     The  active  source  was 
placed    in  a  quartz    crucible    between    the 
poles  at  12  centimetres    from    the    electro- 
scope.   The  absorbing  screens  were  put  very 
near  the  leaf  which  closed  the  electroscope. 
Measurements  and  Results. 
The    absorption    curves    were    traced    as 
abscissae. 

The  examination    of  the  curve    ohtained 
shows  that  the  intensity  could  be  expressed  : 

I  =  I^c-V  +  Le-V  +13^- V 

thp^f^f""  "  f^^^  P^""  ^^"'"^^^   centimetre  of 
the  interposed  screens;  I^,  I^,  i^,  the  initial 


JUNE  15,  1923. 


THE  CHEMICAL  NEWS. 


371 


intengity    of    the    three   rays,    w^,    w,,    Wg, 
their    coefficients    of    mass    of    absorption 

/^ 
(often  denoted  b\   —  ). 
p 
It  is  necessary  to  note  that  the    y-ray  of 
Polonium,     whose  mass    coefficient  of    ab- 
sorption wa.s  found  equal  to  230  (indicated 
by  Chadwick    and  recently    confirmed     by 
Mme.  Curie)  is  too  much  absorbed  to  inter- 
vene in  the  curves  with  which  we    are  con- 
cerned.     After  obtaining  certain  dat.-i,    the 
authors  proceeded  to  some  chemical  opera- 
tion with  a  view  to  separate  the  Radium  D 
and  Radium  E. 

The  mixture  was  dissolved  in  hot  nitric 
acid  and  Radium  D,  crystallised  on  cooling 
after  concentration,  lead  nitrate  being  in- 
soluble in  concentrated  cold  nitric  acid, 
liadium  E,  separated  in  this  way  is  still 
slightly  mixe<l  with  lead  and  Radium  D. 
The  polonium  was  finally  separate^l  by  de- 
position on  a  silver  blade. 

The  absorption  curves  corresponding  to 
the  two  portions,  Radium  D  and  Radiiun 
E,  were  traced  as  soon  as  ipossible  after 
separation. 

The  changes  shown  in  the  curves  by  the 
destruction  of  Radium  D  in  one  portion 
separated  by  its  reformation  into  the  other 
were  studied  at  the  same  time  as  we  fol- 
lowed the  evolution  of  the  quantity  of 
Radium  E  by  measuring  these  j3-raya  with 
the  aid  of  an  electrometric  installation. 

A  study  of  the  curves  obtained  shows 
that  the  penetrating  rays  III  arise  from 
Radium  E. 

The  results  are  shown  to  be  in  gfxxl  ac- 
cord with  those  of  Rutherford  and  Richard- 
son, who  give  mass  coefficients  16.5  and 
0.36  H'spectively  for  rays  I  and  II. 

The  authors  have  established  the  exist- 
ence of  penetrating  rays  III,  attributable 
to  Radium  E.  Their  coefficient  of  absorp- 
tion has  also  been  determined. — (ComptcH 
RetuluH.  1023.  CLXXVI..   1301-4.) 


IS  rUEHE  .\N  ELEMENT  OF  ZERO 

ATOMIC  NUMBER?— III.* 

By  F.  H.  Lorikg. 

In  pursuance  of  this  study,    it  is    of    in- 
terest   t.o    note    that    Sir    E.    Rutherford 


*  See  "  Chewicnl  Neus,"    thin    rohiwr, 
pages  307  and  325. 


(Bakerian  Lecture:  Prof.  Roy.  Soc,  1P20, 
Vol.  XCVII.,  ip.  398)  suggests  that  it  is  by 
no  means  impossible  for  an  atom  of  mass 
1  to  exist  with  zero  nuclear  charge.  "  On 
present  views,"  quoting  from  the  above  lec- 
ture, "  the  neutral  hydrogen  atom  is  re- 
garded as  a  nucleus  of  unit  charge  with  an 
electron  attached  at  a  distance,  and  the 
spectrum  of  hydrogen  is  ascribed  to  the 
movements  of  this  distant  electron.  Under 
some  conditions,  however,  it  may  be  pos- 
sible for  an  electron  to  combine  much  more 
closely  with  the  H  nucleus  (proton),  form- 
ing a  kind  of  neutral  doublet.  Such  an 
atom  would  have  very  novel  (properties.  Its 
external  field  would  be  practically  zero,  ex- 
cerpt very  close  to  the  nucleus,  and  in  con- 
sequence it  should  be  able  to  move  freely 
through  matter.  Its  presence  would  prob- 
ably be  difficult  to  detect  by  the  spectro- 
scope, and  it  may  be  impossible  to  contain 
it  in  a  sealed  vessel.  On  the  other  hand,  it 
should  ent^er  readily  the  structure  of 
atoms     .  ." 

Prof.  Eddington,  in  his  book,  Mathemati- 
cal Theory  of  Relativity,  discusses  this 
problem  from  the  energy  or  mass  side,  and 
he  points  out  that  the  comiplete  neutralisa- 
tion of  a  proton  by  an  electron  might  give 
rise  to  an  appreciable  loss  of  mass  that 
would  pass  out  as  electromagnetic  radia- 
tion. 

It  will  be  seen  that  these  ideas  involve  a 
nuclear  atom  of  zero  atomic  number;  only 
in  the  cast>  of  complete  neutralisation  such 
an  element  would  become  more  or  less 
massless.  if  Eddington  is  correct  in  his  sur- 
mise. 

In  the  nist.ince  of  complete  neutralisa- 
tion, it  is  supposed  that  the  electron  and 
the  proton  coalesce,  i.e.,  that  they  merge  to 
form  one  entity  if  such  an  entity  can  pre- 
serve its  existence  as  such.  Now,  Sir  .7.  .1. 
Thomson  puts  forward  the  view,  which  has 
been  under  consideration  for  some  time, 
that  when  the  electron  approaches  suffi- 
ciently near  to  the  tpositive  nucleus,  then  a 
repulsion  st^s  in.  Sh-  J.  J.  Thomson,  in 
the  Journal  of  the  Franklin  Institute,  May, 
1923,  page  597,  says:  —  "  I  shall  assume 
that  the  law  of  force  between  a  positive 
chargi'  and  an  electron  is  expressed  by  the 
equation — 

Ee         /'  ,  c      \ 


where  .,        , 

F=  attraction  between  the  charges. 


372 


THE  CHEMICAL  NEWS. 


JUNE  15,  1923. 


E=ithe  positive  charge  ou  the  core, 

6  =  the  negative  charge  on  the  electron, 

r  =  the  distance  between  them, 

c  =  a  constant  varying  from  one  kind  oi 
atom  to  another;  it  is  the  distance  at 
which  the  force  changes  from  attrac- 
tion to  repulsion  and  is  of  the  order 
of  10-^  cm. 

Sir  J.  J.  Thomson  remarks  that  if  the 
law  of  force  is  that  just  given,  "  then  a 
number  of  electrons  can  be  in  stable 
equilibrium  round  a  charge  N^ithout  neces- 
sarily describing  orbits  round  it."  In  this 
connection,  Sir  J.  J.  Thomson  calls  atten- 
tion to  Ernshaw's  theorem:  that  no  stable 
configuration  in  which  the  electrons  are  at 
rest  or  oscillate  about  stable  positions  is 
ipossible  when  using  only  the  in  verse- square 
law  of  distance.  Furthermore,  an  example 
is  given  which  makes  planetary  phenomena 
non-applicable  to  the  atom,  for  in  the  case 
of  Saturn's  rings,  the  particles  do  not  repeJ 
eaeh  other  as  the  electrons  do.  In  this 
treatment  of  the  problem  it  is  assumed  that 
the  ordinary  law  of  attraction  applies  at 
considerable  distances,  but  when  the  dis- 
tance becomes  sub-atomic,  so  to  speak, 
then  the  law  no  longer  applies,  and  this  in- 
troduces a  new  law,  as  indicated  above. 

The  argument  in  its  present  develop- 
ment leads  again  to  the  improbability  of 
there  being  an  atom,  or  nuclear  magnitude, 
of  zero  atomic  number,  and  it  is  necessary 
to  fall  back  upon  the  reasoning  of  Part  II., 
in  which  the  electron  was  the  only  entity 
that  could  have  a  place  before  hydrogen 
and  its  zero  atomic  number  was  only 
acquired  by  virtue  of  its  neutralising  qual- 
ity, though  this  property  is  limited  if  the 
views  of  Sir  J.  J.  Thomson  are  correct.  In 
short,  the  electron  cannot  coalesce  with 
the  proton  and  form  a  stable  system. 

We  have  here  a  case  of  scientists  of  great 
eminence     working     out  different     explana- 
tions of  phenomena  which  seem  at  variance , 
in  some  fundamental  resipects. 

The  subject  is  of  interest,  in  the  writer's 
opinion,  and  some  further  views  may  be 
offered. 


A  PEEIODIC  FUNCTION  OF  ATOMIC 
WEIGHTS. 

By  Alexandkk  Sakoscuanskv,  13. So. 

There  exists  in  the  periodic  system,  cer- 
tain groups  of  elements,  which  establish  a 
numerical  relationship  between  the  ele- 
ments, and  with  which  atomic  weights  can 
be  calculated. 

The  arrangement  of  the  elements,  cal- 
cium, rubidium,  vanadium,  cerium,  and 
phosphorus,  in  the  a  group  of  six  elements, 
can  be  described  in  the  following  way :  Ca 
is  diagonally  adjacent  to  Rb  on  its  left,  and 
V  is  separated  by  an.  interval  of  two  ele- 
ments to  the  right;  Ce  is  vertically  adjacent 
to  the  element  which  is  diagonally  adjacent 
to  the  left  to  V.  Phosiphorus  of  the  same 
valency  as  V  is  the  eighth  element  from  it. 
Tlie  sixth  member  of  the  group  is  bound  by 
the   arithmetical-chemical  identity  :  — 

Ce     Ca  4 

V     Rb  P  " 

In  the  following  group  CI.  forms  a  pair 
with  S  in  the  same  way  as  P  and  Ar  or  Ca, 
CI.  is  the  seventh  element  from  Cr.  The 
pair  of  elements  on  the  right-hand  side  of 
the  equation  ajce  adjacent  in  the  periodic 
system,  with  the  exception  of  phosphorus. 
The  five  groups  are  tabulated,  with  inter- 
vals and  valencies  shown. 


III. 
Fe    Zr 


III. 

So  (5) 


Ag*  V 

Ti 

VII. 

VII. 

Mn    T 

CI 

—  .  —     = 

Cd    Ti 

K  (6) 

VI. 

VI. 

Cr     Sr 

s 

In     So 

CI  (7) 

Ce     Ca 

4 

U   'Rb 

P     (8) 

La    K 

1 

Ti     Kr 


Al^*   (9) 


JUNE  15.  1923. 


THE  CHEMICAL  NEWS. 


873 


EINSTEIN'S  THEORY  OF 
RELATIVITY. 

Further  Eclipse  Test  Photographs  Not 
Necessary. 

The  examination  of  the  photographs 
taken  during  last  September's  total  eclipse 
of  the  sun  has  resulted  in  a  remarkable 
verification  of  the  curvature  of  space  and 
the  bending  of  light  rays  demanded  by 
Einstein's  theory  of  Relativity  Gravitation. 
The  American,  Canadian  and  Australian 
parties  submitted  the  theory  to  critical  test. 

The  photographs  obtained  by  Prof. 
Chant,  of  Toronto,  and  Dr.  Campbell,  of 
the  Lick  Observatory,  have  now  been  care- 
fully measured,  and  the  necessary  mathe- 
matical computations  made,  with  the  result 
that  all  the  stars  shown  have  l>een  found  to 
be  displaced  by  the  exact  amount  predicted 
by  Einstein.  It  was  proposed  to  repeat  the 
test  next  September,  at  the  time  of  the  total 
eclipse  visible  in  N.  America,  but  Dr. 
Campbell  is  so  convinced  by  the  results  of 
last  year's  eclipse,  and  those  of  1919  by 
Oreenwich  astronomers  in  Brazil,  that  there 
can  now  be  no  possible  doubt  as  to  the  cor- 
rectness of  the  Relativity  theory,  and  that 
further  corroboration,  so  far  as  the  eclipse 
test  is  concerned,  is  quite  unnecessary. 

The  measurements  of  tlie  Australian 
plates  have  not  yet  been  completed,  the  task 
being  now  in  progress  at  Greenwich,  but 
they  are  believed  to  be  as  conclusive  as 
those  taken  by  the  Canadians  and  Ameri- 
cans. It  may  now  be  taken  that  Relativity 
has  survived  two  of  the  three  tests  to  which 
it  can  be  subjected — those  depending  on  the 
deflection  of  light  passing  near  massive 
l)odies  in  space  and  the  movement  of  the 
orbit  of  the  planet  Mercury  in  defiance  of 
Newton's  laws.  The  third  test,  which  in- 
volves a  change  in  the  position  of  certain 
lines  in  the  sun's  spectrum,  is  the 
most  difficult  of  the  three  to  apply,  and 
no  definite  result  has  yet  been  obtained. 
Hut  Professor  Einstein  is  confident  he  will 
obtain  clear  evidence  of  this  shift  of  the 
solar  spectral  lines  by  means  of  a  special 
apparatus  he  has  had  erected  at  Potsdam 
Observatory. 

There  is,  however,  no  likelihood  of  any 
more  Ivinstein  photojfrajjhs  being  taken 
when  the  siui  is  eclii)sed.  It  is  a  costly  work, 
and  prevents  astrotioincrs  undertaking 
other  eclipse  observations. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  June  14. 

Papers  reaH:  — 

C.  Chree,  F.R.S.  Magnetic  Phenomena 
m  the  Region  of  the  South  Magnetic  Pole. 

O.  R.  Howell.      The  Catalytic    Decom- 
position of  Sodium  Hypochlorite  by  Cobalt 
Peroxide.       Communicated  by  Prof    T    M 
liowry,  F.R.S. 

Nina  M.  Hosali.  The  Seismic  Waves  in 
a  I  isco- Elastic  Earth.  Communicated  by 
Prof.  L.  N.  G.  Filon,  F.R.S. 


Papers  read  in  title  only:— 

J.  W.  Landon  and  H.  Quinney.  Experi- 
ments with  the  Hopkinson  Pressure  Bar 
^,^|^^^^"°icated      by     Sir    Alfred      Ewingi 

S.  F.  Grace.    Free  Motion  of  a  Sphere  in 
a  Rotating  Liquid    at  Right  Angles    to  the 
Axis  of  Rotation.     Communicated  by  G    I 
lay  lor,  F.R.S.  *^ 

H.  F.  J.    ScHONLAND.      The  Passage    of 

Cathode  Rays  through  Matter.  Communi- 

cHtcd     by    Prof.     Sir    Ernest  Rutherford, 
1"  .R.b. 

TiiirRSDAY,  June  7. 

PapcrH  read :  — 

Sir  Charles  Sherrington,  P.R.S.,  and 
E.  G.  T.  LiDDELL.  Stimulus  Rhythm  in 
Reflex  Tetanic  Contraction. 

K.  N.  Moss.  Some  Effects  of  High  Air 
Temperatures  and  Muscular  Exertion  upon 
Colliers.  Communicated  by  Dr.  J.  S.  Hal- 
daue,  F.R.S. 


Paper  read  in  title  only:  — 

F.  A,  E.  C'uRW.  The  Significance  of  an 
Anchondroplasia-like  Condition  met  with  in 
Cattle.  Communicated  by  Sir  Arthur 
Keith,  F.R.S. 


374 


THE  CHteMICAL  NEWS. 


JUNE  16,  1923. 


The  Croonian  Lecture  Mail  be  delivered 
on  June  21,  by  Dr.  F.  F.  Blackman, 
F.K.S.,  on  Plant  Respiration  as  a  Catalytic 
Process. 


THE  FARADAY  SOCIETY. 

General  Discussion  on  the  Physical 
Chemistry  of  the  Photoguapiiic  Process. 

At  the  meetings  on  May  28. 

(Concluded  from  Page  362.) 

On  the  Sensitivity  of  a  Silver  Bromide 
Emulsion,  by  Walter  Clark,  M.Sc, 
A.I.C. 

Consideration  of  some  of  the  older  work 
of  Liiippo-Cramer,  Reinders,  Bancroft  and 
others  establishes  beyond  doubt  the  hetero- 
geneity of  the  silver  haloid  grains  of  a  photo- 
graphic emulsion.  In  a  purely  mathemati- 
cal or  physical  investigation  of  the  corniplcx 
problems  of  the  iphotographic  p]ati\  such  a 
course  would  probably  be  a  natural  one  to 
pursue,  as  representing  the  simplest  pos- 
sible case.  Since,  however,  the  whole 
problem  of  sensitivity  seems  to  be  bound  up 
with  the  presence  of  traces  of  material 
which  is  not  silver  haloid,  the  problem  is 
one  which  is  not  capable  of  solution  By  the 
mathematician  or  the  physicist  alone.  Be- 
fore the  physical  laws  underlying  the  photo- 
graphic process  can  be  completely  eluci- 
dated it  will  be  necessary  for  a  complete 
chemical  investigation  to  be  carried  out  in 
connection  with  the  actual  process  of  emul- 
sion making  and  the  effects  of  subsequent 
treatment  on  the  finished  plate.  The  prob- 
lem will  probably  involve  the  application  of 
the  laws  of  heterogeneous  equilibria,  and  of 
a  study  of  the  formation  of  complexes  and 
of  the  process  of  adsorption. 

The  sensitivity  of  a  fast  plate  is  due  pri- 
marily to  grains  of  material  which  is  not 
silver  bro'mide.  By  removal  of  the  latent 
light-image  with  chromic  acid  solution,  the 
speed  of  a  fast  plate  is  reduced  to  a  certain 
low  minimum.  This  is  a  natural  conse- 
quence of  the  existence  of  a  limited  amount 
of  substance  in  the  grains,  to  which  their 
high  sensitivity  is  due.  It  is  quite  prob- 
able that  the  sensitivity  promoting  material 
has  of  itself  little  or  no  sensitivity  to  light, 
but  that  it  acts  as  a  sort  of  photocatalyst  by 
increasing  sensitivity. 


The  reduction  of  sensitivity  of  a  plate  by 
destruction  of  the  latent  light  image  by 
chromic  acid  is  much  more  marked  than 
that  brought  about  by  merely  bathing  a 
plate  in  chromic  acid  without  a  preliminary 
exposure.  Also  the  fog  resulting  from  the 
action  of  hydrogen-peroxide  turpentine 
vapour,  nitric,  suliphuric,  and  hydrochloric 
acids  is  elmiinated  by  bathing  the  plate  in  a 
mixture  of  pina-flavol,  alkali  bromide  and 
acetic  acid. 

The  product  of  the  action  of  light  (and 
fogging  agents)  on  the  plate  is  much  more 
readily  attacked  by  chromic  acid  (and  acid- 
bromide-dye  mixtures)  than  is  the  sensitiv- 
ity-giving material  itself,  although  this  lat- 
ter is  slowly  attacked. 

The  Chemistry  of  the  Red  Toning  of  Sul- 
phide-Toned Prints,  by  A.  and  L.  Lumiere 
and  A.  Seyewetz  (Paris).  Communicated 
by  A.  P.  Clero  (Paris). 

Summary : 

Silver  images  which  have  been  sulphide 
toned  obtain  a  colour  ranging  from  brown  to 
red  chalk  in  a  solution  of  gold  chloride  to 
which  has  been  added  a  sulphur  compound, 
such  as  thiourea,  thiosinamine,  ammonium 
sulphocyanide,  or  ammonium  thiosulphate. 

This  toning  takes  place  only  with  silver 
sulphide  and  only  on  the  condition  that  a 
sulphur  compound  is  present  in  the  gold 
toning  bath. 

The  silver  sulphide,  during  the  toning 
process,  fixes  a  very  considerable  quantity 
(about  138  per  cent,  of  the  weight  of  the 
silver)  of  gold  and  also  a  certain  proportion 
of  sulphur,  somewhat  greater  than  that 
con-esiponding  with  the  formation  of  gold 
sulphide. 

The  toned  image  thus  apipears  to  consist 
of  a  double  sulphide  of  silver  and  gold. 

Some  Future  Problems  in  Photography, 
by  J.  Plotnikov. 

From  the  standpoint  6f  pure  photo- 
cheinioal  research  the  investigation  of  the 
properties  of  the  photographic  plate  is  full 
of  difficulties,  because  the  photochemist  is 
interested,  before  everything,  in  the  inves- 
tigation of  reactions,  taking  place  under 
simple  conditions,  where  the  photo-chemi- 
cal f)roperties  and  laws  ai'e  most  obvious. 
Tht!  photngratphic  plate,  however,  is  the 
most  complicated  thing  imaginable,  the 
complications  being  artificially  increased  in 
order    to  obtain  various  desired    technical 


JUNE  15.  1923. 


THE  CHEMICAL  NEWS 


375 


effects.  For  photochemical  investigations 
the  pure  salts  of  silver  should  be  used,  as 
was  done  only  recently  by  Schwarz  and 
Stock,  Hartung,  Koch  and  du  Prel,  Fajans, 
and  others;  even  more  desirable  would  be 
an  investigation  of  pure  solutions  of  silver 
salts. 

The  silver  salts  are  in  a  state  of  fine  dis- 
persion in  the  medium  (gelatin),  which,  it- 
self, is  colloidal  and  therefore  not  homo- 
geneous. The  molecular  wei<,'ht  of  the  sil- 
ver salts  under  such  conditions  is  unknown, 
and  is  a^pparently  dependent  on  the  way  in 
which  they  are  obtained.  They  form,  with 
the  gelatin,  complex  salts  of  an  unknown 
structure  and  probably  also  of  variable 
composition.  The  gelatin  itself,  as  a 
medium,  will  have  an  influence,  which  can- 
not be  strictly  defined,  on  the  photo 
chcmical  reaction,  and  this  influence  will 
vary  with  the  source  and  the  mode  of  pre- 
paration of  the  gelatin.  Mcn-eover,  the 
gelatin  adsorbs  and  binds  chemically  the 
free  halogens.  The  silver  salts  also  adsorb 
various  im,purities.  which  again  may  in- 
fluence the  photo-chemicai  process. 

The  blackening  of  the  plate  is  an  un- 
known function  of  the  dis,persity  and  of  the 
j,".an\i!ar  size  of  the  grains  of  the  silver 
salt  .  The  extent  of  the  surface  of  the 
grains  exposed  to  the  influence  of  light  is 
unknown  and  variable ;  also  the  gelatin  acts 
as  a  screen.  It  follows  that  the  conditions 
of  light  in  such  a  dull  medium  cannot  bt 
simple,  since  there  is:  reflection  of  light 
fro  mthe  outer  surface  of  the  gelatin  out- 
wards, from  the  inner  surface  of  the  glass 
into  the  gelatin,  and  from  the  individual 
grains;  mutual  covering  f>f  the  individu.i 
grains;  scattering  of  the  light  and  phott»- 
chemical  and  thermal  adsm-ption  of  light  in 
the  grains  themselves  and  in  the  medium. 

The  blackening  of  the  photogi-aphic 
(plate  is  not  a  true  representation  of  the 
primary  iphoto-ohemical  process  but  a  sum- 
mation effect  of  all  the  innumerable  and  in- 
definable factors  referred  to  above,  which 
factors  are  sometimes  quite  accidental  nn<] 
arbitrary  in  character.  Just  as  it  was  in 
the  time  of  Daguerre.  the  photograpliic 
plate  is  a  work  of  art,  which  can  be  us<h1  as 
an  aid  in  scientific  investigations,  but  can- 
not be  the  object  of  scientific  research. 

NucleuH  Inolation  and  DescnHitisaiion,  by 
Dr.  Lpppo-Cramer  (Schweinfurt,  Bavaria). 

Sinct'  my  first  comnnmicatinn  T  have  oh 
tained  results  which  (»pen  up  new  points  of 


view  in  the  consideration  of  dye-reactions. 
One  piece  of  evidence  in  support  of  the  oxi- 
dation tJieory  of  desensitisation  was,  that  if 
an  exposed  silver  bromide  plate  was  bathed 
in  a  solution  containing  a  bromide  and  a  de- 
sensitising -dye,  further  exiposure  to  light 
bleached  the  latent  image.  At  fii-st,  sensi- 
tising dyes,  for  example,  erythrosin  and 
rhodamine,  did  not  give  this  reaction,  which 
consequently  aippeared  to  me  to  be  due  to 
the  desensitising  (oxidising)  action  of  the 
safranines.  In  a  new  series  of  experi- 
ments, however,  and  contrary  to  expecta- 
tion, it  has  been  found  that  some  typical 
sensitisers,  for  example,  ethylcyanine  and 
pinaflavol  in  the  presence  of  a  bromide  and 
in  weakly  acid  solutions,  have  a  much  more 
destructive  action  on  the  latent  image  than 
the  safranines.  Moreover,  in  the  presence 
of  bromide,  some  sensitisers  destroy  the 
latent  image  to  a  great  extent  even  in  neu- 
tral solutions,  whereas  phenosafranine,  fo»- 
example,  has  only  a  slight  photo<?raphic  re- 
ducin  action  even  in  the  presence  of  bro- 
mide. Developers  (metol,  and  even  quinol) 
in  the  presence  of  potassium  bromide,  also 
reduced  phot(^aphical]y  the  latent  image 
to  a  greater  (jr  les-ser  extent,  whilst  in  all 
these  cases  bromide  alone  is  practically 
without  action.  It  appears  that  in  all  these 
ivactions  the  bromide  is  the  real  oxidising 
agent,  the  d\es  and  developers  only  facili- 
tating the  atttvck  of  the  oxidiser.  In  a  pre- 
liminary way,  I  have  assumed  that  the 
•lyes,  ot-c.,  when  they  are  adsorbed  by  the 
silver  brounde.  isolate  the  exposed  nuclei 
by  a  kind  of  adsorption  roplacement,  and 
thus  make  p<>;sible  the  attack  of  even  very 
weak  oxidising  agents.  As  is  well  known, 
S.  E.  Sheppard  and  G.  Meyer  assume  that 
developers  are  adsorbed  by  silver  bromide, 
although  I  am  not  in  agi'cement  with  their 
view  that  the  accelerating  action  whicli 
iodides  have  on  development  can  be  ex- 
plained in  this  way. 

I  have  previously  considered  the  desensi- 
tising action  of  the  safranines  to  be  due  to 
their  l)ehaviour  as  oxidising  agents,  but  in 
the  light  of  the  facts  just  mentioned,  the 
bleaching  of  the  latent  image  in  the  pre- 
sence of  potassium  bromide  can  no  longer 
bo  ascrilnd  to  an  oxidising  action  of  the 
dye.  and  consequently  the  facts  in  support 
of  my  theor\-  go  by  the  board.  This  theory 
however,  is  not  completely  overthrown, 
since  all  known  desenaitisers  possess  weakly 
oxidising  properties. 


376 


tSe  chemical  T^EWS. 


JUNE  15,  1923. 


Strict  proofs  in  favour  of  or  against  the 
oxidation  theory  of  desensitisers  are  cer- 
tainly to  be  desired,  but  it  is  scarcely  to  be 
expected  that  a  definite  decision  can  be 
arrived  at  by  means  of  reactions  carried  out 
in  a  test  tube,  since  it  is  just  their  relatively 
small  oxidising  power  which  appears  to 
make  the  desensitisers  suitable  for  their 
typical  reactions.  If  the  dyes  were 
stronger  oxidising  agents  they  would  of 
themselves  (without  bromide)  reduce  iphoto- 
graphically  the  latent  imake,  that  is,  they 
would  be  of  no  practical  use. 

I  give  reasons  for  discarding  the  chief 
proofs  which  I  gave  originally  in  support  of 
my  oxidation  theory,  but  one  must  demand 
of  other  theories  that  they  are  also  sup- 
ported by  experimental  proof. 


KOYAL  SOCIETY  OF  AliTS. 
The  Sir  George  Birdwood  Memorial  Lec- 
ture, entitled  The  Infiuence  of  Race  on 
Early  hidian  Art,  by  Sir  John  H.  Mar- 
shal, CLE.,  M.A.,  LiTT.D.,  F.S.A., 
Director-General  of  Archaeology  in  India, 
will  be  delivered  on  Friday,  June  15,  1923, 
at  4.30  p.m.  The  Most  Hon-urable  the 
Marquess  Curzon  of  Ked'e>t;>n,  K.G., 
G.C.S.L,  G.C.I.E.,  P.C,  F.K.S.,  Secre- 
tary of  State  for  Foreign  Affairs,  will  pre- 
side. 


EOYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

The  Friday  evening  discourse  on  June  15, 
at  9  o'clock,  will  be  delivered  by  Sir  Ernest 
Rutherford,  LL.D.,  D.Sc,  F.R.S.. 
M.R.I. ,  Prof,  of  Natural  Philosophy.  The 
subject  is  The  Life  History  of  an  Alpha 
Particle  from  Radium. 

Afternoon  Lecture  at  3  o'clock.- — On  Sat- 
urday, June  16,  Sir  Ernest  Rutherford, 
LL.D.,  D.Sc,  F.R.S.,  will  give  his  sixth 
lecture  on  Atoinic  Projectiles  and  their  Pro- 
perties. 

A  General  Meeting  of  the  members  of 
the  Royal  Institution  was  held  on  June  4, 
the  Duke  of  Northumborland  (President)  in 
the  chair.  It  was  announced  that  the 
Managers  had  elected  Sir  William  Bragg, 
Fullerian  Professor  of  Chemistry,  Director 
of  the  Laboratory,  Superintendent  of  the 
House,   and  Director  of  the  Davy  Faraday 


Research  Laboratory.  The  thanks  of  the 
members  were  returned  to  Dr.  J.  J.  S. 
Rowe  for  his  donation  of  £1  to  the  fund  for 
experimental  research.  The  Seci-etary  re- 
ported the  decease  of  Professor  E.  W.  Mor- 
ley,  an  honorary  member  of  the  Institu- 
tion, and  a  resolution  of  condolence  with 
the  relatives  was  passed.  Mr.  G.  E.  Gask, 
Mr.  John  Lister,  Mr.  P.  Ainsworth  Means, 
Mrs.  Robert  Mond,  Mr.  F.  C.  Oldfield,  Mr. 
Edward  Talbot  Paris,  Sir  Frederick  Rice, 
Mr.  C.  M.  0.  Rovsing,  and  Mr.  W.  S. 
Rowntree  were  elected  members. 


THE  CHEMICAL  SOCIETY. 

A  lecture  was  delivered  by  Profess(JR 
Charles  Moureu  (President  of  the  Societc 
Chimique  de  France),  entitled  Los  Gaz 
Rates  des  Sources  Thermales,  des  Grisous 
ct  Autres  Gaz  Naturels,  on  Thursday,  June 
14,  at  8.30  p.m.,  in  the  Society's  Rooms, 
Burlington  House. 


PHYSICAL  SOCIETY  OF  LONDON. 

At  the  meeting  held  on  May  25,  Alexan- 
der Russell,  M.A.,  D.Sc,  in  the  chair,  the 
following  papers"  were  read:  — 

The  Effect  of  Torsion  on  the  Thermal 
and  Electrical  Cojiductivities  of  Metals,  by 
Prof.  C.  H.  Lees,  D.Sc,  F.R.S.,  and  J. 
E.  Calthrop,  B.A.,  B.Sc 

A  method  is  described  which  enables  the 
effect  on  the  thermal  conductivity  of  a  wire 
of  twisting  the  wire  to  be  measured.  In 
each  of  the  steel,  aluminium,  copper  and 
lead  wires  tested  the  twist  decreases  the 
conductivity  along  the  wire  by  a  small 
amount  which  is  approximately  propor- 
tional to  the  square  of  the  twist  per  unit 
length . 

The  change  of  electrical  conductivity  is 
found  to  be  in  general  less  than  the  change 
of  thermal  conductivity,  but  is  also,  ap- 
proximately proportional  to  the  square  of 
the  twist  per  unit  length. 

In  the  discussion,  Mr.  C.  R.  Darling  said 
that  the  method  described  seemed  an  ad- 
mirable one,  but  wishc^d  to  know  whether 
the  wires  were  annealed  before  the  (xpori- 
I  ment?  The  initial  condition  of  the  speci- 
j  mens  would  doubtless  affect  the  results  ob- 
i       tained,     and  might  account  for  the  discre- 


JUNE  15,  1923. 


THE  CHEMICAL  NEWS. 


377 


pancies  between  the  conclusions  arrived  at 
by  different  observers. 

Mr.  Rollo  A(ppleyard  also  referred  to  the 
effect  of  annealing  the  wire  under  test,  and 
added  that  the  effect  of  stretching  on  re- 
sistance is  at  least  as  important  as  that  of 
twisting.  In  stranding  copper  wires  for  a 
cable  the  outer  wires  are  stretched  as  well 
as  twisted,  and  any  permanent  increase  of 
resistance  due  to  such  causes  is  of  some 
consequence  in  practice.  It  would  be  in- 
teresting if  the  experiments  could  be  car- 
ried out  on  a  large  scale,  instead  of  on  a, 
laboratory  scale. 

Prof.  A.  0.  Kankine  inquired  whether 
the  effect  differs  according  as  the  direction 
of  twist  is  clockwise  or  counter-clockwise 
as  viewed  in  the  direction  of  flow  of  the 
heat  or  electric  current. 

Mr.  F.  E.  Smith  suggested  that  the  ex- 
periments might  be  simplified  by  means  of 
au  an-angement  for  producing  a  potential 
dilTureuce  between  the  two  clamps  C,  shown 
in  the  paper,  at  the  ends  ot  the  wire.  The 
necessary  heating  would  be  effected  by  the 
current  thereby  set  up  along  the  wire, 
which  would  have  a  maximum  temperaturi' 
at  its  middle  point  owing  to  the  cooling 
effect  of  the  maeses  of  metal  at  its  ends. 
The  required  thermal  and  electrical  mea- 
surements could  be  made  by  means  of  wires 
twisted  on  to  the  principal  wire  as  do- 
scribed  in  the  paper. 

Dr.  Alexander  Russell  expresRod  his 
admiration  for  the  methods  of  measure- 
ment devised  by  the  authors.  He  pointed 
out  that  the  twisting  of  the  strands  in  a 
stiunded  cable  produces  a  somewhat  simi- 
lar effect. 

Prof.  Lees,  in  reply,  said  that  the  wires 
were  soft  and  not  annealed.  The  object  of 
the  exiperiments  was  to  test  the  electron 
theory  of  conduction,  and  it  was  sufficient 
for  this  purpose  that  the  state  of  the  wire 
should  merely  be  the  same  for  the  electrical 
as  foi'  the  thermal  measurements.  The 
large  scale  tests  which  had  been  suggested 
presented  attractions  for  the  engineer,  but 
any  accuracy  lost  by  performing  the  experi- 
ments on  a  small  scale  was  fully  compen- 
sated by  the  more  precise  methods  avail- 
able in  a  laboratory,  while  the  relatively 
small  cost  of  the  latter  methods  is  a  serious 
consideration  to  the  physicist.  The  oflFeot 
of  stretching  has  been  inve8tigal('<l  by 
-lohnstone,  and  a  refenaice  t/<>  his  work  is 
^iven  in  the  paper.  The  thermal  conduc- 
tivity is  increased    by  stretching  while  the 


electrical  conductivity  is  diminished — an- 
other instance  of  failure  in  the  relation  pre- 
dicted by  the  electron  theory.  Prof.  Kan- 
kine's  suggestion  was  an  interesting  one. 
It  had  been  considered,  but  rejected  as  im- 
probable ;  it  might,  however,  be  worth  in- 
vestigation. The  method  suggested  by  Mr. 
Smith  was  somewhat  similar  to  that  of 
•Jager  and  Diesselhorst,  but  the  latter  re- 
quu-es  the  thermal  flow  to  pass  through 
joints,  and  inaccuracies  arise  from  this  cir- 
cumstance. As  regards  stranded  cables, 
the  effects  of  twisting  and  stretching  are  in 
opposite  directions  for  thermal  conductiv- 
ity, but  aid  one  another  in  the  case  of 
electrical  conductivity,  so  that  the  matter 
would  probably  repay  investigation. 

The  Use  of  the  Wien  Bridge  for  the 
Measurement  of  the  Losses  in  Dielectrics 
at  High  Voltages,  with  Special  Reference  tu 
FAectric  Cables,  by  A.  Kosen,  B.Sc, 
A.M.l.E.E. 

In  the  preliminary  section,  the  loss  angle 

of  an  imperfect    condenser  is  defined,    the 

.  equations  for  the  Wien  bridge  are  derived, 

and  the  i-ffects    of  variations  of    frequency 

and  voltage  on  the  balance  are  discussed. 

One  of  the  difficulties  in  the  application 
of  large  potential  differences  to  a  bridge  is 
the  effect  on  the  arm  which  has  to  with- 
stand tile  high  voltage.  In  the  arrange- 
ments due  to  Monasch  and  Sobering,  this 
arm  is  the  known  condenser;  in  the  bridge 
as  used  by  the  author,  the  voltage  is  ap- 
plied to  tiie  ratio  coils.  The  errors  intro- 
<luoed  by  earth  innpedance  are  eliminated  by 
using  the  Wagner  auxiliary  bridge. 

The  applications  to  measurements  on 
cables  are  considered,  and  the  use  of  the 
double  bridge  in  determining  the  "wirc-to- 
wire"  and  "wire-tcvsheatli"  losses  in  a 
umlti-core  cable  is  des(9*ibed. 

An  Experiment  on  the  Production  of  an 
Intermittent  Pressure  by  Boiling  Water,  by 
CiiAs.  U.  Darling,  F.Inst. P.,  F.I.O. 

If  a  glass  tubi',  open  at  both  ends,  and  of 
about  .')  mm.  bore,  be  placed  in  a  beaker  of 
briskly  boiling  water  so  as  to  rest  on  the 
bottom  of  the  beaker,  steam  bubbles  will  be 
observed  to  foiin  at  the  point  of  contact, 
causing  the  water  to  rise  to  a  definite 
height  in  the  tube.  The  column  of  water 
thus  raised  sinks  aftK'r  a  time,  and  then 
rises  again,  the  rising  and  falling  (K'curring 
at  irri'gular  intervals.  If,  however,  the 
tube  be  narrowed  to  a  bore  of  about  1  mm. 


378 


THE  CHEMICAL  NEWS. 


JUNE  15,  1923. 


near  the  top  of  the  water,  and  widened  out 
considerably  just  above  the  water  surface, 
it  will  then  be  seen  that  the  phenomenon 
becomes  regular  in  action.  After  rising  to 
the  height  of  about  3  cm.  in  the  widened 
part,  the  water  discharges  back  again  into 
the  beaker,  and  after  a  short  interval  again 
rises  and  is  discharged,  the  cycle  being  re- 
peated indefinitely. 

The  explanation  appears  to  be  that  the 
water  is  superheated  at  the  points  of  con- 
tact of  the  tube  and  beaker,  so  that  the 
steam  produced  can  sustain  a  higher  pres- 
sure of  water.  When  the  water  reaches  the 
widened  part,  however,  it  is  cooled  and  in- 
creases in  density  until  the  extra  steam 
pressure  at  the  bottom  of  the  tube  is  over- 
come, when  it  discharges  completely.  The 
capillary  bore  slows  down  the  rate  of  flow  in 
both  directions,  and  so  causes  the  move- 
ments to  be  steady.  A  separating  funnel 
with  open  tap  and  short  stem  is  well  suited 
to  the  experiment. 

It  will  be  observed  that  the  arrange- 
ment constitutes  a  simple  heat  engine,  witB 
source  and  sink,  automatically  passing 
through  a  regular  cycle  of  operations,  and 
forms  a  useful  lecture  demonstration  of  the 
conversion  of  heat  into  work. 

A  Demonstration  of  A  Novel  Instrument 
for  Recording  Wireless  Signals  was  given  by 
N.  W.  McLachlan,  D.Sc,  M.I.E.E. 

The  device  consists  essentially  of  a  drum 
of  Swedish  iron  with  an  annular  reces.s,  in 
which  are  situated  coils  of  fine  wire,  the 
ends  of  the  coils  being  connected  to  corres- 
ponding slip  rings.  The  periphery  of  the 
drum  is  faced  with  cast  iron  rings  which  are 
machined  to  run  true  to  0.0001  in.  A 
small  steel  shoe  rides  on  the  rings,  and  side 
play  is  prevented  by  a  brass  guide-piece 
with  a  projection  which  fits  into  the  annu- 
lar recess.  At  each  end  of  the  guide-piece 
a  hook  is  formed,  and  one  of  the  hooks  is 
connected  by  a  light  rod  to  a  duralumin 
lever  pivoted  to  turn  in  a  horizontal  plane. 
A  silver  syphon  passes  through  the  lever 
from  an  ink  well  overhead,  and  rests 
lightly  on  a  moving  paper  tape.  To  the 
other  side  of  the- lever  is  attached  a  strong 
spring  whose  tension  can  be  varied,  while 
the  remaining  hook  is  attached  to  a  lisht 
spring  which  prevents  the  shoe  from  rocking 
on  the  drum. 

The  drum  is  revolved  by  a  small  electric 
motor,  and  when  a  current  flows  in  one  of 
the  coils  the  shoe  is  attracted  to  the  drum 


and  a  large  pull  ia  required  to  prevent  re- 
lative motion  o  fthe  two.  This  pull  is  used 
to  actuate  the  syphon  lever  mechanism  so 
that  the  transverse  movement  over  the 
paper  tape  inscribes  the  incoming  message 
as  a  series  of  rectangles,  the  tops  of  which 
represent  the  dots  and  dash'es  of  the  Morse 
code. 

The  tangential  pull  on  the  shoe  is  many 
times  that  calculated  from  the  formula 
/jlB-AJStz,  where  /j.  =  coefficient  of  friction, 
B  =  flux  density  at  shoe  contact,  and  A  = 
area  of  contact.  The  ratio  of  the  actual  to 
the  calculated  pull  depends  on  the  flux  den- 
sity, and  has  a  maximum  value  of  about  80 
for  steel  or  cast  iron. 

Owing  to  this  phenomenon,  which  gives 
amiplification,  and  to  the  fact  that  there  is 
no  air-gap  in  the  magnetic  circuit  through 
the  shoe,  the  instrument  is  extremely  sen- 
sitive, and  will  work  at  a  speed  of  150  words 
a  minute  with  a  current  of  25  micro- 
amperes. It  will  work  in  a  thermionic 
valve  circuit,  and  for  wireless  it  is  fitted 
with  relay  contacts  so  that  incoming  mes- 
sages in  Morse  may  be  relayed  to  a  printing 
or  other  machine  direct. 

A  meeting  of  the  Society  was  held  on 
Friday,  June  8,  when  Prof.  James  G.  Gray, 
D.Sc,  F.R.S.E.,  Cargill  Professor  of  Ap- 
plied Physics  in  the  University  of  Glas- 
gow, delivered  a  lectiu-e  entitled,  A  General 
8olutio7i  of  the  Problem  of  Finding  the  True 
Vertical  for  All  Types  of  Mariyic  and  Aerial 
Graft.  The  lecture  was  accompanied  by 
demonstrations  with  gyroscopes,  and  dis- 
cussion followed. 


THE  CHEMICAL  SOCIETY  OF  JAPAN. 
Papers  communicated  to  the  Society:  — 

On  the  Beckmann  Transformation  of  Ni- 
trosolcetones,  by  Shintaro  Kodama. 

On  the  Alleged  Phenylglyoxal,  by  Shin- 
TAKo  Kodama. 

On  the  Proteins  in  Fagopyrum  esculcn- 
turn,  and  their  Nutritive  Values,  by  Yoshi- 
iiiKo  Matsuyama. 

On  the  Quantities  of  Tryptophan  in 
Various  Proteins,  by  Yosiiihiko  Matsuyama 
and  Takajiko  Mori. 


JUNE  15,  1923. 


THE  CHEMICAL  NEWS 


379 


On  the  Condensation  of  Nitriles  with 
Thianiides.  Part  II.  Acetnitrile  with  Thio- 
benzaniide;  and  Benzoniirile  with  Thioace- 
taiuide,  by  Seiichi  Ishikawa. 

On  the  Destructive  Action  of  Nitric  Acid 
upon  Phenols,  by  Motoe  Iwata. 

On  the  Ternary  System  :  Ethyl  Alcohol — 
Ethyl  Ether— Water,  by  Masutabo  Kono. 


THE  INSTITUTE  OF  PHYSICS. 
At  the  last  meeting  of  the  Board,  the  fol- 
lowing Corporate  Members  were  elected  :  — 
Fellows:  J.  H.  G.  Monypunny,  J.  H.  T. 
Roberts,  R.  C.  Richards,  G.  C.  Simpson. 
Associates:  A,  Adderley,  W.  T.  Aetbury. 
F.  G.  C.  Bratt,  P.  A.  Curry,  G.  A.  R.  Fos- 
ter, A.  E.  Owen,  and  J.  H.  Smith. 


••  THE  JOURNAL  OF  SCIENTIFIC 
INSTRUMENTS." 

The  preliminary  arrangements  in  cou- 
neotion  with  tlu;  regular  publication  of  Thr 
Journal  of  Scientific  hiHiruments  have  now 
been  made  by  the  Institute  of  Physics  in  co- 
operation with  the  National  Physical  Lab- 
oratory. The  special  attention  of  those 
workers  who  have  new  designs  for  instni- 
ment«  is  called  to  the  fact  that  the  Journal 
is  to  serve  as  a  medium  of  publication  of 
detailed  descriptions  and  critical  surveys  of 
the  l)ohavi(>ur  of  such  instruments.  Origi- 
nal papers  f>r  laboratory  and  workshop 
notes  dealing  with  the  practical  or  theoreti- 
cal aspects  of  scientific  instruments  should 
be  sent  to  the  Editor,  Dr.  John  S.  Ander- 
son, The  National  Physical  Laboratory, 
Teddington,  Middlesex. 


GENERAL  NOTES. 


In  the  House  of  Commons  recently,  Mr. 
Herbert  Spencer  iisked  the  President  of  the 
Board  of  '1  rade  whetlnu*  he  was  aware  that 
on  the  8th  of  March,  10*23,  an  a{)plication 
was  made  to  import  one  ton  each  of  rosa- 
zeine  B  extra  and  rhodaniine  B  extra ;  whe- 
ther permission  was  refused  and  the  dye 
user  referred  t.o  British  dyfMuakers;  whether 
the  British  pri<'<'  (jUottid  wns  £1,730  more 
f(n*  the  two  tons  of  dyeware ;  and  whether, 
in  view  of  the    large  amount  of  unemploy- 


ment caused  in  the  dyeing  trade  by  dear 
dyewares,  he  would  state  what  steps  he  pro- 
posed to  take  to  remedy  this  evil '.' 

Sir  Philip  Lloyd-Greame  replied:  The 
applications  to  which  the  hou.  member  re- 
fers were,  I  understand,  made  by  the  British 
Cottcm  and  Wool  Dyers'  Associaticm.  They 
were  refused  by  the  DyestufiEs  Advisory 
Licensing  Conmiittee  after  full  considera- 
ti<m  of  all  the  circumstances  relating  to  the 
particular  cousignnients  in  question,  and  I 
do  not  ipropose  to  take  any  action  in  the 
matter.  I  am  unable  to  assent  to  the  pro- 
position that  the  establishment  of  a  dyo- 
making  industry  in  this  country  is  injurious 
to  employment  in  the  dyeing  industry.  The 
foi-mer  is,  on  the  contrai'y,  essential  to  the 
security  of  the  latter. 

Sir  Wilfrid  Sugden  and  other  Members 
asked  the  President  of  the  Board  of  Trade 
whether  his  attention  had  been  drawn  to 
the  description  in  the  press  of  a  method  of 
treating  gas  by  a  Mr.  Tully,  whereby,  so  it 
was  alleged,  the  percentage  of  carbon  mon- 
oxide was  very  greatly  reduced;  and 
whether  he  had  any  information  as  to  the 
practicability  of  pnxiucing  such  a  gas  u<pon 
a  connuercial  scale ".' 

Sir  Philip  Lloyd-Greame  said :  The  latest 
analysis  which  1  have  seen  of  gas  produced 
by  Tully  plant  at  present  in  industrial  use, 
which  was  published  on  the  16th  May  in  the 
Gas  .Journal,  gives  the  carbon  monoxide 
content  as  37  per  cent.,  but  1  observe  that 
in  a  pro6|H?ctU8  just  issued,  it  is  stated  that 
by  means  of  a  new  converter  the  carbon 
monoxide  content  can  be  reduced  to  a  neg- 
ligible quantity.  I  am  not  in  a  position  to 
express  an  authoritative  opinion  as  to  the 
practicability  of  producing  town  gas  on  a 
oonmiercial  scale  by  the  new  process.  The 
matter  is,  however,  being  carefully  watched 
by  the  (rovernment  Departments  concerned- 
Mr.  Darbishire  asked  the  President  of  the 
Board  of  Trade  if  he  was  aware  that  it  was 
not  with  the  Ji^pproval  of  the  Colour  Users' 
.\s90ciation  that  the  distribution  of  repara- 
tion tlyestuflfs  was  transferred  from  the 
Central  Importing  Agency  to  the  British 
DyestufTs  Corporation,  and  that  on  many 
fKJcasions  the  prices  of  reparations  dyes  was 
more  than  the  prices  at  which  they  could 
be  obtained  from  Germany  under  licence; 
and  if  he  would  consider  the  advisability  of 
removing  all  restrictions  upon  the  free  im- 
port of  foreign  dyestuffs? 

Viseouiit  Wolmer,  Under-Secretary  to 
the  Biiiu-d  of  Trade,  replied:  In  nnswer  to 
the  first  part  of  the  qucsfion,  the  Chairman 


380 


tSe  chemical  news. 


JUNE  16,  192a. 


of  the  Colour  Users'  Association  has  pub- 
Hcly  expressed  (the  last  occasion  being  on 
the  14th  April)  the  Association's  apprecia- 
tion of  the  manner  in  which  the  distribution 
of  reparation  dyestuffs  has  been  handled  i;\ 
the  British  Dyestuffs  Corporation.  As  re- 
gards the  second  part,  an  advisory  commit- 
tee on  prices  has  been  formed,  on  which 
two  out  of  the  four  members  are  represen- 
tatives of  the  Colour  Users'  Association. 
The  answer  to  the  last  part  of  the  question 
is  in  the  negative. 


NOTES  ON  THE  ESTIMATION  OF 

TUNGSTEN  IN  ORES. 

By  J.  R.  Pound,  M.Sc. 

The  following  notes  sum  up  the  writer's 
experience,  which  extended  over  a  very 
busy  period  of  some  three  years,  dealing 
with  wolfram  ores  and  concentrates.  The 
three  methods  for  the  estimation  of  tung- 
sten that  are  discussed  below  are  well 
known,  but  these  results  of  their  trials  and 
comparison  under  technical  conditions  may 
be  interesting. 

Method  1. — The    routine    procedure    for 
the  assay  of  rich    wolfram  ores  or  concen- 
trates was  as    follows: — Take    1    gram    of 
finely-ground  sample;  digest  with  HCl  and 
HNO3  for  about  2  hours,  evaporating  down 
to  near  dryness.       To  the  remaining  5  cc, 
say,  of  liquid,  add  water,  warm  or  boil  for 
•^  to  ^  hour,  filter    through  a  small    filter 
paper,  and  wash    the  beaker    and  the    in- 
soluble matter  (WO3,    SiOg,     etc.)    in    the 
beaker  at  this  stage.     Then  place  a  weighed 
porcelain    dish  under  the  filter    funnel  and 
wash  the  beaker  and  the  filter  paper    with 
successive     small       quantities     of     strong 
NH4OH,   finally  bringing    all  the  insoluble 
matter  on  to  the  filter  paper,  and  collecting 
the  ammoniacal    filtrates  in  the    porcelain 
dish.      Then  place  the  filter  paper  with  the 
insoluble    matter    in    a  porcelain    crucible, 
dry  and  bum  off  the  paper,  cool,  and  brush 
the  contents  of  the  crucible    on  to  an  agate 
mortar,  grind    f^  to  flour,     and  brush    this 
back  to  the  original  beaker  without  loss.  In 
the  absence  of  draughts    this  can  be    done 
safely.     Re-treat  this  residue  with  acid  and 
ammonia    as  above,     running    the    second 
ammoniacal  filtrate  into  the  previous  porce- 
lain dish,  which  in  the  meantime  has  been 
heating  on  a  water-bath.       Finally  evapor- 
ate to  dryness  on  the  water-bath  the  com- 
bined ammoniacal    filtrate,     and  then  heat 


gradually  to  a  red  heat  over  a  Bunsen 
burner,  cool,  and  weigh.  Then  the  contents 
of  the  porcelain  dish  give  the  WO3  (tung- 
stic  acid)  directly. 

The  final  filter  paper  and  insoluble  mat- 
ter may  be  ignited  in  a  porcelain  crucible, 
thus  giving  the  "  insoluble  matter."  If 
the  ore  is  only  wolfram  with  insoluble  mat- 
ter,    which       is     often     the     case,       then 

4 
(per  cent.    WO3    x   —  +    per    cent,    insol.) 

o 
should  reach  100  per  cent.,  and  this  is 
sometimes  a  useful  check.  Pure  wolfram 
FeMn)  WO^,  contains  about  76  per  cent. 
WO3.  Some  authorities  quote  a  maximum 
value  of  76.6  per  cent.  WO3,  but  the  Tas- 
manian  wolfram  best  known  to  the  writer 
contained  at  the  most  75.8  per  cent.  VvOg. 

Notes  on  Method  1. — (1)  The  attack  of 
HCl  or  aqua  regia  on  wolfram  produces  the 
insoluble  WO3,  and  thus  the  action  is  slow, 
and  the  last  portion  of  the  wolfram  is  liable 
to  be  protected  from  decomposition.  Fine 
grinding  is  essential,  therefore,  and  espe- 
cially for  material  containing  over  08  per 
cent,  of  WO3 — i.e.,  over  50  per  cent,  of 
wolfram.  The  actual  assay  sample  of  such 
material  must  be  ground  to  flour  in  an 
agate  mortar.  This  is  easier  said  than  done. 
Also,  during  the  acid  treatment  the  sample 
is  liable  to  "  crust  up  "  and  thus  to  protect 
thte  lower  layers  from  the  action;  this 
crust  should  be  broken  up  several  times 
during  the  action.  When  products  con- 
taining less  than  50  per  cent,  wolfram  are 
ground,  and  the  wolfram  is  the  softest  con- 
stituent, then  a  ground  product  is  easily 
obtained  in  which  all  the  wolfram  is  fine 
enough  to  be  completely  and  readily  decom- 
posed by  acids;  and  if  the  other  constitu- 
ents of  the  ore  are  insoluble  in  the  acids, 
their  presence  keeps  the  wolfram  particles 
separated,  and  considerably  helps  the  com- 
plete decomposition  of  the  wolfram,  and  in 
this  case  the  second  acid  and  ammonia 
treatment  is  unnecessary.  Such  common 
constituents  of  wolfram  ores  are  silica,  sili- 
cates,  and  cassiteritc. 

(2)  The  writer  could  see  little  if  any  ad- 
vantage accruing  from  prolonged  action  of 
HCl  alone;  therefore,  after  treatment  with 
HCl  for  about  ^  hour  the  HNO3  was  added 
and  the  solution  slowly  evaporated  down. 
The  usual  amounts  of  acids  were  about  40 
ec.  HCl  and  5  cc.  HNO3,  and  the  time  of 
treatment  would  vary  from  1  to  3  hours.  It 
is  doiibtful  if  prolonged  action  of  acid  is 
worth  the  time — i.e.,  probably  the  bulk  of 
the  wolfram  is  decomposed  within  an  hour. 


TUNE  15,  1923. 


THE  CHEMICAL  NEWS. 


381 


The  second  acid  treatmeut,  necessitated  by 
the  imperfect  grinding  or  the  incomplete 
decoiiiijosition  in  the  first  case,  is  com- 
pleted in  a  sliort  time  -  say,  ^  lioiir. 
Evaporation  of  the  acid  right  to  dryness  is 
liable  to  render  the  WO^  rjifficultly  soluble 
in  ammonia, 

(3)  It  is  necessary  to  wash  the  WO,  on 
the  filter  paper  with  strong  ammonia, 
otherwise  colloidal  silica  will  run  through 
and  ultimately  be  weighed  as  \V0,.  It  is 
not  necessary  to  add  anmionium  chloride  to 
the  ammonia  wash  liquor,  and  the  presence 
of  exc4'ssive  ammonium  chloride  with  the 
ammonium  tungstate  in  the  tporcelain  dish 
causes  the  contents  to  fl.ikc  and  jump  off 
the  dish  during  the  ignitifxi,  thus  produc- 
ing mechanical  loss  of  WO^.  The  ammonia 
washmg  of  the  WO,  sometimes  becomes 
slow;  possibly  the  silica  for  silicic  acid) 
clogs  the  pores  of  the  filter  paper.  It  is 
thus  best  to  bring  the  bulk  of  the  insoluble 
matter  on  to  the  filter  paper  only  with  fTi(> 
last  ammonia  washes.  The  ammonia  fil- 
trate should  fit  comfortably  in  an  80-cc 
porcelain  dish. 

(4)  The  use  of  a  water  bath  is  recom- 
mended, as  the  ammoniacal  liquor  then 
evaporates  to  dryness  qvu'etly  and  safelv. 
and  needs  no  watching. 

(6)  In  this  method  there  is  a  tendency  for 
colloidal  silica  U>  run  through  wk..  the 
ammonia  liquor,  but  this  may  be  kept  at  a 
niinimum  by  the  conditions  described  under 
note  (8).  If  the  ammoniacal  filtrates  arv 
coIlecU'd  in  a  platinum  dish  the  RiO  mav 
be  removed  by  the  usual  II^SO,  an4  TTF 
treatment,  and  this  treatment  might  he 
necessary  for  low-grade  mat<>rial  contain - 
mg  easily  deconnpoKable  silicates;  it  was 
not  adf>pted  in  the  work  covered  bv  these 
notes. 

The  filtrate  ater  the  first  acid  treatment 
can  be  tested,  after  dilution,  with  H  S  and 
thus  CuS,  Bi,S,.  etc.,  can  be  preciVitated 
and  Qualitatively  and  quantitatively  esti- 
mated, and  afterwards,  of  course,  other  con 
stituents  of  the  ore— e.j;..  the  calcium  fron. 
scheehte,  CaWO,— can  be  detected  and 
estimated  in  the  usual  way. 

The  final    insoluble  matter    may  be    in- 
spected for  silica  or    rock  minerals  (white) 
titamferous  iron  ore  (black),  and  especiallv 
for  cassiterito    (after    the    acid    treatment 


brownish).  Such  an  inspection,  after  a 
Uttle  experience,  will  enable  the  tin  content 
of  the  wolfram  concentrates  to  be  estimated 
to  the  nearest  per  cent.,  especially  when 
the  amount  is  small — say  less  than  5  per 
cent.  Sn.  In  any  case  the  tin  content  of 
the  sample  may  be  obtained  with  accuracy 
by  Pearce's  method  applied  to  this  insoluble 
matter— i.e.,  by  fusing  it  with  Na.O,,  dis- 
solving the  melt  in  HCl,  reducing  the 
strongly-acid  hot  solution  with  nickel,  cool- 
ing in  COj,  and  diluting  and  titrating  the 
SnClj  solution  with  an  iodine  solution  which 
has  l)een  standardised  similarly  against 
pure  metallic  tin.  The  writer  found  this  to 
be  the  most  satisfactory  method  of  estinjat- 
ing  the  tin  in  all  cassiterite- wolf  ram  con- 
centrates. 

When  dealing  with  or  purchasing  various 
and  unfamiliar  wolfram    concentrates,     the 
above  acid  method  thus    enables  the  other 
constituents  to  be  detected    and  estimated, 
if  necessary,  with  the  minimum  of  trouble, 
and  this  is  an  important  feature.       Never- 
theless, as  will  be  seen  later,  with  concen- 
trates rich  in  wolfram  care  is  necessary  to 
avoid  low  results  for  the  tungstic  acid  con- 
tent, and  in  general  the  higher  of  two  dupli- 
cates will  give  the  m<M^  cwrect  per  cent. 
WO,.       The  common  tendency  is  for  some 
of  the  wolfram  to  remain  unattaeked  or  for 
some  of  the    WO,    to  remain    occluded    as 
anmionium  tungstate  in    the  filter    paper. 
In  the  latter  case  the  yellow  WO,  will    be 
seen  in  the  final  ignited  insoluble    matter. 
By  this  methfKl    duplicate    results    should 
agree  to  within  1  per  cent,    of  the  wolfram 
content  of  the  sample, 

Mithod  2,— A  modification  of  the    above 
methfKl,  which  obviates  the  last-mentioned 
source  of  error,  is  to  grind  perfectly  nV  the 
start  so  as  to  ensure    comiplete  decomposi- 
tion of  the  ore  in  one  acid  treatment,    and 
after  washing  the    WO,  free  from  acid,    to 
plac<^  it,    filter  paper    and  all,    in    AmOH 
solution  in  a  graduated  flask  or  beaker    (the 
original  beaker    may  serve),    and  after    its 
dis.solution     as    ammonium     tungstate     to 
make  up  to  the  definite  volume,  and  then  to 
take  of  the  clear  supernatant    liquid  a  defi- 
nite aliquot  part,  which,  on  evaporation  to 
dryness  and  ignition,    gives  the  WO,      and 
hence  the  per  cent.  WO,    of  the  sample  is 
calculated.       This  method  does    not  neccs- 
sanly  demand    complete    disintegration    of 
the  ore    in  one  acid    treatment,    but    such 
would  be  advisable.        Excepting  that  the 
remainmg  insoluble  matter    is  not  directly 


382 


THE  CHEMICAL  NEWS. 


collected,  this  modified  acid  method  is  per- 
haips  better  than  the  i)revious  one — i.e.,  it 
is  incUned  to  give  higher  results  for  the  per 
cent.  WO3. 

Method  3. — The  writer  also  used  the 
well-known  mercurous  nitrate  method  of 
estimating  tungsten,  and  by  this  means 
correct  results  may  be  obtained.  This 
method  was  carried  out  as  folloM's  : — Take 
^  gram  of  wolfram  concentrates  and  fuse 
with  NaOH  in  a  nickel  dish  for  15  minutes ; 
then  dissolve  the  melt  in  hot  water,  a  little 
NajOa  being  "added,  and  then  filter  hot  from 
the  insoluble  Fe  and  Mn  oxides,  unattacked 
SnO,,  etc.,  and  wash  well  with  hot  water. 
Then  slightly  acidify  the  filtrate  with 
HNO3,  heat  till  the  COg  escapes  and  the 
separated  silicic  acid  (and  stannic  acid)  is 
coagulated,  and  then  make  alkaline  with 
ammonia,  heat  and  filter,  and  wash.  Again 
slightly  acidify  the  filtrate  with  HNO  and 
precipitate  the  tungsten  as  mercurous 
tungstate,  HggWOj,  a  pale  yellow  coagul- 
able  precipitate,  by  the  addition  of 
Hg2(N03)3  solution.  This  last  step  de- 
mands a  nearly  neutral  solution,  but  as  the 
Hg2(NO,)2  solution  can  only  be  made  with 
excess  HNO3,  the  assay  solution  becomes 
more  acid  during  the  precipitation;  small 
excess  of  Hg5,(NO,)2  is  added  and  then  di- 
lute AmOH  drop  by  droip  till  the  liquor  is 
neutral  or  slightly  acid,  when  all  the  tung- 
sten is  precipitated  as  Hg,W04,  along  with 
more  or  less  black  Hg  and  mercury  amino- 
compounds.  As  HgjWO^  is  soluble  (wifFi 
decomposition)  in  excess  of  AmOH  or  of 
HNO3,  ^'^^  conditions  of  precipitation  must 
be  carefully  observed,  otherwise  it  is  pos- 
sible to  leave  tungsten  in  the  solution.  The 
tungsten  bearing  precipitate  is  well  washed 
with  hot  water  containing  a  little 
Hg2(N03)2,  the  precipitate  is  dried,  /placed 
in  a  porcelain  crucible,  and  ignited,  and 
the  resulting  WO3  is  weighed. 

This  is  probably,  when  combined  with 
suitable  modifications  (vide  note  "  5 
above),  the  most  accurate  method  of 
separation  of  the  tungsten  from  all  other 
constituents  of  most  wolfram  ores,  e.g. — 
SiOa,  SnO,,  Nb,  and  Ta;  but  it  is  not  suit- 
able for  scheelite  or  for  ores  containing  Ca 
and  similar  metals,  appreciable  metallic 
sulphides,  especially  arsenical  pyrites,  or 
phosphates,  in  which  cases  the  acid  method 
is  preferable.  In  the  Hg2(N03)2  method 
the  "fiddUng  about"  necessary    to    ensure 


JUNE  15,  1923. 


the  complete  precipitation  of  the  wolfram 
takes  time,  and  also  the  other  constituents 
of  the  original  ore  are  not  separated  in  a 
form  in  which  they  can  be  readily  detected 
or  estimated,  and  finally  this  method  is 
rather  expensive.  These  facts,  and  the  al- 
most general  adoption  of  the  acid  method 
by  others  (buyers  or  sellers),  led  to  the  re- 
stricted use  of  the  Hg2(N03)2  method. 

The  following  table  will  indicate  some  re- 
sults on  wolfram  ores  or  concentrates  ob- 
tained by  means  of  these  three  methods. 
The  figures  quoted  are  in  all  cases  the 
means  of  duplicates.  The  results  by 
methods  (1)  and  (3)  were  obtained  by  the 
writer  on  the  same  bulk  assay  sample ;  the 
results  by  method  (2)  were  obtained  by  an 
independent  assayer  on  his  own  sample, 
and  thus  between  (1)  or  (3)  and  (2)  there  is 
a  possible  divergence  due  to  the  two  samp- 
lings, but  as  these  were  carried  out  on  ap- 
proximately 5-ton  parcels  of  the  fine 
material  (minus  6  mesh),  shipped  in  bags 
of  1  cwt.  capacity,  the  possible  errors  of 
sampling  should  be  very  small. 

Percentage  weight  of  tungstic  acid 
(\A'03)  in  wolfram  ores  as  determined  by — 

(1)  The      (2)  The  modi-     (3)  The 

stock  acid     fied  acid       Hg2(N03)2 

method.       method.      method. ' 


p.c. 
WO3 
71.3 
68.8 
67.3 
68.2 
59.2 
71.3 


p.c. 
WO3 
72.4 
69.6 
67.1 


p.c. 
WO3 
72.6 
69.8 
67.4 
68.1 
59.5 
72.4 
72.4 


(«) 
(b) 
('■) 
id) 
(e) 
if) 

ig)  —  71.5 

[h)  64.6  65.3  — 

It  will  be  seen  that  method  (1)  tends  to 
give  the  lowest  results,  which  occasionally 
are  below  those  of  methods  (2)  and  (3)  by 
more  than  desirable  limits,  which  may  be 
placed  at  0.6  per  cent.  WO3  on  this  class  of 
material,  e.g.~{a),  {h),  and  (/).  Method 
(2)  agrees  well  with  method  (3),  but  the 
latter  method  inclines  to  give  the  higher  re- 
sults. It  need  only  be  stated,  in  conclusion, 
that  the  above  results  represent  average 
results  obtained  in  the  -writer's  practice. 

{From  the  Proceedings  of  the    Australa- 
sian  Inntitnte    of  Mining    and    Metallurqy 
Sept.,  1922,  pp.  291-6.)' 


JUNE  15,  1923. 


THE  CHEMICAL  NEWS. 


mn 


NOTICES  OF  BOOKS. 

Theoretical  Chcmislry,  by  Prof.  W. 
Nernst,  Ph.D.  KeviseJ  in  accordance 
with  thf  eighth-tenth  German  edition  bv 
L.  W.  CoDD,  M.A.  P,p.  XX.  +  902. 
London:  Macmillan  &  Co.,  Ltd.,  St. 
Martin's  Street,  W.C.  1023.  Price  28s. 
net. 

The  English  translation  of  Prof.  Nernst 's 
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edition. 

The  important  advances  in  physics  and 
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One  or  two  minor  but  obvious  slips  have 
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The  Examination  of  Hydrocarbon  Oils, 
and  of  SaponifiaJilc  Fats  and  Waxes,  by 
Prof.  Dr.  D.  Holde.  Authorised  trans- 
lation from  the  fifth  German  edition  by 
Edward  Mueller,  Pn.I).  Second  Eng- 
li»h  edition.  Pp.  XIX.  +  572.  London : 
Messrs.  Chapman  &  Hall,  11,  Henrietta 
Street,  W.C.     1022.     Price  SOs.  net. 

This  second  English  edition,  which 
brings  Prof.  Holde 's  valuable  technological 
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man edition,  which  appeared  soon  after  the 
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been  commendably  well  condensed  into 
tables,  where  this  mode  of  treatment  was 
possible. 

Of  thi'  other  new  matter,  English  scien- 
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including  such  remote  material  as  graipe 
seeds  and  beech  nuts,  was  exploited. 

The  general  subject,    as  indicated  in  the 


title,  is  very  fully  covered,  and  there  is  a 
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BOOKS  KECEIVED. 

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384 


1 


THE  CHEMICAL  NEWS. 


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197223 — Baumgartner,    E. — Manufacture     of    cliro- 
mato  of  soda. 


189432 — Farhwerke  Vorm.  Meister  Lucius  &  Brun- 
ing.— Manufacture  of  formaldehyde. 


Abstract  Published  tliu  Week. 


195444 — Piocess  for  reduction  of  grain. — Chemical 
Eng.  Co.  (Manchester),  Ltd.,  &  Spensley, 
J.   W.,  49,  Deansgate,   Manchester. 


Grain  is  reduced  by  treatment  in  a  combina- 
tion of  break  rolls,  or  other  ordinary  milling  ap- 
pliances, with  high-speed  centrifugal  pin-disc 
mills.  The  grain  may  be  subjected  to  lighter 
trea,tment  in  the  earlier  break  rolls  and  the  final 
tailings,  consisting  mainly  of  bran,  are  then 
treated  in  a  pin-disc  mill  to  obtain  a  further  yield 
of  flour.  Or  fewer  sets  of  break  rolls  may  be  em- 
ployed. The  earlier  break  rolls,  except  the  first, 
may  be  replaced  by  pin-disc  mills  which  are  run 
at  a  lower  si>eed.  The  air  blast  produced  by  the 
diso  mills  may  be  utilised  to  perform  a  prelimi- 
nary separation  of  the  product. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  pr!ce  of  Is.  6d. 
each. 


195295— Alumina.— Pedemonte,       A.      L.,     2,      Rue 
Emile-Zola,  Toulon,  France. 

Alumina;  aluminium  chloride  and  sulphide. — 
Pure  alumina  is  obtained  from  ferruginous  baii.x- 
ite  by  heating  in  a  reducing  atmosphere  to  ren- 
der the  iron  and  titanium  magnetic,  separating 
tliese  impurities  by  magnetic  action,  dissolving 
the  purified  bauxite  in  hydrochloric  or  sulphuric 
acid,  digesting  to  render  silica  and  any  remain- 
ing titanium  insoluble,  filtering,  and  evaporating 
the  filtrate  to  dryness  and  calcining  the  alu- 
minium salt  to  obtain  alumina  and  recover  the 
acid. 


JUNE  22,  1923. 


THE  CHEMICAL  NEWS. 


385 


THE   CHEMICAL  NEWS, 

VOL.  CXXVL       No.  3297. 


A  NOTE  ON  THE  ATOMIC  WEIGHT  OF 
TITANIUM. 

By  F.  H.  Loring. 

In  the  Journal  of  the  American  Chemical 
Society  for  May  1923,  p.  1228,  G.  P.  Baxter 
and  G.  J.  Fertig  announce  in  a  preliminary 
paper  a  new  determination  of  the  atomic 
weight  of  titanium  by  the  analysis  of  ti- 
tanium tetrachloride.  The  value  obtained 
from  an  average  of  four  fairly  cMicordant 
analyses  is  47.88,  which  may  be  rounded 
off  to  47.9.  The  present  but  older  value 
obtained  by  Thorpe  is  48.1.  The  mean  of 
the  values  =  47.99. 

In  this  Journal  (1920,  CXXL,  105),  the 
present  writer  developed  a  scheme  for  eval- 
uating certain  atomic  weights  based  upon 
the  existence  of  certain  isotopes,  but  the 
calculated  atomic  weight  of  titanium  was 
incident  upon  hypothetical  isotopes  48  and 
50.  Thev  may  be  48  and  46,  as  the  follow- 
ing calculation  will  show. 

If  the  starting  values  in  the  scheme  are 
11x4+4  =  48  and  11x4+2  =  46,  thm 
the  calculation  becomes:  (4' x  48+2' x  4fi)/ 
(4' +2'),  and  the  value,  which  is  a  mean 
one,  comes  out  47.94.  The  a,  b,  c,  d,  values. 
1,  2,  3,  4,  respectively,  have  either  to  be 
raised  to  the  third  or  first  powers.  In  this 
case  4-^  =  64  and  2*  =  2,  obviously,  as  pre- 
viously indicated  in  principle,  with  saliv. 
factory  results  in  some  instances;  e.g.. 
nickel,  which  involved  2'  and  4'. 


THE  ELECTROMETRIC  TITRATION 

OF  MOLYBDENUM  WITH  A 

TITANOUS  SALT. 

By  H.  H.  Willard  and  Florence  Fenwuk 

[Contribution  from   the  Chemical    Lahnrn 

tory  of  the  University  of  Michigan.'^ 

Introduction. 

The  reduction  of  molybdic  acid  to  a  salt 
of  pentavalent  molybdenum  by  means  of 
triv.ilent  titanium  was  observed  by  Kneeht 
and  Hibbert.'      They  failed  in  the  attempt 

*  Knecht  and  Hibbert,  "New  Reduction 
Methods  in  Volumetric  Analysis,"  Long- 
mans, Qreen  and  Co.,  1918,  p.  99. 


to  base  a  volumetric  method  for  the  deter- 
mination of  molybdeouin  upon  this  fact  be- 
cause of  the  lack  of  a  suitable  indicator  lor 
the  end-point.  An  investigation  of  the 
applicability  of  the  electrometric  titration 
showed  that  the  reaction  is  sufficiently 
rapid  for  this  to  be  used.  The  character  of 
the  end-point  with  the  polarised  bimetallic 
electrode  system  with  platinum  electrodes 
is  essentially  as  has  been  described  for  other 
titrations.*  After  enough  of  the  titrating 
solution  has  been  added  for  equilibrium  to 
be  established,  there  is  practically  no  fur- 
ther change  until  within  about  0.5  oc.  of 
the  end-point.  The  potential  difference  in- 
creases slightly,  decreasing  again  on  the 
addition  of  excess  titanium.  Normally  tht^ 
maximum  is  perfectly  definite  when  the  ti- 
tration is  carried  out  slowly  as  the  end  is 
approached  so  that  equilibrium  may  be 
maintained.  Otherwise  a  transient  and  ir- 
regular decrease  In  e.m.f.  may  occur  before 
the  reaction  is  quite  complete.  It  is  safest 
to  add  several  drops  more  of  the  titanous 
solution  after  the  supposed  end-point  has 
been  reached  to  insure  that  th'^  potential 
decrease  is  permanent  an3  increasing.  The 
reduction  is  not  ideally  fast.  For  this 
reason  it  is  probable  that  a  better  end-point 
would  be  obtained  with  the  usual  mono- 
metallic electrode  system.  This  point  was 
not  investigat<^d. 

The  acid  concentration  of  the  molyb- 
denum solution  is  an  important  factor; 
5-10  per  cent,  by  volume  of  cone,  hydro- 
chloric acid  is  the  most  desirable ;  too  high 
a  concentration  weakens  the  reducing 
power  of  trivalent  titanium  appreciably. 
Sulphuric  acid  is  unsatisfactory.  Heat  in- 
creases the  velocity  of  the  reaction  hut  is 
imnecessary  except  in  special  cases. 

Tttrattok  of  Sodium  Molybdatk  with 
TiTAxoii.s  Sulphate. 

An  approximately  0.017  M  solution  of 
c.  P.  sodium  molybdate  was  titrateJT  with 
titanous  sulphate'  standardised  by  the 
method  of  Thornton  and  Chapman*  against 
ferric  sulphate  prepared  from  electrolytic 
iron  of  known  purity. 


'  WiUiard  and  Femvick,  Jour.  Amer. 
Chem.  Soc,  1922,  XLIV.,  2616. 

•  Prepared  by  the  electrolytic  reduction 
of  titanic  sulphate  and  stored  in  an  atmos- 
phere of  hydrogen. 

*  Thornton  and  Chapman,  Jour.  Amer, 
Chem.  Soc.,  1921,  XLIII.,  91. 


386 


THE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


Table    I. 
TiTKATioN  ov  Pure  Sodium  Molybdate 

WITH  TiTANOUS  SULPHATE. 

The  solutions  contained  about  8  per  cent, 
by  volume  of  cone.  HCl  and  were  heated  to 
about  80°.  0.05  N  Ti  factor  against  Fe, 
1.4002. 


0.05  N  Ti 

0.017  M  NaaMoO^ 

taken 

req. 

5.00 

2.17 

10.00 

3.92 

15.00 

5.61 

20.00 

7.42 

(SO,)^ 


A  finite  exC^s  of  the  titan ous  solution  is 
required  over  that  theoretically  necessary 
for  a  reduction  to  the  pentavalent  state. 
This  excess  must  be  independent  of  the 
total  amount  of  molybdenum  present,  and 
may  be  determined  by  titrating  solutions  of 
varying  molybdenum  content  and  solving 
the  equation,  n(a-x)  =  (b-x),  where  a  nnd 
b  are  the  number  of  cubic  centimetres  of 
the  titrating  solution  required  for  2  solu- 
tions of  known  molybdenum  content,  x  is 
the  required  excess,  and  n  the  ratio  of  the 
weight  of  molybdenum  in  Solution  b  to 
that  in  Solution  a. 

Using  the  given  formula,  the  excess  of 
titanous  solution  required  to  give  the  end- 
ipoint  was  determined  from  the  data  in 
Table  I.  By  combining  Expt.  1  with  Expts 
2,  3,  4,  X  was  found  to  be  0.42,  0.45,  0.42 
oc,  respectively;  by  combining  Expt.  3 
with  Expt.  4,  0.18  cc.  was  obtained.  The 
value  of  a;  is  to  some  extent  a  function  of 
the  electrode  system  used  and  the  magni- 
tude of  the  polarising  voltage.  For  the 
most  accurate  results  the  titanium  solution 


should  be  standardised  against  a  molyb- 
denum solution  of  known  strength,  using  a 
volume  of  the  titrating  solution  as  nearly  as 
possible  equal  to  that  required  for  the  un- 
known. It  was  concluded  from  the  results 
of  a  considerable  number  of  titrations  that 
an  accuracy  greater  than  0.1  cc.  of  0.05  A- 
solution,  which  is  the  equivalent  of  0.48 
mg.  of  molybdenum,  cannot  be  claimed  for 
the  method. 

Titration  of  Molybdenum  in  Ammonium 
Phosphomolybdate. 

The  titration  of  the  molybdenum  in  a  pre- 
cipitate of  ammonium  phosphomolybdate 
is  an  excellent  method  of  determining  the 
phosiphorus  content  of  steels.  No  special 
refinements  are  necessary  in  standardising 
the  titanous  solution  for  this  purpose,  since 
37.11  mg.  of  molybdenum  corresponds  to  1 
mg.  of  phosphorus,  and  the  effect  of  any 
slight  eri-or  in  the  titration  falls  far  below 
the  limit  of  accuracy  of  the  precipitation. 

After  precipitation  of  the  phosphorus  in 
the  usual  way^  the  ammonium  phospho- 
molybdate is  dissolved  in  ammonia,  filtered 
to  remove  any  iron,  and  the  acidified  solu- 
tion titrated  with  titanous  sulphate.  If  the 
precipitate  is  very  large  it  tends  to  repre- 
cipitate  upon  the  addition  of  acid.  This 
may  be  prevented  by  the  addition  of  a  few 
drops  of  phosphoric  acid  to  the  ammoniacal 
solution,  but  the  character  of  the  end- 
point  is  thereby  altered.  In  the  cold  there 
is  no  voltage  drop  with  excess  of  the  titrat- 
ing solution.  Just  preceding  the  end-point 
the  normal  rise  begins,  ceases,  then  con- 
tinues with  increased  velocity  just  as  the 
equivalent  point  is  passed.     If  the  solution 

•"'  Scott,  "  Standard  Methods  of  Chemical 
Analyais,"  D.  Van  Nostrand  Company, 
'^rd  Edition,  1922,  p.  365. 


Tabic    II. 
Detkkmination  of  I'ftosphorus  i\  Steel. 


Sample 
Steel  G. 

0.4  C  2.000 

Bessemer        2.001 

0.1   C    5.003 

B.   0.   H 5.002 

5.004 

0.1   C   2.003 

Bessemer       2.001 


%  P 

H,PO, 

%  P 

%  P 

Cer- 

Sp. gr. 

].7Ti  +  +  + 

re(j.     from 

from 

tificate 

Cc. 

Cc. 

Mo  factor 

Fe  factor 

value 

1 

9.37 

0.1016 

0.1027 

0.102 

0 

9.57 

0.1016 

0.1028 

1 

7.20 

0.0312 

0.0316 

0 

7.22 

0.0313 

0.0316 

0.031 

0 

7.30 

0.0316 

0.0320 

0.5 

10.31 

0.1116 

0.112 

0.5 

10.29 

0.1100 

JUNE  22,  1923. 


THE  CHEMICAL  NEWS. 


387 


is  titrated  hot,  however,    the  end-point    ia      i 
prrfectly  norniai  and    as  distinct  a«  in    the 
absence    f»f    the    phoaphoric    acid.         Tlio       ' 
separation  of  titanic    phosphate  sometimes 
occurs  but  has  no  effect  upon  the  sharpness 
of  the  end-point. 

Three  Bureau  of  Standards  steels  were 
analysed  by  this  method ;  the  results  are 
shown  in  Table  II.  The  0.05  N  factor  of 
the  titanium  solution  against  molybdenum 
was  1.6765;  against  iron,  1.6956. 

The  colour  of  the  reduced  solution  is  an 
extremely  intense  bluish  purple,  and  forms 
an  excellent  qualitative  test  for  molyb- 
denum, even  in  amounts  less  than  1  mg.  in 
the  absence  of  tungsten  and  vanadium. 
Effect  of  Tungstk.v. 

One  of  the  mrwt  interesting  pmnts  in  con- 
nection with  the  molybdenum  titration  is 
the  non-interference  of  tungsten  even  when 
present  in  large  amounts.  If  anything, 
the  end-point  is  rendered  more  distinet. 
Certainly,  results  seem  to  be  more  imi- 
form.  There  is  greater  necessity  for  pro- 
ceeding slowly  near  the  completion  of  the 
titration  than  when  no  tungstic  acid  is  pre- 
sent. Very  transient  decreases  in  potential 
occur  near  the  end-point  as  tBe  titrating 
solution  is  added  drop  by  drop,  but  cease 
just  before  the  reaction  is  cofftpTete,  and 
the  permanent  end-point  drop  is  verj'  dis- 
tinct. The  colour  is  as  characteristic  as 
that  of  the  comiplex  phosphate,  and  is  due 
to  an  intense  blue-black,  finely  divided  pre- 
cipitate or  a  solution  in  case  phosphoric 
acid  is  also  present. 

Various  amounts  of  tungsten,  in  the  form 
of  a  solution  of  pure  sodium  tungstate. 
were  added  to  15.00  oc.  samples  of  sodium 
bolybdate,  and  the  molybdenum  was  ti- 
trated. The  molybdate  was  standardised 
gravimetrically' ;  the  0.05  N  factor  w.-is 
1.0005.  The  titanous  solution  was  stan- 
dardised against  iron;  0.05  N  factor,  1.2904. 
All  samples  contained  about  5  per  cent,  of 
cone,  hydrochloric  acid  and  were  titrated 
cold. 

Table  III. 
Effect  of  Tungsten. 
0.05  M  Na,WO,.2H30        0.05  N  TiJSO,), 
added  req. 

Cc.  Cc. 

0  15.38 

1  15.10 

2  15.07 
5  15.02 

16  15.06 

75  16.06 


•  Weiser,   J.  Phyn. 
657. 


Chew.,    1916.    \X. 


If  the  calculated  excess  of  titanous  solu- 
tion, 0.40  cc.  (p.  030),  is  subtracted  from 
1.").38  cc.  it  leaves  14.98  cc.  The  results 
obtained  in  the  presence  of  tungsten  are  in 
very  fair  agreement  with  this  theoretical 
value. 

Separation  of  Molybdenum  from  Iron. 

Two  methods  are  in  general  use  for  the 
separation  of  molybdenum  from  iron  prior 
to  the  determination  of  the  former  element 
in  steels:  (1)  precipitation  of  molybdenum 
as  sulphide  from  slightly  acid  solution'  and 
(2)  precipitation  of  iron  as  ferric  hydroxide 
by  pouring  the  aeid  solution  into  hot  sodium 
hydroxide  solution.*  An  attempt  was  made 
to  use  another  method  based  upon  the  in- 
solubility of  lead  molybdate  in  2  per  cent, 
perchloric  acid.  This  gives  a  complete 
separation  from  chromium  and  vanadium. 
If  no  other  strong  acids  are  present  precipi- 
tation is  complete,  but  iron  is  always 
occluded  to  some  extent  and  must  be  re- 
moved by  treatment  with  sodium  hydrox- 
ide, thus"  detracting  from  the  value  of  the 
proposed  method. 

Svnthetic  steels  were  prepared  from 
ferric  nitrate  and  a  standard  solution  of 
sodium  molybdate.  The  caleulateil  amount 
of  60  jM^r  cent,  (perchloric  aeid  to  form 
ferric  perch  lorate  and  9  g.  in  exeesfl  was 
added  to  each  of  the  samples  and  the  solu- 
tions wen'  evaporated  until  fumes  were 
evolved.  .\  partial  dehydration  of  the 
molybdic  acid  occurs,  but  this  presents  no 
difficulties.  Chromium,  if  present,  is  oxi- 
dised and  lead  chromate,  which  is  much  less 
soluble  than  the  molybdate,  will  later  pre- 
cipitate. After  the  evaporated  samples 
were  dissolved  in  water  the  chromic  acid 
was  reduced  with  a  slight  excess  of  fer- 
rous perchloratt\  The  reduced  solutions 
were  heated  to  boiling  and  the  molybdenum 
was  precipitated  by  slowly  adding  to  the 
boiling  solution*  a  solution  of    10  g.  of  lend 


'  Johnson,  "  Chemical  Anah/ttis  of  Spe- 
cial Sfrch,"  John  Wiley  and  Sons,  3rr?  Ed., 
1920.  /).  1.56. 

•  Ref.  5.  p.  314. 

•  Tjead  violnbdate  preeipitaies  imme- 
diateUi  and  completehj  in  the  cnhl  in  5  per 
cent,  perchloric  acid  in  the  absence  of  iron. 
The  latter  interferes  in  the  precipitation. 
With  large  samples  of  steel,  2  g.  or  over, 
considerable  boiling  is  required  for  complete 
precipitation.  No  precipitation  at  all  occvrs 
in  the  cold. 


388 


THE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


perchlorate.^'^  The  final  valunie  was  3O0 
cc.  After  the  sokitions  had  stood  over- 
night they  were  filtered  through  Gooch 
crucibles,  washed  with  2  per  cent,  per- 
chloric acid,  then  with  water,  and  the  pre- 
cipitates dissolved  in  sodium  hydroxide. 
The  asbestos  and  ferric  hydroxide  were  fil- 
tered off,  the  filtrates  acidified  with  a  5  per 
cent,  excess  of  hydrochloric  acid,  and  ti- 
trated with  titanous  sulphate. 


Table  IV. 

Determination  of  MoLYRDExrM  in 
Synthetic  Steels. 

In  all  experiments  1  g.  of  iron  and  0.0720 
g.  of  molybdenum  were  added.  The  latter 
required  theoretically  10.00  cc.  of  titanous 
solution.  This  solution  was  standardised 
against  the  standard  molybdate  solution. 
Cr  added     V  added     Ti+  +  + req        Error 


Mg.       Mg. 


Cc. 


Mg.  of  Mo 


0 

0 

9.95 

-0.36 

0 

0 

9.90 

-0.72 

20 

0 

10.00 

0.0 

20 

5 

9.98 

-0.14 

20 

5 

10.00 
Summary. 

0.0 

The  reduction  of  hexavalent  molybdenum 
to  the  pentavalent  state  by  titanous  salts  is 
sufficiently  rapid  for  employment  of  elec- 
trometric  titration.  This  gives  a  means  of 
determining  molybdenum  in  alkali  molyb- 
dates  accurate  to  within  0.5  mg.  and,  in- 
directly, phosphorus  in  the  precipitate  of 
ammonium  phosphomolybdate.  Tungstic 
acid  presents  no  interference,  and  it  also 
eliminates  the  necessity  of  applying  a  cor- 
rection for  the  excess  titanous  solution  re- 
quired to  give  the  end-point. 

Ann  Arbor,  Michigan. 


— {From  the  Journal  of  the  American 
Chemical  Society,  1923,  XLV.,  928-33.) 

^^  Made  by  dissolving  the  theoretical 
quantity  of  pure  litharge  in  perchloric  acid. 
The  oxide  was  added  slotvly  to  the  cold,  di- 
lute Gicid,  heated  to  boiling,  cooled  and 
filtered. 


THE   ELECTEOMETBIC   TITRATION 

OF  SELENIUM  IN  THE  PRESENCE  OF 

TELLURIUM,  IRON  AND  COPPER. 

By  H.  H.  Willard  and  Florence  Fenavtck. 

[Contribution  from  the  Chemical  Labora- 
tory of  the   University  of  Michigan.] 

Introduction. 

The  reduction  of  selenious  acid  to  metal 
by  titanous  chloride  was  observed  by 
Moser^  and  also  by  Monnier.-  Moser  at- 
tempted to  develop  a  volumetric  met>hod  for 
selenium  based  on  this  reaction,  using 
methylene  blue  as  indicator,  but  the  results 
obtained  were  invariably  too  high.  This 
was  due  to  the  further  reduction  of  the 
selenium  to  hydrogen  selenide,  a  compound 
whie'i  had  been  shown  to  exist  under  simi- 
lar conditions  by  PleischP  and  Trautmann.* 

Under  the  condition  imposed  by  Moser, 
namely,  a  hot  hydrochloric  acid  solution, 
the  electrometric  end-point  is  either  absent 
or  very  poor,  but  in  a  cold  solution  contain- 
ing 25  to  75  per  cent,  of  cone,  hydrochloric 
acid  and  satvirated,  or  nearly  so,  with 
sodium  chloride,  the  end-point  with  the  pre- 
viously described  polarised  bimetallic  elec- 
trode system-"'  with  platinum  electrodes  is 
excellent.  The  presence  of  the  sodium 
chloride  is  important.  It  insures  rapid  and 
uniform  coagulation  of  the  selenium  hydro- 
sol  and  increases  the  sharpness  of  the 
change  in  voltage  at  the  end-point.  The  use 
of  a  cold  solution  also  eliminates  the  almost 
inevitable  loss  of  selenium  by  volatilisation. 

The  character  of  the  end-point  for  this 
titration  is  somewhat  difficult  to  describe 
but  is  readily  discovered  by  experiment. 
After  enough  of  the  titrating  solution  has 
been  added  to  give  a  constant  potential, 
thi're  is  little  change  until  within  a  short 
distance  of  the  end-point.  Slight  fluctua- 
tions in  the  e.m.f.  may  be  manifested;  the 
resistance  of  the  solution  is  so  low  that  the 
galvanometer  is  extremely  sensitive.  The 
characteristic  rise  occurs,  with  the  fall  im- 


'   Moser,  Z.,  anal.   Chcm.,  1018,    LVII 

277. 

^  Monnier,  Ann.  cliim.  anal,  appl.,  1915 
XX.,  1. 

^  Pleischl,  Kastner  Arch.,  XCIIL,  430. 

^  Traut)nann,  Bull.  soc.  ind.  Miilhousc, 
1891,  LXL,  87. 

^  Willard  and  Femvick,  Jour.  Amer. 
Chem.  Soc,  1922,  XLIV.,  2516. 


JUNE  22,  1923. 


THE  CHEMICAL  NEWS. 


889 


mediately  following.  The  condition  of  the 
solution  with  respect  to  acidity  and  foreign 
salts  determines  which  of  the  two  predomi- 
nates. Incrqasing  the  polarising  e.m.f. 
from  0.1  to  1.0  volt  makes  no  appreciable 
difference  in  the  character  of  the  end-p<Mnt. 
As  is  the  case  with  ether  titanous  titra- 
tions, the  actual  voltage  change  may  not  be 
large,  in  fact  may  not  amount  to  more  than 
a  few  millivolts.  The  galvanometer  should 
be  sutBciently  sensitive  to  give  a  distinct 
deflection  for  a  change  in  potential  of  1  mv. 
between  the  electrodes. 

It  is  inadvisable  to  clean  the  electrodes 
between  titrations  mwe  than  to  wash  them 
with  distilled  water.  The  small  amount  of 
selenium  adhering  after  the  first  titration 
increases  the  sharpness  of  the  end-point. 
The  coagulation  of  the  colloidal  selenium 
in  the  near  vicinity  of  the  end-point  is  quit'O 
distinct,  and  affords  a  fairly  close  visual 
check  on  the  titration. 

Titration  of  Selenious  Acid  with 
Titanous  Sulphate. 

A  pure  commercial  selenium  was  dis- 
solved in  nitric  acid,  evaporated  to  dryness, 
and  the  selenium  dioxide  pbtained  purified 
by  two  sublimations.  An  aipproxim!it<>ly 
0.05  N  aqueous  solution  of  selenious  ncid 
was  prepared  and  standardised  gravimetric- 
ally  by  reduction  with  hydrazine  sulphate 
according  to  the  method  of  Gutbier,  Metz- 
ner  and  Lohmann.*  In  four  experiments 
the  weights  of  selenium  obtained  from 
100.00  cc.  of  the  solution  were  0.0994, 
0.0995,  0.0997,  0.0996  g.,  or  an  average  of 
0.0995  g. 

The  solution  was,  therefore,  0.0503  N. 
The  purity  of  the  selenium  dioxide  was 
99.1  per  cent.,  the  rest  being,  doubtless, 
moisture. 


•  Outbier, 
anorg.  Chem. 


Metzner    and    LoKntann 
,  1904,  XLI.,  297. 


Z. 


Table  I. 

Titration  of  Selenious  Acid  with 
Titanous  Sulphate. 


Total 

taken 
Oc. 

10.00 
10.00 
l.l.OO 
lo.OO 
15.00 
15.00 
20.00 
20.00 
30.00 
30.00 
30.00 
30.00 
40.00 
40.00 


initial  volume  in  all  cases,  100  cc. 

Ti2(S03)  Ti2(S0  )      Ti2(S0  3) 

Fe  factor    KMn04  factor 
Av.      calc.  from    calc.  from 
Co.  Cc.  Cc. 


req. 
Cc. 

6.85 
6.75 
10.15 
10.17 
10.18 
10.10 
13.52 
13.52 
20.15 
20.26 
20.15 
20.20 
26.80 
26.80 


6.80         6.70 


6.72 


10.15       10.05       10.08 


13.52       13.40       13.44 


20.19      20.10      20.16 


26.80      26.80      26.88 


Samples  of  this  solution  were  titrated 
electrometrically  with  titanous  sulphate^  in 
solutions  containing  40  per  cent,  of  cone, 
hydrochloric  acid  and  saturated  with 
sodium  chloride.  .Vll  titrations  were  con- 
ducted in  a  current  of  carbon  dioxide.  The 
titanium  solution  was  standardised  against 
ai  8olutif>n  of  ferric  sulphate,'  prepared 
from  electrolytic  iron  of  known  purity,  and 
against  potassium  permanganate. >°  Against 


Total  initial  volume  in  all 


'  Prepared  by  the  electrolytic  reduction 
of  titanic  Hulphatc  and  Htored  in  an  atmos- 
phere of  hydroijen.  Thornton  and  Chap- 
man, Jour.  Amcr.  Chem.  Soc,  1921. 
XLIII.,  91. 

•  Titrated  to  the  disappearance  of  the 
colour  of  ferric  thiocyanate .  Thornton  and 
Chapman,  Ref.  7. 

'*•  Titrated  by  adding  it  to  the  permangan- 
ate in  srilphuric    acid  solution.       The    per- 
manganate was  standardised  against  sodium 
oxalate  from  the  Bureau  of  Standards. 
Table  II. 
Effect  of  Hydrochloric  Acid. 
cases,  100 


cc. 
Vol.  of  HCl 


SeO, 

Ti,(S0,)3  . 

(Sp.  gr. 

1.18) 

taken 

required   in 

100  cc.  of 

soln. 

Cc. 

Cc. 

Cc. 

Character  of  end-point. 

15.00 

11.44 

75 

Very  goo<l.    Fall  at  end-point    not    ipcniia- 
nent  but  definite. 

i5.on 

11.40 

50 

Hiso  and  fall  extremely  sharp. 

15.00 

11.42 

35 

Very  good. 

.'iO.OO 

22.77 

35 

\'«'ry  goo(l. 

15.(X) 

11.43 

25 

|{is('  more  marked  than  fal! 

30.00 

22.70 

25 

Good. 

20.00 

15.08 

25 

Go(xl. 

10.00 

7.63 

25 

Good. 

16.00 

... 

10 

Poor. 

396. 


TitE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


the    former   it  was  found    to  be    0.0750   N, 
against  the  latter,  0.0748  N. 

From  a  comparison  of  the  volumes  of  ti- 
tanous  sulphate  used  in  the  several  deter- 
minations it  is  evident  that  the  excess  of 
the  titrating  solution  required  to  give  the 
end-point  reaction  was  very  close  to  0.10 
cc.  (The  titrations  with  the  40.00  cc. 
samples  were  evidently  a  little  low.)  When 
this  correction  is  made,  the  check  with  the 
amount  of  titanium  calculated  from  the  iron 
factor  is  usually  within  0.02  cc.  The  titra- 
tion of  the  selenious  acid  proceeds,  then, 
according  to  the  equation :  SeO,  +  4HC1  + 
4TiCl3  =  Se  +  4TiCl,  +  211^0. '  There  can 
be,  therefore,  no  secondary  reaction  such  as 
found  by  Moser'  and  no  empirical  stand- 
ards are  necessary  in  the  determination. 


Effect  of  Varying  the  Concentration  of 
Hydrochloric  Acid. 

The  effect  of  varying  the  hydrochloric 
acid  concentration  is  shown  in  Table  II. 

An  acidity  of  25  to  75  cc.  of  cone,  hydro- 
chloric acid  in  100  cc.  of  solution  is  entirely 
satisfactory. 

Effect  of  Sulphuric  Acid. 
In  the  preparation  of  an  actual  sample  of 
metallic  selenium  for  analysis  it  is  very  de- 
sirable to  avoid  the  use  of  hydrochloric 
acid  for  removing  the  nitric  acid  in  which 
the  material  is  dissolved.  In  hydrochloric 
acid  solution  selenium  chloride  is  appreci- 
ably volatile  at  the  boiling  point.  For  this 
reason  the  effect  of  sulphuric  acid  upon  the 
titration  was  studied. 


Table  III. 
Effect  of  Sulphuric  Acid. 


15.00  cc.  of  0.05  N    selenious    acid    solu- 
tion was  used  in  each  titration.     The  solu- 
tions were  saturated    with  sodium    chloride 
and  had  an  initial  volume  of  100  cc. 
Vol.  of  cone,  acid"' 
Ti,(S0j3         in  100  cc  of  soln. 
'Cc.  Cc. 

11.37  50HC1 

11.40  50HC1+    5H,S0, 


11.40 


50  HCl  +  10  H,SO, 


Character  of  end-point. 

(Control  titration). 

liise  long  and  marked,  fall  slow.  Titrated 
to  end  of  rise. 

Not  quite  as  good  as  the  ijreceding.  No  per- 
manent fall.  Not  difficult  to  deter- 
mine end-point. 


'Refers  to  HCl,  d.  1.18,    or  to  H^SO,,   d.  1.84. 


The  acid  may  be  present  in  amounts  up 
to  5  or  10  CO.  per  100  cc.  of  solution,  but  is 
to  be  avoided  in  any  considerable  quantity. 

The  non-volatility  of  selenium  in  hot 
sulphuric  acid  was  shown  by  the  eva^pora- 
tion  of  samples  of  the  selenium  solution 
with  5  cc.  of  cone,  sulphuric  acid  until 
dense  fumes  formed  and  then  titration  after 
the  addition  of  sodium  chloride  and  hydro- 
chloric acid.  The  maximum  variation  was 
0.06  mg.  in  a  total  of  15  mg.,  or  0.4  per  cent. 
The  end-point,  however,  was  not  quite  as 
sharp  as  when  the  fuming  had  been  omitted. 

Effect  of  Tellurium. 
Of  the  common    associates    of  selenium, 
tellurium    is  probably    of  the  greatest    in- 
terest in  its  effect  upon  the  titration  of  the 
former  element.       In    a    hot    hydrochloric 


acid  solution  of  moderate  concentration  tel- 
lurium is  rapidly  reduced  by  titanous  salts, 
but  in  the  cold  the  reduction,  if  any  takes 
place,  is  very  slow. 

Metallic  tellurium  was  carefully  treed 
from  selenium  by  Keller's  method, ^^  repre- 
cipitated  as  metal,  again  dissolved  in  nitric 
acid,  evaporated  to  fumes  of  sulphuric  acid 
and  dissolved  in  hydrochloric  acid.  Various 
amounts  of  this  solution  were  added  to 
known  amounts  of  selenious  acid  solution 
and  determinations  made  as  outlined  in 
Table  IV. 


'^  Keller,  Jour.  Amer.  Chem.  Soc,  1897, 
MX.,  771.  Scott,  "  Htandard  Methods  of 
Chemicid  Analysis,"  D.  Van  Nnstrand 
Company,  3rd  ed.,  1922,  ip.  423. 


JUNE  22,  1923. 


THE  CHEMICAL  NEWS 


391 


Table  IV. 
Effect  of  Tellurium. 
15.00  cc.  of  0.05  N  selenious  acid  was 
vsfd  in  each  titration.     Total  initial  volume 
100  cc. 


wt.  Te 


Ratio, 

:wt.  Se 

4:5 
4:5 
8:3 
4:1 
8:1 
8:1 
8:1 
8:1 


Vol.  of  HCl 
Ti,(S0j3     (Sp.gr.  1.18) 
Cc.    in  100  cc.  of  solu 


11.34 
11.33 
11.35 
11.35 
11.35 
11.35 
11.30 
11.35 
11.35 


50 
50 
50 
50 
50 
60 
25 
25 
25 


Tellurium  even  in  large  amounts  does  not 
interfere  in  the  titration  of  selenium,  but  it 
seems  to  a£Eect  the  character  of  the  end- 
point  much  as  does  sulphuric  acid.  The 
fall  in  potential  as  the  end-pcMnt  is  passed 
does  not  always  occur,  bul  the  rise  is  fully 
as  »hanp  as  in  the  absence  of  these  sub- 
stances. There  is  no  difficulty  in  recognis- 
iii;,'  the  completion  of  the  reaction. 
Effect  of  Iron. 

Ouu  of  the  most  surprising  and  interest- 
ing things  in  conne<>tion  with  the  selenium 
determination  is  the  fact  that  the  volume 
of  titanium  solution  used  in  titrating  mix- 
tures of  selenium  and  ferric  iron  is  identical 
with  thut  for  the  selenium  alone,  although 
ferrous  ir<Mi  is  formed  during  the  precipi- 
tation. The  character  of  the  end-point  is 
much  the  same  as  that  described  later  with 
mixtures  of  selenium    and  copper,  but    no 


Character  of  end-point. 
(Control  titration) 
Sharp  rise,  no  fall  with  excess 
Regular  fall  with  excess 
Distinct  rise,  no  fall  with  excess 
No  fall  with  excess 
Xo  fall 
A  fall 
A  fall 
No  fall.     End-point  a  change  in  rate  of  rise 

seccmd  end-point  is  obtainable  at  the  point 
of  complete  reduction  of  both  elements. 

In  Table  V.  the  solutions  contained  30.00 
cc.  of  cone,  hydrochloric  acid  in  a  volume 
of  100  cc.  and  were  saturated  with  sodium 
chloride. 

The  behaviour  of  selenium  under  these 
conditions  seemed  at  first  paradoxical.  It 
was  observed,  however,  that  with  large 
amounts  of  iron  the  precipitation  was  ap- 
parently incomplete.  From  two  samples, 
one  of  which  contained  twice  as  much  ferric 
iron  as  the  other,  the  selenium  was  filtered 
at  the  end  of  the  titration,  thiocyanate  was 
added,  and  more  of  the  titanous  solution 
run  in.  No  sharp  colour  change  occurred. 
The  deep  red  faded  slowly  only  to  reapipear 
in  a  few  seconds.  The  amount  of  titanium 
reijuired  for  an  approximate  end-point  was 
twice  as    much  in  the    solution    containing 


Table  V. 
Effect  of  Iron. 


SeOj  taken 
Cc. 
15.00 
15.00 
15.00 
15.00 
30.00 
30.00 


0.05  .V  I'\'+  +  + 


added 
Cc. 

1 
5 

10 
1 

10 


Ti+  +  +  req. 
Cc. 
10.60 
10.58 
10.52 
10.61 
21.25 
21.20 


Remarks. 


Second    Series. 


15.00 
15.00 
15.00 
15.00 
ao.O't 
10.00 


25 

no 
r,() 
76 


10.15 
10.22 

10.17 

10.15 

20.20 

6.82 


Ppfn.  very  incomplete 

l*f>tn.  very  incomplete 

I'pln.  slight 

l*|)hi.  "Tenter  tbnn  pieocding 

No  piptn.     End-point  a  little  slow. 


392 


TSE  Ca^MlCAL  NfiVVi^. 


JUNE  22,  192B. 


double  the  amount  of  iron.  After  much 
more  titanous  sulphate  had  been  added 
there  was  a  further  precipitation  of 
selenium.  It  appeared  that  ferric  iron  and 
selenious  acid  might  form  a  rather  unstable 
compound  in  which  the  selenium  is  reduced 
only  with  difficulty,  requiring  a  large  excess 
of  titanium.  An  amount  of  ferric  iron 
equivalent  to  the  combined  selenium  is  re- 
duced along  with  the  free  selenious  acid  and 
the  numerical  result  of  the  titration,  there- 
fore, is  unaffected.  In  the  second  series  the 
amount  of  iron  was  increased  until  no  pre- 
cipitation occurred,  without  affecting  the 
results,  thus  supporting  this  view.  The 
exact  com^position  or  the  compound  was  not 
investigated. 

Effect  of  Copper. 
In  hydrochloric  acid  solution  trivalent  ti- 
tanium reduces  cupric  salts  to  the  cuprous 
form.  ^2       When     present     with     selenium, 

^"^  Rhead,  J.  C'hem.  Soc,  1906,TxXXIx7 
1491.  Knecht  and  Hihbert,  "  New  Reduc- 
tion Methods  in  Volumetric  Analysis." 
Longmans,  Green  and  Co.,  1918.  Moscr, 
Cheni.-Ztg.,  1912,  XXXIV.,  1126.  Mon- 
nier,  Ann.  chim.  anal.,  1916,  XXI.,  109. 
Mach  and  Lederle,  Landw.  Vers.  Sta., 
1917,  XC,  191.  Thornton.  Jour.  Amer. 
Chem.  Soc,  1922,  XLIV.,  998. 


however,  the  latter  is  reduced  first  and  ap- 
parently selectively.  The  electrometric  ti- 
tration gives  two  end-points,  one  when  the 
selenium  is  entirely  precipitated  and  a 
second  at  the  completion  of  the  reduction 
of  the  copper.  Toward  the  end  of  the  first 
reaction  the  voltage  starts  to  rise  slightly. 
There  is  then  a  long,  distinct,  Uipward  swing 
that  marks  the  end-point,  followed  usually 
by  continued  rise.  The  copper  end-point  is 
a  second  sharp  rise.^^  It  is  not  quite  as 
clea  ras  the  first  but  readily  distinguishable 
after  a  little  experience. 


Table  VI.  records  a  number  of  titrations 
carried  out  in  the  presence  of  copper. 


'^  It  is  obvious  that  the  method  may  he 
adapted  to  the  determination  of  copper 
alone.  A  number  of  very~accuraie  titrations 
ivere  made  in  this  ivay,  but  this  application 
is  not  stressed  because  of  the  rather  larqc 
amount  of  other  work  on  this  reaction  al- 
ready 2)iiblished. 


Table  VI. 
Effect  of  Copper. 
All  solutions  titrated  had  an  initial  vol 
ume  of  100  cc,  contained  30-40  p.c.  of  oonc. 
hydrochloric  acid  and  were  saturated  with 
sodium  chloride. 


Ti+  +  +  req 

SeO^ 

taken 

Cc. 

15.00 

0.05  N 

CuSO,  added 

Cc. 

5.00 

for  Ss 
end -point 
Cc. 

I0V5O 

Total  Ti  +  +  + 

used 

Cc. 

Ti+-f-+  r 
for  Cu 

Cc. 
3.55 

15.00 

10.50 

15.00 
15.00 
15.00 

5.00 

10.00 

1.00 

10.53 
10.50 
10.52 

14.02 
17.60 

3.40 
7.10 

Second    Series. 

15.00 

10.65 

15.00 

5.00 

10.65 

. 

30.00 

5.00 

21.24 

Summary. 
1.  The  volumetric  reduction  of  selenious 
acid  to  selenium  by  titanous  sulphate  is 
rapid  and  accurate  to  within  0.1  mg.  in  cold 
hydrochloric  acid  solution  saturated  —■'■'- 
sodium  chloride. 


with 


2.  Under  these  conditions  tellurium  is 
not  reduced,  and  its  only  effect  is  to  modify 
the  nature  of  the  end-point. 

3.  Moderate  amounts  of  sulphuric  acid 
Have  no  deleterious  effect  upon  the  deter- 
mmation  of  the  end-point    and  there  is  no 


J  UiNE  -A'l,  1928. 


THE  CHEMICAL  NEWS 


393 


volatilisation    of    selenium  at    the    fuming 
temtperature  in  this  acid. 

4.  The  titration  of  selenium  is  quantita- 
tively independent  of  the  concentration  of 
iron,  although  ferrous  iron  is  formed  in  the 
reaction. 

5.  The  reducing  effect  of  trivalent  ti- 
tanium upon  mixtures  containing  copper 
and  selenium  is  selective,  the  latter  being 
reduced  first,  and  both  elements  may  be 
determined  in  a  single  titration. 

.  Ann  Arbor,  Michigan. 

— {From  the  Journal  of  the  American 
Chemical  Society,  1923,  .XJ.V.,  988-9.) 


GENERAL  NOTKS. 


NEW  COLOUR  INDEX. 

Notable  Bkitish  Achievemknt  in  Dye 

Technology. 

Dye-Users'  Vade  Mecum. 

The  new  "  Colour  Index,"  now  approach- 
ing completion,  will  add  greatly  to  the 
prestige  of  the  British  dye  industrj-,  and  at 
the  same  time  represent  one  of  the  most 
valuable  achievements  of  the  Society  of 
Dyers  and  Colourists.  That  there  should 
be  a  thoroughly  up-to-date  and  c<Mnprehen- 
sive  index  of  dyes  is  extremely  desirable, 
but  up  to  the  present  the  best  availub1<- 
authority  has  been  a  German  pre-war  pub- 
lication, now  inevitably  far  from  complete, 
(treat  Britain  has  the  distinction  of  having 
pr(xluced  what  has  already  been  accepted 
by  colour  manufacturers,  dye-users  and 
technological  experts  throughout  the  world 
as  a  standard  work  of  supreme  importance 
Old  Dyes  with  New  Names. 

The  stoppage  of  German  su()p1ie8  of  dyes 
(luring  the  war  led  to  the  rapid  development 
of  existing  colour  works  in  other  countries 
and  the  establishment  of  important  new 
works.  Great  strides  have  thus  been  made 
in  the  production  of  dyestuffs,  and  many 
firms  are  placing  on  the  market  dyes  whieli 
have  new  commercial  names,  but  whieh 
nmy  not  be  new  in  constitution.  A  number 
of  them  are  replicas  of  the  German  pro- 
ducts with  which  users  had  become  familiar. 
In  the  absence  of  definite  knowledge  as  to 
their  constitution,  the  dye- user  has  been  at 
a  disadvantage  in  selecting  his  dyestuffs, 
and  has  l)cen  bewildered  bv  the  multiplicity 
f>f  iproducts  submitted  to  liim. 

From  a  dye-user's  point  of  view,  there- 
fore, it  is  a  matter   of  great  importance    to 


know  all  the  different  commercial  names 
used  to  denote  the  particular  dye  he  re- 
quires, and  the  firms  who  make  such  pro- 
ducts. No  such  iuformation  has  been 
available,  for  the  most  comprehensive  work 
of  reference  on  the  subject  was  the 
Farbstofftabellen  of  Dr.  Gustav  Schultz, 
published  in  1914,  which  necessarily  lacks 
information  with  regard  to  the  great  de- 
velopments which  have  taken  place  in  this 
and  other  countries  during  the  past  nine 
years. 

In  order  to  remedy  this  defect,  the  So- 
ciety of  Dyers  and  Colourists,  whose  head- 
HUHrt^rs  aie  at  Bradford,  decided  to  under- 
take the  work  of  compiling  an  up-to-date 
and  comprehensive  Colour  ludex.  The 
arduous  work  of  editorship  was  placed  in 
the  hands  of  Dr.  F.  M.  Rows,  of  the  Man- 
chester College  of  Technology,  assisted  by 
Mr.  C.  Lea,  and  a  Revision  Committee  was 
formed  under  the  chairmanship  of  Mr. 
Ernest  Iiicks<Mi,  of  Bradford,  on  which  the 
leading  dyestuff  manufacturers  and  dyestuff 
users  of  all  classes  were  represented,  as 
well  as  the  leading  professors  and  experts 
on  the  technical  side. 

To  be  Finished  this  Yeak. 

The  Colour  Index  has  been  published  in 
monthly  parts,  the  first  being  issued  in 
September,  1922.  In  order  to  ensure  the 
greatest  possible  accuracy,  150  copies  of  the 
proofs  o£  each  part  are  circulated  all  over 
the  world  to  colour  manufacturers,  colour 
users,  and  technical  experts,  and  the  cor- 
rections and  suggestions  thus  embodied 
have  been  exceedingly  valuable.  Fourteen 
parts  are  required  to  complete  the  Index. 
The  ninth  has  been  issued,  and  the  matter 
for  the  remaining  parts  is  now  in  the  hands 
of  the  printers.  The  end  of  this  great 
undertaking,  therefore,  is  now  within  sight, 
and  there  is  no  doubt  that  the  remaining 
five  parts  will  be  published  before  the  end 
of  1928. 

Scope  of  the  Work. 

One  of  thi>  features  of  the  Index,  when 
completed,  will  be  the  comprehensive  in- 
dices which  it  will  contain.  These  will 
cover  the  names  of  many  thousands  of 
conunercial  dyes,  and  will  also  deal  with  the 
patent  numbers,  the  intermediate  products 
used,  and  so  on.  Some  idea  of  the  magni- 
tude of  the  undertaking  may  be  gained  from 
the  fact  that  the  number  of  distinct  syn- 
thetic dyes  dealt  with  will  exceed  1,320,  as 
against  the  1,000  dealt  with  by  SchuHz. 
Mast  of  these  dyes  have  a  number  of  com- 
mercial names — many    of    them    thirty    or 


394 


THE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


more— and  in  all  oases  these  names  and  the 
respective  makers  are  given.  The  products 
of  over  a  hundred  colour-making  firms  are 
included,  and  the  matter  covers  700  large 
quarto  pages  of  closely-printed  and  con- 
densed matter. 

A  dye  user  who  requires  a  particular  dye 
can  thus  find  a  complete  list  of  the  manu- 
facturers who  make  it,  the  scientific  name 
of  the  product,  its  components  and  formula, 
details  of  its  preparation,  its  discoverer, 
exhaustive  references  to  the  literature  on 
the  subject,  its  properties,  uses,  and  modes 
of  application. 

Many  Industries  Covered. 

In  addition  to  the  Synthetic  dyestuffs, 
the  Colour  Index  will  include  the  principal 
colouring  matters  and  the  pigments.  Dyes 
are  used  not  only  in  the  great  textile  indus- 
tries, but  in  a  large  number  of  other  indus- 
tries, such  as  the  paint  and  varnish,  paper 
making,  soap  and  oil,  in  photography, 
medicine,  foodstuffs,  and  so  on.  Details 
are  given  of  dyes  specially  used  in  photo- 
graphy, which  have  not  been  included  in 
any  previous  work.  There  are  some  parti- 
cularly valuable  references  to  the  suit- 
ability of  dyes  for  calico  printing,  especially 
with  regard  to  dischargeability. 

This  great  work  will  supersede  all  former 
reference  books,  and  there  is  no  doubt  that 
it  will  be  of  great  practical  as  well  as 
scientific  utility.  It  will  guide  the  dye- 
user  safely  through  the  maze  of  modem 
dyestuff  names,  and  enable  him  to  make 
the  fullest  use  of  the  enormous  develop- 
ments in  the  dye-making  industry  in  recent 
years. 


THE  DEPARTMENT  OF  SCIENTIFir 
AND  INDUSTRIAL  RESEARCH. 

The  Lord  President  of  the  Council  has 
accepted  with  much  regret  the  resignation 
of  Sir  George  Beilby,  LL.D.,  F.R.S.,  after 
nearly  seven  years'  voluntary  service  as 
Director  of  Fuel  Research  and  Chairman  of 
the  Fuel  Research  Board  under  the  Depart- 
ment of  Scientific  and  Industrial  Research. 
The  Board  was  established  in  1917  to  in- 
vestigate the  nature,  preparation  and  utili- 
sation ol  fuel  of  all  kinds. 

The  Lord  President  has  appointed  Mr.  C. 
H.  Lander,  D.Sc,  M.I.Moeh.E.,  A. M.- 
Inst.C.E.,  to  bo  Director  of  Fuel  Research, 
and  Sir  Richard  Threlfall,  K.B.E.,  F.R.S.. 
a  present  member  of  the  Board,  to  be 
Chairman.     The  Hon.   Sir  Charles' Parsons, 


K.C.B.,  F.R.S.,  will  continue  his  member- 
ship of  the  Board  for  a  further  period.  Sir 
George  Beilby  retains  his  membership  of 
the  Advisory  Council  of  the  Department, 
and  has  consented  to  act  as  Honorary 
Adviser  to  the  Board. 

The  following  gentlemen    have   accepted 
appointment  as  additional  members  of  the 
Boards- 
Mr.  R.  A.  Burrows,  Sir  John  Cadman, 
K.C.M.G.,  D.Sc,  Dr.  Charles  Carpenter, 
C.B.E.,   D.Sc,   Mr.    Samuel  Tagg,   Prof. 
Sir     James     Walker,      D.Sc,       LL.D., 
F.R.S.,  Prof.  R.  V.  Wheeler,  D.Sc. 


DYESTUFFS    (IMPORT  REGULATION) 
ACT. 

Applications  for  Licences  in  May. 

The  following  statement  relating  to  aip- 
plications  for  licences  under  the  Dyestuffs 
(Import  Regulation)  Act,  1920,  made  dur- 
ing May,  has  been  furnished  to  the  Board 
of  Trade  by  the  Dyestuffs  Advisory  Licens- 
ing Committee. 

The  total  number  of  applications  re- 
ceived during  the  month  was  497,  of  which 
409  were  from  merchants  and  dealers.  To 
these  should  be  added  the  17  cases  out- 
standing on  May  1,  making  a  total  for  the 
month  of  514.  These  were  dealt  with  as 
follows  :  — 

Granted— 304  (of  which  293  were  dealt 
with  within  seven  days  of  receipt). 

Referred  to  British  makers  of  similar 
products— 136  (of  which  130  were  dealt 
with  within  seven  days  of  receipt). 

Referred  to  Reparation  Supplies  avail- 
able— ^53  (all  dealt  with  within  two  days 
of  receipt). 

Outstanding  on  May  31 — 21. 
Of  the  total  number,  514,  of  applications 
received,  458,    or  89  per  cent.,    were    dealt 
u  ith  within  four  days  of  receipt. 

Board  of  Trade. 
June  12,  1923. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 

Thursday,  June  14. 
Papers  read  :  — 

C.  Ciirrr,  P.R.S.     Marjnetir.  Phenomeno 
'\/r^^  ^^^^'^^  of  t^e  South  Magnetic  Pole 
Magnetographs     were     in     simultaneous 


JUNE  22,  1923. 


THE  CHEMICAL  NEWS. 


395 


operation  from  April  to  October,  1912,  at 
the  base  stations  of  the  British  and  Austra- 
lasian Antarctic  expeditions.  These 
stations  were  situated  on  opposite  sides  of 
the  south  magnetic  pole.  A  comparison  is 
made  of  the  regular  diurnal  inequalities  and 
the  amplitudes  of  the  absolute  daily  ranges 
of  the  magnetic  elements  at  the  two  sta- 
tions. The  data  are  employed  to  illustrate 
tTie  remarkable  sensitiveness  of  the  regular 
diurnal  variations  in  high  latitudes  to  the 
presence  of  magnetic  disturbance.  The  re- 
sults are  also  a^pplied  to  the  question  of  a 
suitable  criterion  for  the  daily  activity  of 
magnetic  disturbance. 

0.  R.  Howell.  The  Catalytic  Decom- 
position  of  Sodium  Hypochlorite  by  Cobalt 
Peroxide. 

1.  The  rate  of  decomposition  of  sodium 
hypochlorite  solution  by  cobalt  peroxide  is 
directly  proportional  to  the  amount  of  per- 
oxide present. 

2.  The  rate  is  accelerated  by  sodium  salts 
and  (m  the  case  of  sodium  chloride)  is 
directly  pruporti(xial  to  the  square  root  of 
the  concentration  of  sodium  ions  present. 
'I'his  is  exiplaincd  by  assuming  the  mechan- 
ism of  the  reaction  to  consist  in  the  linka^'< 
of  hypochlorite  ions  to  the  positive  oxygen 
and  sodium  ions  to  the  negative  oxygen  of 
the  peroxide,  with  subsequent  immediate 
deoompositiiMi  of  the  quadrivalent  oxygen 
compound.  In  the  presence  oi  n  fixed 
amount  of  hypochlorite  the  rate  is  then 
proportional  to  the  degree  of  adsMption  of 
the  sodium  ions. 

8.  The  rate  is  retarded  by  alkali  and  the 
retardation  is  proportional  to  the  adsonption 
of  hydroxvl  ions.  This  is  explained  by  the 
fact  that  hydroxyl  ions  are  attracted  by  the 
positive  oxyger;  of  the  peroxide  yielding  an 
inactive  compound  to  the  exclusion  of  hy- 
poc!hlorite  iwis. 

4.  The  rate  of  the  reaction  has  been 
measured  between  25®  and  50".  The  aver- 
age temperature  coefficient  over  this  range 
is  2.37  and  the  Arrheniua  activation  co- 
efficient E  =  16,574. 

5.  The  catalyst  is  not  affected  by  any  of 
the  common  catalytic  poisons. 

N.  M.  HosALi.  On  Seismic  Waves  in  a 
Visco-Elastic  Earth.  Communicat^^d  by 
Prof.  L.  N.  G.  Filon,  F.R.S. 

The  effects  of  viscosity  on  the  propaga- 
tion of  seismic  waves  are  considered,  the 
medium    being    assumed    to    obey    certain 


stress-strain  relations  given  recentlv  bv 
Prof.  L.  N.  G.  Filon. 

It  is  found  that  the  waves  are  subject  to 
damping  and  dis^persion  dependent  on  the 
period.  For  each  type  of  wave — dilata- 
tionaF,  distortional  or  surface — there  exists 
a  minimum  period  below  which  a  wave  can- 
not be  transmitted,  and  for  any  period 
above  the  minimum  two  distinct  waves  can 
be  propagated,  one  heavily  damped  and 
slow  travelling,  and  one  lightly  damped 
and  quick  travelling. 

The  observed  recfuction  in  the  amplitude 
of  oscillations  in  the  main  shock,  as  the 
upicentral  distance  increases,  indicates  that 
if  the  material  in  the  outer  layers  of  the 
earth  obeyed  the  theory  here  developed,  it 
would  have  a  viscosity  of  order  10»  or  io» 
c.g.s.  units.  Such  a  viscosity  would  have 
no  uippreciable  effect  on  the  velocity  of  pro- 
pagati<Hi  of  earthquake  waves. 

The  vibrations  of  an  incompressible, 
visco-c'lastic  sphere  are  briefly  discussed, 
and  it  is  shown  that  viscosity  produces 
damping  and  lengthening  of  period.  The 
oscillatory  mcxles  of  any  species  are  finite 
in  uuniber  and  can  bo  divided  into  two 
groups,  one  more  heavily  damped  than  the 
other. 

Pai)ers  read  in  title  only: — 

.1.  W.  Landon  and  H.  Quinney.  Experi- 
ments irith  the  Hopkinson  Pressure  Bar. 
Coinnumicated  by  Sir  A.  Ewing,  F.H.S. 

Th«'  |>aper  deals  with  some  experiments 
carried  out  sinco  the  late  Prof.  Bertram 
Hopkinson 's  paper  (Phil.  Trans.,  1914). 

It  is  found  that  when  the  firing  end  of 
tho  bar  is  coned  down  to  a  smaller  diameter 
and  tin-  time-piece  is  sufficiently  long,  the 
bar  itself  is  left  with  a  negative  momen- 
tum. \  theoretical  investigation  of  the 
propagation  of  a  pressure  wave  along  a  cone 
of  small  angle  shows  that  as  the  wave  pro- 
ceeds along  the  cone  a  tail  of  tensile  stress 
is  f(MTned.  Experimental  results  agree 
fairly  closely  with  theoretical. 

The  experimental  observations  show  that 
with  a  bar  of  uniform  diameter  the  pressure 
wave  produced  by  detonation  of  giin-cotton 
is  considerably  distorted  as  it  is  ipropagatod, 
but  that  the  rate  of  distortion  decreases  as 
the  wave  travels  along  the  bar. 

A  graph  is  deduced  from  experiments 
j<howinj»  variation  of  pressure  over  cross- 
section  of  the  bar  when  a  gim-cofton  prinicr 
is  detonated    |  inch    away    from  ilic    end. 


396 


THE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


Pressure  falls  away  rapidly  as  distance  from 
axis  of  the  bar  increases. 

One  of  the  objects  of  further  experiment 
was  to  determine  with  greater  accuracy  the 
maximum  pressure  produced  in  the  detona- 
tion of  gun-cotton.  It  was  hoped  that  the 
overstrain  might  be  reduced  by  special  heat 
treatment  of  the  bars,  and  that  the  pres- 
sure transmitted  would  be  more  nearly  the 
true  pressure  at  the  firing  end.  There  is  no 
evidence  from  the  exiperiments  that  any 
substantial  improvement  has  been  effected 
by  heat  treatment  except  in  so  far  as  the 
life  of  the  bars  has  been  increased. 

The  highest  inaximum  pressures  recorded 
were  117  tons  .per  square  inch  for  a  1-ounce 
gun-cotton  primer  in  contact  with  the  end 
of  the  bar,  and  82  tons  per  square  inch  with 
the  primer  f  inch  away  from  the  end. 
These  results  were  obtained  with  a  short  bar 
of  |-inch  diameter. 

with  concrete  bars  the  phenomena  ex- 
hibited are  the  same  in  general  as  with 
steel  bars,  except  that  the  front  of  the  wave 
appears  to  be  entirely  obliterated,  and  only 
the  part  in  which  pressure  is  less  than  the 
crushing  stress  of  the  concrete  is  propagated 
along  the  bar. 

S.  F.  Grace.  Free  Motion  of  a  Sphere  in 
a  Rotating  Liquid  at  Right  Angles  to  the 
Axis  of  Rotation.  Communicated  by  G.  I. 
Taylor,  F.R.S. 

The  paper  forms  a  companion  to  a  pre- 
vious one  dealing  with  the  motion  of  a 
sphere  parallel  to  the  axis  of  rotation.  The 
density  of  the  sphere  is  equal  to  that  of  the 
liquid,  and  the  motion  a  small  disturbance 
from  one  of  uniform  rotation  like  a  rigid 
body ;  the  system  is  free  from  bodily  forces 
and  initially  disturbed  by  a  motion  sud- 
denly communicated  to  the  sphere.  The 
subsequent  motion  of  the  centre  of  the 
siphere  is  wholly  in  a  plane  perpendicular 
to  the  axis  of  rotation  (the  equatorial 
plane),  and  the  disturbed  motion  of  the 
liquid  is  symmetrical  with  respect  to  this 
plane.  The  path  of  the  centre  of  the  sphere 
is  a  spiral  with  a  definite  pole.  The  sphere 
winds  round  the  pole  in  a  direction  oppo- 
site to  that  of  the  rotation  of  the  liquid 
while  continually  approaching  it,  the 
motion  being  such  that  the  time  of  a  com- 
plete turn  tends  to  become  constant  and 
equal  to  one-half  the  time  of  a  revolution 
of  the  undisturbed  liquid.  The  motion  of 
the  liquid  in  the  equatorial  plane  tends 
rapidly  to  zero  away  from  the  sphere.  At 
points  along  the  prolongation    of  the    polar 


axis  of  the  sphere  the  motion  is  parallel  to 
the  equatorial  plane  and  is  a  maximmn  at 
the  sphere.  At  any  point  in  the  sphere  the 
velocity  of  the  liquid  relative  to  the  sphere 
is  the  component  in  the  tangent  plane  of  a 
vector  of  constant  magnitude  which  uni- 
formly describes  a  right  circular  cone. 
Parts  of  the  solution  are  not  applicable  for 
large  values  of  time. 

B.  F.  J.  ScHONL.\ND.  The  Passage  of 
('athode  Hays  through  Matter.  Communi- 
cated by  Prof.  S.  Ernest  Rutherford,  F.K.S. 

1.  The  absorption  of  cathode  rays  of 
velocity  6.10»  to  1  •  2.101*'  cms. /sec.  in 
various  metals  has  been  studied  with  an 
arrangement  designed  to  eliminate  inter- 
ferencee  from  secondary  rays  and  to 
measure  both  the  fraction  of  the  beam 
passed  through  and  that  actually  absorbed 
in  the  foil. 

2.  The  latter  fraction  varies  with  thick- 
ness and  velocity  in  the  same  manner  for 
all  elements;  the  nature  of  the  variation  of 
the  former  depends  upon  the  absorbing 
material. 

3.  The  conception  of  a  range  for  these 
particles  is  established  by  two  independent 
inethods  of  measurement. 

4.  The  results  are  explained  by  applying 
the  theory  of  absorption  due  to  Bohr,  with 
which  they  are  in  quantitative  agreement. 


THE  CHEMICAL  SOCIETY. 
Ordinary  Scientific  Meeting,    Thursday, 
June  21. 
The  following  papers  were  read:  — 
The  Constitution  of  the  Higher  Oxide    of 
\^ickel.     O.  K.  Howell. 

The  Relationship  of  the  Tautovieric  Hy- 
drogen Theory  to  the  Theory  of  Ind^iced 
Altcrnaic  Polarities.  F.  Allsop  and  J. 
Kenner. 

Electron  Valency  Theories  and  Stereo- 
chemistry.    S.   Sugden. 

The  Relative  Influences  of  Water  Vapour 
and  Hydrogen  upon  the  Combustion  of  Car- 
ban  Monoxide — Air  Mixtures  at  High  Tem- 
peraturen.  W.  A.  Bone,  D.  M.  Newitt, 
and  I).  T.  A.  Townend. 

Metallic   Hydroxy-Acid    Complexes.   Part 
I. — Cuprilactates.     I.  W.  Wark. 

Metallic   Hydroxy-Acid   Complexes.  Part 
II. — Cuprimalates,     their  Formation,     Pro- 
perties, and  Composition.     I.  W.  Wark. 
Cholesterol  and  its  Role  in  the  Orqanism . 

S.   MiNOVICI. 


JUNE  22,  1923. 


THE  CHEMICAL  NEWS. 


397 


THE  KOYAL  INSTITUTION. 

"  Atomic  Pr<jjkctiles  and  Their 

Properties." 

On     Saturday,     Juno     16,     Sir    Erne.st 

Rutherford  delivered  his  postpcmed  lectun* 

on  the  above  subject. 

He  gave  some  of  the  results  he  and  Dr. 
Chadwiek  have  obtainerl  in  the  Cavendish 
Laboratory  by  utilising  a  particles,  spon- 
taneously fired  from  radio-active  substances 
at  incredible  speeds,  in  their  attempts  to 
disintegrate  the  atoms  of  various  elements. 
Remarkable  results  have  been  obtained 
with  certain  elements,  including  boron,  ni- 
trogen, s<Klium,  aluminium,  fluorine,  and 
phosphorus.  Constituents  of  the  atoms  of 
these  elements  have  been  expelled  by  a  par- 
ticles, and,  at  least  temporarily,  something 
like  the  transmutation  of  the  elements  has 
been  accomplished. 

With  special  aipparatus  it  has  been  do- 
monstratcd  that  the  particles  thus  expelled 
are  in  all  cases  hydrogen  atoms,  sometimes 
in  that  form  and  at  others  in  the  form  of 
helium  nuclei,  which  consist  of  four  hydro- 
gen nuclei  bound  together. 

It  seems  almost  certain,  therefore,  that 
the  ultimate  "bricks"  from  which  all  sub- 
stance are  built  up  arc  hydrogen  nuclei,  the 
manner  in  which  they  arc  combined  in  any 
particular  atom  determining  the  nature  of 
the  element  of  which  it  is  a  part. 

The  fact  that,  when  an  alpha  particle  en- 
tered the  atomic  nucleus  of  substances  like 
aluminium,  hydrogen  nuclei  were  fre- 
quently projected  backwards  as  well  as  for- 
wards was  a  strong  irorroboration  of  the 
theory  thnt  the  central  nucleus  of  an  atom 
was  surrounded  by  electrons  moving  rapid  I  v 
round  the  nucleus. 

The  speed  and  direction  of  motion  of  any 
of  these  "satellite"  electrons,  when  stnick 
by  an  intruding  a  particle,  would  depend  on 
its  position  in  its  orbit  when  hit,  and  Sir 
Ernest  showed  by  a  diagram  how,  imder 
certain  conditions,  an  electron  would  be  pro- 
jected in  such  a  way  as  to  sweep  close 
around  the  nucleus  and  return  on  the  other 
side  in  the  same  direction  as  it  approached 
the  central  region. 

Experimental  work  in  this  field  is  \.  i\ 
difficult  and  expensive,  but  the  results  are 
Sf>  fundamental  in  their  nature  as  to  pro- 
mise the  solution  of  many  of  the  problems 
of  physics  and  chemistry  w  hich  a  few  years 
ago  seemed  incapable  of  toluticm.  Among 
these  are  fhe  actual  transmutati<Mi  of  the 
elements — and  the  possibility  of  harnessing 
the  stupendous  energy  at  present  locked  up 
in  the  complex  structure  of  the  atom. 


ROYAL  AGRICULTURAL  SOCIETY. 

Proceedings  at  Monthly  Council, 

Wednesday,  June  C,  Lieut. -Col.  E.  W. 

Stanyforth  (President)  in  the  Chair. 

The  Reports  of  Committees  included :  — 

Chemical. 

Mr.  Luddington  (Chairman)  reported 
that  a  list  of  the  samples  analysed  by  the 
Consulting  Chemist  during  the  past  month 
had  been  submittedi 

A  letter  had  been  received  from  the 
Ministry  of  Agriculture  stating  that  the 
personnel  of  the  proposed  Departmental 
Conmiittee  on  the  Fertilisers  and  Feeding 
Stuffs  Act  was  under  consideration,  and 
that  an  announcement  on  the  subject  would 
be  made  shortly.  A  further  letter  had  been 
received  from  the  Ministry,  asking  for 
copies  of  any  report  embodying  any  conclu- 
sions that  had  Ix'en  arrived  at  by  the  Con- 
ference of  representatives  of  the  Society 
with  other  bodies.  It  had  been  left  to  the 
Chairman  and  Dr.  Voelcker  to  draw  up  a  re- 
port for  submission  to  <he  Ministry. 

Dr.  Voelcker  had  reported  to  the  Com- 
mittee regarding  various  matters  arising 
out  of  his  correspondence. 

Ik)TAN'IcAL    AND    ZoOLOi.IC  AL. 

Mr.  Plumptrc,  in  the  unavoidable  absence 
of  Mr.  Coltman-Rogers  (Chairman),  pre- 
sented the  following  Reports  that  had  been 
made  to  the  Committee  by  the  Botanist 
(Professor  R.  H.  Biffen,  F.R.S.),  and  the 
Zoologist  (Mr.  Cecil  Warburfcon,  M.A.). 

Research. 

Manuring  of  Pasture  Land. — An  interim 
report  was  received  on  the  experiments 
initiated  in  Ix>icestershire  on  the  effect  of 
basic  slag  and  other  fertilisers  on  pasture 
land  as  measured  by  the  increase  in  weight 
of  cattle  and  sheep.  The  ground  has  been 
prepared  and  fenced  into  plots  and  water 
supplied.  The  stock  was  placed  on  the 
plots  on  May  31,  and  the  first  year's  con- 
trol experiment,  during  which  no  fertilisers 
are  to  be  used,  has  thus  been  begun. 

EnailacfC. — Experiments  have  been  ar- 
ranged under  the  superintendence  of  Mr. 
A.  Amos,  of  Cambridge,  on  the  value  of 
silage  as  food  for  dairy  cows,  and  its  effedt 
on  the  yield  and  quantity  of  the  milk.  Not 
every  farmer  has,  or  can  afford  to  build,  a 
tower  silo,  and  Mr.  Amos  is  going  to  pre- 
serve the  silage  in  clamps — pits  in  the 
ground,  in  which  the  fodder  is  compressed 
and  covered  with  earth. 


398 


THE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


Another  related  research  is  to  be  parried 
out  by  Mr.  Oldershaw  hi  East  Suffolk. 
Tower  ensilage  will  bo  made  this  summer 
and  fed  to  dairy  cows  next  winter  to  test 
how  far  the  protein  contents  of  silage  can 
be  used  to  save  exipensive  cakes,  the  de- 
ficiency in  carbohydrates  being  balanced  by 
other  foods,  such  as  oats  or  barley  or 
molasses. 

It  was  resolved  that  £100  be  devoted  to 
these  experiments. 


MINERALOGICAL  SOCIETY. 
Tuesday,  June  19. 

Papers  received :  — 

Dr.  L.  J.  Spencer  (with  chemical  ana- 
lyses by  E.  D.  Mountain):  New  Lead- 
Copper  Minerals  from  the  Mendip  Hills 
(Somerset). 

Dr.  W.  F.  p.  McLintock  :  On  a  Petalite- 
hearing  Roch  from  Devonshire. 

Messrs.  A.  Brammall  and  H.  F.  Har- 
WOOD  :  Dartmoor  Granite  :  Monazite  and 
other  accessory  Minerals;  tourmalinisation. 

Seitaro  Tsuboi  :  Optical  Dispersion  of 
three  Intermediate  Plagioclases. 

Seitaro  Tsuboi  :  A  Method  of  Determin- 
ing Plagioclascs  in  Fine  Grains. 

C.  S.  Garnett  :  The  toadstone  clays  of 
Derbyshire. 

Dr.  G.  T.  Prior  :  On  the  Meteoric  Stone 
which  fell  at  Ashdon,  Essex,  on  March  9, 
1923. 

Dr.  G.  T.  Prior:   The  Sinai  Meteorite. 


LIVINGSTONE    COLLEGE 
COMMEMORATION  DAY. 

A  very  successful  commemoration  day 
was  held  at  Livingstone  College  on  June 
13.  The  chair  was  taken  bv  Sir  Leonard 
Rogers,  CLE.,  F.R.S. 

Short  statements  were  made  by  the  Prin- 
cipal, Dr.  Tom  Jays,  and  the  Treasurer,  Mr. 
R.  L.  Barclay,  as  to  the  work  of  the  past 
year,  and  the  financial  and  general  position 
of  the  College. 


SOCIETY  OF  GLASS  TECHNOLOGY. 

A  meeting  was  held  at  the  Leeds  Insti- 
tute, on  Wednesday,  June  20.  The  follow- 
ing papers  were  received  and  discussed  :  — 


Specifications  in  the  Glass  Industry,  bv 
Prof.  W.  E.  S.  Titrnbr,  D.Sc. 

Notes  on  the  Design  of  Pot  Arclies,  by 
Tii.  Teisen,  B.Sc. 

Notes  on  the  Ashley  Bottle  Machine,  by 
S.  English,  M.Sc. 

The  Effect  of  Titania  on  the  Properties  of 
Glass,  by  A.  R.  Sheen  and  Prof.  W.  E.  S. 
Turner. 


INDUSTRIAL    PHYSICAL    RESEARCH 
IN  AMERICA. 

In  his  recent  Pi^esidential  Address  to  the 
Institute  of  Physics,  Sir  J.  J.  Thomson  gave 
some  account  of  the  work  he  had  seen  dur- 
ing his  recent  visit  to  America  in  the  re- 
search departments  of  some  of  the  great 
manufacturing  firms.  Tbese  laboratories 
were  established  in  the  face  of  considerable 
opposition,  but  now  the  universal  opinion 
appears  to  be  that  the  research  department 
is  one  of  the  most  profitable  in  manufactur- 
ing concerns,  and  however  great  the  neces- 
sity for  economy  its  cost  would  be  the  last 
to  be  reduced. 

The  scale  of  these  laboratories  was  far 
greater  than  anything  we  have  in  this  coun- 
try, and  much  of  the  work  carried  out  is  not 
merely  what  might  be  called  development 
work,  but  is  fundamental  scientific  work, 
worthy  of  a  university  laboratory. 

On  the  other  hand  the  American  universi- 
ties do  not  seem  designed  to  produce  a  large 
number  of  jnen  qualified  to  take  up  ad- 
vanced research  work.  For  example,  few 
of  the  science  students  have  the  necessary 
equipment  in  mathematics  and  the  stern 
training  which  a  good  Honours  man  in  a 
great  English  university  has  to  go  through 
aippears  to  be  unknown.  The  system  is 
doubtless  good  for  the  average  man,  but  a 
successful  research  institute  requires  some- 
thing more  than  the  average  man ;  it  needs 
men  with  high  scientific  knowledge.  In 
this  regard  this  country  has  a  distinct 
advantage  we  shall  sorely  need  if  we  are  to 
hold  our  own  in  competition. 


NOTICES  OF  BOOKS. 

The  Manufacture  of  Acids  and  Alhalis, 
by  George  Lunge,  completely  revised 
and  rewritten  under  the  Editorship  of 
Alexander  Charles  Gumming,  D.Sr.. 
F.I.C.  Volume  I. — Raw  Materials  for 
the  Manufacture  of  Sulphuric  Acid  and 
Sulphur  Dioxide,  by  Wilfrid  Wvld.    Pp. 


JUNE  22,  1923. 


THE  CHEMICAL  NEWS. 


399 


XIII.  +  558.  London :  Gumey  &  Jack- 
son, 33,  Paternoster  Row,  E.C.  1028. 
i*ric(j  3Gs.  net. 

Prof.  Lunge's  Sutiihuric  Acid  and  Alkali 
first  appeared  in  1879.  The  last  edition, 
for  which  he  was  still  responsible,  was  ipub- 
lished  in  1913.  In  the  meantime  the  pro- 
gress in  chemical  industry  has  necessitated 
various  revisions  and  much  extension. 
Much  of  the  earlier  editions  is  naturally  now 
obsolete,  and  even  the  security  of  old- 
established  Lead  Chamber  process  is  seri- 
ously threatened  by  the  newer  Catalytic 
processes. 

The  present  edition,  dealing  with  the 
heavy  chemical  industry,  has  been  based 
upon  a  very  thorough  revision  of  the  older 
work.  Much  new  matter  has  been  intro- 
duced, more  particularly  concerning  the  by- 
products, which  have  latelyr  assumed  in- 
creasing importance.  Illustrations  and  de- 
scriptions of  new  plant  have  also  been  in- 
troduced. 

Perhaps  the  most  useful  parts  of  this 
volumr  are  those  dealing  with  the  proper- 
ties and  technical  analyses  of  the  oxides  of 
sulphur,  and  the  detailed  account  of  the 
varicms  types  of  natural  and  recovered  sul- 
phur used  in  the  heavy  chemical  industry. 

Volume  V. — The  Mnnufaciun    of  Hy- 
drochloric Acid  and  Salt  Cake,    by  Alex- 

ANDRR  ChARLEH  CUMMINd.  l^.Sc,   F.I.C. 

pp.  XV.  +  423.    Price  IJU.  Od.  net. 

In  this  volume,  the  numerous  industrial 
methods  for  making  salt  cake  and  also  hy- 
drochloric acid  are  given  in  adequate  detail. 

Early  chapters  describe  the  raw 
materials.  The  chapt-er  on  the  manufac- 
ture of  salt  cake  and  hydrochloric  acid  is 
naturally  the  longest,  but  there  is  much  of 
importance  to  inmistrialists  in  the  awounts 
of  various  processes  for  making  sodium  sul- 
phate as  the  main  product  from  salt.  This 
is  also  true  of  the  chapter  dealing  with  this 
substance  as  a  by-prfxluct. 

The  Hargreaves  process,  which  has  been 
the  subject  of  so  many  pat^'nts,  is  still  de- 
scribed in  good  detail,  although  it  is  recog 
nised  that  such  old  processes  are  rapidly 
being  superseded. 

The  later  chapters  on  the  winning  of  hv- 
drochloric  acid  are  largely  taken  up  with  tlir 
mechanical  and  absorbing  nrrnngements  of 
the  plant. 

The  constantly  increasing  over-produc- 
tion of  electrolytic  chlorine  has  led  to  this 
element  being  combined  with  hydrogen, 
either  directly  or  by  interaction  with  steam. 


The  account  of  these  methods  should  iprove 
very  instructive  to  those  for  whom  these 
treatises  have  been  compiled.  Doubtless 
when  a  new  edition  of  this  higlily  impor- 
tant work  is  issued,  this  section  will  need 
to  be  enlarged  with  more  dettdl. 

The  other  volumes  of  this  revised  edition 
will  be  awaited  with  interest  by  industrial 
and  technical  chemists. 


BOOKS  RECEIVED. 

The  Constitution  of  Matter,  by  Max 
Born,  translated  by  E.  W.  Blair,  D.I.C, 
B.Sc,  and  T.  S.  Wheeler,  B.Sc, 
.\.K.C.Sc.I.  Pp.  VII.  +  80.  1923.  Messrs. 
Methuen  &  Co.,  Ltd.,  36,  Essex  Street, 
W.C.2.    68.  net. 

Alcoholic  Fermentation,  by  Arthur  Har- 
DEs,  Ph.D.,  D.Sc.,  F.R.S.  Pp.  194.  Third 
Edition.  1923.  Messrs.  Longmans,  Green 
&  Co.,  39,  Paternoster  Row,  E.C.4.  6s.  6d. 
net. 

['radical  Bacteriology  for  Chemical  Stu- 
dents, by  David  Ellis,  Ph.D.,  D.Sc, 
K.U. S.E.  Pp.  VIII.  +  136.  1923.  Messrs. 
Longmans,  Green  &  Co.,  39,  Paternoster 
How,  E.C.4.     4s.  6d.  net. 

Chemistry,  Inorganic  and  Organic,  vHh 
Experiments,  by  Charles  Loudon  Bloxam. 
Pp.  IX.  +  832.  Eleventh  Edition.  1923. 
Messrs.  J.  &  A.  Churchill,  7,  Great  Marl- 
borough Street.  W.l.     368.  net. 


ITBLICATIONS  RECEIVED. 

In  the  Bulletin  No.  211,  published  by 
the  U.S.  Dept.  of  the  Interior  (Bureau  of 
Mines),  entitled  The  Chloride  Volatilisa- 
tion Process  of  Ore  Treatment,  by  Thomas 
Varley,  E.  p.  Barrett,  C.  C.  Stevenson, 
and  R.  H.  Bradford,  it  is  point^'d  out  that 
the  art  of  treating  ores  by  the  chloride 
volatilisation  process  is  still  in  the  experi- 
mental stage.  The  process  has  not  yet 
been  sufficiently  developed  along  metallur- 
gical lines  to  warrant  a  definite  statement 
as  to  the  exact  place  it  will  occuipy  in  the 
industry.  The  basic  theory  of  the  process 
has  attracted  the  attention  of  prominent 
metallurgists,  and  considerable  research 
and  experimental  work  has  been  accom- 
plished. 


400 


THE  CHEMICAL  NEWS. 


JUNE  22,  1923. 


Much  of  the  experimental  work  done  has 
not  been  published;  but  if  the  accumulated 
results  were  made  known,  they  would 
greatly  aid  the  further  development  of  the 
process.  The  bulletin  aims  to  bring  the 
salient  features  of  the  process  to  the  atten- 
tion of  metallurgists  for  the  purpose  of  fur- 
nishing information  to  and  receiving  com- 
ments from  interested  parties  with  the  ulti- 
mate hope  that  the  process  will  be  a  com- 
mercial success. 

If  commercially  utilised,  the  process  will 
fill  a  long-felt  want  in  metallurgy,  especi- 
ally in  the  treatment  of  oxidised  and  semi- 
oxidised  or  "carbonate"  ores  of  copper, 
lead,  and  silver.  Such  ores  are  difficult  to 
treat  by  gravity  concentration  or  by  flota- 
tion; in  the  former  their  tendency  to  slime 
upon  crushing  and  their  being  of  lower  spe- 
cific gravity  than  the  sulphide  minerals 
cause  serious  losses;  in  the  latter  much  has 
been  done  in  sulphidising  oxidised  ores  and 
subsequently  recovering  the  artificiaF  sul- 
phides by  flotation.  Difficulties  in  proiper 
sulphidising  and  the  low  recoveries  obtained 
have  not  balanced  the  cost  of  the  treatment 
in  many  plants,  and  in  very  few  has  it 
proved  successful. 

Evidently  there  is  a  big  void  to  fill  in  the 
treatment  of  these  ores.  No  radical  changes 
in  present  methods  are  forecast,  but  it  is 
obvious  that  chloride  volatilisation  can  have 
a  distinct  place  as  a  method  of  treatment 
for  ores  that  are  not  reaclily  amenable  to 
present  methods.  In  many  plants  it  might 
replace  concentration  methods,  especially 
where  part  of  the  mineral  content  in  the 
ores  exists  in  forms  other  than  sulphides. 

In  addition  to  the  minerals  named  above, 
gold  in  ores  has  been  readily  volatilised. 
Zinc  does  not  form  a  volatile  chloride,  if  an 
oxidising  condition  is  maintained  in  the 
roasting  operations.  Some  excellent  re- 
sults have  been  obtained  with  carbonate- 
zinc  concentrates  containing  silver  and  lead. 
Practically  all  the  silver  and  lead  were 
volatilised,  but  very  little  of  the  zinc.  Ex- 
periments have  proved  that  the  process  is 
probably  one  of  the  best  for  making  a  clean- 
cut  separation  of  lead  and  zinc. 

Not  much  work  has  been  done  on  sul- 
phide ores,  because  the  need  is  pressing  for 
a  volatilising  method  for  treating  oxidised 
and  carbonate  ores.  Experiments  on  sul- 
phides have  been,  however,  encouraging. 
When  the  sulphur  content  is  above  5  per 
cent,  a  preliminary  roast  is  usually  neces- 
sary before  chloride  roasting  and  volatilisa- 
tion. 

The  effect  of  sulphur  is  discussed  by 
Croasdalo  in  his  chapter    on  the  history  of 


the  process.  He  and  other  investfgators 
declare  that  sulphur  is  a  consumer  of  salt, 
and  when  it  is  present  in  an  ore  in  excessive 
amounts  a  pioportionately  larger  amount  of 
salt  is  ro([uiied  to  eftect  the  chloridisation 
and  volatilisation  of  the  metals  present. 

The  process  would  doubtless  be  favour- 
able for  use  in  regions  not  well  supplied 
with  water.  All  the  apparatus  required  for 
the  construction  of  a  plant  are  practically 
standard  mechanical  devices  and  machin- 
ery. The  most  important  raw  materials  in 
the  operation  of  a  plant  are  the  fuel  and  the 
salt  or  other  haloid.  In  mining  districts 
remote  from  railroads  these  materials,  of 
course,  would  be  the  largest  factor  in  the 
cost  of  running  a  plant.  Nevertheless,  the 
cost  would  often  be  more  than  off.set  by  the 
freight  charges  on  the  concentrates  and 
other  supplies  necessary  for  a  plant  using 
almost  any  other  kind  of  process.  These 
conditions  will  be  discussed  in  some  detail 
in  describing  the  operations  of  plants  that 
have  been  built. 

The  experiments  described  cover  part  of 
the  investigations  carried  on  by  the  U.S. 
Bureau  of  Mines  on  ores  from  all  parts  of 
the  United  States.  Large  quantities  of 
different  types  of  ores  not  amenable  to  any 
other  process  were  available,  and  the 
method  developed  gives  promise  of  great 
commercial  importance. 


I'His  lisL   is  specially  compiled   for     The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chance.-y  Lane,  Ijondon,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  ccn  be  obtained  gmtuitously. 
Abstract  Published  this   Week. 
195849— Cellulose    acetate    solutions      and    composi- 
tions;  celluloid;   films;   varnishes.— British 
Cellulose   &   Chemical   Manufacturing   Co., 
Ltd.,   8,   Waterloo   Place,   Tx>ndon;     Bader, 
W.,   and   Dickie.   W.   A.,   British   CpHuIosc 
&  Chemical     Manufacturing     Co.     Works, 
Spondon,   near   Derby. 
Celluloid-like   products,      plastic    masses,     films, 
varnishes,    solutions   and   other    preparations   and 
compositions  having     a  basis  of  cellulose  acetate, 
are   prepared    with     the   employment  of   tri-chlor 
tertiary     butyl    alcohol   as    solvent     or    plastifier; 
celluloid  prepared   in   this  manner   is  tough,  elas- 
tic and  non-inflammable.      According   to   the   use, 
volatile     or  other   solvents,     diluents,     plastifiers, 
filling  materials,   colouring  matters,  &<:■.,     may  be 
added.     In  examples,  celluloids  are  prepared  witli 
the     aid  of  the     tri-ohlor  tertiary  butvl     alcohol 
with    or    without    the   addition   of  tri'ph'enyl    phos- 
Phate  or    castor  oil ;     films,     using  a  solu'tion     to 
^hicn     acetone  has  been  added;     and  a    varnish, 
^^\r  addition  of  acetone  or  methyl  acetate. 

Alessrs.  Rayner  &  Co.  will  obtain  printed  copies 
ot  the  published  specifications  only,  and  forward 
on  post  free  for  the  price  of  Is.  6cl.  each 


JUNE  29,  1923. 


THE  CHEMICAL  NEWS. 


401 


THE   CHEMICAL  NEWS, 


VOL.  GXXVI.       No.  3298. 


NOTE  UPON  THE  PROrERTIES  OF 
MUSCARINE. 

By  John  Missenden,  B.Sc. 

Muscarine,  which  is  a  content  product  of 
a  number  of  poisonous  fungi  (notably  the 
Amanita  muscaria),  has  the  formula 
CjHjjOjN,  but  its  constitution  is  unknown. 
Formerly,  it  was  believed  to  be  a  choline 
oxy-substitution  product.  Schmiedeberg 
and  Hamack,'  in  their  reaction  with  cho- 
line and  nitric  acid,  gave  the  base  obtained 
(which  they  believed  to  be  iimscarine)  as 
OHX.  (CH^Ij.CHjCH  (OH),.  The  argu- 
ments of  both  Berlinerblau^  and  Boohm', 
however,  very  conclusively  show  that  this 
base  possesses  neither  the  properties  nor 
constitution  of  muscarine,  the  conclusions 
being  the  outcome  of  careful  compari.son 
with  the  natural  product.  At  the  same 
time,  until  more,  is  known  of  the  subject, 
the  synthetic  iprotluct  may  be  accepted  as  a 
choline  ester  of  the  constitution  OHX. 
(CH,),CH3.CH,0N0.  Natural  muscarine, 
we  believe,  possesses  a  totallv  different  con- 
stitution; I.e.,  N0.CH,.(CH,),.CH,.CH,.- 
NO.OH,  although  there  is  some  doubt  ns 
to  the  e.xao<  placeruent  of  the  initial  nitro- 
syl  group. 

Natjiral  muscarine  is  certainly  not  n 
choline  ester,  inasmuch  that  its  solutions 
are  not  decomposed  by  boiling  in  acid  and 
alkaline  solutions.  Discussions  upon  the 
matter  were  reported  by  W(  inhngen.*  It 
is  worth  noting  that  the  physiological 
action  of  muscarine  resembles  that  of 
acetyl-choline. 


»  Arch.  ex.  Pafh.  Pharm..  1877,  VI..  101. 

*  Ber.  Dent.,  1884.  XVIL,  114L 

'Arch.  ex.  Path.    Pharm.,    188.'),    XTX., 
187. 

*  Jovrn.  Awer.  Chem.  Soc,  1920.  XLIL. 
1670. 


DISTRIBUTION  OF  INSECTICIDE 
BY  AEROPLANE. 

Mr.  R.  O.  Wahl,  Lecturer  in  Entomo- 
logy in  South  Africa,  who  recently  returned 
to  that  country  from  America,  reports  that 
when  visiting  the  State  Experiment  Station 
at  Wooster,  Ohio,  during  last  year,  his  at- 
tention was  drawn  to  an  experiment  carried 
out  by  that  Experiment  Station  and  the 
City  of  Cleveland,  in  co-operation  with  the 
United  Statos  Air  Service,  in  combating  an 
outbreak  of  the  catalpa  sphinx  (Ceratomia 
caialpas,  Bvd.)  in  a  catalpa  grove  by  dis- 
tributing the  insecticide  from  an  aeroplane. 
Through  the  courtesy  of  the  officers  con 
ducting  the  experiment  it  was  possible  for 
Mr.  Wahl  to  take  an  active  part  in  the 
work,  seeing  the  dusting  from  the  ground 
and  the  air,  and  in  assisting  in  checking  the 
results  immediately  after  the  dusting  after 
a  lapse  of  24  hours  and  again  a  week  later. 
The  section  of  the  wood  sprayed  was  a 
dense  grove  cwitaining  trees  of  different 
kinds,  elm,  spnice.  maple,  etc.,  and  varying 
in  size  from  (K)  ft.  down.  There  was  con- 
siderable thick  undergrowth  as  well  as 
nuich  bracken  and  large  plantings  of  rhodo- 
dendrons. The  penetration  of  the  dust  was 
remarkable  and  the  killing  very  successful. 
Unfortunately,  a  heavy  thunderstorm  and 
torrential  downpour  occurred  a  few  hours 
after  the  competion  of  the  dusting  and 
robbed  it  of  much  of  its  value.  A  portion 
was  redusted  the  following  day,  resulting  in 
a  practically  total  killing  of  the  caterpillars. 

Much  more  experimental  work  is  neces- 
sary, but  a  new  field  of  investigation  in  this 
directfon  is  opened  to  the  entomologist  and 
other  scientists  and  one  that  apponrs  to 
have  great  possibilities. 


M.XCHINERY  FOR  PHARMACEUTICAL 

PREPAR.\TI()NS  REQUIRED  IN 

AUSTRALIA. 

Mr.  S.  W.  B.  McGregor,  -.M.  Senior 
Trade  Commissioner  in  Australia,  reports 
tbat  a  Melbourne  firm  of  manufacturing 
chemists  specialising  in  the  production  of 
galenicals  and  other  pharmaceutical  pre- 
parations, are  desirous  of  receiving  particu- 
lars from  British  manufacturers  of  any 
machinery,  appliance,  apparatus.  etc.. 
used  in  the  manufacture  of  such  products 
in    a  wholesale    way,    such  as    percolators 


402 


THE  CHEMICAL  NEWS. 


JUNE  29,  1923. 


(mechanical  and  otherwise),  evaporators, 
boiling  pans,  filters  (not  water  filters). 
They  are  particularly  interested  in  any 
plant  that  would  be  of  service  in  the  manu- 
facture of  extract  of  glycyrrhizee  and  ex- 
tract of  cascara  on  a  large  scale. 

The  firm  are  understood  to  be  of  good 
reipute  and  standing. 

British  firms  interested  in  this  enquiry 
can  obtain  the  name  and  address  of  the 
enquirers  upon  application  to  the  Depart- 
ment of  Overseas  Trade  (Eoom  52),  35,  Old 
Queen  Street,  S.W.I. 


GERMANY'S  TRADE  AND    INDUSTRY 
IN  MAY. 

Mr.  F.  Thelwall,  Commercial  Secretary 
at  Berlin,  has  forwarded  to  the  Depart- 
ment of  Overseas  Trade  information  on 
German  trade  and  industry  during  Mnv. 

In  spite  of  the  unfavourable  general 
situation,  there  was  a  not  inconsiderable 
improvement  in  business  in  many  branches 
of  industry.  The  special  feature  in  trade 
was  the  rise  of  the  dollar,  which  again  led 
to  an  increased  desire  to  purchase  on  the 
part  of  inland  customers,  while  foreign  sales 
improved  in  consequence  of  the  greater 
span  between  prices  and  of  the  easier  ex- 
port conditions.  German  industry  also 
benefited  by  the  altered  conditions,  al- 
though its  outlook  for  the  future  continues 
melancholy.  New  diflRculties  arose  in  pro- 
curing British  coal,  the  import  of  which, 
owing  to  the  depreciation  of  the  mark,  had. 
of  course,  to  be  restricted.  The  coal  stocks 
had,  therefore,. to  be  broken  into  to  a  larger 
extent.  In  occupied  territory  the  strike  did 
not  greatly  affect  the  industrial  situation. 
In  imoccupied  Germany  also,  as  a  result  of 
the  rise  in  prices  amounting  to  33.8  pf>r 
cent,  as  compared  with  April,  new  wage  de- 
mands were  made. 

Mining. 

The  coal  position  of  industry  in  occupied 
territory  continued  to  depend  on  the 
measures  of  the  occupying  Powers.  Many 
cokeries  ceased  work.  Most  pits  only  pro- 
duced sufficient  coal  to  meet  the  needs  of 
their  own  foundries.  In  many  cases  trans- 
port between  the  foundries  and  the  nits  has 
been  interrupted  by  the  occupying  Powers. 
The  price  of  coal  was  raised  to  '\4PJ^0 
marks  per  ton. 

In  the  potash  industry,  inland  trade  had 
at  first    still    to    suffer    from    considerable 


ditheulties.  The  freight  reductions  for  the 
summer  introduced  by  the  German  Potash 
Syndicate  Ji-d,  howevei",  to  a  substantial  im- 
provement of  sales  in  the  second  half  of 
May.  By  the  summer  reductions,  the  pot- 
ash industry  gave  agriculture,  as  in  the  pre- 
vious year,  the  opportunity  of  covering 
during  the  summer  months  a  considerable 
portion  of  its  autumn  requirements  at  re- 
duced freights.  Foreign  business  also  be- 
came lively  on  the  renewed  depreciation  of 
the  mark  and  exportation  took  place,  par- 
ticularly to  America.  Alsatian  competition 
made  itself  increasingly  felt  in  foreign 
trade.  Coal  deliveries  left  nothing  to  be 
desired. 

Electro-Technical  Industry. 

Measuring  instruments  found  a  good 
market,  and  business  activity  in  the  high- 
pressure  current  industry  increased. 

Chemical  Industry. 

The  chemical  preparations  industry  still 
suffered  at  the  beginning  of  the  month 
under  the  prevailing  disinclination  to  buy. 
On  the  rise  of  the  dollar,  business  revived 
on  a  continually  increasing  scale.  Many 
orders  from  abroad  were  also  received,  so 
that  at  present  the  degree  of  employment 
is  comparatively  favourable.  Practically 
no  benefit  accrued  to  the  woi'ks  from  the 
new  export  facilities,  as  the  reduction  of 
the  export  duty  did  not  go  nearly  far 
enough.  In  the  sheet  glass  industry,  ex- 
ports at  first  declined  auiiier  compared 
with  the  preceding  month;  then,  as  a  result 
of  the  fall  of  the  mark,  a  considerable  de- 
mand from  abroad  set  in.  Exportation  to 
Italy,  Reval,  and  also  to  America  and 
Africa  took  place  from  accumulated  stocks. 

In  the  hollow  glass  industi'y  the  supply 
of  raw  materials  and  of  coal  was  adequate ; 
soda  deliveries  improved.  Work  for  stock 
had  in  tpart  to  be  done.  In  the  case  of  some 
special  articles  a  slight  improvement  of 
sale  conditions  was  reported. 

Indiaruhhcr. 

Conditions  in  the  indiarubber  industry 
much  improved  as  a  result  of  the  further 
depreciation  of  the  mark.  Fearing  a  fur- 
!  ther  rise  of  foreign  values,  consumers 
!  sought  to  cover  their  requirements  anew 
I  and  to  effect  substantial  purchases  whicTi 
I  presumably  did  not  correspond  with  the 
i       actual  consumption. 


JUNE  29,  1923. 


THE  CHEMICAL  NEWS. 


403 


GENERAL  NOTES. 


DIE  CASTING  RESEARCH. 
Aids  to  Mass  Production. 

The  British  Non-Ferrous  Metals  Re- 
search Association  has  undertaken  an  ex- 
tensive series  of  investigations  on  Die  Cast- 
ing Alloys  which  will  spread  over  at  least 
three  years,  and  entail  an  extpenditure  ex- 
ceeding £10,000.  Full  particulars  of  the 
scheme  can  be  obtained  from  the  Associa- 
tion's headquarters,  71,  Temple  Row,  Bir- 
mingham. 

The  development  and  support  of  die  cast- 
ing in  this  country  as  a  means  of  rapid  pro- 
duction, is  recognised  as  of  great  national 
importance  both  for  ordinary  commercial 
production,  in  the  most  diverse  industries, 
as  also  for  munitions  and  equipment  of  the 
fighting  services. 

The  Department  of  Scientific  and  Indus- 
trial Research,  after  holding  conferences  of 
thf>se  interested  in  die  castings,  has  ipro- 
mised  most  substantial  financial  support  to 
the  research.  The  Research  Associations 
of  the  British  Motor  and  Allied  Industries, 
of  the  Scientific  Instruments,  and  of  the 
Electrical  and  Allied  Industries  have  also 
afforded  their  support,  and  are  represented 
on  the  Committee  controlling  the  investiga- 
tions. It  remains  for  the  industry — makers 
and  users — to  provide  their  quota  of  the 
fund  required,  as  without  this  it  will  be  im- 
possible to  fully  develop  the  work,  the  re- 
sults of  which  will  be  primarily  available 
to  those  who  support  the  research. 

Since  die  castings  serve  chiefly  as  com- 
ponents of  plant  and  machinery,  it  is  not 
always  recognised  how  important  they  are. 
but  anyone  enquiring  into  the  subject  will 
come  across  very  varied  uses  in  the  a»ito- 
mobile  industry,  and  such  applications  ns 
brusK  gear  of  electrical  machinery.  }jas 
meter  parts,  vacuum  cleaner  fittings,  etc  . 
etc. 

Sooner  or  later,  almost  every  branch  of 
industry  in  which  metal  parts  of  any  com- 
plicateft  shape  are  required,  turns  to  die 
castings  as  the  ideal  for  economical  pro- 
duction. The  sphere  of  application  will 
extend  considerably  if  the  research  work 
contemplated  succeeds  in  improving  the 
quality  and  assuring  the  reliability  of  the 
alloys  used. 

Various  types  of  alloys  are  used  in  die 
casting,  and  recognising  the  wide  field,  th? 
proposed    research    has  been    divided    into 


three  sections:  1,  Brass  and  Bronze  Alloys; 
2,  Aluminium  Alloys;  3,  Low  Melting 
Point  Alloys  (Zinc,  Tin,  Lead,  etc.).  These 
three  branches,  \\ith  suitable  arrangements 
for  co-operation,  will  be  dealt  with  in  separ- 
ate institutions,  under  the  supervision  of 
recognised  leaders  of  metallurgical  re- 
search. 

Every  care  is  being  taken  in  the  consti- 
tution of  the  Committee  which  controls  the 
work,  to  ensure  that  both  the  manufac- 
turers and  the  users  are  represented. 

Work  of  this  nature  demands  the  close  in- 
terest of  the  industry,  and  it  is  hoped  that 
no  difficulty  will  be  experienced  in  obtain- 
ing the  small  subscriptions  required  to 
a.s8ure  the  substantial  Government  support, 
which  is  only  available  in  a  measure  depen- 
dent on  the  backing  of  the  scheme  by  the 
industrv. 


PHYSICAL  AND  CHEMICAL    SURVEY 

OF  THE  NATIONAL  COAL 

RESOURCES. 

One  of  the  main  functions  of  the  Fuel 
Research  Board  is  a  survey  and  classifica- 
tion of  the  coal  seams  in  the  various  min- 
ing districts  by  means  of  chemical  and 
phy.sical  tests  in  the  laboratory,  supple- 
mrnted  where  desirable  by  large  scale  tests 
at  H.M.  Fuel  Research  Station,  East 
Greenwich,  or  elsewhere.  The  Board  con- 
sider that  the  best  way  to  carry  out  this 
work  is  by  means  of  local  committees,  the 
personnel  of  which  would  include  colliery 
owners,  managers,  representatives  of  the 
Fuel  Research  Board,  and  of  the  Geological 
Survey  of  Great  Britain,  as  well  as  of  out- 
side scientific  interests.  Each  committee 
would  be  charged  with  the  duty  of  superin- 
tending the  work  of  the  survey  in  a  coal 
mining  area ;  and  in  this  way  the  survey- 
would  become,  from  the  commencement, 
of  practical  value,  since  local  knowledge 
and  experience  would  be  made  available, 
and  the  selection  of  seams  would  be  decided 
by  those  most  likely  to  estimate  correctly 
the  relative  importance  of  the  problems  to 
be  solved.  The  seams  selected  would 
undergo  physical  and  chemical  examination 
by  the  local  experts,  after  which  a  final 
selection  would  be  made  of  those  likely  to 
justify  experiments  on  a  practical  scale  to 
test  their  suitability  for  particular  uses  or 
methods  of  treatment. 

The  first    of  these    committees  hns    now 


404 


THE  CHEMICAL  NEWS. 


JUNE  29,  1923. 


been  actively  at  work  in  the  Lancashire  and 
Cheshire  area  for  nearly  eighteen  months, 
and  the  Board  have  recently  appointed  a 
committee  to  deal  with  the  survev  in  the 
South  Yorkshire  area.  The  South  York- 
shire Coal  Trade  Association  and  the  Mid- 
land Institute  of  Mining,  Civil  and 
Mechanical  Engineers  are  co-operating  in 
the  work.  The  comtposition  of  the  com- 
mittee is  as  follows:  — 

Mr.  J.  Brass,  Mr.  Eobert  Clive  (hon. 
secretary)  and  Mr.  H.  Danby — represent- 
ing the  South  Yorkshire  Coal  Trade  Asso- 
ciation. 

Lieut. -Col.  H.  Rhodes,  M.Inst.C.E.. 
M.I.Min.E.,  F. S.I. —representing  the  Mid- 
land Institute  of  Mining,  Civil  and 
Mechanical  Engineers. 

Prof.  R.  V.  Wheeler,  D.Sc. 

Mr.  C.  H.  Lander,  D.Sc,  M.I.Mech.E., 
A. M.Inst.C.E.,  Director  of  Fuel  Research 
(Chairman  yro  tern) — ^representing  the  Fuel 
Research  Board. 

Mr.  Walcot  Gibson,  D.Sc. — ^represontina 
the  Geological  Survey  of  Great  Britain. 


The  Federation  of  British  Industries  has 
issued  an  interim  reiport  on  inter- Imperial 
trade. 

The  report  does  not  cover  every  aspect 
of  inter-Imperial  trade,  and  the  Federation 
propose,  at  a  later  date,  to  address  one  or 
more  further  reports  to  the  Government, 
dealing  with  the  questions  which  are  not 
dealt  with  in  the  present  report. 

In  the  Federation's  opinion,  the  fullest 
possible  development  of  inter-Imperial 
trade  is  essential  in  the  interests  of  the  Em- 
pire as  a  whole,  both  for  economic,  political 
and  social  reasons.  The  problem  should  be 
approached  not  merely  from  the  point  of 
view  of  the  advantages  likely  to  accrue  to 
Great  Britain,  but  from  the  point  of  view  of 
mutual  advantage  to  all  parts  of  the 
Empire. 


FINE  GLASS  IN  THE  MANSARD 
GALLERY. 

An  extremely  interesting  exhibition  of 
fine  glass  has  recently  been  opened  at  the 
Mansard  Gallery,  196,  Tottenham  Court 
Road,  London,  W.l. 

Carefully  selected  from  a  number  of  coun- 
tries, the  play  of  light  on  the  varied  colours 
and  textures  gives  an  atmosphere  of  fairy- 


laud.  Light  shapes  in  clouded  topaz  and 
smoke  grey  come  from  Sweden.  Sea  green 
and  pole  amethyst  fantasies  of  the  Vene- 
tians contrast  with  the  deep  richness  of  our 
own  Old  Bristol  blue  and  puce.  Limpid 
crystal  from  the  old  Whitefriars  works,  and 
the  sturdy  cut  table  glass  from  Edinburgh 
reflect  in  their  facets  the  shimmer  of 
Czecho-Slovakia's  amber  lustre  and  the 
orange  glow  of  bowls  from  France.  The 
comsummate  artists  of  Murano  have  sent  a 
few  pieces  flecked  with  gold,  while  a  table 
set  with  iridescent  glass  from  Holland 
holds  all  the  glories  of  a  bubble  in  the  sim. 
The  revival  of  industries  in  Palestine  is 
shown  by  some  characteristic  peacock  blue 
glass  from  Hebron. 

Alongside  these  contributions  from  far 
lands  are  tables  laid  with  sinnple,  well- 
shaped  wine-glasses  and  tumblers  in  plain 
crystal ;  practical  and  graceful  vases  for 
flowers,  aud  larger  ones  for  tall  spikes  of 
delphiniums  or  spreading  boughs.  A  col- 
lector's piece  is  the  tall  engraved  goblet 
nuule  to  commemorate  the  Armistice,  bear- 
ing the  appropriate  inscription :  Doniinus 
loquitur — arnia  silent,  and  dated  the 
eleventh  hour  of  the  eleventh  day  of  the 
eleventh  month,  1918. 

The  revival  of  the  iprismatic  lustre  glass 
for  electric  lighting  is  particularly  happy. 
A  series  of  these  lustre  light  pendants  and 
w^all  brackets  will  be  of  particular  interest 
to  architects. 

The  exhibition,  which  has  been  organised 
by  Messrs.  Heal  and  Sons,  of  Tottenham 
Court  Road,  is  being  held  during  the  pre- 
sent and  the  next  month.  Admission  is 
free.  — The  Board  of  Trade  Journal. 


FHOCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  June  28. 
Paper  read :  — 

Prof.  V.  H.  Blackman,  F.R.S  A  T 
Legg,  and  F.  G.  Gregory.  The  Effect  of  a 
Direct  Electric  Current  of  venj  Low  Inten- 
sity on  the  Bate  of  Growth  of  the  Colcop- 
fde  of  Barlnj.  ^ 

Papers  read  in  title  only:  — 

Miss  R.  M.  Tupper-Carey  and  Prof.    J. 


JUNU  29,  1923. 


THE  CHEMICAL  NEWS. 


405 


H.  Priestley.  The  Composition  of  the 
Cell  Wall  at  the  Apical  Meristem  of  Stem 
and  Root.  Communicated  by  Dr.  F.  F. 
Blackman,  F.R.S. 

L.  J.  Harris.  The  Titration  of  Aviino- 
and  Carboxyl  Groups  in  Amino-Acids, 
Polypeptides,  etc.  Communicated  by  Prof. 
F.  G.  Hopkins,  F.R.S. 

Db.  M.  S.  Pembrky,  F.R.S.,  N.  W.  Mac- 
Keith,  W.  R.  Spurrrll,  E.  C.  Warner. 
and  H.  J.  Westlakk.  Observations  on  the 
Adjustment  of  the  Human  Body  to  Muscu- 
hir  Work. 

F.  A.  E.  Crew.  Studies  in  Intersexual- 
ity.  II. — Sex-reversal  in  the  Fowl.  Com- 
municated by  Prof.  R.  C.  Punnett,  F.R.S. 

Prof.  W.  Finkler.  Analytical  Studies 
on  the  Factors  causing  the  Sexual  Display 
in  the  Mountain  Newt  (Triton  alpestres). 
Communicated  by  Prof.  E.  W.  MacBrido, 
F.R.S. 

(i.  A.  SciIOTT,  F.R.S.  On  the  Srattcrini] 
of  X  and  y  Rays  by  Rings  of  Electrons — 
The  Effect  of  Damping  of  the  Incident 
Radiation. 

Major  P.  A.  MacMahon,  F.R.S.  On  a 
Class  of  Transcendents  of  which  the  Bessel 
Functions  are  a  Pariicv'nr  Cn-'c. 

L.  C.  Martin,  D.Sc.  The  Photometric 
Matchimf  Field.  Communicated  bv  Prof. 
H.  L.  Callendar,  F.R.S. 

G.  P.  Thomson.  Test  of  a  Theory  of 
Radiation.  Communicated  by  Sir  Jot^eph 
Thomson.  F.R.S. 

A.  Ll.  Hughes,  D.Sc,  and  P.  Lowe. 
Intensifies  in  the  Helium  Spectrum.  Com- 
municated by  Prof.  H.  A.  Wilson.  F.R  S. 

A.  .\.  Dee.  The  Effect  of  Quenching 
from  above  the  Carbide  Transition  Tem- 
perature upon  the  Magnetism  of  Steel. 
Communicated  by  Prof.  S.  W.  J.  Smith. 

T.  S.  P.  Strangeways  and  H.  E.  H. 
Oakley.  The  Immediate  Changes  obsen^rd 
in  Tissue  Cells  after  exposure  to  Soft  X- 
Raiis  while  growing  "  in  vitro."  Comnnmi- 
c.iti'.l  l)v  W."  B.  Hardv,  Sec.  R.S. 


Thursday,  June  21. 

CROONIAN  LECTURE,  by  F.  F. 
Blackman,  F.R.S.  The  Problems  of  Plant 
Respiration  considered  as  a  Catalytic  Pro- 
cess. 

In  recent  years  much  progress  has  been 
made  in  analysing  the  complex  series  of 
molocuhir  changes  that  are  summarised  in 
the  crude  equation  of  respiration, 
^-'eHi.Os  +  OO,  =  6CO3  +  6H3O,  and  it  is 
clear  that  catalytic  "Snzymes  of  protoplasm 
are  the  specific  agents  detennining  the 
sequence  and  magnitude  of  these  changes. 

In  this  lecture  an  attempt  is  made  to  face 
the  other  asipect  of  respiration,  which  is 
pi^culiarly  the  problem  of  plant  physiolo- 
gists. This  is  the  problem  of  the  meaning 
of  the  varj'ing  intensity  of  respiration  as 
shown  in  different  nutritional  states  of 
activity  of  the  same  cell,  in  the  different 
phases  of  dormancy,  development  and 
senescence,  and  in  experimental  conditions 
which  Ho  outside  natural  experience. 

Our  knowledge  of  this  wide  subject  is 
fragmentary,  but  a  useful  purpose  should 
be  served,  for  future  research,  by  an 
attempt  to  examine  these  variations  of  res- 
piratwy  intensity  in  terms  of  the  factors 
which  are  known  to  affect  the  rate  of  activ- 
ity of  catalytic  processes  of  the  type  studied 
in  vitro  as  enzyme  catalysis.  These  factors 
are  (1)  the  amount  of  the  catalytic  agent, 
(2)  the  concentration  of  the  substrate  acted 
upon,  (8)  the  presence  of  depressant  sub- 
stances which  reduce  the  effective  surface 
of  the  catalyst,  (4)  the  influence  of  end  pro- 
ducts of  activity  as  depressants  of  a  similar 
nature,  (5^  hydrogen  ion  concentration  con- 
trolling tne  dissociation  of  these  ampho- 
teric enzyme  catalvsts,  and  (6)  dehydrating 
agents  affectin;^'  tne  imbibition  and  water 
relations  of  the  catalyst. 

A  comipletc  formulation  of  biological 
variations  of  respiration  in  these  physico- 
chemical  terms  is  an  ultimate  goal  of  plant 
physiology;  at  present  we  are  only  at  the 
beginning,  determining  the  orientation  of 
future  researches. 

The  problem  that  may  first  be  considered 
in  some  detail  is  the  problem  of  the  relation 
of  respiration  intensity  of  a  cell  to  the  con- 
centration of  the  substrate,  hexose  sugar. 
Several  isolated  sets  of  data,  bearing  on 
this,  are  available.  With  plants  in  their 
natural  existence  this  relation  is  intimately 
linked  with  another  relation — that  of  the 
hydrolysis  of  starch  to  supply  the  substrate 
sugar  or  respiration.     This  is  illustrated  bv 


406 


THE  CHEMICAL  NEWS. 


JUNE  29,  1923. 


the  starch-sugar  balance  of  the  cell  and  its 
significant  variations  with  temperature. 

In  certain  natural  dormant  conditions  of 
vegetative  organs,  such  as  tubers,  and  in 
artificial  starvation  of  active  tissues,  the 
concentration  of  hexose  may  be  reduced 
apparently  to  zero.  Respiration  does  not 
then  cease,  but  is  maintained  at  a  certain 
definite  minimal  value.  At  this  phase  res- 
piration passes  out  of  its  normal  position  of 
being  merely  the  end  link  in  a  chain  of  float- 
ing carbohydrate  catabolism,  beneficially 
supplying  energy  for  the  service  of  meta- 
bolism, and  becomes  a  devastating  force. 
Jjaeking  the  "protection"  of  carbohydrates, 
nitrogenous  substances  now  undergo  oxida- 
tion; in  this  way  the  actual  texture  of  pro- 
toplasm seems  ultimately  to  be  destroyed, 
and  the  end  of  vital  organisation  takes  the 
form  of  sudden  failure  of  the  semi-per- 
meability of  the  protoplast. 

Variations  of  catalytic  activity,  by  steady 
seasonal  drift,  characterise  the  life-history 
of  individual  plant  organs.  These  are  most 
marked  in  the  phases  of  early  development, 
of  dormancy,  and  of  senescence;  here  the 
experimenter  has  to  face  the  difficulty  that 
the  essential  efficiency  of  respiration  may, 
under  constant  conditions,  not  be  abso- 
lutely the  same  on  any  two  succc^ssive  days. 
Some  of  these  phenomena  can  be  referred 
to  variations  in  the  amount  of  catalytic 
agent,  others  may  be  due  to  the  presence  of 
depressants. 

Variations  of  respiratory  intensity  may 
also  be  brought  about  by  the  accumulation 
of  the  end  product,  carbon  dioxide,  acting 
as  a  depressant  of  respiration.  The  quan- 
titative relations  indicate  that  carbon  di- 
oxide unites  with  the  catalyst  and  lowers 
its  effective  activity,  unless  it  can  escape 
adequately  by  diffusion. 

The  whole  of  the  relations  of  the  cataly- 
tic system  of  plant  respiration  outlined 
above  deal  with  normal  conditions  in  which 
adequate  oxygen  concentration  is  main- 
tained at  the  active  centres.  With  inade- 
quate oxygen  the  molecular  sequence  of 
changes  undergone  by  sugar  is  deflected  and 
there  is  set  up  a  new  system  of  relations, 
those  of  anaerobic  respiration,  which  are  at 
present  also  being  explored  quantitatively. 


THE  GEOLOGICAL  SOCIETY 
OF  LONDON. 

June  6. 

The     following      communications      were 
read:  — 


On  a  New  Blattoid  Wmg  from  the  Har- 
row Hill  Mine,  Drybrooh  (Forest  of  Dean), 
by  Herbert  Bolton,  D.Sc,  F.R.S.E., 
F.G.S. 

The  author  describes  a  new  type  of  fossil 
insect-wing  found  in  shale  on  the  waste- 
heap  at  the  Harrow  Hill  Mine,  and  since 
recognised  as  being  derived  from  the  roof  of 
the  Coleford  High  Delf  Seam.  The  speci- 
men was  discovered  by  students  of  the  Im- 
perial College  of  Science  and  Technology  in 
the  summer  excursion  of  1921. 

Coiitact-Metamorphism  in  the  Gomrie 
Area  of  the  Perthshire  Highlands,  by  Cecil 
Edgar  Tillev,  Ph.D.,  B.Sc,  F.G.S. 

Lantern-slides,  etc.,  were  exhibited  by 
Dr.  H.  Bolton;  and  rock-specimens,  micro- 
scope-sections, and  lantern-slides  were  ex- 
hibited by  Dr.  C.  E.  Tilley,  in  illustration 
of  their  respective  papers. 

A  meeting  of  the  Society  was  held  on 
Jiine  20,  when  Dr.  Herbert  H.  Thomas, 
M.A.,  V.P.G.S.,  gave  a  demonstration  on 
"  The  Source  of  Origin  of  the  Stones  of 
Stonehenge." 

The  following  communications  were 
read :  — 

The  River-Gravels  of  the  Oxford  Dis- 
trict, by  Kenneth  Stuart  Sandford,  B.A., 
F.G.S. 

The  Deposits  of  Paleocene  Mammalia  in 
Belgium,  by  Prof.  Louis  Dollo,  Sc.D., 
For.Mem.G.S.,  and  Prof.  P.  Teilhard  de 

CUARDIN,   D.Sc. 


PHYSICAL  SOCIETY  OF  LONDON. 

A  meeting  of  the  Societv  was  held  on 
Friday,  June  22. 

A  lecture,  entitled  The  Excitation  and 
Ionization  Potentials  of  Gases  and  Vapours, 
was  delivered  by  Prof.  F.  Horton,  M.A., 
D.Sc,  F.R.S.,  Royal  Holloway  College, 
University  of  London. 

Proceedings  at  the  meeting  held  on  June 
8,  Alexander  Russell,  M.A.,  D.Sc,  in  the 
chair. 

Prop.  .James  G.  Gray,  D.Sc,  F.E.S.E., 
Cargill  Professor  of  Applied  Physics  in  the 
University  of  Glasgow,  delivered  a  lecture, 
entitled  A  General  Solution  pf  the  Problem 


JUNE  29,  1923. 


THE  CHEMICAL  NEWS 


407 


of  Finding  the  True  Vertical  for  all  Types 
of  Marine  and  Aerial  Craft.  The  lecture 
was  accompanied  by  demonstrations  with 
gyroscopes. 

In  the  first  part  of  the  lecture  it  was 
shown  that  the  difficulties  presented  by  this 
problem  arise  from  the  horizontal  accelera- 
tions which  result  from  the  turning  of 
vehicles.  A  gyroscopic  pendulum  to  suc- 
ceed must  possess  a  real  precessTonal 
period,  or  a  virtual  processional  period  dur- 
ing turning  motion  of  the  vehicle  on  which 
it  is  mounted,  which  is  measured  in  hours. 

Pioneer  forms  of  Gray  stabiliser  were 
described.  These  were  devised  by  the 
author  and  his  brother  for  use  in  the  Royal 
Naval  Air  Service.  A  system  composed  of 
a  single  gyroscope  (mounted  with  its  axis 
normally  vertical)  and  an  erector  connect<»d 
rigidly  to  one  another,  is  pivoted  to  a  gim- 
l).il  frame  by  means  of  two  cross  pivots;  and 
this  frame  is  in  turn  attached  by  means  of 
fore  and  aft  pivots  to  uprights,  or  the 
equivalent,  carried  by  the  aeroplane.  The 
system  con)iposed  of  the  gyroscope  and 
erector  is  mounted  and  balanced  up  so  thnf 
the  centre  of  gravity  of  the  entire  system 
coincides  with  the  intersecticMi  of  the  pivot 
axes. 

Various  Uynm  of  erector  made  use  of  with 
these  pioneer  instruments  were  describofl 
and  their  dynamical  action  discussed.  On« 
form  consists  of  a  circular  track  carried  by 
the  pivoted  system,  and  so  arranged  that 
when  the  pivoted  system  is  upright  th. 
track  is  horizontal.  One,  two,  or  more  buIK 
rotate  on  the  track,  each  controlled  by  .» 
pusher  and  a  check  carried  by  a  member 
which  rotates  slowly  (about  12  revolutions 
per  minute)  In  the  direction  of  spin  of  the 
gyroscope.  When  the  system  is  upright 
the  balls  move  round  the  track  in  contact 
with  their  pushers,  and  form  a  balanced 
svstem.  When  the  system  is  inclined  to 
the  vertical  the  track  is  inclined  to  the  hori- 
zontal, and  each  ball  when  ascending  the 
slope  of  the  track  rests  against  its  pusher, 
but  after  crossing  the  crest  of  the  slope  it 
is  accelerated  down  the  track  and  rests 
against  its  check.  The  motion  of  the  balls 
relative  to  the  pushers  and  checks  results 
in  the  application  to  the  pivoted  system  of 
an  inti'gral  erecting  couple. 

It  was  shown  how  the  contrivance  could 
be  arranged  so  that  the  stabiliser  possessed 
the  prf<,perty  that  it  was  blind  to  the  appnr- 
ent  v<'rtical  during  turning  motion  of  an 
aeroplane    on  which    it  was  mounted,    hut 


conscious  (so  to  speak)  of  the  true  vertical 
during  the  ordinary  flight  of  the  aeroplane. 

These  pioneer  forms  of  the  instrument 
were  found  to  possess  an  accuracy,  for 
bombing  purposes,  amounting  to  one-eighth 
or  one-tenth  of  a  degree,  or  about  20  feet  on 
the  ground  from  a  height  of  12,000  feet. 

Previous  work  on  the  problem  failed  be- 
cause the  devices  produced  possessed  the 
property  that  they  left  the  true  vertical 
quickly  in  the  presence  of  the  accelerations 
which  accompany  turning  motions  of  the 
aeroplane,  and  returned  to  the  true  vertical 
tmly  very  slowly  after  the  resumption  of 
ordmary  flight.  The  pioneer  forms  of  Gray 
stabiliser  (when  properly  used)  moved  only 
very  slowly,  if  at  all,  towards  the  apparent 
vertical  when  the  aeroplane  was  turning, 
and  after  the  resumption  of  ordinary  flight 
moved  towards  the  true  vertical  (su,pposing 
an  error  to  exist)  relatively  quickly. 

Finally  the  latest  forms  of  Gray  stabiliser 
were  described.  These  set  themselves  into 
the  true  vertical  even  when  the  vehicles  on 
which  they  are  mounted  are  turning,  and 
this  holds  for  all  speeds  of  turning.  Con- 
trf>l  is  never  lost.  This  result  is  obtained 
by  constructing  the  apparatus  so  that  a 
horizontal  component  of  spin  lies  across  the 
pivoted  system,  that  is,  parallel  to  the  cross 
pivots.  The  pivoted  system  is  mounted  so 
as  to  be  pendulous  with  respect  to  the 
|)iyot8,  and  the  direction  of  the  horizontal 
spin,  and  its  amount,  is  arranged  so  that 
when  the  vehicle  turns  there  comes  into 
existence  a  gyroscopic  couple,  applied  about 
the  fore  and  nft  pivots,  which  is  exactly 
equal  and  opposite  to  the  so-called  centrifu- 
gal couple  applied  to  Ehe  ipivoted  system. 
Both  couples  are  proportional  to  the  angu- 
lar speed  at  which  the  vehicle  turns,  and 
both  change  sign  with  that  of  the  turning 
motion.  Hence  the  compensation  is  cor- 
rect for  ail  speeds  of  turning. 

This  type  of  stabiliser,  when  fitted  with 
special  erectors,  a  simple  example  of  which 
was  describefl,  supplies  a  complete  solution 
of  the  vertical  problem.  Assuming  an  error 
made  (small)  in  adjusting  the  compensat- 
ing component  of  spin  the  resting  position 
of  the  device  is  one  in  which  it  is  inclined  to 
the  true  vertical  at  a  very  small  angle.  The 
'Jevices  solve  the  problem  completely  for 
the  ra/pid  and  slow  turning  movements  of 
aeroplanes,  and  for  the  turning  motions  of 
ships. 

PrscTi.ssioN. 

Sir  James  Henderson,  after  compliment- 


408 


THE  CHEMICAL  T^EWS. 


JUNE  29,  1923. 


ing  Professor  Gray  on  his  lecture,  referred 
to  the  great  difficulties  of  the  problem. 
These  difficulties  vary  with  the  accuracy 
aimed  at.  If  it  be  only  required  to  main- 
tain the  vertical  within  one  degree  the  prob- 
lem is  very  easy,  but  if  it  be  requireld  to 
maintain  it  within  one  minute  of  arc  the 
difficulties  are  very  great,  almost  if  not 
quite  unsurmountable.  The  difficulties  in- 
crease almost  as  the  square  of  the  accuracy 
aimed  at. 

Professor  Gray  had  concentrated  upon 
the  problem  of  the  bomb-drqpping  sight  for 
aircraft,  and  had  achieved  considerable 
success  during  the  war.  The  practical 
accuracy  then  aimed  at  in  this  connection 
was  to  maintain  the  vertical  to  about  ^  de- 
gree, and  to  this  degree  of  accuracy  Profes- 
sor Gray  had  attained,  as  stated  in  his  lec- 
ture. 

The  accuracy  of  any  instrument  of  this 
type  could  be  calculated  accurately  if  the 
method  of  control  were  continuous.  In 
Professor  Gray's  instrument  the  method  of 
control  involves  a  discontinuity  which  does 
not  lend  itself  to  easy  computation.  There 
are  other  methods  of  control,  however, 
which  are  continuous  and  which  enable 
accurate  calculations  to  be  made. 

Professor  Gray  had  said  nothing  in  his 
lecture  to  give  any  idea  of  the  amount  of 
damping  he  employed.  This  determines 
the  accuracy,  because  if  the  damping  be 
very  great  the  gyro  follows  the  virtual  ver- 
tical at  corresponding  rates  and  the  devia- 
tion increases  accordingly.  On  the  other 
hand,  if  the  damping  be  greatly  diminished 
a  considerable  deviation  arises  from  -  the 
rotation  of  the  earth  and  a  connection  to 
the  gyro-compass  is  required  to  compensate 
it.  Thus  when  great  accuracy  is  required 
the  problem  becomes  excessively  difficult. 

Professor  Gray's  method  of" eliminating 
the  effects  of  the  centrifugal  force  during 
a  turn  was  ingenious.  If  the  speed  adjust- 
ment be  perfect,  then  any  deviation  which 
the  pendulum  has  relatively  to  the  vertical 
at  the  beginning  of  the  turn  turns  azimuth 
with  the  plane.  The  deviations  due  to  any 
change  of  velocity  either  fore  or  aft  or  dur- 
ing a  turn  are,  however,  not  so  easily  com- 
pensated. 

M.  Paul  Schilowsky  said  that  naval  ex- 
perts ask  for  a  degree  of  accuracy  which 
must  be  the  despair  of  gyroscopic  inventors, 
but  accuracy  to  a  degree  or  half  a  degr&e  of 
angle  is  by  no  moans  unattainable.  He  had 
tried  a  different  solution  from  that  given 
by  the  lecturer,    viz.,    that  of    suspending 


the  gyroscopic  pendulum  in  neutral  equiH- 
brium  on  knife  edges  passing  through  its 
centre  of  gravity.  In  time,  however,  pre- 
cession takes  place  with  this  arrangement, 
and  the  penduluna  errs  progressively  froni 
the  true  vertical.  What  is  required  is  that 
the  pendular  suspension  should  be  neutral 
for  curved  motion  but  stable  for  rectilinear 
motion.  Sir  James  Henderson  has  designed 
an  instrument  for  indicating  the  curvature 
of  the  path  of  the  aeroplane.  A  combina- 
tion of  the  two  devices  should  make  it  pos- 
sible to  meet  the  requirement  mentioned. 
The  lecturer's  plan  was  open  to  the  objec- 
tion that  very  raipid  changes  of  rotary  speed 
in  the  gyroscope  would  be  necessary  to  com- 
pensate for  the  rapidity  with  which  an  aero- 
plane changes  its  linear  speed.  His  admira- 
tion for  the  lecturer's  work  was  sincere, 
and  he  should  expect  great  results  if  the 
latter  would  take  up  the  problem  of  altering 
the  suspension  of  the  gyroscope  accwding 
to  the  curvature  of  the  path. 

Mr.  T.  Smith  said  that  all  present  would 
have  followed  the  lecture  with  the  greatest 
interest.  It  was  not  easy,  however,  for 
those  less  familiar  than  the  lecturer  with 
the  practical  handling  of  gyroscopic  appara- 
tus to  appreciate  all  the  points  at  issue  in 
the  absence  of  a  formal  mathematical  treat- 
ment. Possibly  mathematical  difficulties 
would  arise  from  the  discontinuities  which 
had  been  mentioned  by  Sir  James  Hender- 
son, but  the  modern  methods  for  dealing 
with  discontinuous  quantities  developed  in 
connection  with  the  quantum  theory  might 
perhaps  give  a  hint  as  to  the  line  of  attack 
to  be  adopted  in  the  present  case. 

The  lecturer,  in  reply  to  the  discussion, 
dwelt  mainly  on  the  point  raised  by  M. 
Schilowsky,  and  claimed  that  his  apparatus 
did  become  automatically  "blind"  during 
curved  motion  of  the  aeroplane  in  a  manner 
satisfying  M.  Schilowsky's  requirement. 
The  effect  of  the  earth's  rotation  on  the 
gyroscope  is  very  small  provided  the  preccs- 
sional  period  is  long. 

The  President  congratulated  the  lecturer 
on  his  solution  of  an  important  and  difficult 
iproblem,  and  proposed  a  vote  of  thanks, 
which  was  carried  with  acclamation. 


SOCIETY  OF  GLASS  TECHNOLOGY. 

The  last  ordinary  meeting  of  the  Society 

for  the  session  1922-23    was  hold  in  Leeds 

on  June  20.     Prof.  W.  E.  S.  Turner,  D.Sc., 

read    a  paper    on    "  Specifications    in    the 


JUNE  29,  1923. 


THE  CHEMICAL  NEWS 


400 


Glass  Industry."  He  pointed  out  that  cer- 
tain types  of  glass,  such  as  that  used  for 
optical  purposes,  were  bought  oa  specifica- 
tion, and  had  to  conform  strictly  to  certain 
{)roperties.  In  the  enormous  industry, 
however,  which  was  concerned  in  the  pro- 
duction of  such  things  as  containers  for 
liquids  and  solids,  no  one  seemed  to  have 
attempted  to  make  or  even  purchase  on  this 
basis.  Cases  had  arisen  which  had  eunpha- 
sised  lack  of  precision.  For  example,  a  re- 
cent law  case  was  fought  round  the  quality 
of  bottles  supplied,  and  from  the  evidenet- 
it  was  quite  evident  that  the  actual  quality 
ol  the  glass  did  not  seeni  to  have  been 
specified.  Several  other  cases  had  arisen, 
pointing  to  the  need  of  deciding  to  what 
spcification  different  glass  articles  should 
conform.  If  the  industry  was  to  insist  on 
fumact!  material  makers  providing  refrnc- 
tories,  to  specification,  then  the  glass  manu- 
facturers nmst  show  they  were  prepared  lo 
su(pply  their  goods  to  specification.  Prof. 
Turner  dealt  with  specificaticms  which 
might  be  made  the  working  basis  for  such 
articles  as  medicine  bottles,  beverage 
bottles,  ami  other  types  of  container. 

Mr.  Tu.  Teisen,  B.Sc,  contributed 
Some  Notes  on  the  Design  of  Pot  Arches. 
his  remarks  being  illustrated  by  lantern 
slides. 

Criticising  the  old  type  of  pot  arch,  Mr. 
Teisen  said  the  flue  outlet  for  burnt  gases 
at  the  back  wall  near  the  bottom  gave  cold 
pockets  inside  the  furnace.  On  the  (ither 
blind,  the  ensuing  lack  of  .proper  heat  dis- 
tribution could  be  somewhat  helped  by 
longer  soaking.  The  fire  boxes  being  open, 
the  fire  itself  was  not  under  proper  control. 

The  Continental  tyiix-,  with  direct  fired 
furnace,  fire-box  below,  combustion  flues 
and  air  flues  leading  to  the  uptake  at  the 
back  of  the  chamber,  and  fumes  passing 
through  holes  in  the  fl(K>r  near  the  front  and 
thence  to  the  chimney,  was  better  but  not 
so  practical.  With  the  entry  of  the  gas- 
fired  pot  furnace  in  the  glass  industry,  a  de- 
mand had  arisen  or  a  more  modem  type  for 
heating  pots.  That  type  should  contain 
Ix'tter  facilities  for  heat  ili^tribution  and 
control;  it  should  also  combine  good  con- 
ditions for  working  and  firing  with  easy  in- 
stallation and  economy  of  space.  A  gas- 
fired  recuperative  pot-arch,  designed  on 
these  lines  some  years  ago,  and  which 
proved  a  supx5ess,  was  described,  as  well  as 
a  pot-arch  at  Messrs.  MoncrieflF's.  wlien*. 
(luring  th«>  first  stage  of  burning,  a  low  fin- 
was  kept  on  the  grate,  fed  through  the  ash 
door.     The  secondary  air  sliile  was  closed. 


and  the  furnace  was  in  other  ways  directly- 
fired.  For  the  purpose  of  driving  out 
natural  and  combined  water  without  pro- 
ducing surface  cracks,  water  was  kept 
drippmg  on  the  firebars,  as  well  as  on  a 
plate  tu-ranged  iu  front  of  them,  thereby 
producing  a  certain  amount  of  steam,  which 
lielped  to  retard  a  too  quick  drying  of  the 
surface  parts  and  allowed  tiie  inside  to 
evaj)orate  its  moisture  at  the  same  rate  as 
lUe  outside.  The  steam  produced  made  it 
necessary  to  run  with  the  usual  density  of 
smoke.  That  type  took  up  little  space  with 
propoitionately  less  building  cost,  and  re- 
sults in  |)ractice  were  quite  satisfactory. 

Mr.  JS.  Enolisii,  M.Sc,  gave  a  paper 
entitled  \oics  on  the  Ashley  Buttle 
Machine.  He  remarked  that  to  one  fami- 
liar only  with  modem  glass  forming 
machines,  it  might  be  surprising  to  hear 
that  the  home  of  bottle  maJdng  machinery 
was  on  this  side  of  tne  Atlantic,  but  such 
was  the  case,  and  it  was  only  after  the  pos- 
sibility of  making  narrow  mouth  bottles 
satisfactorily  by  machines  had  been  proved 
here,  that  such  bottle  making  machinery 
was  introduced  in  America.  The  first 
machine  to  make  narrow  mouth  bottles  at 
all  satisfactorily  wan  designed  and  built  by 
H.  M.  Ashley  in  W^rshire.  About  1866,  Jo- 
siah  Arnall,  ^xtstmaster  at  Ferrybridge,  con- 
ceived an  jdea  which  would  enable  bottles 
to  be  blown  by  machinery.  He  submitted 
his  idea  to  a  bottir  manufacturer,  but  ap- 
parently it  was  loo  crude  or  too  revolution- 
ary. Nearly  twenty  years  later,  H.  M. 
Ashley,  the  manager  of  an  iron  foundry 
near  the  post  office,  went  to  live  with  Ar- 
nall, and  there  can  be  no  doubt  that  Amall 
discussi'd  with  Ashley  his  ideas  concerning 
the  poHsibility  of  blowing  bottles  by 
machinery. 

As  a  result  of  such  discussion,  Ashley 
built  an  experimental  machine  in  which 
glass  was  poured  into  an  inverted  mould, 
which  was  fitted  with  a  plug  to  form  the  in- 
side of  the  neck  and  with  a  movable  top 
plungi-r.  When  a  charge  of  glass  had  been 
placed  in  the  mould,  the  sliding  plunger 
was  brought  down  on  top  of  it,  thus  press- 
ing it  down  around  the  fixed  plug  and  form- 
ing the  neck.  Compressed  air  was  then  ad- 
mitted through  the  plug,  blowing  up  the 
bottle  and  at  the  same  time  raising  the 
sliding  plunger,  to  the  desired  «!xtent.  Such 
an  arrangement  was  very  simple,  and  was 
naturally  unsuccessful,  but  it  had  sufficient 
good  points  to  cause  Ashley  to  try  to  de- 
velop it  into  a  useful  machme.       The  first 


410 


THE  CHEMICAL  NEWS. 


JUNE  29,  1923. 


step  in  its  improvement  apipeared  to  have 
been  an  appreciation  of  the  fact  that  three 
moulds  were  necessary,  one  for  forming  the 
neck  of  the  bottle,  the  second  for  giving  a 
preliminary  form  to  the  main  body  of  the 
glass,  and  the  third  for  blowing  the  finished 
bottle.  This  provision  of  a  ring  mould, 
parison  mould  and  blow  mould  was  the 
foundation  on  which  all  Ashley's  experi- 
mental machines  were  built,  and  has  been 
incorporated  in  every  successful  machine 
since. 


MINERALOGICAL  SOCIETY. 

June  19. 

Dr.  A.  Hutchinson,  F.R.S.,  President,  in 
the  chair. 

Dr.  L.  J.  Spencer  (with  chemical  analy- 
ses by  E.  D.  Mountain) :  New  copper-lead 
Minerals  from  the  Mendip  Hills  (Somerset). 

Mendipite  (2PbO.PbCl2),  which  occurs 
as  crystalline  nodules  in  manganese-ore,  is 
recorded  from  new  localities.  Chlorox- 
iphite  (2PbO.Pb(OH)2.CuCl2)  as  green 
monoclinic  blades  resembling  epidote,  and 
Diaboleite  (2Pb(OH),.GuCl2)  as  bright-blue 
tetragonal  plates  resembling  boleite,  both 
occur  embedded  in  the  mendipite.  Hydro- 
cerussite  (2PbC03.Pb(OH)2)  is  abundant, 
sometimes  as  large  crystals  (i.e.,  crystal- 
lised "white  lead").  Crednerite  (CuO.- 
MngOg)  forms  fan-like  aggregates  of  thin 
plates.  Pyromorphite,  which  some  cen- 
turies ago  was  evidently  an  important  ore 
of  lead  in  the  Mendips,  has  been  preserved 
(together  with  mendipite,  hydrocerussite, 
etc.)  in  the  Woodwardian  collection  (1728) 
at  Cambridge.  Wulfenite  and  mimelite 
have  been  found  at  Higher  Pitts,  near 
Priddy.  The  various  minerals  show  pro- 
gressive stages  of  alteration  with  some  well- 
marked  pseudomorphs :  mendipite— ^hydro- 
cerussite -^  cerussite ;  chloroxiphite  -> 
hydrocerussite  +  malachite  I  cerussite  + 
crednerite  — ^  malachite  II. 

W.  F.  P.  McLintock:     On  a  petaWe- 
hearing  Rock  from  Devonshire. 

The  well-known  aplite  from  Meldon,  in 
Devonshire,  is  shown  to  have  developed  in 
certain  parts  of  the  intrusion  a  soda-litliin 
iphase  rich  in  the  rare  lithium-aluminium 
silicate,  petalite.  This  mineral,  not  pre- 
viously known  from  Britain,  occurs  as  one 


of  the  final  products  of  consolidation  of  the 
aplite  either  in  coarse-grained  veins  of  peg- 
matite, associated  with  quartz,  orthoclase, 
aibite,  a  lithia-bearing  mica,  tourmaline, 
and  apatite,  or  as  irregularly-shaped  masses 
throughout  the  rock  itself.  The  petalite 
gives  rise  by  decomposition  to  the  pink  clay, 
montmorillonite,  so  well-known  from  this 
locality.  Certain  other  veins,  free  from 
petalite,  are  also  present,  the  most  inter- 
esting constituents  of  the  rarer  types  being 
prehnite,  axinite  and  a  pleochroic  cordier- 
ite.  The  apatite  in  the  aplite  is  shown  to 
be  a  pneumatolytio  mineral,  occurring  not 
only  in  the  rock  as  ophitic  patches  enclos- 
ing quartz  and  felspar,  but  also  impregnat- 
ing certain  xenoliths  of  ipeculiar  type. 
Deep-blue  crystals  developed  in  the  druses 
of  a  coarse  grained  modification  of  the 
aplite  and  associated  with  pink,  yellow,  and 
green  tourmaline,   are  described. 

A.  BuAMMALL  and  H.  F.  Harwood  :  The 
accessory  Minerals  of  the  Dartmoor  Qran- 
ite. 

The  complete  list  of  minerals  identified 
by  the  authors  is  as  follows :  Biotite  and 
muscovite;  tourmaline,  topaz,  fluor;  zircon, 
apatite,  monazite,  garnet,  sphene,  and  pale 
amphibole  (edenite);  ilmenite,  magnetite, 
pyrites,  pyrrhotite,  and  molybdenite ;  gold 
and  silver;  rutile,  brookite,  anatase,  cassi- 
terite,  and  specular  iron  ore;  barytes  and 
allanite;  andalusite,  sillimanite,  cordier- 
ite,  spinel,  and  corundum.  Tourmaline 
originated  at  fwo  stages  in  the  cooling  his- 
tory of  the  intrusion :  (1)  pre-solidification 
— primary  and  secondary;  (2)  post-solidifi- 
cation— secondary.  The  more  severe  and 
widespread  pneumatolysis  and  the  lodes 
are  referred  to  a  post-solidification  stage. 

Seitaro  Tsuboi  :  Optical  dispersion  of 
Three  Intermediate   Plagioclases. 

The  principal  refractive  indices,  a,  ft,  y, 
of  (1)  oligoclase  from  Hawke  Mine,  Bakers- 
ville.  North  Carolina;  (2)  andesine  from 
Maeyama,  Shinano,  Japan;  and  (3)  labro- 
dorite  from  County  Down,  Ireland,  for  light 
of  9  different  wave-lengths  (700,  671,  644, 
610,  589.3,  554,  535,  527,  508.57r;r)  were  de- 
termined. The  optical  orientations  of  the 
first  and  the  third  of  the  above  three  fels- 
pars, for  light  of  5  different  wave-lengths 
(700,  644,  589.3,  535,  508.5^/i)  were  also 
determined. 


JUNE  29,  1923. 


THE  CHEMICAL  NEWS. 


411 


Seitaro  Tsuboi  :  A  Dispersion  Method 
of  Determining  Plagioclases  in  Cleavage- 
Flakes. 

This  new  method  is  based  on  the  prin- 
ciple of  H,  E.  Merwin's  improved  immer- 
sion method.  By  means  of  a  diagram  a 
quick  and  exact  determination  of  plagio- 
clases is  possible.  It  is  applicable  to  such 
small  crystals  as  are  common  in  rocks, 

G.  S.  Garnett  :  The  "Toadstone-clays" 
of  Derbyshire. 

The  olivine-dolerites  ("toadstones")  of 
Derb^  shire  under  two  types  of  alteration  : 
(1)  by  ordinary  weathering  to  limonite  or 
ochreouH  deposits;  (2)  in  the  absence  of  \ 
o.xidising  agents  under  a  limestoile  cover- 
ing, they  may  pass  through  dolerite-green- 
stone  and  "green-earth"  to  a  greenish - 
white  or  almost  white  clay  ("toadstonr 
clay")  with  the  composition  2Al,0,.6SiOj.- 
SHjjO. 

Db.  G.  T.  Priob:  The  Meteoric  Stone 
which  tvas  seen  to  fall  at  Ashdon,  near  Saf- 
fron Walden,  Essex,  on  March  9,  1923. 

The  stone,  which  weighed  about  l,3f)0 
grams,  is  a  white  chondrite  showing  on  one 
face  well-marked  radiating  lines  of  flow  of 
the  fused  crust. 


Dr.  G.  T.  Prior:  The  Sinai  Meteoriic. 

The  meteoric  stone  of  1,455  grams  which 
was  seen  to  fall  near  Kantarah,  in  the 
north  of  the  Sinai  Peninsula,  in  July,  1916, 
is  an  intermediate  hypersthene-chondrito. 
having  a  percentage  of  nickeliferous  iron  of 
about  8.6,  in  which  the  nickel  amounts  to 
about  15  per  cent. 

G.  Greenwood:  Communicationa  from 
the  Crystallographio  Laboratory  of  the  Uni- 
versity of  Manchester.  No.  1  :  The  Detec- 
tion of  Rotatory  Polarisation  in  an  Ortho- 
rhombic  Crystal  exhibiting  Crossed  .ixial 
Dispersion. 

A  plate  perpendicular  to  the  acute  bisec- 
trix of  a  crystal  of  tri-iphenyl-hismuthine  di- 
chloride,  when  in  the  extinction  position, 
transmits  a  brilliant  green  monochromatic 
light  duo  to  circular  polarisation. 

A.  F.  Hallimond:  The  Chemical  ChtHHi- 
fication  of  the  Mica  Qroup  I. — The  Acid 
Micas. 


THE  COLOUR  USERS'  ASSOCIATION. 

The  Annual  :Meeting  of  The  Colour 
Users'  Association  was  held  at  The  Milton 
Hall,  Deansgate,  Manchester,  on  June  19, 
Mr.  H.  Sutcliffc  Smith  presiding. 

Throughout  the  year  many  conferences 
had  been  held  between  the  users'  represen- 
tatives of  this  Committee  and  the  Council, 
at  which  ditiiculties  and  grievances  had 
been  discussed  with  beneficial  effect.^  Ap- 
plications on  the  ground  of  superiority  of 
foreign  quality  were  now  dealt  with  expe- 
ditiously. The  chief  difficulty  was  with  re- 
gard to  applications  because  o!  price  differ- 
ences. The  Licensing  Committee  officially 
informed  the  Association  on  September  30 
last  that,  as  a  temporary  measure,  applica- 
tions would  be  granted  where  the  British 
prices  were  more  than  three  times  pre-war 
level  and  where  higher  than  the  current 
f foreign  prices.  When  an  application  was 
made  for  a  licence  the  user  had  to  state  the 
prict'  at  which  he  could  buy  the  foreign 
colour,  if  the  colour  could  be  made  in  this 
cfHintry,  the  British  makers  were  given  the 
opportunity  of  taking  the  business  at  the 
foreign  price  (juoted.  or  at  three  times  pre- 
war price,  whichever  was  the  higher.  If 
the  makers  could  not  accept  the  order  on 
this  basis,  then  a  licence  was  granted  to  the 
users  to  import.  It  was  understood,  how- 
ever, that  the  makers'  representatives  on 
the  Licensing  Committee  only  agreed  to 
meet  this  foreign  price  competition  pro- 
vided financial  assistance  was  furnished  to 
the  dye  manufacturers  by  the  Government. 
The  makers  definitely  state  they  cannot  at 
present  bring  their  prices  down  to  thre(> 
times  pre-war  level  without  financial  as- 
.si  stance. 

Prices  of  Dye  wares. 

The  import  prices  of  dyes  and  dyestuffs, 
:i>  recorded  in  the  Hoard  of  Trade  Returns, 
are  at  a  very  bif^h  level.  For  finished  Coal 
Tar  dyestuffs  (exclusive  of  Indigo  and  .Mi- 
zarine),  the  following  are  the  averaged 
prices  per  pound :  Hn3,  lis.  7d. ;  1020. 
79s.  2d.;  1921,  66s.  7d. ;  and  1922,  65s.  9d. 
Many  conferences  have  been  held  through- 
out the  year  with  the  makers  and  with  the 
Board  of  Trade  on  this  subject.  The  users' 
request  to  reduce  prices  to  200  per  cent, 
above  pre-war  was  not  on  unreasonaT)lo 
one,  but  the  mak(>rs  had  stated  lliat  with- 
out financial  assistance  they  could  not  pos- 
sibly get  down  to  a  basis  selling  price  of  a 
maximum    of   three    times    pre-war.      The 


412 


THE  CHEMICAL  NEWS. 


JUNE  29,  192S. 


whole  cost  of  establishing  the  dye-making 
industry  in  this  country  was  now  being 
borne  by  the  users.  There  was  a  further 
serious  aspect  of  this  situation  which  re- 
quired to  be  considered,  and  that  was  the 
effect  of  the  high  prices  of  British  products 
upon  the  prices  of  foreign  colour  sold  in 
this  country.  The  British  makers  were 
not  the  sole  beneficiaries  of  these  high 
prices,  for  the  foreign  producer  undoubtedly 
took  full  advantage  of  the  artificial  condi- 
tion of  the  British  market  consequent 
upon  the  Prohibition  Act. 

Reparation  Dyestuffs. 
A  deputation  from  the  Council  had  had 
an  opportunity  of  visiting  the  ofl&cial  in 
charge  of  the  dyestuffs  section  of  the  Re- 
paration Commission  in  Paris.  Germany 
furnished  a  list  monthly  of  25  per  cent,  of 
its  output,  which  was  available  for  the 
Allies,  who  were,  within  a  stiipulated  period, 
requii'ed  to  indicate  the  quantities  of 
colours  they  desired  according  to  agreed 
proportions.  This  country's  share  was 
about  4  per  cent,  of  the  25  per  cent.  It 
was  found,  in  practice,  however,  that  the 
U.K.  proportion  of  25  per  cent,  of  Ger- 
many's output  of  a  great  many  special 
types  of  dyes  was  short  of  this  country's 
actual  needs;  on  the  other  hand,  there  were 
large  quantities  of  dyestuffs  available 
which  were  of  no  interest  to  us.  After  seve- 
ral conferences,  it  was  arranged  that  the 
German  makers  should  supply  more  than 
25  per  cent,  of  specific  dyes  on  Reparation 
Account,  provided  that  quantities  were  not 
taken  in  excess  of  the  home  consumption, 
that  the  export  prices  were  credited  to  Ger- 
many for  all  quantities  above  25  per  cent. 
of  each  specific  dyeware,  and  that  the  total 
quantities  were  not  in  excess  of  25  per 
cent,  of  Germany's  total  production  stipu- 
lated under  the  Committee.  At  the  begin- 
ing  of  each  quarter,  the  Allies  were  called 
upon  to  lodge  with  the  German  makers  par- 
ticulars of  their  requirements  under  this 
new  arrangement,  whereby  the  German 
makers  would  make  certain  specific  colours, 
which  were  charged  on  the  following  basis : 
50  per  cent,  at  the  world's  lowest  price 
(generally  the  internal  German  price). 

50  per  cent,  at  the  lowest  price  the  I.G. 
shall  have  sold  at  in  the  receiving  coun- 
try during  the  month  preceding  the 
month  of  delivery,  or  during  the  month  of 
delivery,  whichever  is  the  lower. 
Tlie  users  consider  this  new  arrange- 
ment of  considerable  advantage  to  them,  in 


that  it  is  a  satisfactory  means  of  oBtaining 
through  reparation,  colour  either  not  made 
here  or  not  made  in  adequate  quantities. 

Unfortunately,  however,  the  price  ruling 
in  this  country  which  regulates  50  per  cent, 
of  the  quantities  so  imported  is  an  arbitrary 
one,  since,  if  the  bulk  of  the  colour  is  taken 
under  Reparation,  there  is  no  competitive 
market;  the  result  is  that  the  I.G.  can 
charge  such  a  figure  for  50  per  cent,  of  the 
colour  as  the  resultant  average  with  the  re- 
mainder at  the  internal  German  price  gives 
them  a  substantial  overall  selling  price. 
The  Association  was  in  close  contact  with 
the  officials  in  charge  of  Reparation  dye- 
stuffs  in  Paris,  and  it  was  hoped  to  bring 
before  them  more  adequately  the  users' 
needs  and  requirements  at  regular  intervals, 
and  in  such  a  form  as  would  be  of  practi- 
cal assistance  to  them  in  the  taking  over  of 
Reparation  colour.  According  to  the  infor- 
mation furnished  by  the  Board  of  Trade,  it 
was  obvious  that  this  country  was  not  mak- 
ing the  fullest  use  of  the  facilities  afforded 
by  the  Reparation  Committee,  and  he 
would  suggest  that  the  whole  procedure  of 
obtaining  Reparation  dyestuffs  should  now 
be  reviewed  in  the  light  of  the  exiperiencc  of 
the  past  two  years. 

Pricing  of  Reparation  Dyestuffs. 

Upon  several  occasions  it  had  been  stated 
in  the  House  of  Commons  that  prices  had 
been  revised  from  time  to  time  by  repre- 
sentatives of  the  Colour  Users'  Association. 
This  was  not  quite  in  accordance  with  the 
actual  facts.  The  Association  had  pro- 
tested on  many  occasions  against  the  high 
prices  of  Reparation  dyestuffs,  and  they 
had  had  considerable  correspondence  with 
the  Board  of  Trade  upon  the  subject. 

British    Dyemakers. 

At  the  last  annual  meeting  he  submitted 
three  distinct  suggestions  bearing  on  the 
establishment  of  the  dye  making  industry 
with  particular  reference  to  the  British 
Dyestuffs  Corporation,  Limited,  namely:  — 
(1)  That  the  Government  should  wijpe  out 
their  loan  to  the  Company;  (2)  that  the 
Company  should  face  a  scheme  of  recon- 
struction; (3)  that  the  Directors  should 
eventually  see  their  way  to  arrange  that  the 
Corporation  shall  be  managed  by  men  who 
have  been  brought  up  in  the  industry,  on 
the  lines  of  the  big  textile  associations. 

Much  progress  had  undoubtedly  been 
made  by  this  Corporation  in  the  variety 
and  types  of  the    colours  which  they    now 


•TUNE  29,  1923. 


THE  CHEMICAL  NEWS. 


413 


made,  and  in  the  improvement  in  their 
quality,  but  there  was  considerable  dissatis- 
faction atiioij},'  the  usei*s  on  the  question  of 
high  prices.  He  wanted  to  make  it  per- 
fectly clear  that  the  users  did  not  ask  the 
makers  to  bring  their  prices  down  to  the 
general  economic  iprice  level,  but  the 
makers  stated  they  could  not  effect  any 
further  reductions  without  serious  losses. 


FOURTH  INTERNATIONAL 

CONFERENCE  ON  PURE  AND 

A  PPT  JED  CHEMISTRY. 

The  Fourth  Intc^rnational  Crmference  on 
Pure  and  Applied  Chemistry  was  held  from 
June  18  to  20  at  Cambridge.  Various  re- 
ports were  presented,  and  four  scientific 
communications  were  rec('iv<d  and  dis- 
cussed. 

Among  the  matters  considered  were  the 
reforms  in  the  nomenclature  of  inorganic 
and  organic  chemistry,  and  the  compilation 
of  tables  of  constants. 

Certain  matters  of  importance  in  indus- 
trial chemistry,  such  as  the  preservation  of 
foodstuffs,  and  standardisation  in  various 
chemical  industries  were  discussed. 

Prof.  J.  W.  McBain.  F.R.S..  read  a 
paper  on  The  Study  of  Sooj)  iSnlntions  am} 
its  braring  upon  Colloid  Chr wintry. 

The  author  pointed  out  that  the  study  of 
soaps  has  ho  many  ramifications,  and  the 
phenomena  met  with  are  so  manifold,  that 
it  is  only  by  the  exercise  of  the  severest  le- 
striction  that  a  clear,  general  picture  can 
be  obtained.  Sonips,  nevertheless,  lend 
themselves  particularly  to  a  study  of  the 
colloidal  condition  ana  its  relation  to  other 
states.  He  dealt  with  the  properties  of 
fluid  solutions  and  clear  transparent  jellies 
in  the  state  of  complete  true  reversible 
equilibrium. 

Dilute  soap  solutions  are  ordinary  crystal- 
loids, whereas  more  concentrated  ones  are 
colloidal  electrolytes.  Excess  of  soap 
above  a  saturation  alue  separnt<^s  out  in  the 
form  of  true  crystals.  The  transpan-nt 
jellies  an>  confined  to  a  portion  of  the 
region  in  which  the  soap  is  n  colloidal  elec- 
trolyte. Many  soaip  solutions  afford  ex- 
amples of  anisotropic  liquids. 

Dr.  E.  K.  Rideal  read  a  paper  on  Recent 
Developments  in  Contact  Catalysis.  It  is 
now  generally  admitted  that  contact  cata- 


lysis proceeds  through  actual  contact  of  the 
reactants  with  the  catalytic  material,  al- 
though the  actual  mechanism  by  which  re- 
action is  caused  may  be  brought  about  by 
means  other  than  molecular  collision,  such 
as  radiation  or  electron  transfer.  The 
author  discussed  diffusion  as  a  factor  rn 
catalytic  change,  the  influence  of  poisons  on 
catalysts,  the  nature  of  adsorption  com- 
pounds, promoter  action,  etc. 

Prof.  J.  F.  Thorpe  read  a  paper  by  him- 
self and  Dr.  C.  K.  Ingold  on  Some  New 
Aspects  of  Tautowerism,  in  which  he  de- 
fined the  term  tautomerism  and  dealt  with 
1  tautomerism  involving  the  movement  of 
a  hydrogen  atom  and  2  tautomerism  which 
does  not  involve  this  movement.  The  re- 
port was  based  upon  the  authors'  own  con- 
tributions on  the  subject. 

Prof.  F.  G.  Hopkins  gave  a  report  on  the 
Mechanism  of  Oxidation  in  the  liiving 
Body.  He  reviewed  the  previous  work  on 
this  subject,  and  drew  attention  to  the 
problems  encountered. 

These  reports  were  discussed  at  sittings 
of  the  confeience. 


CORRKSl'oNDENCE. 


.\NALYSIS  OF  ANCIENT  BRONZE. 
To  the  Editor  of  The  Chemical  News. 

Sir, — Analysis  of  several  bronze  relics 
dating  to  the  Phcenician  and  Assyrian 
periods  refute  the  belief  that  the  bronzes  of 
this  time,  in  some  cases,  were  artificial. 
The  unequal  distribution  of  the  constituents 
coupled  with  the  presence  of  extraordinary 
impurities  show  considerable  indications  of 
unaltered  constitution  through  castings. 

A  comparison  between  an  alloy-ore  mined 
(according  to  ancient  records)  at  Tel-el-Sifr 
in  South  Chaldea  {ca.  1500  B.C.)  bears  con- 
siderable similarity  to  that  mined  recently 
in  the  same  locality,  showing  a  general 
average  content  of  99.5  per  cent.  Cu.,  0,2 
per  cent.  P.,  0.04  per  cent.  Sn.,  and  traces 
of  As.  Bi,  Fe,  Co,  Ni,  S  and  N.  That  pro- 
duced from  Cyprus  {ca.  3500  b.c.)  contains 
less  copper  and  more  tin.  The  propor- 
tions, however,  are  such  as  to  suggest  the 
original  natural  forms. 

These  observations  ma^y  be  supported  by 
the  following  three  Biblical  references:  — 


414 


THE  CHEMICAL  NEWS. 


JUNE  29,  1923. 


(1)  Gen.  VI.,  22:  "And  Zillah,  she  also 
bare  Tubal-cain,  an  instructor  of  every  arti- 
ficer in  brass  and  iron."     (3870  B.C.). 

(2)  Deut.,  VIII.,  9:  "A  land  whose 
stones  are  iron,  and  out  of  whose  hills  thou 
mayest  dig  brass."     (2600  b.c). 

(3)  Job.,  XXVIII.,  2:  "  Iron  is  taken  out 
of  the  earth,  and  brass  is  molten  out  of  the 
stone."     (856  b-c). 

Yours   faithfully, 

F.    E.    LlECHTI. 

Church   Crookham,    Hampshire. 
June  16,   1923. 


NOTICES  OF  BOOKS. 

Qualitative  Organic  Analysis — An  Ele- 
mentary Course  in  the  Identification  of 
Organic  Compounds,  by  Oliver  Kamm. 
Pp.  VII.  +  260.  London :  Messrs.  Chap- 
man 5;  Hall,  Ltd.,  11,  Henrietta  Street, 
Covent  Garden,  \V.C.2.  1923.  12s.  6d. 
net. 

The  multiplicity  of  elementary  practical 
manuals  on  Organic  Chemistry  is  such  that 
a  new  volume  on  this  subject  needs  to  ex- 
hibit some  outstanding  feature  in  order  to 
justify  its  existence. 

In  the  preface  of  this  new  American  pub- 
lication on  the  subject  the  author  states 
that  in  1005  practical  organic  chemistry  was 
taught  in  only  two  or  three  universities,  but 
in  1918  it  was  prescribed  for  all  colleges 
undertaking  the  training  of  chemists  under 
the  supervision  of  the  U.S.  Government. 

The  course  outlined  in  Prof.  Kamm's 
work  follows  that  which  he  adopted  him- 
self at  the  University  of  Illinois,  and  has  for 
its  basis  the  analytical  methods  of  Prof. 
Mulliken.  It  is  arranged  to  cover  32  labora- 
tory periods  of  3  hours,  and  includes  the 
usual  experimental  work  done  by  students 
in  colleges  and  technical  institutes  in  quali- 
tative organic  derivatives  and  quantitative 
analysis.  There  are  also  short  chapters  on 
the  preparation  of  characteristic  exercises. 
The  book  should  form  a  useful  guide  to 
lecturers  and  demonstrators,  and  will 
doubtless  be  adopted  by  some  as  a  class 
textbook. 

Klinisches  Kolhidchcmic,  von  Dr.  Er- 
nest Joel.  Pp.  124.  Dresden  and  Leip- 
zig :  Verlag  von  Theodor  Steinkopff. 
1923.     Price  2s.  2d. 

Dr.  Joel's  volume  on  the  clinical  applica- 
tions of  colloid  chemistry    is  based  upon  a 


course  of  nine  lectures  delivered  by  him  ou 
this  subject.  The  lectures  and  the  book 
are  both  primarily  intended  for  advanced 
students  and  specialists.  It  is  interesting 
to  note  how  wide  are  the  applications  of 
such  an  apparently  academic  subject  as 
colloid  chemistry.  The  author  has  applied 
the  physico-chemical  theories  of  colloid  gel 
formation  and  of  swelling  to  the  problems 
of  the  medical  practitioner,  for  whom  much 
of  the  book  will  probably  be  new. 

Prof.  K.  Spiro,  of  Basle,  has  contributed 
a  foreword  drawing  attention  to  the  coming 
importance  of  a  knowledge  of  the  applica- 
tions of  colloid  chemistry. 


The  Department  of  Glass  Technology  of 
Sheflfield  University  has  published  Volume 
V.  of  the  Experimental  Researches  and. 
Reports  which  have  been  collected  from  the 
Journal  of  Glass  Technology,  in  which  pub- 
lication they  have  appeared  during  the 
year. 

These  Reports  are  collected  from  the 
work  of  Prof.  Turner  and  his  collaborators, 
and  include  papers  on  the  action  of  various 
analytical  reagents  on  glassware,  the  action 
of  water  and  steam  under  pressure  on  some 
soda-lime-silicate  glasses;  and  some  con- 
tributions to  the  science  of  glassmaking, 
and  a  few  articles  of  a  more  general  type. 

The  paper  on  the  present-  position  of  the 
glass  industry  in  Czecho-Slovakia  is  a  very 
discerning  one,  but  it  is  regrettable  that  the 
Czech  currency  is  persistently  called  kroner 
instead  of  kronen.  This  is  perhaps  a  small 
point,  since  the  volume  contains  much 
that  is  of  considerable  value  and  interest. 


BOOKS  RECEIVED. 

The  Synthetic  Dyestuffs  and  the  Inter- 
mediate Products  from  which  they  are  de- 
rived, by  John  Cannell  Cain,  D.Sc,  and 
JocELYN  Field  Thorpe,  C.B.E.,  D.Sc.  Pp. 
XV.  +  423.  Sixth  Edition.  1923.  Messrs. 
Charles  Griffin  &  Co.,  Ltd.,  Exeter  Street, 
Strand,  W.C.2.     21s.  net. 

Tiber  Naturprodiilde,  by  Max  Honig. 
Pp.  X.  +  181.  1923.  Verlag  von  Theodor 
Steinkopff,  Dresden  und  Leipzig.  Price 
4s.  4d. 

Atomic  Structure  and  Spectral  TJnes,  by 
Arnold  Sommerfeld,  translated  by  Henry 


JUNE  29,  1923. 


THE  CHEMICAL  NEWS. 


415 


L.  Brose,  M.A.  Pp.  XIII;  +  626.  Third 
Editioii.  1923.  Messrs.  Methuen  &  Co., 
36,  Essex  Street,  \V.C.2.     32s.  net. 

The  Mellon  Institute  of  Industrial  He- 
search  of  the  University  of  Pittsburgh  has 
just  issued  its  tenth  annual  report,  exiplain- 
ing  its  objects  and  achievements. 

The  Ministry  of  Agriculture  &  Fisheries 
has  issued  a  leaflet,  No.  114,  entitled,  The 
Scientijic  PrincipUs  of  Feeding  Poultry. 


PUBLICATIONS  RECEIVED. 

Bulletins  published  by  the  U.S.  Depart- 
ment OF  The  Interior  :  — 

501 :  Surface  Water  Supply  of  the  United 
States,  1919-1920.  PaH  IV.-— 8t.  Law- 
rence River  Basin.  By  Nathan  C.  Grover, 
W.  a.  HoYT,  C.  C.  Covert  and  C.  H. 
PlERCK.      Pp.   188. 

729 :  Oil  Shale  of  the  Roeky  Mountain 
Region.  Bv  Dean  E.  Winchp:8ter.  Pp. 
204. 

734:  Deposits  of  Manganese  Ore  in  the 
Hates ville  District,  Arkansas.  By  Hugh 
I).  Miser.  With  a  chapter  on  the  mining 
and  preparation  of  the  ores,  by  W.  R. 
Crane.     Pp.  271. 

785  i. :  Diamond-bearing  Peridotite  in 
Pihe  County,  Arkansas.  By  Hugh  D, 
Miser  and  Clarence  S.  Ross.  Pp.  279- 
322. 

785  j. :  The  los  Burros  Dinirict,  Monter- 
ley  Countif,  California.  By  James  M.  Hill. 
Pp.  323-329. 

751  A.  :  Continuity  of  some  Oil-bearing 
Sands  of  Colorado  and  Wyoming.  By  Wil- 
lis T.  Lkk.     Pp.  22. 

L29:  Summary  of  Mineral  Production  in 
Foreign  Countries,  1919  and  1920.  By  L. 
M.  JoNE.s.     Pp.  518-564. 

I.  80:  Iron  Ore,  Pig  Iron  and  Steel  in 
1921.  By  Ernest  F.  Burcitard  and  Hr- 
BERT  W.  Davis.     Pp.  565-597. 

n.  1  :  Fuel  Briquets  in  1922.  By  W,  F. 
McKennky.     Part  II,     Pp.  4. 

Revision  of  the  Flora  of  the  Green  River 
Formation  with  Descriptions  of  New 
Species.  By  F.  H.  Knowlton.  Pp.  183- 
182, 

Fossil  Plants  from  the  Tertiary  Lake 
Beds  of  South-Central  Colorado.  By  F.  H. 
Knowlton.     Pp.  183-197, 

The  Fauna  of  the  So-called  Dakota  for- 
mation of  Northern  Central    Colorado    and 


lis  Equivalent  in  South-Eastem  Wyoming. 
By  John  B.  Reeside,  Jun,    Pp.  199-207. 


PUBLICATIONS  RECEIVED  FROM 
THE  U.S.  DEPARTMENT  OF  THE 
INTERIOR,  BUREAU  OF  MINES. 

The  Universal  and  the  Fireman's  Gas 
Masks,  by  S,  H.  Katz,  J.  J.  Bloomfield, 
and  A.  C.  Fieldner.     Pp.  22. 

Metal-Mine  Accidents  in  the  United 
States  during  the  Calendar  Year  1921,  by 
William  W.  Adams.     Pp.  96. 

The  Chloride  Volatilisation  Process  of 
Ore  Treatment,  by  Thomas  Varley,  E.  P. 
Barrett,  C,  C.  Stevenson,  and  Robert  H. 
Bradford.    Pp.  99. 

Bibliography  of  Petroleum  and  .Ulied 
Substances  in  1919  and  1920,  by  E,  H,  Bur- 
roughs.    Pp,  374. 

Preparation,  Transportation,  and  Com- 
bustion of  Powdered  Coal,  by  John  Blizard, 
Pp.  127. 

The  Dominion  Bureau  of  Statistics, 
Canada,  has  just  published  a  report  en- 
titled Chemicals  and  Allied  Products  in 
Canada,  1921.  It  contains  a  summary  of 
the  .ntntistics  on  the  production  of  chemicals 
in  Canada  during  the  year. 

From  a  perusal  of  these  statistics  in  the 
various  chemical  industries,  it  is  noticed 
that  production  in  almost  every  industrial 
fi«'ld  during  the  pa.st  three  years  shows  the 
effect  of  post-war  influences.  In  1919,  as  a 
result  of  the  largo  scale  production  during 
the  war  years,  the  accumulation  of  stocks 
was  considerably  in  excess  of  current  re- 
quirements, with  the  result  that  production 
was  much  curtailed.  Most  of  these  stocks 
were  disposed  of  in  1919  with  the  result 
that  in  the  early  ipart  of  1920  an  appreciable 
advance  in  prices  occurred  which  reached  a 
maximum  about  the  middle  of  the  year. 
This  advance  was  followed  by  increased 
production  in  many  industries.  During  the 
closing  months,  however,  demands  from 
consumers  for  lower  prices  became  more  in- 
sistent, and  in  1921  a  deflation  in  prices 
oc<jurred.  At  the  close  of  that  year,  al- 
though prices  were  at  a  much  lower  level 
than  at  the  beginning,    cfwidHIons  through- 


416 


THE  CHEMICAL  NEWS. 


JUNE  29,  1923. 


out  the  industry  were  much  improved,  and 
prospects  were  much  better. 

An  illustrated  catalogue  of  Astronomical 
Photographs,  including  lantern  slides, 
transparencies,  and  prints  from  negatives 
made  at  the  Ycrkes  Observatory,  has  just 
been  issued.  It  is  the  third  edition  of  this 
catalogue  issued  by  the  University  of 
Chicaofo  Press. 


iHis  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Ctanoe.-y  Lane.  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent   Applications. 

13835— Coswav,  H.  C— Manufacture  of  methyl 
chloride  and  ethyl  chloride.    May  25. 

137.52— Metals  Production,  Ltd.— leaching  copper. 
&c.    May  24. 

13.502— Oderberger  Chemische  Werke  Akt-Ges.— 
Production  of  colloidal  solutions  and  re- 
soluble dried  residues  from  irreversible 
colloids.    May  22. 

14501— Chemische  Fabrik  Grieshaim-Elektrom.— 
Manufacture  of  azo-dyestuffs.    June  1. 

14268— Brutkzus.  M.— Process  for  effeeting  chemi- 
cal reactions.    May  30. 

14079— Chemisohe  Fabrik  auf  Action  vorm  E. 
Schering.— Manufactui-e  of  barbiturioacid 
compounds.    May   28. 

14293— Grasselli  Chemical  Co.— Manufacture  of 
concentrated   acetic  acid.    May  30. 

14013— Green,  H.— Reduction  of  oxides  and  oxy- 
compounds.    May  28. 

14325— Jaques,  A.— Manufacture  of  barium  sul- 
phate.   May  31. 

14672— Chemische  Fabrik  Griesheim-Elektron.— 
Manufacture  of  acylacetyl  compounds. 
June  4. 

14945— Soc.  of  Chemical  Industry  in  Basic- 
Manufacture  of  naphthioindoxyls.     June  7. 


Specifications   Published  this   Week. 

183419— National  Aniline  &  Chemical  Co.,  Inc.— 
Production  of  vat  dyes. 

197573— Marks,  E.  C.  R.— Zirconium  alloys  and 
and  Hirschberg,  Z.  von.— Manufacture  of 
processes  of  making  same. 


182781— Deatsch-Englisohe  Quarzschiaelze  Ges., 
quartz  amd  the  like  articles  non-pervio,ye 
to  gases. 


Method     of  producing 


197706    Meter,  J.  W.   van. 
lx>isouous  gases. 

197724— Pease  &  Partners,  Ltd.,  and  Stephenson, 
G. — Manufacture  of  sulphate  of  ammonia. 

197845— Prentice,  A.  T.— Method  of  and  apparatus 
for  burning  sulphate. 

197898- Rhenania  Verein  Chemischer  Fabriken 
Akt-Ges.-Zweigniederslassung  Mannheim 
and  Rusberg,  Dr.  F.— Manufacture  of  al- 
kali thiosulphate. 

Abstract  Published  this  Week. 

196023— Methane.— Hilditch,  T.  P.,  Birchdene, 
Cross  Lane,  Grappenhall,  Cheshire,  and 
Crossfield  &  Sons,  Ltd.,  J.,  Warrington, 
Lancashire. 

Methane  is  produced  by  passing  commercial 
water  gas,  containing  approximately  equal  pro- 
portions of  carbon  monoxide  and  hydrogen,  over 
a  catalyst  maintained  at  a  temperature  of  220- 
300°  C.  and  preferably  not  higher  than  280°  C. 
The  reaction  takes  place  according  to  the  equa- 
tion :—  2  CO  +  2112  -  CO  *  +  CH  4.  Thp  cata- 
lyst is  nickel  or  cobalt  or  a  mixture  thereof,  and 
is  preferably  mounted  on  a  carrier.  The  process 
may  be  applied  to  the  methanation  of  water  gas 
or  to  the  production  of  pure  methane.  In  the 
latter  case,  carbon  dioxide  is  first  eliminated  and 
then  residual  traces  of  carbon  monoxide  and  hy- 
drogen are  removed  by  passage  over  heated  cop- 
per oxide  at  a  temperature  of  200-250°  C,  the 
methane  being  finally  separated  from  nitrogen  by 
liquefaction. 


Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each. 


ROYAL  COMMERCIAL  TRAVELLERS' 
SCHOOLS,  PINNER. 

There  are  now  365  orphan  boys  and  girls 
in  the  Royal  Commercial  Travellers' 
Schools  at  Pinner — a  trade  charity,  con- 
cerning every  trade  employing  commercial 
travellers. 

The  members  of  the  Board  of  Manage- 
ment feel  that  if  only  they  could  induce 
more  business  men  to  visit  the  schools, 
they  could  not  fail  to  take  a  permanent  in- 
terest in  them. 

Subscriptions  may  be  sent  to  the  Secre- 
tary of  The  Royal  Commercial  Travellers' 
Schools,  17,  Cheapside,  E.C.2. 


AUGUST  3,  1923. 


Index. — Supplement  to  the  Chemical  News. 


fii 


419 


INDEX. 


ABERRATION  and  the  D6p- 
pler  effect    as    treated    in 
the     theory     of     relativity, 
283. 
diffraction  effects,  187. 
Absorption  bands.     Coincidcn<:-<> 
method  for  the  wave-lengtli 
measurement  of,  102. 
Acetone     and       ethyl      alcohol. 
Estimation  in  a  mixture  of 
the  two.  235. 
for  the  United  States,  186. 
Acid,  Boric,  in  liquid  eggs  and 
other  foodstuffs,  Elstimation. 
232. 
Cresylic,     for       the       United 

States.  186. 
Formic.     Decomposition       by 

flulphario  acid,   149. 
Fumaric,    Use    in   volumetric 

analysis.  42. 
IlydroDromio,       of     constant 
boiling  point,    Preparation, 

Hydroxy  stearic.  78. 

Maleic.  and  malic.  Use  in 
volumitric  analvsis,  42 

/3-Naphthol-4-8ulpnonio.  Pre- 
paration,  154. 

Oxalic,  Board  of  Trade  An- 
nouncement,   15. 

Phosphoric,  Influence  of  hu- 
mic  acids  on  the  assimila- 
tion of,  229. 

Sarcolactio,   Preparation,  251. 

Silicic,  gels,  Colloidal  gold 
in.  37. 

Sulphuric.  Decomposition  of 
formic  acid  by,  149. 

Titanic,     Behaviour     towards 
dyestuffs,  75. 
Acids,     AminobouKoio,    , Decom- 
position   by  boiling     water. 

Ilumio,  Influence  on  the  assi- 
milation of  phosphoric  acid, 
22». 


Naphtheiio,     from    JapaiMM 
petroleum.  220. 

Adam,  N.  K..  Structure  of  thin 
films.  S58. 

Adsorption  of  bases  by  solids 
and  th«  thickness  of  the 
adsorbed  layer,  103. 

Aerial  and  marine  craft.  Find- 
ing the  true  vertical  for  all 
types  of.  406. 

Africa.  East.  Reptilian  remains 
from  the     Karroo  beds    of. 
108. 
Soath.  Union  of.  Department 
of   Agriculture.    123. 

Agricultural  exports.  Sanitary 
inKpcction  of,  318. 

Ainslie,  D.  S..  and  J.  C.  Mc- 
Lennan. {See  MoIiMinan,  J. 
C.) 

Air  temperature  at  great 
heights,  280. 

Alchemy  and  chemistry.  Ara- 
bian. 197,  285. 

Alexander,    Jerome,  "Qlne  and 
Gelotin"    iRcrietr),  221. 
Projected  coiniH-ndiuni  of  col- 
loid ohemistry.  191. 

Alkali  polyhaliden.  Significance 
of  the  experimentally  de- 
termined civstal  structure* 
of,   291. 

Alloys,  Heat  and  acid  resistini; 
246. 
Structure  of,  .301. 
X  ray  spectrum  of.  330. 

Alpha-ray  tracks.  Forked.  171. 

Alumina  and   iron.   Rapid  esti- 
mation, 128. 
and   other  oxides.     Action   in 
promoling  activity  of  nickel 
cntalyst,  358. 

Aluminium    alloys.     Estimation 
of  magnesium   in,  17. 
cry  t;il.   Distortion    dnrinp    n 

tensile   test,    139. 
(•:y«'nl«.   Large,   328. 


sal>-group.    Series  spectra  of. 

186. 
America,     Industrial      physical 

research  in,  398. 
American  rubber  growing  pro- 
posals, 138. 
Ammonia     and     sodium    hypo- 

bromitc.   Reaction    between, 

235. 
Spectrum  of,  359. 
.\mraoniiim    hy<lrate    and  mer- 

carouH       bromide.        Inter- 
action, 225. 
Analysis.     Volumetric,     Use  of 

malic,   maleio  and   fumaric 

acids  in,  42. 
Anatase.   Dartmoor  occurrences 

of,  58. 
.inglo-Persian     Oil      Company, 

Limited,      Lubricating    oils 

under    electrostatic     stress. 

332. 
Animal  tissues.  Effect  of  X  rays 

of     different       wave-lengths 

upon   some.  3.')7. 
.\nrep,  G.  V.,     The  irradiation 

of  conditioned   reflexes.   118. 
Antimony  and  arsenic,  (liemis- 

try  of  the  Reinsch  test  for, 

and     its  extension     to     bis- 
muth. 232. 
and     lead     alloys.     Electrical 

potential  of,   141. 
A;  paratus    for  measuring    th« 

compressibility       of     gases. 

332. 
for   the  recovery    of  bromine 

from    sodium    hypobromite, 

.55.  95. 
Optical,  for  research,  332. 
Scientific,  for  British    Colum- 

bio,  267. 
Apples,     r)dorons     constituents 

of.  45. 
Appleton,    E.    v.,    and    R.     A. 

Watson  Watt.     {See    Watt. 

H.  A.  W.) 


420 


Index. — Supplement  to  the  Chemical  News. 


AUGUST  3.  1923. 


Arabian  alchemy  and  chemis- 
try. ]37,  285. 

Argentine  agricultural  exports, 
Sanitary  inspection  of,  318. 

Armstrong,  E.  F.,  and  T.  P. 
Hilditch,  A  study  of  cata- 
lytic actions  at  solid  sur- 
faces, 88,  358. 

Armstrong,  H.   E.,  Electrolytic 
conduction,  310. 
Origin  of  osmotic  efiects,  310. 

Arnott,  John,  Monel  metal, 
247. 

Arsenic  and  antimony.  Chemis- 
try of  the  Reinsch  test  for, 
and    its    extension    to    bis- 
muth, 232. 
Detection   and     estimation   of 

small  quantities,  110. 
in  cocoa,  19. 

White,  and  calcium  arsenate 
for  the  United  States,  170. 

Arterial  elasticity,  Variation 
with  blood  pressure  in 
man,  119. 

Ashley  bottle  machine,  409. 

Asphalt,  Sensitiveness  to  light 
as  function  of  its  degree  of 
dispersion,  350. 

Association  of  British  Chemi- 
cal Manufacturers,  "OflBcial 
Directory  of  Members" 
(Review),  96. 

Aston,  F.  W.,  Critical  search 
for  a  heavier  constituent  of 
the  atmosphere  by  means 
of  the  mass-spectrograph, 
310. 
Isotopes,  353. 

Atack,  F.  W.,  "The  Chemists' 
Ye&r  Book"   (Review),  207. 

Atmosphere,  Search  for  a 
heavier  constituent  of,  by 
means  of  the  mass-spectro- 
graph, 310. 

Atmospherics,'  Nature  of,  279. 

Atomic  magnitudes.  Compressi- 
bility, internal  pressure 
and,  215.  274. 
nucleus.  Explanation  of  the 
theory  of  the  rotation  of, 
262,  321,  337. 
number,  Is  there  an  element 

of  zero?  307,  325. 
projectiles    and  their  proper- 
ties, 397. 
theories,   270. 
weight  of  titanium,  385. 
weights.  Periodic  function  of, 
372. 

Atoms,  Influence  of  the  atomic 
nucleus  upon  valence,  orien- 
tation and  the  induced 
polarity  of,  129. 

Australia,  Machinery  for  phar- 
maceutical preparations  re- 
quired by,  401. 

Austrfa,  Foreign  trade  of,  in 
1922,   170. 


t>ACTIARACH,    A.  L.,  Deter- 

■■-'     mination  of  lactose  by  the 

polarinietric     and  gravi- 
metric method,  299. 


Bairstow,  L..  Miss  B.  M.  Cave 
and  Miss  E.  D.  Lang,  Resis- 
tance of  a  cylinder  moving 
in  a  viscous  fluid,  103. 

Baker,  T.  Thoi-ne,  "The  Spec- 
troscope and  its  Uses  in 
General  Analytical  Chemis- 
try"  (RevieiD),  253,  288. 

Balls,  W.  Lawrence,  Deter- 
miners of  celhilose  struc- 
ture as  seen  in  the  cell 
walls  of  cotton  hairs,  298. 
Mirxor-image  structures  in 
cell  walls  of  cotton  hairs, 
330. 

Baluohitherium  osborni,  73. 

Bancroft,  Wilder  D.,  Theory  of 
photography,   359. 

Baroroft,  T.,  Observations  on 
the  effect  of  high  altitude 
on  the  physiological  pro- 
cesses of  the  human  body. 
72. 

Barimar,  Limited,  Change  of 
address,  170. 

Barium  in  natural  brines,  300. 

Bases,  Adsorption  by  solids, 
103. 

Beck,  Conrad,  Ttluminator  for 
opaque  objects  under  the 
microscope,  328. 

Benzene  and  tohiene.  Nickel  in, 
172. 
nucleus,  Problem  of  substitu- 
tion in,  241,  257. 

Berry,  A.,  and  Lorna  M.  Swain, 
Steady  motion  of  a  cylinder 
through  infinite  viscous 
fluid,   102. 

Birmingham,     Irish    chemistry 
students   at,   111. 
University,   61. 

Bismuth,  Chemistry  of  the 
Reinsch  test  for  arsenic  and 
antimony  and  its  exten- 
sion to,  232. 

Blackett,  P.  M.  S.,  Study  of  the 
forked  Alpha-ray  tracks, 
171. 

Blackman,  F.  F.,  The  problems 
of  plant  respiration  con- 
sidered as  a  catalytic  pro- 
cess, 405. 

Blackmore,  H.  S.,  Miss  Violet 
Dimbleby,  and  W.  E.  S. 
Turner,  Rapid  method  of 
testing  the  durability  of 
glassware,  217. 

Blanchard,  Arthur  A.,  and 
Joseph  W.  Phelan,  "Syn- 
thetic Inorganic  Chemistry" 
(Review),  319. 

Blattoid  wing  from  the  Harrow 
Hill  Mine,  Drybrook,  For- 
est of  Dean,  406. 

Bloch,  Olaf,  Plate  sensitome- 
try,  351. 

Boerce,  A.  R.,  and  D.  L.  Ham- 
mick.  (See  Hammick,  D.  L.) 

Bolton,  Herbert,  New  blattoid 
wing  from  the  Harrow  Hill 
Mine,  Drybrook,  Forest  of 
Dean,  406. 

Bone,  W.  A.,  D.  M.  Hewitt,  and 
D.  T.  A.  Townsend,  Gase- 
ous combustion  at  high 
pressures,   278. 


Books,  Reviews,  and  Notices  of  : 

"Acid,       Hydrochloric,       and 

Saltcake,  Manufacture  of," 
399. 

"Acid,  Sulphuric,  and  Sul- 
phur Dioxide,  Raw  Materi- 
als for  the  Manufacture  of," 
398. 

"Analysis,  Qualitative  Or- 
ganic," 414. 

"Analysis,  Qualitative,  Pre- 
liminary Experiments  in," 
142. 

"Atomic  Theories,"  253. 

"Atoms,"   271. 

"Back  to  Prosperity,"  207. 

"Blestcln^g  Powder  and  its 
Action  in  Bleaching,"  80. 

".ffritish  Association  of  Trade 
and  Teclinical  Journals, 
Limited,  OflBcial  Hand- 
book," 287. 

"Calculator,  The  Rapid  Dc- 
cima:l,"  159. 

"Canada,  Chemicals  and  Al- 
lied Products  in,"  415. 

"Carotinoids  and  Related  Pi;,'- 
raents.  The  Cliromolipoids," 
78. 

"Cements  and  Artificial 
Stone,"  159. 

"Chemical  Engineering  Cata- 
log," 144. 

"Chemists'   Year   Book,"  207. 

"Chemistry,  Anorganische 

Chemie."  222. 

"Chemistry,  Applied  Diction- 
ary of,"  79. 

"Chemistry,  Applied,  Reports 
on  the  Progress  of,"  368. 

"Chemistry,  Colloid,  Clinical 
Applications  of  (Klinische 
Kolloidchemie),"  414. 

"Chemistry,  Colloid,  Einfiih- 
rung  in  die  Kolloidchemie," 
319. 

"Chemistry,   Inorganic,"  95. 

"Chemistry,  Inorganic  and 
Theoretical,  Comprehen- 
sive Treatise  on,"  270. 

"Chemistry,  Inorganic,  Syn- 
thetic," 319. 

"Chemistry,  Inorganic,  Text 
Book  of,^'  80. 

"Chemistry,  Organic,  or 
Chemistry  of  the  Carbon 
Compounds,"   111. 

"Chemistry,  Physical,  Lab- 
oratory Manual  of,"  239. 

"Chemistry,    Practical,"   335. 

"Chemistry,  Questions  and 
Problems  in,"  142. 

"Chenaistry,  Readable 

School,"  223. 

"Chemistry,  Second  Year 
College,'^  36,  127. 

"Chemistry,  Smith's  Interme- 
diate," 15. 

"Chemistry,  Theoretical,  from 
the  Standpoint  of  Avogad- 
ro's  Rule  and  Thermodyna- 
mics," 383. 

"Chemistry,  Theoretical,  Out- 
lines of,"  126. 

"Cold,  Generation  and  Utili- 
sation of,"  239. 

"Colouring  Matters,  Synthe- 
tic, Vat  Colours,"  207. 


AUGUST  3,  1923. 


Index. — Supplement  to  the  Chemical  News. 


42l 


"Dictionary  of  Applied  Chem- 
istry,"  79. 
"Discoveries     and    Inventions 
of  the  Twentieth  Century," 
175. 
"Dyes  and  their    Application 

to  Textile  Fabrics,"  158. 
"Eastman     Kodak      Company 
Abridged     Scientific     Publi- 
cations," 239. 
"Explosives,     Annual    Report 
of  H.M.  Inspectors  of,"  336. 
"Foods,  Vital  Factors  of,  Vi- 
tamins and  Nutrition,"  23S 
"Glass-blowing,  Elements  of,' 

271. 
"Gin©  and  Gelatin."  221. 
"Hvpnosis,      The       Mysteries 

of,"  15. 
"Ink,"  271. 

"Journal  of  Scientific  Instru- 
ments," 379. 
"Lalx>ratory    Manual    of    Ex- 
orcises," 36,  127. 
"Laboratory         Orpranifwition, 

Teeted  Methods  of."  255. 
"Mysore     Agricultural   Calen- 
dar." 287. 
"Xitrate  Facts  and     Figure; 

1923,"  287. 
"Oil-shale,  a  Historical,  Tech- 
nical and  Economic  Studv." 
143. 
"Oils,    Hydrocarbon,     Exami-   ' 
nation   of,   and  of  Saponifi- 
able  Fats  and  Waxes."  3f3. 
"Optical  Methods  in    Control 
and        Research         Labora- 
t'^ries."  95. 
"Ore     Treatment.        Chloride 
Volatilisation     Process   of." 
399. 
"Organic       Compounds,         \ 
Method     for    tne  Identifica- 
tion of  Pure."  158. 
"Organic  Svnthepps."  127. 
"Oxidations     and    Reductions 

in  the   Animal   Hody."  238. 
"Pent.   Occurrence  and    Uses 

of."  148. 
"Perfumer.  Formulary  of  the 

Parisian.*'  .36. 
"Petroleum.     Handbook   on," 

157. 
"Pharmacy,    Tear-Book    of." 

79. 
"Phase  Rule  and  its  Applica- 
tions." 286. 
"Relativity.   The    Mathemati- 
cal Theory  of."  223. 
"Saltcake.       Manufacture     of 
Hydrochloric      Acid     and," 
399. 
"Science,  Common."  95. 
"Science     in   Natural     Life." 

143. 
"Seifen  und  Eiweisstoffe."  Ill 
"Sheffield  University.  Depart- 
ment of   Glass    Technology. 
Exnerimeiital         Researches 
ann  Reports,"  414. 
"Skinner's  Cotton   Trade    Di- 
rectory for  1923."  254. 
"The     Spertroscopp     and     its 
Uses  in  General  and  Analy- 
tical  Chemistry."  253.   288. 
"Spectrum     Analvs'f*.     Wave- 
length Tables  for."  286. 


"Sulphur    Dioxide,    Raw    Ma- 
terials for  the  Manufacture 
of  Sulphuric  Acid  and,"  398. 
"Surface  Tension     and     Sur- 
face Energy,     and  their  In- 
fluence    on   Chemical     Phe- 
nomena," 253. 
"Technology,    Chemical,     and 
Analysis  of  Oils,     Fats  and 
Waxes,"  222. 
"Urea.    Chemistry   of,"   367. 
"Volatile   Solvents,     The    Re- 
covery of,"  272. 
"Von  Hohenheim.  Theophras- 

tus  Bombastu.*,"  174. 
"Wood,   Destructive     Distilla- 
tion of,"  287. 
Borate  of  lime.     Concentrated, 

214. 
Boric  oxide.  Effect  on  the  melt- 
ing and     working  of  glass, 
152. 
Borough   Polytechnic   Institute. 

109. 
Bottle    machine.    The    Ashley, 

409. 
Bourlet,  C.     W.     L.,    and     W. 
Thomas,    A  new  distinction 
between     sodium     and     po- 
tassium, 193. 
Bousfield,  W.  R.,     and    C.  Els- 
peth  Bousfield.  Vapour  pree- 
sure  and  density  of  soaium 
chloride  solutions.  280. 
Brammall.  A.,  and  H.  F.  Har- 
wood,  The  accessory  miner- 
als of  the  Itairtmoor    gran- 
ite, 410. 
Dartmoor  occurrences    of  rn- 
tile    brookitc,    and  anatace 
and  of  zircon,  56. 
Bramwell,  J.  C.    R.  J.  S.  Mc- 
Dowall,   and    B.    A.    McSwi- 
ney.  The     variation  of    ar-    ' 
teriul  elasticity  with    blj'>d   ; 
pressure  in  man.  119.  ; 

Brines.     Presence    of     barium    j 
and  strontium     in   natural, 
SCO.  I 

British  Columbia,  Scienitllo  ap- 

^ratus  for,  267. 
British   Empire  Exhibition  :- 
Chemical  industry  and.  257. 
Chemical   Section,   17. 
Electrical  exhibits,  65. 
Power  station  and  plant,  77. 
Science  and   scientific   instra- 
ments.  305. 
British    Industries    Fair,   192S, 
138. 
Stationery   and    printing  sec- 
tions, 65. 
British     Non-Ferrous       Metals 
Research  Association.  145. 
Die  casting  research.  403. 
British       chemical       standard. 
Basic  slag  "A."  137. 
chemical       standards      move- 
ment.   General      meeting   of 
the  co-operators.  168. 
industry     and  the     European 
situation.  308. 
Bromine.  Apparatus  for  the  re- 
covery of.  from  sodium   h.v- 
pobroniite.  55.  05. 
Use  of  potassium    or  sodium 
bromine  as  a   source  of.  for 
urea  estimations,   180. 


Bronze,  Analysis  of  ancient, 
413. 

Brookite,  Dartmoor  occur- 
rences of,  58. 

Brooks,  E.  E.,  Photographs  of 
lines  of  electric  force,  327. 

Browne,  A.  W.,  and  A.  J.  Cur- 
rier.    (See  Currier,  A.  J.) 

Building  stones.  Arresting  de- 
cay in,  307. 

Bulgaria,  Medicaments  for,  201. 

Bullock,  E.  R.,  Theory  of  pho- 
tographic dye  mordanting, 
352. 

Bunbury,  H.  M.,  "Destructive 
Distillaffcn  of  Wood"  {Re- 
view), 287. 

Burettes,  Notes  on,  363. 

Bushill.  J.  H.,  Estimation  of 
acetone  and  of  ethyl  alcohol 
in  a  mixture  of  the  two.  235. 

Business  eflBciencv,  71. 

Butterworth,  S..'  and  C.  V. 
Drysdale.  (.See  Drysdale, 
C.  V.) 


/^ABLE     carrying  alternating 

^^  current.  Distribution  of 
the  magne.tio  field  and  re- 
turn current  round  a  sub- 
marine, 857. 

Ceesium  and  other  alkali  ele- 
ments, Flnorescence  and 
channelled  absorption  spec- 
tra of,  188. 

Calcium  arsenate  and  white 
arseaio  for  the  United 
States,  170,  226. 

Calorimeter,     Boys    integrating 
and  recording  gas,  32i9. 
Iron   meroury,  330. 
New  small  spot  test.  329. 

Calorimetry  of  high  explosives, 
309  o  I- 

Calthrop.  J.  E..  and  C.  H 
I>ees.     (See  Lees,  C.  H.) 

Cambridge  and  Paul  Instru- 
ment Company,  Limited, 
Method  of  running  a  direct- 
current  motor  in  synchron- 
ism with  a  tuning  fork.  329. 

Campbell,  J.  H.  P..  K.  Whyt- 
law-Gray,  and  J.  B.  Speak- 
mnn.  (.See  Whytlaw-Grav. 
R.) 

D-Camphor,  Melting-jwint  and 
iodine  value  of  refined 
natural,  300. 

Canadian     agricultural       fairs. 
294. 
chemical  supplies.  241. 
chemicals     and     allied       pro- 
ducts, 366. 

Carbon.  Spectra  associated 
with.  279. 

Carbon  disulphidc  vapour.  Ab- 
sorption. 63. 

Carbon    monoxide    and    hydro- 
gen.   Tntoraotion      as  c<indi- 
tione<l  by     nickel     at     rela- 
tively low  temperatures.  88. 
combustion.     Energy    absorb- 


422 


Index. — Supplement  to  the  Chemical  News. 


AUGUST  3,  1928. 


ing     function     and     activa- 
tion of  nitrogen  in,  278. 
Carpenter,  H.  C.  H.,  Large  alu- 
minium crystals.  328. 
Carroll,  J.     A.,     Note    on     the 
series     spectra  of     the  alu- 
minium sub-group,  186. 
Catalysis,   Conatet,    Recent     de- 
velopments in,  413. 
Catalyst    poisoning,    149. 
Catalytic    actions  at  solid  sur- 
faces, 88,  358. 
decomposition   of   sodium   hy- 
pochlorite    by     cobalt    per- 
oxide, 395. 
Cathode  ray  oscillograph,  12. 
ray   oscillograph.     Low     volt- 
age, 13. 
rays.     Passage  through    mat- 
ter, 396. 
Cave,  Miss  B.  M.,  L.  Bairstow. 
and  Miss  E.  D.  Lang.     {See 
Bairstow,  L.) 
Cellulose        striicture,        Deter- 
miners of,     as  seen  in     the 
cell   walls  of     cotton  hairs, 
298. 
Cellulose  acetate.    Elasticity  of 

organo-gels  of,  314. 
Celtium  and   liafnium,  254. 

lines,  Urbain's,  254. 
Ceramic  deposits  of  Saskatche- 
wan, 277. 
Chambers,  A.  E.,     Potrero  No. 
4,  a  history  of  one  of  Mexi- 
co's    earliest    and      largest 
wells,  234. 
Chapin,    William   H..     "Second 
Year     College      Chemistry" 
and  "Lalx>ratory  Manual  of 
Exercises"  {Uevieip),  36,  127. 
Chapman,     A.     Chaston.       The 

title  "Chemist,"  206. 
Oiiaraoters,     Inheritance  of  ac- 
quired, 73. 
Cliemical   Societv,   105,  121,  141, 
172,  190,     25{j,  280,  299,     312, 
365,  376,  396. 
Bye-laws  relating  to  the  elec- 
tion   of  President,     OfiBcers 
and  Council.  91. 
Chemical  Societv  of  Japan,  270, 

335,  378. 
Chemical     ohangee,     Riythmie 
series  of,  289. 
industry  and  the  British  Em- 
pire Exhibition,   257. 
industry,  Czecho-Slovak,  218. 
reaction    through      a      solid. 

Speed  of,  183. 
staifdard.  New  British,  Basic 

slag  "A,"  137. 
supplies,  Canadian,  241. 
trade  in  British  Malaya,  156. 
trade  welfare,  139. 
Chemicals  and  drugs     for  Rou- 
mania,  297. 
Import  into  Guatemala,  252. 
Chemist,  The  title,  206. 
Chemistry    and   alchemy,    Ara- 
bian,  137,  285. 
Pure     and     applied,     Fourth 
International       Conference, 
413. 
Ohesnut,  Victor  K.,  and  Freder- 
ick B.  Power.     (See  Power, 
F.   B.) 
Chlorides,  Diffusion  of,  188. 


Chlorine,   Line  spectrum  of,  in 
the  ultra-violet  region,  102. 
Cbxee,     C,       Magnetic    pheno- 
mena    in  the  region  of  the 
south  magnetic  pole,  394. 
Supposed       relationship      be- 
tween    sunspot       frequency 
and  the  potential     gradient 
of    atmospheric     electricity, 
105. 
Circuits.       Alternate      current. 
Null  methods    of     measure- 
ment of     power  factor     and 
effective   resistance     in,     by 
the   quadrant    electrometer, 
106. 
Inductively    coupled      low-re- 
sistance,  150. 
Clark,   George  L.,     Significance 
of  the  experimentally  deter- 
mined crystal  structures  of 
the  alkali  polylialides,  291. 
Clark,  Walter,  Sensitivity  of  a 
silver     bromide      emulsion, 
374. 
Clay,     Evaporation      of    water 

from,  311. 
Coal    resources.     Physical     and 
chemical  survey    of  the  na- 
tional, 403. 
Cobalt  peroxide,     Catalytic    de- 
composition    of  sodium  hy- 
pochlorite by,  395. 
Cochrane,     J.      A.,     "Readable 
School      Chemistry"        {Re- 
view), 223. 
Cocoa,  Arsenic  in,  19. 
Codd,     L.       W.,       "Theoretical 
Chemistry   from  the   Stand- 
point   of    Avogadro's    Rule 
and  Thermodynamics"   {Re- 
view), 383. 
Cbllings,   C.  H.,  Apparatus  for 
the     recovery     of     bromine 
from   sodium     hypobromite, 
56,  95. 
Use  of    potassium  or    sodium 
bromide  as  a  source  of  bro- 
mine for  urea    estimations, 
180. 
Collins,  Hawksworth,  The    law 

of  magnetic  rotation,  197 
Colloid      chemistry.     Projected 

compendium  of,  191. 
Cblloids  in  geologic  problems.  6. 
Moisture  relations  of,  89,  311. 
Periodicity     in     progressively 
increasing        concentrations 
of  electrolytes,  89. 
Colour  index.  New,  393. 
Iridescent,     Studies    of.     and 
the   structure  producing  it, 
150,  188. 
makers,   Making,  302. 
Colour   Users'   Association,  An- 
nual meeting,  411. 

Compressibility,  internal  pres- 
sure and  atomic  magni- 
tudes, 215,  274. 

Conant,  James  Bryant,  "Or- 
ganic Syntheses"  (Review), 
127.  ' 

Conduction,   Electrolytic,  310. 

Cooper,  C.  P.,  Baluchitherium 
osborni,  73. 


Cooper-Key,  A.,   "Hand')Ook  i-n 

Petroleum"   (Review),  157. 
Copper  oxidation,  311. 
Copper-lead  minerals    from  the 
Mendip  Hills,  Somerset,  410. 
Copper  oxide     reduction     by  a 

new  method,  311. 
Cotton,  Constituents  of  raw,  76. 
hairs.     Determiners  of  cellu- 
lose structure  as  seen  in  the 
cell  walls  of,  298. 
hairs.      Mirror-image      struc- 
tures in  cell  walls  of,  330. 
Cressy,     Edward,     "Discoveries 
and  Inventions  of  the  Twen- 
tieth    Century"      (Review). 
175. 
Crystal,  Aluminium,  Distortion 
during  a  tensile  test,  139. 
Ortho-rhombic,  exhibiting 

crossed     axial       dispersion. 
Detection  of  xotatory  polar- 
isation in,  411. 
Crystals,     Metal,     Determining 
the  structure  of.     Modifica- 
tion of  the  powder  method, 
11. 
Metal,     Thermal     conductivi- 
ties of,  357. 
Photomicrographs  of,   in   col- 
our mounted  to  show  chang- 
ing tints,  329. 
Cumming,     Alexander    Charles. 
"Manufacture  of  Acids  and 
Alkalis"  (Review),  398. 
"Manufacture       of        Hydro- 
chloric Acid  and   Saltcake" 
(Review),  399. 
Cuprous  sulphites,  61. 
Curie,  I.,  and  M.  G.  Fournier, 
7  rays  from  radium    D 
and  radium  E,  370. 
Currier,     A.     J.,     and    A.     W. 
Browne,  Absorption  of  car- 
bon disulphide  vapour,  63. 
Curtis,  W.  E.,  The  structure  of 
the  band    spectrum  of     he- 
lium, 187. 
Curtman,  L.  J.,     "Preliminary 
Experiments   in   Qualitative 
Analysis"  (Review),  142. 
Cylinder  moving    in  a     viscous 
fluid.  Resistance  of,  103. 
Steady  motion     through     infi- 
nite viscous  fluid,  102. 
Czecho-Slovakia  chemical  indus- 
try, 218. 
Demand  for     British     chemi- 
cals, 202,  219. 
Economic  position   in,  231 
exports,   295. 


DAKIN,     H.  D.,     "Oxidations 
and  ReductioQS  in  the  Ani- 
mal Body"   (Reuieui),  238. 
Dalby,     W.     E.,     Further     re- 
searches on  the  strength  of 
materials,  103. 
Darling,   Charles     R..     Experi- 


AUGUST  3,  1923. 


Index. — Supplement  to  the  Chemical  News. 


423 


ment  on  the    proiuetion  of 
an  intermittent  pressure  by 
boiling  water,  377. 
Darling,  Charles  R.,  and  C.  W. 
Stopford,     Experiments     on 
the  production     of    electro- 
motive forces,  283. 
Darrow,  Floyd  L.,     "Questions 
and   Problem?     in     Chemis- 
try" (Review),  142. 
Dartmoor     granitia,      Accessory 
minerals  of,  410. 
Ocourrences  of  rutile,  brook- 
ite  and    anatase  and  of  zir- 
con, 58. 
Davies,  Earl  C.  H.,     Lies<»gang 
rings.     Silver  chromate     in 
gelatin  and  colloidal  gold  in 
silicic  acid  gel,  37. 
Davitjon,  Albert  W.,  and  Henry 
S.  Van   Klooster,     "Lal>ora- 
tory    Manual     of     Physical 
Cliemistry"  (Review).  239. 
D'Albe,     E.  E.  Fournier,     "Or- 
ganic Chemistry,  or    Chem- 
istry    of  the    Carbon  Com- 
pounds"  (Review),  111. 
D©  Dubor,  Georgee,    "Iah  Mys- 
t^res     de  I'Hypnose"     (Re- 
view), 15. 
Dennis,  L.  M.,  and  F.  E.  Hance, 

Qermanium,  115,  135. 
Density  determinations,  171. 
Department     of  Scientific     and 

Industrial  Kosearch,  394 
Derbyshire,       The       toadstone- 

days  of,  411. 
Devonshire,         Petalite-beering 

rock  fr nil.  410. 
Dewar,     Sir    James.    Obituary, 

220. 
Diaphragms,       Telepjione       re- 
ceiver.    Sand  figures    show- 
ing thu  numerous   resonant 
modes  of  vibration  of.  327. 
Dickson,  William,  Quantitative 
determination  of  hemp  and 
wood   in     pai-ars     ontaning 
these  two  fibres,  289. 
Die  casting  reseirch,  403. 
Dielectrics    at     high     voltaKes, 
Use  of  the  Wien  bridge  tor 
the    measurement      ol    '.he 
losses  in,  377. 
Diffraction.   Aberration,   effects, 

187 
Dimbleby,  Violet.    H.  S.  Black- 
more,  and  W.  E.  S.  Turner. 


(.S'ee  Tumor,  W.  E.  8.) 
nbleby,  Violet.     S.     Engupii. 
and  W.  E.  S.  Turner,  Some 


phymcal  properties  of  Jjorio 
oxide-containing  glasses,  152. 

Dispersion  method  of  deter- 
mining plagioolases  in  cleav- 
age-flaK©8,   *11-  .    ,  ... 

Optical,  of  three  intermediate 
plagioolases,  *15-   „    _, 

Dixon7M.,  and  H.  E.  Tunni- 
cliffe,  Oxidation  of  reduced 
gluthatliione  and  other  sul- 
phydryl  compounds,  119. 

Dobtfon,  U.  M.  h.,  and  F.  A. 
Lindemnnn.  (See  Linde- 
mnn.  F.  A.) 

Dolley.  L.  Q.  F.,  and  I.  Masson. 
(See  Masson,  I.) 


Donnan    equilibrium,  Potential 
difference  occurring  in.  and 
the  theory    of  colloidal     be- 
haviour, 88. 
Doyle,  N.  Gratt&n.    The    Ruhr 

and  British  dyes.  142. 
Druce,  J.  G.  F.,  A  convenient 
method  for  the  preparation 
of  aqueous  hydrobromic 
acid  of  constant  boiling 
point,  1. 
Degree  of  Doctor    of  Natural 

Science,  78. 
Interaction  of  ammonium  hy- 
drate and   mercurous     bro- 
mide. 225. 
Drugs  and  chemicals    for  Rou- 
mania,  297. 
required  in  Switzerland.  '27S. 
Drysdale,  C.  V..  and  S.  Butter- 
worth.     Di8tributi«m  of  the 
magnetic  field    and     return 
current   round  a  submarine 
cable    carrying    alternating 
current,   357. 
Duddell  medal,  345. 
Dye,  D.  W.,     Valve-maintained 
tuning  fork    as  a  precision 
time  standard.  105. 
Dye  industry,  267,  G79. 
mordanting.  Theory  of  photo- 
graphic, S52. 
Dyes  boom,  British.  217. 
Fast.  277. 

The  Ruhr  and  British.  142. 
Dyestufls     Adviwry      Licensmg 
Committee.  63. 
Behaviour  of  titanic  ai-Jd  ti>- 

wards  75. 
(Import  Regulation)  V'»    '<»■">. 

138.  2:.2.  319.  394. 
importation^  156. 
Reparation,  297. 


EAHTITS.     Rare,     and      their 
metals.  51.  97. 

Eclipse  tests.  252. 

Ecuador,  Photographic  mate- 
rials for,  278. 

Eddington,  A.  S..  "The  Mathe- 
mntical  Theory  of  Relativ- 
ity"  (Rrrirw),  223. 

Edinow,  A.,  and  Leonard  Hill. 
(See  Hill.  L.) 

Edwards,  Vincent,  Estimation 
of  lactose,  191. 

Egerton.  A..  Vapour  pressure 
of  lead,  171. 

Egerton.  A.  C.  and  W.  B.  Lee, 
Separation    of    isotopes    of 
sine,  171. 
Some  density   determinations. 
171. 

Eggs,  Liquid,  and  other  food- 
stuffs. Estimation  of  boric 
acid   in.  232. 

Egypt.  Oils,  paintrt  and  var- 
nishes for,  202. 


Egyptian       crude    ^  petroleum, 

Heavy  grade,  317. 
Einstein's  theory    of  relativity. 

373. 
Elam.  C.  F.,  and  G.  I.  Taylor. 

(See  Taylor,  G.  1.) 
Electric  force.   Photographs    of 

lines  of,  327. 
Electricity.  Atmospheric,     Sup- 
posed relationship     between 
sunspot  frequency    and    the 
potential  gradient  of,  105. 
Electro-capillary       relay         for 

wired  wireless,  107. 
tlectrolv.si8  with  an  aluminium 

ano<ie,  140. 
Electrolytic  conduction,  310. 
Electrometer,     Quadrant.     Null 
metliods  of  measurement  of 
power  factor     and     effective 
resistance  in  alternate  cur- 
rent circuits  by.  106. 
Electromotive     forces,     Eximjii- 
mentd  on  the  production  ol. 
283. 
Element,  New,  belonging  to  the 
fourth  group  of  the  periodic 
system,  81. 
New,     Isolation    of  the  oxide 

of,  297.  . 

of  zero    atomic    number.     Is 
there  an.  307.  325,  371. 
Elements.  Chemical.    Report  of 
the   International     Commit- 
tee on,  145. 
EUett.  A.,    and    R.    W.  Wood. 

(See  Wood,  B.  W.) 
Elliott,  F.  A..^  8.  E.  Shepnard 
and  S.  8.  Sweet.  (See  ^hcp- 
pard,  8.  E.  „    .       • 

Ellipsoidal  particles.  Motion  in 

a  viscous  fluid,  103. 
Ellis.  Carleton,     and  Annie     L. 
MacLeod,  "Vital  Factors  of 
Foods,     Vitamins  and     ^u- 
trition"  {^Review),  238. 
Emulsion,  Silver  bromide.  Sen- 
sitivity of,  374. 
English,   5.,     Measurements    of 
the  viscosity  of  glasses  near 
their  annealing  points,  94. 
Natural     sillimanite      as      a 

glass  refractory,  364. 
Notes    on  the  Ashley     bottle 
machine,  409.  ^.    , ,  . 

English,  S..  Violet  Dimbleby 
and  VV.  E.  S.  Turner.  (See 
Dimbleby.  V.)  . 

Ephraim.     F.,      "Anorganische 

Chemie"  (Review),  222. 
Equations,  On  a  certain  family 
of  periodic  solutions  of  dif- 
ferential. 335. 
Equilibrium.     Potential     differ- 
ence oc-curring     in     a  Don- 
nan,  and  the  theory  of  col- 
loidal behaviour,  88. 
Errera.  Jacques.     Sensitiveness 
to  light  of  asphalt  as  func 
tion  of     its  degree     of  dis- 
persnon,  3.50. 
Ethyl  alcohol  and  acetone,   fts- 
tiniation     in  a   mixture     of 
the  two,  235. 
Evans,  B.  8.,    Investigation  in- 
to   the    chemistry    of    the 


424 


Index. — Supplement  to  the  Chemical  News. 


AUGUIST  3,  1928. 


Reinsch  test  for  arsenic 
and  antimony,  and  its  ex- 
tension to  bismuth,  2K. 

Evans,  M.  H.,  and  H.  J. 
George,  Note  on  the  adsorp- 
tion of  bases  by  solids  and 
the  thickness  of  the  ad- 
sorbed layer,  103. 

Evans,  Uliok  E.,  The  mechan- 
ism of  the  so-called  dry  cor- 
rosion of  metals,  248. 

Excoecaria  agallocha.  Potas- 
sium permanganate  appli- 
cations to,  303. 

Explosives,  Calorimetry  of 
high,  309. 

Exposure  theories,  349. 


FAKADAY    Society,     22,     140, 
246,  312,  345,  359,  374. 
Fat  in     dried     milks,     Estima- 
tion, 299. 
Felspar,   Labrador,   Colours  of. 

151. 
Fenwiok,  Florence,     and  H.  H. 
Willard.     (See  Willard,  H. 

Ferguson,  A.,     New  method  of 

glass  melting,  363. 
Fielding,   William  E.,  Valency, 

177,  193,  209,  226. 
Films,  Structure  of  thin,  358. 
Filon,  L.  N.  G.,  and  F.  C.  Har- 
ris,    Dipliasic       nature     of 
glass  as    shown    by    photo- 
elastio  observations,  3^. 
Filter,  Stream-line,  309,  327. 
Findlay,      Alexander,      "Phase 
Eule  and  its    Applications" 
(Review),  286. 
Firearms  and    projectiles.     Ex- 
amination of,  173. 
Fireclay     materials.     Effect    of 
saltcake  in  corroding,  217. 
refractory     material.     Corro- 
sion    by     glass     and     glass- 
making  materials,  217. 
Firth,  Edith  M.,  F.  W.  Hodkin 
and  W.  E.  S.   Turner,     ];f- 
fect  of  saltcake     in  corrod- 
ing fireclay  materials.  217. 
Fischer,     Martin     H.,     "Seifen 
und   Eiweisstoffe"    (Review), 
111. 
Fisher,  E.  A.,     Some    moisture 
relations  of  colloids,  89,311. 
Fleming,     E.  L.,     Concentrated 

borate  of  lime,  214. 
Flint,  H.  T.,     Generalised  Vec- 
tor analysis  of  four  dimen- 
sions, 188. 
Fluorescence  and  channeled  ab- 
sorption spectra    of  csesinm 
and  other     alkali  elements, 
188. 
Formaldehyde  and     the     nitro- 
naphthylamiues.        Interac- 
tion, 154. 


Fournier,  M.  G.,  and  I.  Curie. 
(See  C\irie,  I.)  ' 

Fowler,  A.,  Series  spectrum  of 
trebly-ionised  silicon,  309. 

Francis,  A.  G.,  Presence  of  bar- 
ium and  strontium  in  natu- 
ral  brines,  300. 

Eraser,  Eonald,  and  James  Er- 
nest Humphries,  The  prob- 
lem of  substitution  in  the 
benzene  nucleus,  241,  257 

Frederick,  Robert  C.,  Interpre- 
tation of  the  results  ob- 
tained in  the  analysis  of 
potable  waters,  173. 

Friend,  J.  Newton,  "Text  Book 
of     Inorganic      Cliemistry"' 
(Review),  80. 

Fries,  H.  S.  J.  Substances  dis- 
solved in  rain  and  snow,  113. 

Frog,  Eeflex  contractions  of  the 
cruralis  muscle  in  the  de- 
cerebrate and  spinal,  119. 

Fuel  problems,  122. 

Furnaces,  Pot,  Organising  for 
production   from,   152. 


GABB,  GEORGE  H.,  Bust  of 
Galileo,     carved     in    pear 
wood,  331. 
Galileo,  Bust  of,  carved  in  pear 

wood,  331. 
Galvanometer   of   rapid   indica- 
tion. New  moving-coil,  282. 
Garner,  W.  E.,  and  Sir  R.  Rob- 
ertson.       (See      Robertson, 
Sir  R.) 
Garoett,  C.   S.,     The  toadstone- 

clays  of  Derbyshire,  411. 
Gas,  81,  379. 
calorimeter.     The  Boys     into 
grating  and   recording,   329. 
Exhibition,    Netherlands     In- 
ternational, 145. 
Gases,   Apparatus     for  measur- 
ing the  compressibility    of, 
332. 
Gaseous     combustion     at     high 
pressures,  278. 
mixtures.  Pressures  of,  279. 
Gatter  fosse,     R.     M.,     "Formu- 
lary   of  the  Parisian     Per- 
fumer"  (Review),  36. 
Gavin,  Martin  J.,  "Oil-shale,  a 
Historical,     Technical     and 
Economic       Study"         (Re- 
view), 143. 
Geber,     Authenticity        of     the 
Latin  works  of,  157,  191,  221. 
Gelatin,  Imitations    of  organic 
forms  by     drops   and     vor- 
tices of,  330. 
Photoyraphic     chemistry     of, 

347. 
Silver  chromate  in,  37. 
Gels,  Indicator  method  for   the 
determination  of  coeflBcients 
of  diffusion  in,  188. 


Geologic  problems,   Cblloids  in. 

6. 
Geological   Society,   74,   108,  141, 
246,  300,  315,  364,  406. 
Annual  General  Meeting,  189 
Geology,     Bearing  of     some   re- 
cent advances     in    physical 
science  on,  315. 
George,     H.     J.,     and     M.     H. 
Evans.     (See  Evans,  M.  H.) 
Germanium,   115,   135. 
Germany,   Potash  and  nitrogen 
industries,  276. 
Potash    industry,   230. 
Report  on  the  economic     ;.nd 
huanoial   conditions  in,  340. 
Trade  and  industry,  2<(1,  266. 
341,  402. 
Getman,   Frederick    II.,     "Out- 
lines of    Theoretical   Cliem- 
istry"    (Review),   126. 
Gibson,   W.,     and     L.  G.     Kad- 
cliffe.    (Sec  Radcliffe,  L.  G.) 
Glacial       succession       in       the 
Thames        catchment-basin, 
108. 
Glass  and  glass-nmking     mate- 
rials.  Corrosion    of  fireclay 
refractory  material  by,  21V. 
Diphasic  nature  as  shown  by 
photo-elastio      observations, 
334. 
I'ffect  of    boric  oxide    on  the 
working     and     melting    of, 
152. 
Fine,  ip    the     Mansard     Gal- 
lery, 404. 
industry.         Application       of 

stainless  steel  to,  93. 
industry.        Specifications     in 

the,  408. 
making.   The   year   in    review- 
in  the  world  of,  281. 
melting.  New  method,  363. 
Optical,       Refractive       inrlex 
changes  in,  by  chilling  and 
cooling,  363. 
refractory.   Natural   sillimaii- 
ite  as,  364. 
Glasses,  Measurements    of     the 
viscosity  of,  near  their   an- 
nealing points,  94. 
S<ane  physical    properties     of 
boric  acid-containing,   152. 
Glassware     durability.       Rapid 

method  for  testing,  217. 
Glew,   F.   Harrison,     A   levitat- 
ing magnet,  330. 
Gluthathione     and     other     sul- 
pliydryl     compounds,      Oxi- 
dation of,  119. 
Gold,  Colloidal,   in  silicic    acid 

gels,  37. 
Goldsmi!'.,     J      N..       "Optical 
Methods  in  Control   iud  Re- 
search    Laboratorit-s"     (Re- 
view),  95. 
Qrace,  S.  F.,  Free  luolion  of  a 
splie"-*  in  a   rotating  liquid 
at  right  angles  to  the  axis 
of  rotation,  396. 
Grainger,  H.  H.,     Note    on    p- 
icitrabenzylpyridiiiium 
salts,  182. 
Granite,  Daitmuor,      Aocesso-y 
lainerals  of,  410. 


AUGUST  3,  1923. 


Index. — Supplement  to  the  Chemical  News. 


425 


Gray,  Ja:nes  G  ,  A  ennoral  sc- 
latun  of  the  problem  of 
finding  the  true  vertical  for 
all  types  of  marine  and 
aerial  craft,  406. 

Greaves,  W  M.  H.,  On  a  cer- 
tain family  of  periodic  solu- 
tions of  differential  equa- 
tions, 335. 

Greenwood,  G.,  Detection  of  ro- 
tatory polarisation  in  an 
ortho-rhombic  crystal  ex- 
hibiting crossed  axial  dis- 
persion, 411. 

Griffin,  J.  J.  and  Sons,  Ltd., 
The  Boys  integrating  and 
recording  gas  calorimeter, 
329. 
New  small  spot  test  calori- 
meter, 329. 

Griffiths,  Ezer.  and  G.  W.  C. 
Kaye,  Measurement  of  ther- 
mal conductivitv,  357. 

Griffiths,  Ezer.  and  F.  H. 
Schofield,  Iron  mercury 
calorimeter,  330. 

Griffiths-Jones,  E.,  Titanium  in 
Nile  silt,  120. 

Guatemala,  Import  of  chemi- 
cals into,  2.52. 

Guthrie,  W.  ,\.,  Heavy  grade 
Egyptian  crude  petrofoura, 
317. 

Gyromagnetic  ratio,  Magnitude 

of,  vn. 


H 


AFNIUM  and  .pltiiim.  2M. 


Identity  of.  254. 

ITall,  X.  J..  "DycH  and  tlicir 
Application  to  ToxtiU'  FaV 
rics"   (Review),  158. 

Hammick.  D.  L.,  "Atoms" 
(Review).  271. 

Tlanimirk,  D.  L.,  and  A.  R. 
Boorco.  Preparation  of  a 
trioxj-niethylene.  62. 

Hnnce  .F.  E..  and  L.  M  Den- 
nis.   (Sec  Dennis,  T,.   M.) 

Hardy,  G.  H..  and  .1.  K.  LitMp- 
wood.  Lindelof's  iiypothe- 
sis  concerning  the  Ricmann 
Zeta-function.  280. 

Harris.  F.  C,  and  L.  N.  O. 
Filon.  (See  Filon.  L.  X.  O.) 

Hnrtridgp,  H..  Coincidpnr<> 
method  for  the  wave-lengih 
measurement  of  absorption 
hands.  102. 

Harwood.  H.  F..  and  .A.  TJram- 
mnll.     (See  Brammall,   A.) 

Hatfield.  W.  H..  Stainless  steel, 
witli  some  considorntion  of 
its  application  to  the  glass 
industry.  93. 

llatscJick,  E..  Tmititions  of  or- 
ganic forms  by  drops  and 
vortices  of  gelatin,  330. 


Hatschek,  E.,  and  P.  C.  L. 
Thorne,  Metal  sols  in  noa- 
dibsociating   liquids,   172. 

Hatschek,  E.,  and  K.  S.  Wil- 
lows.    (See  Willows,   R.   S.) 

Haugiitou,  Sidney  Henry,  Rep- 
tilian remains  Irom  the 
Karroo  beds  of  East  Africa, 
108. 

Havelock,  T.  H.,  Studies  in 
wave  resistance,  334. 

Heape,  Walter,  Exhibition  of 
three  series  of  photo- 
graphs, 331. 

Hele-Shaw,  H.  S.,  Stream-line 
filter,  309,  327. 

Helium  and  its  uses.  369. 
bund  spectrum.  Structure  of, 
187. 

Hemp  and  wood  in  papers  con- 
taining these  two  fibres, 
Jaantitati«'e  determination, 
209. 

Henstock,  Herbert,  Explana- 
tion of  the  theory  ol  the 
rotation  of  the  atomic  nu- 
cleus. 262,  321.  337. 
liiHiD-iice  of  the  atomic  nu- 
clcutj  upon  valence,  orienta- 
tion and  the  induced  polar- 
ity of  atoms.  129. 

Hewitt,  D.  M..  W.  A.  Bone,  and 
1-).  T.  A.  Townend.  (See 
Bone,  W.  A.) 

Higffins.  W.  F..  and  G.  W.  C. 
Ka.vf.  (See  Kaye,  G.  W.  C.) 

Hilditch,  T.  P.,  and  E.  F.  Arm- 
strong. {See  Armetronc,  E. 
F.)  ^ 

Hill.  A.  v..  The  |N>tentiaI  dif- 
ference occurring  in  a  Don- 
nnn  equilibrium  and  the 
tli<M.ry  of  colloidal  beha- 
•I    ur.   88. 

Hill,  .I'.tnes    M..  Platinum     de- 

p«i-lH.    lo 

Flii;.  Loiird.  and  A.  Edinow, 
iiiflaence  of  temperature  on 
the  biologicil  action  of 
light.  296. 

Hodkin,  F.  W..  Edith  M.  Firth 
end  W.  E.  8.  Turner.  (See 
Firth,  E.  M.) 

Hodkin.  F.  W.,  and  W.  F  8. 
Turner.  Eifert  of  boric 
oxide  on  the  melting  and 
working  uf  glass.  I5"<? 

Holbr'H)k.  Sir   Arthur.  Gas,  81. 

Hclde.  D  ,  "The  Examination 
of  Hy. I  ■or,!  rlxjn  Oi'«  an  <  of 
Si|>oiifiab!e  Fats  ".nd 
Wa.\e!s"   (/icriVif).  383. 

Holker,  J.,  The  periodicity  opa- 

♦'ity  of  r-ertaiii     -colloids   in 

1'  ''ly  increasing 

ions     of     electro- 

i.  '     -     ■:- 

Uoliuyard.   E.  J.,     Arabian   al- 
chemy and  chemi«trv.     137. 
285. 
"I'ractiodI    Chemistry"     (Re- 
view), 335. 

Hopkins,  E.  S..  Stability  of 
sodium  oxalate  solution. 
150. 

Hopkinson  pressure  bar.  Ex- 
periments with.  395. 


Hort,  G.  M.,  "Les  Mysteres  de 
I'Hypnose"  (Review),  14. 

Hosali,  N.  M.,  Seismic  waves  in 
•  a  visoo-elastio  earth,  395. 

Howell,  O.  R.,  Catalytic  decom- 
position of  sodium  hypo- 
chlorite by  cobalt  perox- 
ide. 395. 

Hubbard,  George  D.,  Colloids 
in  geologic  problems,  6. 

Human  body,  Efiect  of  high 
altitude  on  the  physiologi- 
cal processes  of,  72. 

Hume,  C.  W.,  Note  on  aberra- 
tion and  the  Doppler  effect 
as  treated  in  the  theory  of 
relativity.  283. 

liuinphries,  John  Ernest,  and 
Honald  Eraser.  (See  Fra- 
ser,  R.) 

Humphry,  R.  H.,  Double  re- 
fraction due  to  action  of  a 
vanadium  pentoxide  sol, 
284. 

H.vdrohepatosis,  a  condition  an- 
alogous to  hydronephrosis, 
236. 

Uydiogen,  Active,  New  methods 
of  preparation,  215. 
and  carbon  monoxide.  Inter- 
action  as  conditioned  by 
nickel  at  relatively  low 
temperatures,  88. 


I   CE-AOE.  Man  and  the,  74. 

Indian  imports,  202. 
industrial  revival.  289. 

Inglis,  C.  E.,  Stress  distribu- 
tion in  a  rectangular  plate 
having  two  opposing  edges 
sheared  in  opposite  direc- 
tions, 334. 

Inglis,  J.  Gall,  "The  Rapid 
Decimal  Calculator"  (Re- 
view), 159. 

Ingold,  Cliristopher  Kelk,  and 
Jocelyn  Field  Thorpe.  (Sec 
Thorpe,  J.  F.) 

Insi'cticide  distribution  by 
iieroplane,  401. 

ln>>titute  of  Chemistry,  Annual 
General  Meeting,  153. 
Birmingham  Section.  157. 
Pass  lists.  94.  301. 

Institute  of  Metals.  121,  174, 
2:3.3.  282,  301. 

Institute  of  Physiow,  379. 

Institution  of  Electrical  Engi- 
neers, 111,  121.  141.  152,  217, 
233.  246.  281,  285.  301.  345 

Institution  of  Mining  Engi- 
neers. 345. 

Institution  of  Petroleum  Tech- 
nologists, 121.  1.52.  172,  217, 
2U.  301,  317. 

Interferometer,     A      universal, 

Inter  national  Western  Electric 


426 


Index. — Supplement  to  the  Chemical  News. 


AUGUST  3,  1923. 


Company,    Exhibits    at  the 
Eoyal     Society        Conversa- 
zione, 328. 
Inventors,  Caution  to,  285. 
Iron  and     Steel   Institute     An- 
nual Meeting,  233. 
Iron  and  alumina,   Eapid  esti- 
mation,  128. 
compounds,       Reduction       of 

methylene  blue  by,  298. 
mercury  calorimeter,  330. 
Resistance     to     corrosion     of 
stainless  steel  and,  248. 
Iron    tri-carbide.    Etching   pro- 
nertiss  da  and  /3  forms  of, 
313. 
Isotopes,  353. 
of  zinc.  Separation,  171. 


JAMES,  A.  r.  BRODIE.  "Ni- 
trate    Facts     and  Figures, 

1923"   {Review),  287. 
Japanese       Chemical       Society, 

270,  335. 
peti'oleum,   Naphthenic    acids 

from,  220. 
Jeans,  J.  H.,     Present  position 

of  the     radiation     problem, 

344. 
Jefirey,  F.  H.,  Electrolysis  with 

an   aluminium   anode,   140. 
Jephcott,     H.,     Estimation     of 

fat,  lactose  and  moisture  in 

dried  milks,  299. 
Jevon,  W.,     Line  spectrum     of 

chlorine   in  the   ultra-violet 

region,  102. 
Joel,    Ernest,    "Klinische     Kol- 

loidchemie"  (Review),  414. 
Johnson,  R.  C,  and  T.  R.  Mer- 

ton.     (See  Merton,  T.  R.) 
Johnston,     Reginald     G.,      and 

Seymour  Pile.  (See  Pile,  S.) 
Joly,   John,     Bearing     of  some 

recent  advances  in  physical 

science  on  geology,  315. 
Jones,   Eveline,   and  Gilbert  T. 

Morgan.      (See   Morgan,    G. 

T.) 
Jones,  Osman,     Notes    on     the 

examination    of      preserved 

meats,   120. 
Juritz,  Charles  F..     A  note  on 

Kaffir  melon  oil,  356. 
Notes  on  the  active  principles 

of     some        South     African 

plants,  67,  87. 


i,   Q.     W.     C,     and     Ezer 

"Griffiths.    (See  Griffiths,  E.) 

Kaye,  G.  W.  C.,  and  W.  F.  Hig- 
gins.  Photomicrographs  of 
woods,  330. 

Kaye,  G.  W.  C,  and  J.  K.  Rob- 
erts, Thermal  conductivi- 
ties of  metal  crystals,  357. 

Kayser,  J.  Ferdinand,  Heat 
and  aoid  resisting  alloys, 
246. 

Kendall,  James,  and  Edwin  E. 
Slosson,  "Smith's  Inter- 
mediate Chemistry"  ( Jic- 
view),   15. 

Kentucky,  A  recently  found 
meteoric  iron  from  Glas- 
gow, 63. 

Kline,  Harry,  and  N.  A.  Lahge. 
(See  Lange,  N.  A.) 

Knecht,  E.,  and  G.  H.  Streat, 
Investigations  on  the  eon- 
stituentis  of  raw  cotton,  76. 

Koppf,  A.,  "The  Mathematical 
Theory  of  Relativity"  (Re- 
view), 223. 


LTAMM,     OLIVER,     "Qualita- 
*  ^    tive     Organic        Analysis" 
(Review),  414. 


LACTOSE     determination     by 
the  polarimetric  and    gra- 
vimetric method,  299. 
estimation,  191. 
in  dried     milks.     Estimation. 
299. 

Landon,  J.  W.,  and  H.  Quin- 
noy.  Experiments  with  the 
Ilopkinson  pressure  bar, 
395. 

Lang,  Miss  E.  D.,  L.  Bairstow 
and  Miss  B.  M.  Cave.  (See 
Bairstow,  L.) 

Lange,  N.  A.,  and  Harry  Kline, 
The  use  of  n>alic,  maleic 
and  fumaric  aoids  in  volu- 
metric analysis,  42. 

Larch  c-hermes.  Researches 
upon,  and  their  bearing 
upon  the  evolution  of  the 
Chermesinae  in  general 
118. 

Laughton,  N.  B.,  Reflex  con- 
tractions of  the  cruralis 
muscle  in  the  decerebrate 
and  spinal  frog,  119. 

Lead,  Experiments  on  the  hard 
ness  and     spontaneous     an- 
nealing of,  315. 
Vapour  pressure  of,  171 

Lead-antimony  alloys.  Electric 
potential  of,   141. 

Lee,  W.  B.,  and  A.  C.  Egerton 
(See  Egerton,  A.  C.) 

Leeds   University,   277. 

Lees,  C.  H.,  Inductively 
coupled  low-resistance  cir- 
cuits,  150. 

Loes,  C.  H.,  and  J.  E.  Calthrop, 
Effect  of  torsion  on  the 
thermal  and  electrical  ron- 
ductivities  of  metals,  376. 

Lewis,   Dartrey,     Scientific     in- 


vestigations    on   metal   pol- 
ishing and  grinding,  182. 

Lewkowitsch,  J.,  "Chemical 
Technology  and  Analysis  of 
Oils,  Fats"  and  Waxes"  (jRe- 
view),  222. 

Liechti,  F.  E.,  Analysis  of 
ancient  br<)nze,  413. 

Liesegang  rings.  Silver  ohro- 
mate  in  gelatin  and  colloid- 
al gold  in  silicic  acid  gels, 
37. 

Light,  Influence  of  temperature 
on  the  biological  action  of, 
298. 

Linddelof's  hypothesis  con- 
cerning the  Riemann  Zela- 
function,  280. 

Lindemann,  F.  A  ,  and  G.  M. 
B.  Dobson,  Temperature  of 
the  air  at  great  heights, 
280. 

Liquid,  Free  motion  of  a 
sphere  in  a  rotating,  at 
right  angles  to  the  axis  of 
rotation,  396. 

Littlewood,  J.  E.,  and  G.  H. 
Hardy.   (See  Hardy,  G.  II.) 

Livingstone  College  Commem- 
oration Day,  ^8. 

Ljubljana  trade  fair,  319. 

London  University,  King's  Col- 
lege,    and     King's     C^llegfj 
for   Women,  59. 
University  College,  319. 

Loring,  F.  H.,     "Atomic  Theo- 
ries"  (Review),  253,  270. 
Is  there  an  element    of    zeio 
atomic   number?     307,     325, 
371. 
Missing      elements      in      the 

periodic  table,  1. 
Note  on  the  atomic  weight  of 

titanium,  385. 
Valency  and  radiation,  273. 

Lowenfeld,  Henry  and  Mar- 
garet, "Back  to  Prosper- 
ity"  (Review),  207. 

Lucas,  A.,  Examination  of  fire- 
arms and  projectiles,  173. 

Luochesi,  P.,  Rapid  estimation 
of  iron  and  alumina,  128. 

Lumiere,  A.  and  L.,  and  A. 
Seyewetz,  Chemistry  of  the 
red  toning  of  sulphide- 
toned  prints,  374. 

Lunge,  George,  "Manufacture 
of  Acids  and  Alkalis"  (Re- 
view), 398. 

Luppo-Cramer,  Dr.,  The  most 
imjiortant  adsorption  re- 
actions in  the  photographic 
film.  362. 
Nucleus  isolation  and  descn- 
sitisation,  375. 

Lush,  E.  J.,  Oil  hydrogena- 
tion,  235. 


M 


cBAIN,  J.     W.,     Study     of 
soap     solutions      and     its 


AUGUST  3,  1923. 


Index. — Supplement  to  the  Chemical  News. 


427 


bearing  on  colloid  chemis- 
try, iU. 

MacBride,  E.  W.,  Bemarks  on 
the  inheritance  of  acquired 
characters,  73. 

McL>owall,  K.  J.  S.,  J.  C.  Bram- 
well  and  B.  A.  MoSwiney. 
(See  Bramwell,  J.  C.) 

MacGregor-Morris,  J.  T.,  and 
E.  Mallett,  Sand  figures 
showing  the  namerouH  reso- 
nant modes  of  vibration  of 
telephone  receiver  diaph- 
ragms, 327. 

McLachlan,  N.  W.,  Novel  in- 
strument for  recording 
wireless  signals,  378. 

McLennan,  J.  C,  Helium  and 
its  uses,  369. 

McLennan,  J.  C,  and  D.  S. 
Ainslie,  Fluoreecence  and 
channelled  absorption  spec- 
tra of  ceesium  and  other  al- 
kali elements,  188. 

MacLeod,  Annie  L.,  and  Carle- 
ton  Ellis.     (See  Ellis.  C.) 

MacLeod,  D.  B.,  Viscosity  of 
liquid  mixtures  showing 
maxima,  140. 

McLintock.     W.  F.     P..    On     a 

B!talite-bearing  rock     from 
evonshire,   410. 

McMaster,  L.,  und  K.  L.  Shri- 
nor.  Decomposition  of  the 
aminobensoic  ackls  by 
lx>iling  water,  3W. 

McMaster,  Philip  D.,  and  Pey- 
ton Rous^  Hydrohepatosis, 
a  condition  analogous  to 
hydronephrosis,  286. 

McSwinoy,  B.  A..  J,  C.  Bram- 
well and  K.  J.  S.  AfcDow- 
all.     (5ee  Bramwell.  J.  C.) 

Mack,  K.,  Influence  of  hnmic 
acids  on  the  asHiinilntion  of 
phosphoric  acid,  229. 

Magnesium  in  aluminium  al- 
leys,  Estimation,   17. 

Magnet,  A  devitating,  330. 

Magnetic  bodies.  Susceptibility 
as  affected  by  tension,  104 
flelds,  Influence  on  the  polari- 
sation of  resonance,  radia- 
tion, 311. 
phenomena  in  the  region  of 
the     south    magnetic     pole, 

«Xf4. 

rotation,  Law  of,  197. 

Malaya.  British,  Chemical 
trade  in,  156. 

Mallett.  E.,  and  J.  T.  MacG  e- 
gor-Morrie.  (See  MacOre- 
gor-Morris,  J.  T.) 

Mallock,  A.,  Effect  of  tt^mpera- 
ture  on  some  of  the  pro- 
perties  of  steel,  150. 

Man  nnd  the  loe-agp,  74. 
Variation  of    arterial    elasti- 
city with  blood  pressure  m, 

Manley.  J.  .T.,  Further  im- 
provement in  the  Sprongel 
pump.   106. 

Miiniiro.  Town   rofuRo  as,  29.5 

Mnrdlos.  Ernest  Wnlfor  ,Tolin. 
Elasticity  of  organo-Rcls  of 
cellulose  acetate,  314, 

Marine  and  aerial  craft,  Find- 


I  ing  the  true  vertical  for  all 

types  of,  406. 

Marshall,  John  Albert,  Bacter- 
ioidal  properties  of  the  pro- 
ducts of  radium  emana- 
tiim,  31. 

Masson,  Irvine,  Apparatus  for 
measuring  the  compressi- 
bility of  gases,  332. 

Masson,  Irvine,  and  L.  G.  F. 
Dolley,  Pressures  of  gase- 
ous mixtures,  279. 

Materials,  Strength  of,  103. 

Matter,  Passage  of  catlivde 
rays  through,  396. 

Maxted,  Edward  B.,  Catalyst 
poisoning,  149. 

Meats,  Examination  of  pre- 
served, 120. 

Medicaments  for  Bulgaria,  201, 

Mellor,  J.  W.,  "Compi-ehensive 
Treatise  on  Inorganic  and 
Theoretioal  Chemistry" 

(Review),  270. 

Melrose,  C,  Peruvian  petro- 
leum, 142. 

Mendip  Hills,  New  copper-lead 
minerals  from.  410. 

Mercurons  bromide  and  am- 
inoninm  hydrate.  Inter- 
action, 225. 

Merrill,  George  P.,  A  recently 
found  meteoric  iron  from 
Glafigow,  Kentucky,  63, 

Merton,  T.  R.,  and  B.  C.  John- 
son. Spectra  associated  with 
carbon,  279. 

Metal,   Monel.  247. 
polishing  und  grinding.     Sci- 
entific    investigations      on. 

lae. 

Metals,  Colouring  of,  4. 

Effect  of  torsion  on  the  ther- 
mal and  electrical  oonduc- 
tivities  of.  376. 

Empire's  re8oiir<cs  in  the 
le.H6   coinnion,   82. 

**'  of     the     scxalled 

'  ion  of,  248. 

Met«-<trip  iron  from  Glasgow, 
Kentucky,  63. 

stone  which  fell  at  Ashdon, 
Essex,     on   March  9,     1923. 

Meteorite,  The  Sinai,  411. 

Methane  synthesis.  88. 

Methylene  blue.  Reduction  bv 
iron   comimunds,  298. 

Microscope,     Illumination       of 
ordinary  objects     with     po- 
larised light  under,  328. 
Illuminator    for   opaque     ob- 
jects  under,  328. 

Microsoopio  interferometer.  Ex- 
perimental demonstration 
with,  888. 

Milks,  Estimation  of  fat,  lac- 
tose    and  moisture  in,  299. 

Mineral  output  of  Yukon.  268. 

''■waTei""275."'     ''*"       ^^^^'^ 
Mineralogical   Society,     82.     58 

173,  .398,  410, 
Mining  Kxliibition,  365, 
Missondon.  John.     Note  on  the 
preimration    of     saroolactic 
acid,  251. 
Note  upon   the  properties  of 
muscarine,  401. 


Potassium  permanganate    ap- 
plications      to       exooecaria 
agallocha,  303. 
Rare  earths  and  their  metals, 
51,  97. 
Mitchell,   C.   Ainsworth,   "Ink" 

(Review),  271. 
Moll,  W.  J.  H.,    New    moving- 
coil  galvanometer     of  rapid 
indication,  282. 
Tliermopile     for      measuring 
radiation.  282. 
Molybdenum,   Electrometric   ti- 
tration    with     a      titanous 
salt,  385. 
Mouel  metal,  247. 
Monier-Wilfiams,   G,   W.,   Esti- 
mation    of     boric     acid     in 
liquid  eggs  and  other  food- 
stuffs, 232. 
Monochloramine,   .Action  of   po- 
tassium cyanide  on,  100. 
Monypenny,  J.   H    G.,     Itesist- 
ance  to  corrosion    of  stain- 
less steel  and  iron,  248. 
Morgan,  E,  J.,  and  J.  H.  Quus- 
tel.  Reduction  of  methylene 
blue     by    iron     compounds, 
298. 
Morgan,  Gilbert  T.,    The     Em- 
pires resources    in  the  less 
common   metals.  82. 
Interaction     of   foruialdchydo 
and       the      nitro-napht'ivl- 
amines,  154. 
Morgan,  Gilbert  T.,     and  Eve- 
line Jones,  Preparation     of 
/!i-naphthol-4-surphonio  acid, 
154. 
Morley,  A.  M.,  and  J.  K.  Wood. 

(See  Wood,  J.  K.) 
Morocco  phospliate   tieds,  138 
Morpliine  factories,  156. 
Mother-of-pearl,     Colours       of, 

151. 
Motor,  Method  of  running  a  di- 
rect-current,    in     synchron- 
ism with     a    tuning     fork, 
329. 
Moullin,  E.  B.,  Direct     reading 

tliermionic  voltmeter,  331. 
Mueller,  Edward,  "The  Exami- 
nation of  Hydrocarbon  Oils 
and     of     Sajpouifiable     Fats 
and  Wuxca"^  (flcuieir),  383. 
Mulliken,       Samuel       P,,       'A 
Method  for     the    Identifica- 
tion of  Pure  Organic  Com- 
pounds" (Review),  158, 
Muscarine,    Properties  of,  401 
Museum  exhibits,  Cleaning  and 

restoration  of,   159. 
Munaffar,   S,    D„     Electric     po- 
tential of  antimony-lead  al- 
loys, 140. 


NAC.AT.  S„    and    Y,  Tanaka 
'Sec  Tanaka.   Y,) 
Nanii,  D.  R..  and  W.  P.  Shaw. 
Keaction    between  ammonia 


428 


Index. — Supplement  to  the  Chemical  News. 


AUGUST  3,  1923. 


and     sodium     hypobromite, 
235. 

Neplielometer  with  observation 
tubes  of  fixed  height,  327 

Nernst,  Walter,  "Theoretical 
Chemistry  from  the  Stand- 
point of  Avogadro's  Eiile 
and  TheTmodvnami<?s"  (i?e- 
view),  383. 

New  South  Wales,  Mineral  pro- 
duction  of,  275. 

Newth,  G.  S.,  "Inorgc;nic 
Chemistry"    (Revieic),   95. 

Nickel   catalyst.   Action  of  alu- 
mina  and  other     oxidee   in 
promoting  the  activity     of. 
358. 
detecting   in     solution.     New 

method,  200. 
in  toluene  and  iDcnzene,   172. 

Nile  silt,  Titanium  in,  120. 

Nitrates,  New  test  for,  261. 

Nitrogen,  Energy-absorbimr 

function   and   activation   of. 
in     combustion     of     carbon 
monoxide,  278. 
industry,  Germany's,  276. 

Nitronaphthylamines  and  for- 
maldehyde. Interaction,  154. 

Niven,  C.  D.,  The  speed  of 
chemical  reaction  through 
a  solid,  183. 

Nixon,  Ivor  G.,  A  new  test  for 
nitrates,   261. 

Norbury,  A.  L.,  Some  experi- 
ments on  the  hardness  and 
spontaneous  annealing  of 
lead,  315. 

Norrish,  R.  G.  W.,  and  E.  K. 
Eideal.   (See  Rideal.   V..   K.) 

Northall-Laurie,  D.,  Photomi- 
crographs of  crystals  in 
colour  mounted  to  show 
changing  tints,  329. 

Norway's  foreign  trade,  156. 

Nucleus  isolation  and  densiti- 
sation,  375. 


OBITUARY,        Dewar,        Sir 
James,  220. 
Wooley,  W.,   109. 
Oil   hydrogenation,  2.35. 
Kaffir  melon,  356. 
Simonsens,       pyridine        and 

wood  naphtha,  217. 
wells,  Potrero  No.  4,     A  his- 
tory of  one  of  Mexico's  ear- 
liest and  largest,  234. 
Oils,   Lubricating,   under     elec- 
trostatic stress,  332. 
paints     and       varnishes     for 
Egypt,   202. 
Optical  Society,   152,     190,     233, 

312,  345,  364. 
Organic  compounds,  New  sys- 
tem for  the  linear  repre- 
sentation of  the  structure 
of,  33,  49,  66. 
compounds.  Method  for  the 
naming  of  all,  113. 


Osbon,  C.  C,  and  E.  K.  Soper. 
(^ee  Soper,  E.  K.) 

Osoillograpn,  Cathode  ray,  12. 
Cathode  ray.  Low  voltage,  13, 
328. 

O'Shaughnessy,  F.  R.,  Physics 
and   sewage  disposal,  250. 

Osmotic  effects.  Origin  of,  310. 

Overy,  Rev.  Charles,  Glacial 
succession  in  the  Thames 
catchment-basin,   108. 

Owen,  D.,  Null  methods  of 
measurement  of  power  f.ic- 
tor  and  effective  resi.stancc 
in  alternate  current  cir- 
cuits by  the  quadrant  elec- 
trometer, 106. 

Owen,  E.  A.,  and  G.  D.  Pres- 
ton, Modification  of  the 
powder  method  of  deter- 
mining the  structure  of 
metal  crystals,  11. 
X  ray  spectrum  of  alloys, 
330. 

0.xidation  of  copper,  311. 

Oxide  of  a  new  element.  Isola- 
tion of,  297. 


P  A1>UA    Sample  Fair,  367. 

Paget,  Sir  Richard,  The  pro- 
duct of  artificial  vowel 
sounds,  101. 

Palmer,  Leroy  S.,  "Carotinoids 
and  Related  Pigments,  the 
Chromolipoids"  (Review) 
78. 

Palmer,  W.  G.,  A  study  of  the 
oxidation  of  copper  and  tJie 
reduction  of  copper  oxide 
by  a  new  method,  311. 

Papers,  Quantitative  determi- 
nation of  hemp  and  wood 
in,  299. 

Para-  nitrobenzylpyridiniuni 
salts,  182. 

Parsons,  Sir  Charles  Algernon, 
Award  of  the  Faraday 
Medal  to,  141. 

Pasteur,  97. 

Patents  in  1922,  36. 
New,  16,  32,  48,  64,  80,  96,  112. 
128,  144,  160,  176,  192,  208. 
224,  240,  256,  272,  288,  304, 
320,  336,  352,  368,  384,  400. 
416. 

Periodic  table.  Missing  ele- 
ments in,  1. 

Perman,  Edgar  Philip,  and 
Horace  Leonard  Saunders, 
Vapour  pressures  of  con- 
centrated cane  sugar  solu- 
tions, 314. 

Perrin,  Jean,  "Atoms"  (Re- 
view), 271. 

Peru,  63. 

Peruvian  petroleum,  142. 

Petalite-bearing  rock  irom 
Devonshire,  410. 


Petroleum,  Heavy  grade  Egyp- 
tian crude,  317. 
Japanese,     Naphthenic     acids 

from,  220. 
Peruvian,  142. 

Pfestorf,  A.,  Pi-eservation  and 
use  of  articles  made  of  rub- 
ber, 308. 

Pharmaceutical  preparations. 
Machinery  for,  required  in 
Australia,  4^1. 

Phelan,  Joseph  W.,  and  Arthur 
A.  Blanchard.  (See  Blanch- 
ard,  A.   A.) 

Phillips,  Sydney  B.,  Determi- 
nation of  the  purity  of 
vanillin,  173. 

Phosphate  beds,   Morocco,   138. 

Photochemistry  of  potassium 
permanganate,  89. 

Photographic  Fair,  218. 
film.  The  most  important  ad- 
sorption   reactions   in,   362. 
materials  for  Ecuador,  278. 
process.     Physical     chemistry 
of,  318,  346. 

Photographs,  Exhibition  of 
three  series  of,  331. 

Photography,  Some  future  pro- 
blems in,  374. 
Theorv  of.  359. 

Physical  science.  Bearing  of 
some  recent  advances  in,  on 
geology,  315. 

Phvsical  Society,  10,  105,  282, 
342,  376,  406. 

Physics  and  sewage  disposal, 
250. 

Physiological  processes    of     the 
human  body.  Effect  of  high 
altitude  on,  72. 
standards,  232. 

Piloher,  Richard  B.,  Caution  to 
inventors,  285. 

Pile,  Seymour,  and  Reginald  B. 
Johnston,  "Tested  Metliod 
of  Laboratory  Organisa- 
tion"  (Review),  255. 

Pinner,  Royal  Commei-cial  Tia- 
vellers'  Schools,  416. 

Plagioclases     in  cleavage-flakes. 
Dispersion     method   of     de- 
termining, 411. 
Optical     dispersion    of    three 
intermediate,  410. 

Plant  respiration  problems, 
considered  as  a  catalytic 
process,  405. 

Plants,  .South  African,  Notes 
on  the  active  principles  of 
some,  67,  87. 

Plate  sensi.tometry,  351. 

Platinum  deposits,   13. 

Plotnikov,  J.,  Some  future  pro- 
blems in  photography,  374. 

Poisoning,  Catalyst,  149. 

Poland,  Trade  with,  246. 

Polarisation,     Detection    of   ro- 
■  tatory,  in  an  oTtho-rhonibic 
crysfal    exhibiting      crossed 
axial  dispersion,  411. 

Polymorphism  in  an  inter- 
metallic  compoTind,  An  ex- 
ample of,  313. 

Poschl,  Viktor,  "Einfiihrung  in 
die  KoUoidchemie"  (Re- 
vieto),  319. 

Pot  arches.  Notes  on  the  design 
of,  409. 


AUGUST  3,  1923.        Index. — Supplement  to  the  Chemical  News. 


120 


Pota«h  industry,  Germany's, 
230,  276. 

Potassium  and  sodium,  A  new 
distinction   between,   193. 

Potassium  bromide  or  sodium 
bromide.  Use  as  a  source  of 
bromine  for  urea  estima- 
tions,  180. 

Potaaeium  chlorate  crystals, 
Ck)lour8  of,  150. 

Potassium  cyanide,  -\ction  on 
monochloramine,   100. 

Potassiuni     permanganate     ap- 
plications      to       excoecaria 
agallocha^  303. 
Photochemistry  of,  89. 

Potentiometer,  Application  to 
the  study  of  photochemical 
change,  89. 

Poulson,  Joseph,  Experiences 
of  v.>rtical  retorts.  154. 

Pound,  J  R.,  Notes  on  the  es- 
timation of  tungsten  in 
ores,  3ij0 

Power,  Frederick  B.,  and  Vic- 
tor K.  Chesbnut,  The  odor- 
ous const  tuents  of  apples, 
45. 

Power  fnc-tor.  Nu(l  meiho.l3  of 
measurement  of,  and  effec- 
tive resistance  in  alternate 
■urre-it  circuits  by  the 
quadrant  electrometer,  106 

Prague  University,  76. 

Pressure.  Intermittent,  Experi- 
ment on  the  production  of, 
by  boiling  water,  377. 

Preston,  Q.  D.,  and  E.  A.  Owen. 
(See  Owen,  E.  A.) 

Price,  T.  Slater,    Photographic 

frocess.     Physical     chemis- 
ry  of  the     vehicle  and     of 
the  emulsion,  34/6. 
Prince,  C.  E.,  Electro-capillary 
relay     for    wired      wireless. 
107. 
Prior.  O.    T..     Meteoric    stone 
which  fell    at  Anhdon.     Es- 
sex, on  March  1,  1923,  411. 
The  Sinai   meteorite.  411. 
Pyridine,     simonsens    oil     and 
wood  naphtha.  218. 


QUARTZ.       Effect       of      long 
grinding  on,  90. 
gunstel,  J.  H..  and  E.  J.  Mor- 
gan.    (See  Morgan,  E.  J.) 
Quinney.  H.,    and  J.  W.    Lan- 
don.    (See  Landon,  J.  W.) 


DADCLIFPE,    L.  G.,  and  W. 
*^     Gibson.     Hydroxy     eteario 
acid.  78. 


Radiation,   Influence  of  magne- 
tic fields  on  the  polarisation 
of  resonauc-e,  311. 
problem.  Present  position  of. 

Thermopile     for      measuring, 
282. 

Radium  emanation.  Bacterici- 
dal properties  of  the  pro- 
ducts of.  31. 

Radium   D  and  radium  E. 
7 Hays   from,  370. 

Rain  and  snow,  .Substances  dis- 
solved in,  113. 

Rastall,  R.  H..  "Cements  and 
Ajtifirial  Stone"  (Rerieir). 
159. 

Bay,  R.  C.  Effect  of  long  grind- 
ing on  quarts  (silver  sand), 
90. 

Rayleigh.  Lord,  Further  obser- 
vafionf?  on  the  spectrum  of 
the  night  »kv.  187. 
Studies  of  iriaescent  colour, 
and  the  structure  produc- 
ing it.  150.  188. 

7  -Rays  from  radium  D  and 
radium  E.  370. 

Redgrove.  H.  Stanley,  Authen- 
ticity of  the  Latin  works  of 
Gelw-r.  191.  221. 

Redwood.  Sir  Boverton,  and  J. 
H.  Thomson.  (See  Thom- 
son, J.  H.) 

Reflexes,  Irradiation  of  condi- 
tioned.  118. 

Refraction.  Double,  due  to  mo- 
tion of  a  vanadium  pent- 
oxide  sol.  284. 

Refractive  index  of  American 
turpentine.  Tem^rature 
coefficient  of.  29 

Reinsch  test  for  aTMOic  and 
antimony,  Chemistry  of, 
and  itH  extension  to  bis- 
muth, 232. 

Relativitv,   Aberration  and  the 
Ddppior  effect  as  treated  in 
the  theory  of.  aSS. 
Einstein's  theory  of.  373. 
Further  confirmation  of  Ein- 
stein's theory  of.  2S2. 

Reptilian  remains  from  the 
Karroo  beds  of  East  Africa. 
MM. 

Retorts.  Experiences  of  verti- 
cal. 154. 

Richards.  Theodore,  W..  Com- 
pressibility, internal  pres- 
sore  and  atomic  magni- 
tudes. 216.  274. 

Richardson.  Lewis  F..  Theory 
of  the  measurement  of  wind 
by  shooting  spheres  up- 
ward, 104. 

Richardson,  O.  W.,  Magnitude 
of  the  gyromagnetic    ratio, 

Rideal,  E.  K..  Recent  develop- 
ments in  contact  catalysis, 
418. 

Rideal.  E.  K.,  and  R.  G.  W. 
Norrish.  The  photochemis- 
try of  potassium  permanga- 
nate. 89. 

Rimmer,  W.  B.,  Spectrum  of 
ammonia,  369. 

Roberts,  J.  K.,  and  G.  W.  C. 
Kaye.  (See  Kaye.  G.  W.  C.) 


Robertson,  Sir  R.,  and  W.  E. 
Garner,  Caloriuietry  of 
high  explosives,  ;Jn9. 

Kobinovitch,  Louise  G.,  A  che- 
mical basis  for  the  treat- 
ment of  tuberculosis,  369. 

Robinson,  C.  S.,  "The  Kecovery 
of  Volatile  Solvents"  (Uv- 
vieto),  272. 

Rosen,  A.,  Use  of  Wien  bridge 
for  the  measurement  of  the 
losses  in  dielectrics  at  high 
voltages,  377. 

Rosenhain,  W.,  Structure  of 
alloys,  301. 

Roumania,  Drugs  and  chemi- 
cals for,  297. 

Rous,  Peyton,  and  Philip  D. 
McMaster.  (See  McMaster, 
P.  D.) 

Royal      Agricultural       Societv. 
189,  316,  397. 
Institution,     75,   105,   110,   121, 

140,  152.  172,     188,  232,     249 
X8,  280,     301,  312,  335. 
365,  376,  397. 

Microscopical     Societv, 

141,  203.  269,  365.     ' 
Society,  .W,  72,     88,    101. 

130,   150.  170,     186,  203, 

278,     298,  300,  333,  342. 

373.  394.  404. 
Conversasione,  327. 
Society  of  Arts.     22.  35, 

174,  190,     216.  2.12.  246,     . 

280,  300.  312.  345.  359.  376. 
RubJjer       growing       proposals, 

American,  138. 
Preservation  and     use  of  lu- 

tides  made  of,  308. 
vulcanisation,    129. 
Russ,  Sidney,  Effect    of  X  ravs 

of     different       wave-lengtfis 

upon  some  animal  tissues. 

357. 
Rutherford,  Sir     Ernest,     Ato- 
mic  projectiles     and     their 

properties,  397. 
Rutiie,    Dartmoor     occurrences 

of,  68. 


342, 

121, 

118, 
268, 
357. 


140. 
268, 


SAFEGUARDING  of  Indue- 
trios  Act,  156. 

Siikoschansky,  Alexander,  Pe- 
riodic function  of  atomic 
weights,   372. 

.Salainon,  Maurice  S.,  Melting- 
point  and  iodine  value  of 
refined  natural  D-camphor, 
300. 

Sarma,  V.  V.,  Cuprous  sul- 
phites, 61. 

Sa-^katchewan,  Ceramic  depo- 
sits of.  277. 

Saunders.  Horace  Leonard,  and 
Edgar.  Philip  Perman.  (Set- 
Perman,  E.  F.) 

Schiere,  E.  R.  Decomposition 
of  formic  acid  by  sulphuric 
acid,  149. 


430 


Index. — Supplement  to  the  Chemical  News. 


AUGUST  3,  1923. 


Schofield,  F.  H.,  and  Ezer  Gri- 
ffitlis.     (See  Griffiths,  E.) 

Schonland,  R.  F.  J.,  Tlie  pas- 
sage of  cathode  rays 
through  matter,  396. 

Scientific  literature.  The  style 
of,  209. 

Soott,  Alexander,  Isolation  ot 
the  oxide  of  a  new  element, 
297. 
New  element  belonging  to  the 
fourth  group  of  the  period- 
ic system,  81. 

Seismic  waves  in  a  visco- 
elastic  earth,  395. 

Selenium,  Electrometric  titra- 
tion in  the  presence  of  tel- 
lurium, iron  and  copper, 
388. 

Sewage  disposal.  Physics  and, 
250. 

Seyewetz,  A.,  and  A.  and  L.  Lu- 
miere.  (^ee  Lumieje,  A. 
and  L.) 

Shaw,  W.  F.,  and  D.  E.  Nanji. 
(See  Nanji,  D.  R.) 

Shearer,  G.,  Relation  between 
molecular  and  crystal  sym- 
metry as  shown  by  X  ray 
crystal  analysis,  10. 

■Shappard,  S.  E.,  F.  A.  Elliott, 
and  S.  S.  Sweet,  Notes  on 
the  photographic  chemistry 
of  gelatin,  347. 

Sheppard,  S.  E.,  A.  P.  H.  Tri- 
velli  and  E.  P.  Wightman. 
Exposure  theories,  §i9. 

Short,  W.  F.,  Action  of  potas- 
sium cyanide  on  monochlor- 
amine,  100. 

Shriner,  R.  L.,  and  L.  Mc- 
Master.   (See  McMaster,  L.) 

Silicon,  Series  spectrum  of 
trebly-ionised,  309. 

Sillimanite,  Natural,  as  a 
glass  refractory,  364. 

Silver  bromide  emulsion.     Sen- 
sitivity of,  374. 
Solubility  in  ammonium  bro- 
mide and  gelatin,  347. 

Silver  chromate  in  gelatin,  37. 

Simeon,  F.,  The  carbon  arc 
spectrum  in  the  extreme 
ultra-violet,  101. 

Simeons,  F.,  and  F.  Twyman. 
(See  Twyman,  F.) 

Sinai  meteorite,  411. 

.Sky,  Spectrum  of  the  night,  187. 

Slosson,  Edwin  E.,  and  James 
Kendall.     (See  Kendall,  J) 

S^iokes,  Method  of  determin- 
ing the  size  of  the  particles 
they  contain,  90. 
study  of  their  behaviour  and 
method  of  determining  the 
number  of  i>artieles  thay 
contain,  90. 

Snow  and  rain,  Snbstances  dis- 
solved in,  113. 

Soap  solutions.  Study  of,  and 
its  bearing  on  colloid  chem- 
istry, 413. 

Society  of  Chemical     Industry, 
Birmingham     and    Midland 
Section,   154,  235. 
of  Dyers  and  Colourists,  Man- 
chester Section,  75. 
of  Glass  Technology,     92,  121, 


151,  190,     217,  260,  281,     312, 
363,  398,  408. 
of  Public  Analysts,     22,     152, 

172,  232,  281,  299. 
Annual   General   Meeting,  36, 
120. 

Sodium  and  potassium,  A  new 
distinction  between,   193. 

Sodium  bromide  or  potassium 
bromide.  Use  as  a  source  of 
bromine  for  urea  estima- 
tions,  180. 

Sodium  carbonate  compounds 
with  fatty  acids,  214. 

Sodium  chloride  solutions.  Va- 
pour pressure  and  den  sit  v 
of,  280. 

Sodium   hypobromite     and   am- 
monia,    Reaction     between, 
235. 
Apparatus     for  the    recovery 
of  bromine  from,  55,  95. 

Sodium  hypochlorite.  Cataly- 
tic decomposition  by  co- 
balt peroxide,  395. 

Sodium   oxalate    solution,     Sta- 
_  bility  of,  150. 

Soils,  Flocculation  and  de- 
flocculation  in,  330. 

SoUas,  William  Johnson,  Man 
and  the  ice-age,  74. 

Sols.  Metal,  in  non-dissociating 
liquids,  172. 

Soper,  E.  K.,  and  C.  C.  Osbon. 
"The  Occurrence  and  Uses 
of  Peat"  (Review),  143. 

Sounds,  Production  of  artificial 
vowel,  101. 

Spain,  Market  for  surgical  in- 
struments, needles  and 
rubber  goods  in,  341. 

Speakman,  J.  B.,  and  R  Whvt- 
law-Gray.  (See  Whytlaw- 
Gray    R.) 

Speakman,  J.  B.,  R.  Whytlaw- 
Gray,  and  J.  H.  P.  Camp- 
bell. (See  Whytlaw-Gray, 
R.) 

Spectra  associated  with  carbon. 
279. 

Spectrum,     Band,     of     helium. 
Structure  of,   187. 
Carbon   arc,   in   the     extreme 

ultra-violet,  101. 
Line,  of  chlorine  in  the  ultra- 
violet   region,    102. 
of  ammonia,  359. 
of  the  night  sky,  187. 
X  ray,  of  alloys,  330. 

Spencer,  L.  J.,  New  copper- 
lead  minerals  from  the 
Mendip  Hills,  Somerset,  410 

Speyer,  E.  R.,  Researches  upon 
the  Larch  Chermes  and 
their  bearing  upon  the  evo- 
lution of  the  ChermesincE 
m  general,  118. 

Spheres,  Free  motion  in  a  ro- 
tating liquid  at  right  angles 
to  the  axis  of  rotation,  396 

Sprengel  pump,  Further  iml 
provement  in,  106. 

Steel,  Effect  of  temperature  on 
some  of  the  properties     of 
150. 
Stainless,     Resistance   to  cor- 
rosion, 248. 
Stainless,  with  some  consider- 


ation of  its  application     to 
the  glass  industry,  93. 

Steward,  G.  C,  Aberration  dif- 
fraction effects,  187; 

Stibine,  Detection  of  traces  of, 
275. 
Heat  of  formation  of,  237. 

Stiles,  W.,  Indicator  method 
for  the  determination  of 
coefficients  of  diffusion  in 
gels,  188. 

Stillman,  John  Maxson,  "Theo- 
phrastus  Bombastus  von 
Hohenheim  called  Paracel- 
sus"  (Review),  174. 

Stockdale,  David,  An  example 
of  polymorphism  in  an 
inter-metallio  compound, 
313 

Stopford,  C.  W.,  and  C.  E.  Dar- 
ling.    (See  Darling,  C.  R.) 

Stott,  v..  Notes  on  burettes, 
369. 

Stream-line  filter,  309,  327. 

Streat,  G.  H.,  and  E.  Knecht. 
(.See  Knecht,  E.) 

Stress  distribution  in  a  rectan- 
gular plate  having  two  op- 
posing edges  sheared  in  op- 
.    posite  directions,  334. 

Strontium  in  natural  brines, 
300. 

Sugar,  Cane,  solutions.  Vapour 
pressures  of  concentrated, 
314. 

Sulphide-toned  prints.  Chemis- 
try of  the  red  toning  of, 
374. 

Sunspot  frequency  and  the  po- 
tential gradient  of  atmos- 
pheric electricity,  Supixjsed 
relationship,   105. 

Surgical  instruments,  needles 
and  rubber  goods.  Market 
for,  in  Spain,  342. 

Swain,  Lorna  M.,  and  A.  Berry. 
(See  Berry,  A.) 

Sweet,  S.  S.,    S.  E.     Sheppard 
and     P.   A.     Elliott.       (See 
■     Shoppartl,  S.   E.) 

Switzerland,  Drugs  required 
in,  278. 

Symmetry,  Molecular  and  cry- 
stal. Relation  between  as 
shown  by  X  ray  crystal 
analysis,  10. 


"TANAKA,   Y.,   and   S.   Nagai, 

*  •   Naphthenie       acids      from 

Japanese  petroleum,  220. 

Tautomerism,  New  aspects  of, 
413. 

Taylor,  G.  I.,  Motion  of  ellip- 
soidal particles  in  a  viscous 
fluid,  103. 

Taylor,  G.  I.,  and  C.  F.  Elam, 
The  distortion  of  an  alu- 
minium crystal  during  a 
tensile  test,  139. 

Taylor,  R.  L.,  "Bleaching 
Powder     and  its  Action     in 


AUGUST  3,  1923. 


Index. — Supplement  to  the  Chemical  News. 


431 


Bleaching"    {Review),   80. 

Teisen,  Tb.,  Some  notes  on  the 
deKign  of   iwt  arches,  M)9. 

Telephone  receiver  diaphragms, 
baud  figures  showing  the 
nuuicrouti  resonant  modes 
of  vibration  of,  327. 

Temperature  of  the  aix  at 
great  heights,  280. 

Tiiames  catchment-basin.  Gla- 
cial succession  in,  108. 

Therm  charges  committee,  76. 

Thermal  and  electrical  con- 
ductivities of  metals,  Efiect 
of  torsion  on,  376. 
conductivities  of  metal  cry- 
stals, 357. 
conductivity.  Measurement  of. 
357. 

Thermopile  for  measuring  ra- 
diation, 282. 

Thomas,  W.,  and  C.  W.  L. 
Bourlet.  (See  Bourlet,  C. 
W.  L.) 

Thomi>so.n,  F.  C,  end  Edwin 
Whitehead,  Notes  on  the 
etching  properfies  of  the  a 
and  /3  forma  of  tri-carbiJe 
of  iron,  313. 

Thompson,  Gartha,  The  tem- 
perature coefficient  of  the 
refractive  index  of  Ameri- 
can   turpentine,   20. 

Thompson,  J.  Q.,  A  prelimin- 
ary study  of  cirkite  ore,  14. 
23,  4a. 

Thomson,  J.  H.,  and  Sir  Bovor- 
ton  Uedwood,  "Handbook 
on  Petroleum"  (Review), 
167. 

Thome.  P.  C.  L.  and  E.  Hat*- 
chek.     (See  Hatschek,  E.) 

Thorpe,  Sir  Edward,  "Diction- 
ary of  Applied  Chemistry" 
(Review),  79. 

Thorpe,  Jocelyn  Field,  and 
Christopher  Kelk  Ingold. 
Some  new  aspects  of  tauto- 
merism,  418. 
"Synthetic  Colouring  Mat- 
ters, Vat  Colours"  (Re- 
view), 207. 

Titanium,    Atomic     weight     of. 
388. 
in  Nile  silt,  120. 

Titration.  Electrometric,  of 
moly))denum  with  a  titan- 
one  salt.  38S. 

Toadstone-olays  of  Derbyshire. 
411. 

Toluene  and  bensene,  Nickel 
in,  172. 

Torsometcr,  A  wave-length,  333. 

To*r.end,  0.  T.  A.,  W  A.  Bono 
and  D.  M.  Hewitt.  (.See 
Bone,  \V.  A.) 

Toy,  F.  C.  Mechanism  of  t.he 
latent  inag?  form^tio  i, 
S49. 

Trade  fairs,  202. 

Trioxymethylene      preparation. 

Triveili,  A.  P.  H„  S.  E.  Shep- 
pard  and  E.  P.  Wightman. 
(.See  Sllo^)pard,  S.  E.) 

Tsuboi,  Scitaro.  Dispersion 
method  of  determining  p!n- 
gioclases  in  cleavago-fliik.'^. 
411. 


Optical  'dispersion  of  three 
intermediate  plagio<-la«>es, 
410. 

Tuberculosis,  Chemical  biisis 
for  the  treatment  of,  369. 

Tucker,  Alex.  S.,  The  colouring 
of  metals,  4. 

Tungsten  in  ores.  Estimation, 
380. 

Tuning  fork.  Valve-maintained, 
as  a  precision  time  stand- 
ard, 105. 

Tunnidiffo.  H.  E.,  and  M. 
Dixon.     (See  Dixon,  M.) 

Turner,  Donald,  and  W.  E.  S.. 
Corrosion  of  fireclay  re- 
fractory material  by  glass 
and  glass-making  materials, 
217. 

Turner,  W.  E.  S.,  Presidential 
address     to  the  Society     of 
Olaoe  TeohnologT,   281. 
Specifications  in  the  glass  in- 
dnstiT.  406. 

Turner.  W.  E.  S.,  H.  S.  Black- 
more  and  Vi<^et  Dimble- 
by.    (See  Blackmore.  H.  S.) 

Turner,  W.  E.  S..  Violet  Dim- 
Ueby.  and  S.  Engliph.  (See 
Dimbleby,  V.) 

Turner,  W.  E.  S.,  Edith  M. 
Firth  and  F.  W.  Hodkin. 
(fee  Firth.  E.   M.) 

Turner.  W,  E.  S..  and  F.  W. 
Hodkin.  (Ser  Hodkin.  F. 
W.) 

Turpentine.  Temperature  c-o- 
effioiont  of  the  refractive 
index  of  American.  20. 

Tutton.  A.  E.  H..  UniTersal  in- 
terferometer. 333. 
WaT©-length   torsometer.  338. 

Twyman.  P..  "Wnvelength 
Table«  for  Spectrum  Ann- 
lysis"  (Review).  2S6. 

Twyman.  P..  and  F.  Simeons. 
Rafractire  index  changoH  in 
optical  irlaM  oocasinnod  bv 
ooilling      and       temp<>rin^. 


U 


KBAIN'S  r4>ltiuni   lines.  2M. 


Urea  estimations.  Use  <^  po- 
tassium or  sodium  bromide 
as  a  source  of  bromine  for, 
180. 

TJrugtiay.  Tenders  invited  for 
general   stores,  366. 

TJrwin,  Norman.  Laboratory 
enquiry,  286. 


rACTJUM        tul>es. 
cooled,  328. 


Water- 


Valency,  177,  193.  209,  226. 
and  radiation,  273. 
Electronic  theory  of,  3t3. 

Van  Klooster,  Henry  S.,  and 
Albert  W.  Davison.  (A'ee 
Davison,  A.  W.) 

Vanadium  pentoxide  sol.  Dou- 
ble refraction  due  to  mo- 
tion of    284. 

Vanillin,  Determination  of  the 
purity  of,  173. 

Varlev,  Thomas,  and  others, 
"The  Chloride  Volatilisa- 
tion Process  of  Ore  Treat- 
ment"  (Review).  399. 

Vector  analysis  of  four  dimen- 
sions, A  generalised,  188. 

Venkatramaiah,  Y.,  Active  hy- 
drogen, new  methods  of 
preparation.  215. 

Vernon.  C.  G..  New  method  of 
detection  of  nickel  in  solu- 
tion, 200. 

Vertical,  Finding  the  true,  for 
all  types  of  marine  and 
aerial  craft,  406. 

ViraragliJiva.  K.  C,  A  study  in 
rjsrthmic  series  of  chemic.d 
c:  ange),  289. 

V  insosity  of  liquid  niixturets 
showing  maxima,  140. 

Voltmeter.  Direct  reading  thsr- 
m  ionic,  381. 

Von  Kichter,  Victor,  "Organic 
Ohemistry,  (r  t.hcmistry  of 
the  Carbon  Coin|)ounds"' 
(Review),  111. 


WAiiL.  It.  U.,  Distribution  of 
insecticides  by  aeroplane 
401. 

WalwiU,  Foreign  samples  ex- 
hibition at,  318. 

Waran,  U.  P.,  "Elements  of 
Glass-blowing"  (Review), 
271. 

Wnrburton.  George  H.,  "Che- 
mical Technology  and  An- 
alysifl  of  Oils,  Fate  and 
Waxes"   (Review),  222. 

Warren,  W.  W.,  Organising 
for  production  from  pot 
furnaces,  152. 

Washburne,  Carleton  VV., 
"Common  Science"  (Re- 
view), 95. 

Waters,  Interpretation  of  the 
results  obtained  in  the  ana- 
lysis of  potable,  173. 

Watson,  John,  "Cements  and 
Artificial  Stone"  (Review), 
150. 

Watt.  R.  A.  Watson,  and  E. 
V.  Appleton,  Nature  of  at- 
mospherics. 279. 

Wave  resistance.  Studies  in, 
884. 

Webb,  R.,  Low  voltage  cathode 
ray  oscillograph,  13. 


432 


Index.  — SuppLEMEM'i  lo  the  Chemical  News. 


AUGUST  3,  1923. 


Weeks,  Edward  J.,  Detection  of 
traces  of  stibine,  275. 
Heat  of  formation  of  stibine, 
237. 

Weinberg,  J.  F.,  Comiwunds  of 
sodium  carbonate  with  fat- 
ty acids,  214. 

Werner,  Emil  A.,  "Chemistry 
of   Urea"    (Revieir),   367. 

Whale,  E.  E.,  The  authenticity 
of  the  LatiK  works  o"f 
Geber,   157 

Wheeler,    1'.   Sherlock,     Method 
for   the   lamin,?  of     &11  or 
gaai-:!'  co(np>i'i  Is.  113. 
New   system    for    the     linear    j 
represe  itation  ni  the  ftruc-    | 
ture     of  fill     <.rganio    com-    j 
pounils    33,  49,  (56.  | 

White.     Staaley,     Physialogiual    i 
standards    232.  ! 

Whitehead,   Edwin,  and  Frank    | 
Charles     Thompson.        (See 
Thompson,  F.  C.) 

Whytlaw-Gray,  R.,  and  J.  B. 
Speakman,  Smokes,  a 
method  of  determining  the 
size  of  the  particles  they 
contain,    90. 

Whytlaw-Gray,  R.,  J.  B.  Speak- 
man, and  J.  H.  P.  Camp- 
bell, Smokes,  a  study  of 
their  behaviour  and  a 
method  of  determining  the 
number  of  particles  they 
contain,  90. 

Whytlaw-Gray.  R.  W.,  Ap- 
pointment, 277. 

Wightman,  E.  P.,  S.  E.  Shep- 
pard,  and  A.  P.  H.  Trivelli. 
(See  Sheppard,  S.  E.) 

Willard,  H.  H.,  and  Florence 
Fenwick,  Electrometric  ti- 
tration of  molyhdonum 
with  a  titanous  salt.  38.5. 


Electrometric  titration  of  se- 
lenium in  the  presence  of 
tellurium,  iron  and  copper, 
388 

Willow-s,  R.  S.,  and  E.  Hats- 
chek,  "Surface  Tension  and 
Surface  Energy,  and  their 
Influence  on  Chemical 
Phenomena"    (Review),  253. 

Wilson,  Ernest,  Susceptibility 
of  feebly  magnetic  bodies  as 
affected  by  tension,   104. 

Wind  measurement  by  shoot- 
ing  spheres    upward,   104. 

Winther,  Chr.,  Solubility  of 
silver  bromide  in  ammo- 
nium bromide  and  gelatin, 
347. 

Wireless,   Electro-capillary     re- 
lay  for   wired,   107. 
signals.  Novel  instrument  for 
recording,  378. 

Withey,  W.  H.,  Estimation  of 
magnesium  in  ahiminium 
alloys,  17. 

Wood,  A.  B.,  Cathode  ray  os- 
cillograph,  12. 

Wood,  J.  K.  and  A.  M.  Morley, 
The  behaviour  of  titanic 
acid   towards   dyestuffs,   75. 

Wood,  R.  W.,  and  A.  Ellett,  On 
the  influence  of  magnetic 
fields  on  the  polarisation  of 
resonance  radiation,  311. 

Wood  and  hemp  in  papers  con- 
taining these  two  fibres, 
Quantitative  determina- 

tion, 299. 

Wood  naphtha,  pyridine  and 
siinonsens  oil,  218. 

Woods,  Photomicrographs  of, 
330. 

Wool,  Evaporation  of  water 
from,  311. 


Woolcock,  W.   J.     U.,     Making 

colour  makers,  30*2. 
Woolley,  W.,  Obituary,  109. 
Wyld,  Wilfrid,  "Raw  Materials 

for  the  Manufacture  of  Sul- 

ghurio    Acid  and     Sulphur 
•ioxide"   (Review),  398. 


"V  ray     beams,     Detection     of 
■**      feeble,     bv   smoke   clouds, 
332. 
X  lays     of     different       wave- 
lengths.    Effect    upon   some 
animal  tissues,  357. 


YUKON,     Mineral   output  of, 
268. 


Z  ETA-FUNCTION,    Riemann, 
Lindelof's   hypothesis    c-on- 
cerning,  280. 
Zinc,  Separation  of  isotopes  cf, 

171. 
Zircon,     Dartmoor  occurrences 

of,  58. 
Zirkite  ore.   Preliminary  study 
of,  14,  23,  43. 


[End  or  Volume  CXXVL] 


THE  CHEMICAL  NEWS,   FEBRUARY  1,  1924. 


THE 

CHEMICAL  NEWS 

AND 

JOURNAL  OF   INDUSTRIAL   SCIENCE. 

WITH   WHICH  IS  INCORPOBATBD   THE  "  CHEMICAL  OAZETTl." 

%  |ournal  oE  SljaorBtital  anb  ||*ratlital  Sl^jinislr^  anb  y]^ij$if$, 

IN   THEIR   APPUCATION   TO 

ENGINEERING  AND  MANUFACTURES. 

B»ITKD   BY 

JAMBS  H.  GARDINER,  F.lnstP.,  F.C.S. 
and 
J.  Q.  F.  DRUCE,  M.Sc.  {Lond.),  R.Nat.Dr.  {Prague). 

VOLUME  CXXVII.     1928. 

LONDON. 
PUBLISHED  AT  THE  OFFICE,  97,  SHOE  LANE,    EM.  4. 
AND  SOLD  BY  ALL  BOOKSELLERS. 


1928. 


LONDON  : 

Printed  by  Eea,  Walker  &  Fnchbould,  I/td 
224,  blacefriabs  road,  sb.) 


THE    CHEMICAL    NEWS. 

VOLUME    CXXVII. 

Edited  by  JAMES  H.  GARDINER,  F.Inst.P.,  F.C.S.,  and 
J.  G.  F.  DRUCE,  M.Sc.   (.Lond.),  R.Nat.Dr.   (Prague),  &c. 


No.  3299.— JULY  6,  1923. 


THE   CHEMICAL  NEWS. 


VOL.  CXXVII.    No.  3299. 


GLASS  MAKING  IN  ENGLAND. 

The  great  war  and  the  industrial  struggle 
that  is  following  it  has  profoundly  in- 
fluenced many  British  industries,  but  upon 
none  has  the  effect  been  so  pronounced  as 
upon  that  of  glnssmaking. 

Glass  is  so  familiar  to  all  of  us  that  we 
often  fair  to  realise  the  magnitude  of 
the  industry.  There  is  probably  not  a 
man,  woman,  or  child  but  handles 
glass  in  some  form  or  another  many  times 
in  each  day  of  their  life,  and  when  one  con- 
siders the  fragility  of  the  ware,  it  is  appar- 
ent that  the  labour  involved  in  its  prepara- 
tion and  fabrication  must  be  enormous. 

Atpart  from  the  domestic  use  of  glass- 
ware there  is  scarcely  an  industry  in  exist- 
ence that  does  not  need  glass  in  some  form 
or  other,  and  for  the  progress  of  chemistry 
and  physics  the  production  of  good  glass- 
ware is  a  matter  of  vital  importance. 

The  war  brought  home  to  all  of  us  the 
need  for  what  has  been  called  scientific 
glasswaie,  as  without  it  research  in  any 
direction  is  practically  impossible.  The 
immediate  result  was  the  formation  of  the 
Glass  Research  Association,  the  Society  of 
Glass  Technology,  and  other  bodies.  Many 
manufacturers  extended  their  works,  new 
factories  have  come  into  existence,  and 
there  is  every  indication  that  great  progress 
has  already  been  made  in  the  industrv. 
Great  strides  have  been  made    in  America 


in  mechanical  appliances  for  the  produc- 
tion of  glassware,  and  machines  have  been 
erected  in  England  for  .the  rapid  manufacture 
of  bottles,  jars,  and  other  domestic  necessi- 
ties, and  containers  in  glass  are  now  being 
produced  in  England  daily  by  the  million. 

Glassmaking  as  n  fine  art  has  been  prac- 
tised in  England  for  a  great  many  years, 
and  the  recent  publication  of  a  beautifully 
illu8tra{<>d  work  on  the  art  of  glassmaking. 
by  the  late  Harry  J.  Powell.*  who,  until 
lately,  managed  the  old  VVhitefriars  Glass 
Works  in  the  City,  brings  the  beauty 
of  the  craft  into  full  prominence. 
Mr.  Powell  was  probably  the  most  success- 
ful producer  of  truly  art  glassware  in  Eng- 
land, and  he  devoted  his  whole  life  to  the 
work,  his  book  will  for  many  years  rank  as 
one  of  the  art  treasures  of  the  country.  Mr, 
Powell  was  very  much  concerned  lest  the 
art  of  glass-craft  should  die  out  in  England. 
and  there  undoubtedly  are  indications  that 
the  labour  conditions  of  recent  years  are 
such  that  the  production  of  successful 
craftsmen  is  not  promising,  but  for 
all  that  there  are  those  who  do 
not  regard  the  problem  as  hopeless,  and  we 
understand  that  in  the  new  Whitefriars 
glassworks  that  have  been  erected  at 
Wealdstone.  Middlesex,  serious  efforts  are 
already  being  made  for  the  systematic  train- 
ing of  glassworkers  to  take  the  iplace  of  the 
old-worfil  craftsmen  who  produced  the  ex- 
quisite examples  illustrated  in  the  work  in 
question.  The  members  of  the  Soeiety  of 
Glass  Technology,  in  compnny  with  Profes- 
sor Turner,  of  Sheffield  University,  recently 
visited  the  newly  launched  glassworks,  and 
the  party  were  shown  the  modern  furnaces, 
annealing  ovens,  kilns  and  elaborate  work- 


THE  CHEMICAL  NEWS. 


JULY.  6,  1923. 


shops  erected  by  the  company,  and  there 
appears  to  be  genuine  hope  that  the  disas- 
ter feared  by  Mr.  Harry  Powell  will  be 
averted  by  meeting  modern  labour  condi- 
tions by  modern  methods  of  treatment. 
The  educational  advantages  possessed  by 
the  youth  of  the  present  day  should  largely 
comipensate  for  the  fact  that  he  is  not 
allowed  to  take  up  work  that  involves  the 
night  duties  of  a  glassblower  until  he  has 
passed  the  age  of  sixteen,  whereas  some  of 
the  craftsmen  mentioned  in  Mr.  Harry 
Powell's  book  commenced  work  when  eight 
or  nine  years  of  age.  The  fact  that  many 
of  these  men,  although  now  with  records  of 
more  than  40  years'  service,  are  still  hale 
and  hearty,  shows  that  the  work  is  not  un- 
healthy. 

Those  who  read  Mr.  Harry  Powell's  book 
will  not  fail  to  be  impressed  with  the 
beauty  of  the  manufacture,  and  will  en- 
dorse our  Qpinion  that  every  effort  should 
be  made  to  ensure  the  continuance  of  one  of 
the  most  charming  of  British  industries. 

J.H.G. 

*  "  Glass -making  in  England,"  hy  H.  J. 
Powell,  C.B.E.,  Cambridge,  at  the  Univer- 
sity Press,  1923. 


8TUDIES  ON  CATALYTIC  ACTION. 

II.— CATALYTIC  PREPARATION  OF 

PARA-CYMENE  AND  ITS  FORMATION 

IN  SULPHITE  TERPENTINE. 

By  Shigeru  Komatsu,  Hisashi  Nakamura, 

AND   Ma  SAO  KURATA. 

Klason^  first  noticed  that  the  etherial  oil 
collected  during  the  manufacture  of  pulp 
from  spruce  by  the  sulphite  process,  con- 
sists mainly  of  para-cymene  and  not  of  ter- 
penes.  Sulphite  teripentine  from  the  p\ilp 
mills  of  U.S.A.  was  studied  by  Herty  and 
Graham,^  A.  W.  Schorger"  and  M.  Philips* 
with  a  view  to  the  utilisation  of  para-cymene 
in  it.  O.  Aschan^  and  J.  Alfthan^  have, 
gilso,  studied  the  terpentine  in  Finland. 


1  Ber.  D.  Chem.    Ges.,    1900,    XXXIII. , 
2343. 

2  J.  Ind.  and  Eng.  Ohem.,  1914,  VI.,  803. 

3  Ibid.,  1918,  X",  258. 

*  J.  Amer.    Chem.    Soc,    1922,    XLIV., 
1775. 

=  Zellstoff  Chem.  Abhand.,  1920,  1,73. 

•  Ber.  D.  Chem.  Ges.,  1920,  LIIL,  78. 


The  sulphite  terpentine,  we  studied,  was 
obtained  fi'om  the  pulp  mill  at  Ochiai,  Kara- 
futo,  where  sulphite  pulp  was  manufac- 
tured from  Yezo-matsu  and  Todo-matsu. 
The  crude  oil  which  amounted  to  140  grm., 
was  dark  brown  in  colour,  dP  =  0.965.  (t 
was  subjected  to  steam  distillation  and  a 
light-yellow  oil  was  obtained,  which,  after 
drying  with  anhydrous  sodium  sulphate, 
was  distilled : 

First   fraction,    B.p.,    174-270°         70  grrn. 
Second  fraction,  B.p.,  above  270°     35  grm. 

Two  fractions  were  fractionated  on  metal- 
lic sodium,  and  the  fraction  boiling  at  173- 
175°  was  collected.  The  yield  was  50  per 
cent,  of  the  crude  oil. 

The  physical  constants  and  the  elemen- 
tary composition  of  the  purified  substance 
were  determined  with  the  following  results : 

It  o-itve  0=89.33;  TI  =  10.34;  (C,„H,„ 
requires  0  =  89.48;  H  =  10.52),  d  f  ^ 
0.85381;  n25     =i..J821;  M.R.  =44.80. 

For  identification  with  para-cymene,  it 
was  oxidised  with  potassium  permanganate 
into  tere-phthalic  acfd^  and  para-hydroxy- 
isopropyl  benzoic  acid*  and  the  latter  melts 
at  156°  and  gave  on  analysis  0  =  66.23;  H  = 
6.64;  (0,„H,,03  requires  0  =  66.64;  H  = 
6.72). 

On  the  other  hand,  the  substance  was 
sulphonated  with  cone,  sulphuric  acid  fol- 
lowing Clans'  directions,'  and  sodium  salts 
of  mono-  and  di-sulphonic  acids  were 
separated  by  aid  of  their  solubility  in  alco- 
hol solution,  and  di-sulphonic  acirt  salt  was 
analysed;  Ba  =  31.32(C,„Hj,0,S.Bn  re- 
quire Ba  =  31.95). 

Terpenes  of  the  formula  C,„Hjg  by  dehy- 
drogenation,  were  ultimately  converted  into 
ipara-cymone ;  consequently  the  transforma- 
tion was  sometimes  made  use  of  in  the  de- 
termination of  the  constitution  of  the  com- 
pounds. ^° 

Kekule"  has  studied  the  conversion  of 
terpene  into  cymene  by  oxydation  with 
phosphorous  sulphide.  L.  Ruzika,  J. 
Meyer  and  M.  Mihgazzini^^  have  obtained 
para-cymene' from  limonene  and  terpinenc 
by  catalytic   oxydation   with   sulphur,     fol- 


'R.  Fittig,  A.  Korbrich  and  T.  Jilkc : 
Lieh.  Ann.,  1868,  CXLV.,  144. 

«  0.  Wallach:  Ibid.,  1891,  CCVXIV.,  10. 

'  Ber.  D.  Chem.  Ges.,  1881,  XIV.,  2140. 

"  V.  Meyer  and  P.  Jacobson :  Lehrbnch 
d.  Org.  Chem,.,  1902,  II.,  110. 

''Ber.  D.  Chem.  Ges.,  1869,  II.,  121. 

"  Hel.  Chim.  Acta.,  1922,  V.,  356. 


JULY  6,  1923. 


THE  CHEMICAL  NEWS. 


lowing  Vesterberg's  directions, ^^  and  the 
same  process  was  applied  by  W.  Fried- 
mann'*  to  naphthene  hydrocarbons. 

The  authors  have  succeeded  in  the  cata- 
lytic preparation  of  para-cymene,  the  main 
constituent  of  sulphite  terpentine,  from 
pinene  and  menthene  respectively. 

130  grm.  pinene  obtained  from  commer- 
cial terpentine  oil,  were  heated  with  70  grm. 
Ruliphur  in  a  flask  at  200°  for  28  hours,  the 
rea<;tion  product  was  distilled  imder  re- 
duced pressure  and  71.5  grm.  of  the  pro- 
duct was  obtained.  It  was  distilled  under 
ordinary  pressure  after  treating  with  10  per 
cent,  caustic  soda  solution,  dried  with  cal- 
cium chlorfSe,  and  a  fraction  boiling  at  170- 
275°  was  collected.  The  yield  was  55  grm. 
(52  per  cent,  of  the  theoretical). 

The  profluct,  thus  obtained,  on  distilling 
with  metallic  sodium,  was  all  distfiled  out 
between  lfT5-175°.  It  was  purified  by  re- 
peated distillation  with  metallic  sodium. 

The    purified    substance    d25      =0.8.142: 
n25    =1.4743;  M.R.  =44.41,  was  analysed  ; 
.cVve  C  =  88.37;    H  =  11.34;    (C,oH„    re- 
quires C  =  80.45;  H  =  10.55). 

It  was  oxydised  with  potassium  (perman- 
ganate into  para-hydroxyisopropyl  benzoic 
acid"  which  melted  at  156-150.5"  and  gave 
C  =  66.44;  H  =  6.33;  (C.H.CtOHHCH,),- 
COOH  requires  C  =  66.64;  H  =  6.72). 

In  the  same  manner,  menthene  prepared 
from  menthol  by  catalytic  dehydration  with 
thoria  was  transformed  into  para-cymene. 

140  grm,  menthol  were  passed  on  thoria 
heated  at  about  400°,  and  yield  125  grm. 
light  greenish  vellow  liquid  substance, 
d  =0.817,  which  distilled  between  155- 
210^.  It  was  purified  by  repeated  distilla- 
tion with  metallic  sodium,  and  the  follow- 
ing fractions  were  obtained  : 

The  fraction  boils  at  145-164°  under  752 
mm.,  with  10  per  cent,  of  the  yield. 

Other  fraction  boils  at  164-167°  under  752 
mm.,  with  40  iper  cent,  of  the  yield. 

The  second     fraction     was  confirmed     by 
analysis  to  consist    of  menthene, *•    d»5      = 
0.8006;     nK      =  1.4469;     M.R.  =  45.60; 
which  gave"  C  =  86. 10;  H  =  12.02;    (C,„H„ 
requires  C  =  86.87;  H  =  13.13). 


»  Ber.  D.  Chem.  Ges.,  1003,  XXXVI.. 
4200. 

>*  ./.  Chew.  Soc,  1917,  CXII.,  13. 

'«  O.  Wallarh  :   TjOc.  cit. 

'•  P  Walter:  C.R.,  1838,  VL,  473;  Lieh. 
Ann.,  1839,  XXXII..  288. 


Menthene,  thus  obtained,  was  heated 
with  sulphur  at  200°  for  24  hours,  and  the 
reaction  product  was  subjected  to  distilla- 
tion on  metallic  sodium  to  purify.  The  cy- 
mene  fraction  boiling  at  170-173.5°,  d25  = 
0.8389;  n  ^^  =1.4740;  M.R.  =44.94;  gave 
on  analysis"  0  =  87.68;  H  =  10.92,  (C„Hj^ 
requires  C  =  89.45;  H  =  10.55). 

The  conversion-  of  menthol  and  borneol 
by  simply  heating  with  sulphur  at  about 
200°  into  cymene,  was  tried,  but  with  no 
result. 

Terpenes  of  the  formula  CioH,g,  on  the 
contrary,  can  easily  be  transformed  into 
cymene  by  catalytic  oxydation  with  sulphur. 

Aromatic  hydrocarbons  and  their  oxygen 
derivatives,  such  as  para-cymene  and  safrol 
are  widely  distributed,  being  generally  asso- 
ciated with  the  essential  oils  in  plants.  The 
origin  and  the  mecbanism  of  the  formation 
of  the  aromatic  compounds  in  the  flora  were 
interesting  problems. 

As  to  the  formation  of  para-cymene  in 
sulphite  terpentine.  Klason'^  has  already 
put  fwward  the  following  opinion  : 

"  Alles  Terpentinol  soil  ja  auch  nach  den 
vorhandenen  Angaben  etwas  Cymol  enthal- 
ten.  und  im  Holze  sind  die  aetherische  Oele 
lange  Zeit  dem  Eintluss  der  Luft  ausgesetzt 
worden.  Wie  man  nun  diesen  Uebergang 
im  Lichte  der  Engler'schen  Theorie  der 
.'Vutoxydation  erkliircn  soli,  mogen  kiinftige 
Untersuchungen  darthun.  Entweder  wur- 
den  von  der  zunachst  entstandenen  super- 
oxydartigen  Verbindung  zwei  Wasserstoff- 
atome  direct  wegoxydirt  oder  es  entsteht 
intermediftr  ein  Alcohol,  welcher  durch 
Wa-sserabspaltung  in  Cymol  iiT>ergefiihrt 
wird."  Much  more  probably  the  forma- 
tion of  cymene  in  wood  may  be  attributed 
to  the  autoxydation  of  etherial  oils,  as  Kin- 
son  stated.  Whether  the  sulphite  terpen- 
tine was  formed  in  a  digester  during  the 
manufacture  of  pulp,  by  the  same  mechan- 
ism is  very  doubtful. 

Our  hypothesis,  however,  for  jfche  forma- 
tion of  the  sulphite  terpentine,  is  quite  dif- 
ferent from  Klason's,  and  is  grounded  on 
the  experiments  described  above ;  the  ter- 
pene  existing  in  the  wood  would  probably 
be  transformed  during  the  manufacture  of 
pulp  by  the  sulphite  process,  into  (para- 
cymene  by  catalytic  oxydation  with  sulphur 
which  is  liberated  in  a  free  state  in  the 
digester. 


"  Loc.  oit. 


THE  CHEMICAL  NEWS. 


JULY  6,  1923. 


The  evidences  in  favour  of  our  view  of  the 
formation  of  sulphite  terpentine,  are  easy 
to  quote  here  from  literature. 

Shinozaki'*  has  isolated  from  the  essen- 
tial oils  obtained  by  steam  distillation  of 
Yezo-matsu  and  Todo-matsu  pinene  and 
phellandrene,  which  were  proved  by  our 
experiments  to  transform  into  para-cymene. 

We  cannot  pass  over  without  mentioning 
here  the  most  important  fact  that  free  sul- 
phur actually  exists  in  the  acid-liquor  used 
for  pulp  manufacture,  cited  in  Klason's 
article. ^» 

— (From  the  Memoirs    of  the    College  of 
Science,  Kyoto  Imperial     University,     Vol 
IV.,  Mar.,  1923.) 


THE  REPORT  OF  THE  CHEMICAL 

EXAMINER'S  DEPARTMENT  (PUBLIC 

HEALTH),  GOVERNMENT  OF 

MADRAS. 

Read— the  following  papers:  — 
Letter  from  Major  Clive  Newcomb, 
M.D.,  A. I.e.,  I.M.S.,  Chemical  Examiner 
to  Government,  to  the  Secretary  to  Gov- 
ernment, Local  Self-Government  Depart- 
ment (through  the  Surgeon-General  with 
the  Government  of  Madras,  Madras),  dated 
Madras,  the  26th  March,  1923,  No.  538. 

The  following  is  abstracted    from  the  Re- 
port for  1922:  — 

Medico  Legal  Investigations. 
In  the  220  cases  of  suspected  human 
poisoning  investigated,  poison  was  detected 
in  108,  giving  a  percentage  of  detections  of 
49.1  as  compared  with  40.6  in  the  previous 
year. 

It  is  a  matter  for  regret,  as  previous 
Chemical  Examiners  here  have  remarked, 
that  more  time  is  not  available  for  trying 
new  toxicological  methods.  In  all  branches 
of  practical  chemistry,  but  especially  in 
toxicology,  new  tests  or  methods  of  analy- 
sis, even  if  most  carefully  described,  can- 
not be  put  into  practice  without  many  con- 
trols and  personal  investigations  by  the  ana- 
lyst.    A  little,  however,  has  been  done. 

In  the  extraction  of  morphine  from  vis- 
cera, a  method  which  had    been  used  here 


i«  Kogyo-Kumgaku  Zasshi,  1912,  XV., 
730. 

"  Uregelm.as8ige  Oang  v.  Sulphitstoff- 
Kochung  u.  desen  Ursache,  1910,  p.  63. 


before  was    again  tried    on  some  cases,    in 
view    of    its     recommendation     in    Lucas' 
ForensiQ  Chemistry.       Of    the    evaporated 
acid  alcoholic  extract  of  the  viscera,  a  small 
portion  was  extracted  with  ether  in  the  pre- 
sence of  sodium  bicarbonate    for  the    por- 
phyroxin  test.       To  the  remainder    sodium 
hydroxide  was  added,  and    it  was  then  ex- 
tracted first  with  ether,    next    with  chloro- 
form to  remove  other  alkaloids,  and  thirdly 
with  a  mixture  of    ethyl  acetate    and  ether 
to    extract  the    morphine.      In    a    case    in 
which  both  dhatura    and  opium  were    sus- 
pected and    in  which    this    procedure    was 
used,    the  presence  of  a  mydriatic  alkaloid 
was  proved  in  the  chloroform  extract    and 
the  presence  of  morphine  in  the  ethyl  aco- 
tate-ether  extract,    in  addition    to    positive 
porphyroxin  and    meconic  acid    tests.       In 
another  case  an  infant  aged  two  years  was 
suspected  to  have  died  from  an  overdose  of 
opium,   but    in  this    case  the    poriphyroxin 
test  was  the  only  one  which    was  positive. 
The  porphyroxin    test  is  said    to  be    a  very 
di'lieate  and  reliable  one  for  Indian  opium. 
Beam's  test  for  Cannabis  Indica,  both  in 
its  original  and  modified  form  (vide  Lucas' 
Forensic  Chemistry)  was  tried  on  a  sample 
of    charas  from    the  Punjab    and  found    to 
work  well. 

Some  experiments  were    made  by  Dr.  S. 
Rajagopal  Nayudu,  to  try  to  find  tests  for 
madar.    An  alcoholic  extract  of  any  part  of 
the  plant  exceipt  the  juice  after  evaporation 
to  dryness  and  taking  up  in  water  gave  cry- 
stals with  a  saturated  solution  of  iodine  in 
10  per  cent,  potassium  iodide,  which    bore 
some  resemblance    to  Florence's    crystals, 
and  crystals  with  saturated   aqueous  picric 
acid  of  probably  a  characteristic  shape.   The 
alcoholic  extract  of  the  juice  on  evaporation 
left    an    orange    yellow,    bitter,    poisonous 
resin,     which  gave     a    bluish     colour    with 
strong    hydrochloric  acid  and    green  colour 
with  strong  sulphuric  acid.       White  dilute 
acids,    it    gave    a    fine    pink     colouration. 
Beam's  test  was  negative  with  madar  juice. 
In  two  cases  of  susipected  madar  poisoning    . 
we  were  able  to    extract    a  bitterish    resin 
from  viscera  which  proved    fatal  to  a  frog 
and  gave  the  above  reactions.      The  cases, 
therefore,       presumably     were     of     madar 
poisoning,  but  this  could  not  be  considered 
to  be  conclusively  proved. 

The  test  for  arsenic  described  in  the 
J.C.S.Abs.,  1922,  page  584,  was  tried,  and 
found  to  work  well  with  a  solution  of  ar- 
senious  acid.      The  quinine  molybdate  test 


JULY  6,  1923. 


THE  CHEMICAL  NEWS. 


described  in  the  Analyst,    1922,    page  317, 
was  tried  and  found  to  work  satisfactorily. 

Some  experiments  were  made  on  the  ad-  ! 
sorption  of  brucine  sulphate  from  dilute  j 
aqueous  solution  by  kieselguhr  with  a  view  ' 
to  the  possibility  of  using  adsorption  for  , 
the  extraction  of  alkaloids  from  viscera.  j 

In  these  ex^riments  the  brucine  was 
estimated  by  evapwating  to  dryness  and 
weighing  the  residue  of  a  measured  quan- 
tity of  the  solution  before  and  after  adsorp- 
tion, making  a  small  allowance  for  the 
amount  of  soluble  substances  dissolved 
frum  the  kieselguhr. 

The  estimation  of  brucine  in  dilute  solu- 
tion by  precipitation  with  Dragendorfl's  re- 
agent (Bismuth  potassium  icxlide)  was  also 
tried.  The  amount  of  precipitate  was  esti- 
mated by  means  of  a  simple  iorm  of 
nephelometer.  This  was  simply  a  glass  ro<l 
graduated  into  millimetres  along  its  stem 
with  a  short  platinum  wire  bent  at  right 
angles  to  the  rod  at  one  end.  It  was  pushed 
into  the  suspension  of  the  precipitate  hold- 
ing the  stern  vertical  till  the  platinum  wire 
could  no  longer  be  seen  and  tFu'  length  of 
rotl  immersed  noted.  The  niethoa  was 
quick  but  .nly  accurate  to  within  about  10 
per  cent. 

General  Analyses. 

The  number  of  these  analyses  done  dur- 
ing the  year  was-570,  against  !jM  in  19*21. 

The  Customs  department  sent  144,  of 
which  50  were  analys«.'s  of  ^'old  or  silver 
thread  or  lametta.  These  frecjuenlTv  gave 
small  traces  of  gold  or  silver,  probably  in- 
dicating they  were  plated  with  the  real 
metals. 

The  General  Hospital,  Mjidras,  sent  122 
articles  for  analyses,  of  which  106  wen- 
stomach  washes  after  test  meals.  Our  rou- 
tine in  examining  these  is  to  estimate  fn'e 
hydrochlt^nc  acid  by  Buntzberg's  meth(j<l. 
total  acidity  by  titration  wih  N/io  soda.  "«- 
ing  phenolphhalein  as  indicator,  and  U^ 
test  qualitatively  for  lactic  acid  by  Uffel- 
mann's  method.  A  direct  estimation  of  the 
hydrogen  ion  concentration  would  probably 
be  of  more  value,  and  with  this  end  in  view 
solutions  of  standard  Ph  are  l)oing  prepared. 
Whenever  possible,  these  are  prepared  by 
two  methods  and  the  colours  given  by 
various  indicators  compared.  A  great  deal 
of  care  is  needed  in  the  preparation  of  the 
standard  solutions  and  in  purifying  the 
chemicals  used  to  get  perfect  matches. 

The  danger  of  relying  on  the  labels  of 
bottles  for  more  than  an  aiKjiroximate  indi- 
cation of  their  contents  was  well  illustrated 


by  the  case  of  a  bottle  labelled  "Pure  s&c- 
charose,"  which  was  being  used  in  the  Hy- 
giene Laboratory  as  a  standard  in  work 
with  a  polarimeter.  It  was  sent  to  us  be>- 
cause  of  the  discordant  results  which  were 
obtained,  and  on  analysis  was  found  to  con- 
tain a  very  considerable  amount  of  glucose. 

The  accurate  determination  of  the  den- 
sity is  often  a  most  useful  test  of  purity  of 
a  liquid  or  a  check  on  the  determined 
strength  of  a  solution.  To  take  a  specific 
gravity  with  a  bottle  takes  a  considerable 
time  even  at  the  temperature  of  the  labora- 
tory, and  at  any  other  temperature  re- 
quires a  carefully  regulated  thermostat. 
Most  densities  arc  given  at  (15"  C),  and  in 
Madras  to  keep  a  thermostat  at  a  tempera- 
ure  lower  than  about  30*  C.  would  require 
prohibitive  quantities  of  ice.  An  investiga- 
tion was  therefore  made  into  the  accuracy 
obtainable  with  an  ordinary  Westphall's 
balance  and  some  previous  calibrations  of 
one  of  our  balances  carefully  revised.  The 
reading  of  the  balance  can  be  made  very 
jjuickly  and  with  a  liquid  which  is  changing 
in  ten^erature  fairiy  rapidly  a  series  of 
readings  can  be  taken,  the  mean  of  which 
should  be  reliable  to  within  +  0.0003.  Some 
experiments  have  been  made  during  tho 
year,  as  time  could  be  found  for  them,  to 
see  if  a  more  useful  test  tar  the  purity  of 
chloroform  could  n()t  be  devised  u>dng  this 
instrument,  than  the  present  B.P.  test  of 
taking  the  specific  gravity  at  15"  C.  B.P. 
chloroform  contains  a  small  quantity  of 
alcohol  as  a  preservative.  It  was  con- 
sidered that  if  this  alcohol  were  removed 
and  the  density  determined  before  and  after 
removal  this  might  afford  a  measure  of 
both  the  amount  of  added  alcohol  and  the 
puritv  of  the  residual  chloroform.  The 
alcohol  can  be  easily  extracted  from  chloro- 
form bv  washing  it  with  water.  Five  wash- 
ings with  a  biilk  of  water  equal  to  that  of 
the  ohiorofonn  each  time  are  sufficient.  The 
density  of  the  chloroform  may  be  deter- 
mined wet  and  a  small  allowance  made  for 
the  wetness.  Experiments  to  determine  the 
changes  in  density  produced  by  water,  alco- 
h(t\  and  temperature  are  still  going  on. 

We  were  consulted  about  a  "disease" 
developed  by  some  mercury  used  in  a  light- 
house to  float  the  revolvmg  part  of  the 
lamip  so  as  to  make  it  turn  easily.  A  sample 
of  the  diseased  mercury  showed  that  it  hnd 
become  partlv  converted  into  a  grey  viscid, 
slimy  substance.  On  examination  it  turned 
out  to   be  an  emulsion  of  mercury  and  oil, 


THE  CHEMICAL  NEWS. 


JULY  6,  1923. 


of  suoh  a  consistency  as  to  effectually  clog 
almost  any  mechanism. 

On  another  occasion  we  were  asked  to 
match  a  special  lubricating  oil  for  an  elec- 
tric machine  used  at  the  Ophthalmic  Hospi- 
tal, Madras.  We  obtained  two  lubricating 
oils,  one  slightly  more  viscid  and  one  rather 
less  viscid  than  the  sample,  and  by  testing 
the  viscosity  of  mixtures  of  the  two  found 
the  proportion  in  which  they  had  to  be 
mixed  to  match  the  sample  as  regards  vis- 
cosity. The  difficulty  in  this  case  was  that 
only  about  2  cc.'s  of  the  sample  were  avail- 
able, so  that  the  ordinary  types  of  viscosi- 
meter  (except  Ostwald's  which  we  did  not 
then  possess)  were  inapplicable.  The  vis- 
cosities were  measured  by  noting  the  times 
taken  for  0.5  cc.  of  the  oil  to  run  out  of  a  1 
cc.  pipette  graduated  into  1/lOOths.  We 
could  not  match  both  the  viscosity  and  the 
density,  so  we  recommended  a  mixture 
which  made  the  viscosity  right,  and  I 
understand  that  machine  has  been  running 
well  on  our  mixture  since. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  June  28. 
Papers  read :  — 

V.  H.  Blackman,  F.R.S.,  A.  T.  Legg, 
and  F.  A.  Gregory.  The  Effect  of  a  Direct 
Electric  Current  of  very  Low  Intensity  on 
the  Rate  of  Growth  of  the  Coleoptile  of 
Barley. 

The  coleoptile  (sheathed  plumule  or 
young  stem)  of  barley  seedlings  are  exposed 
to  an  electric  discharge  from  a  point 
charged  positively  to  about  10,000  volts 
(crest  value)  and  placed  at  such  a  height 
above  the  coleoptile  that  a  current  of  0.5  x 
10-1"  ^jj^p  passes  through  it,  the  current 
density  being  4  x  10- «  amp.  per  cm.^  Under 
these  conditions  the  rate  of  growth  is 
markedly  accelerafed  from  the  first  hour 
onward,  showing  in  the  third  hour  a  per- 
centage increase  above  that  of  the  control 
plants  of  7.53  +  1.95. 

After  the  cessation  of  the  current  a  well- 
marked  "  after-effect,"  greater  than  th<> 
direct  effect,  is  to  be  observed,  the  en- 
hanced rate  of  growth  steadily  contmumg 
and  showing  a  percentage  increase  of  15.68 


+  2.62  above  that  of  the  controls.  The 
after-effect  is  greater  with  a  short  period  of 
discharge  of  one  hour  than  with  a  longer 
period  of  three  hours. 

When  the  point  is  negatively  charged  the 
rate  of  growth  is  increased  during  the  first 
hour,  but  the  increase,  instead  of  becoming- 
greater  with  time,  as  with  a  current  in  the 
other  dii'ection,  becomes  less.  An  after- 
effect follows  here  also,  but  it  is  markedly 
less  than  that  resulting  from  a  positive  dis- 
charge. 

Experimental  evidence  is  advanced  for 
the  Niew  that  the  gaseous  products  of  the 
discharge  and  the  "electric  wind"  iplay 
little  or  no  part  in  the  stimulation  of 
growth  observed.  The  current  alone  ap- 
pears to  be  of  importance,  a  view  which  is 
supported  by  the  fact  that  its  direction 
exerts  such  a  marked  influence  on  the  de- 
gree of  stimulation. 

M.  S.  Pembrey,  F.R.S.,  N.  W.  Mac- 
Keitu,  W.  R.  Spurrell,  E.  C.  Warner, 
and  H.  J.  Westlake.  Observations  on  the 
Adfustnient  of  the  Hunian  Body  to  Muscu- 
lar Work. 

Papers  read  in  title  only  :  — 

Miss  R.  M.  Tupper-Carey  and  J.  H. 
Priestley.  The  Composition  of  the  Cell 
Wall  at  the  Apical  Meristern  of  Stem  and 
Root.  Communicated  by  Ur.  F.  F.  Black- 
man,  F.R.S. 

The  walls  of  the  apical  meristem  of  stem 
and  root  differ  in  the  ease  with  which  cellu- 
lose may  be  detected  in  them  with  iodine 
reagents.  As  the  result  of  macro- chemical 
and  micro-chemical  experiment  it  is  con- 
cluded that  the  cellulose  in  the  wall  of  the 
root  meristem  is  masked  by  its  combination 
with  other  substances,  particularly  proteins 
and  fatty  acids.  In  the  shoot  meristem 
the  cellulose  is  closely  linked  with  larger 
quantities  of  pectin  but  less  protein  and 
fatty  acid  are  present,  especially  when  the 
shoot  is  growing  in  the  light.  These  conclu- 
sions seem  to  throw  further  light  upon  the 
comparative  difficulty  with  which  diffusion 
appears  to  take  place  through  the  apical 
meristem  of  the  root  compared  with  that 
of  the  shoot. 

L.  J.  Harris.      The  Titration  of  Amino- 
and  Carhoxijl- Groups  in  Amino-Acids,  Poly- 
peptides   etc.      Communicated  by  Prof.  F. 
G.  Hopkins,  F.R.S 


JtJLY  6,  1923. 


THE  CHEMICAL  NEWS 


F.  A.  E.  Ckew.  Studies  in  Intersexual- 
ity. — //.  Sex-reversal  in  the  Fowl.  Com- 
municated by  Prof.  R.  C.  Punnetl;,  F.R.S. 

W.  FiNKLER.  Analytical  Studies  on  the 
Factors  causing  the  Sexual  Display  in  the 
Mountain  Neirt  (Triton  alpestris).  Com- 
municated by  Prof.  E.  W.  MacBride, 
F.R.S. 

G.  A.  ScHOTT,  F.R.S.  On  the  Scatterimj 
of  X-  and  y-Rays  by  Rings  "of  Electrons. — 
The  Effect  oj  Damping  of  the  Incident 
Radiation. 

The  object  of  the  investigation  is  to  ex- 
amine the  effect  of  the  damping  of  inciHeiit 
X-  and  y-rays  on  their  scattering  by  revolv- 
ing rings  of  electron,  with  the  view  of  deter- 
mining whether  the  diminution  of  the  total 
scattering  observed  by  Ishino  ior  alu- 
minium, iron  and  lead  can  be  att^buted 
wholly  or  partly  to  this  cause.  Damping 
of  the  usual  type,  of  an  amount  compatible 
with  the  production  of  moderately  sharp 
lines  in  the  X-ray  spectrum,  is  found  to  in- 
crease slightly  the  total  scattering  of  short 
waves,  such  as  the  hard  y-rays  used  by 
Ishino,  although  it  decreases  slightly  that 
of  long  waves.  A  single  electron  ring, 
however,  such  as  we  postulate  in  hydrogen 
and  ionised  helium  on  Bohr's  theory,  is 
completely  unaffected  by  this  type  of 
damping.  It  is  harHly  possible  that  damp- 
ing can  diminish  the  total  scattering  for 
any  type  of  atom  l)elow  the  amount  re- 
quu*ed  by  the  Sunple  Pulse  Theory,  cer- 
tainly not  to  the  extent  required  by  the  i>x- 
periments  of  Ishino  and  the  more  recent 
ones  of  A.  H.  Compton. 

P.  A.  MacMahon,  F.R.S.  On  a  Class  of 
Transcendents  of  which  the  Bcssel  Func- 
tions are  a  Particular  Case. 

Li.  C.  Martin.  The  Photometric  Match- 
ing Field.  Communicated  by  Prof.  H.  L. 
Callendar,  F.R.S. 

During  a  previous  investigation  it  was 
noticed  that  an  improvement  in  the  visibil- 
ity of  faint  contrasts  observed  with  cenlnil 
vision  could  be  obtained  by  stimulating  the 
peripheral  regions  of  the  retina.  Some  ex- 
planations of  this  and  allied  effects  are  dis- 
cussed. .\s  a  practical  applioation  experi- 
ments are  described  which  show  that  an  in- 
crease in  precision  of  the  order  of  30  per 
cent,  can  be  obtained  in  photometric 
matches    by  surrounding    the    photometrio 


field  with    a  larger  area    of    approximately 
equal  brightness. 

G.  P.  Thomson.  Test  of  a  Theory  of 
Radiation.  Communicated  by  Sir  Joseph 
ihomson,  F.R.S. 

Experiments  are  described  with  positive 
rays  which  show  that  visual  and  photo- 
graphic effects  can  be  obtained  with  trains 
of  waves  shorter  than  those  produced  in 
the  emission  of  a  quantum  of  light. 

A.  Ll.  Hughes  and  P.  Lowe.  Intensi- 
ties in  the  Helium  Spectrum,.  Communi- 
cated by  Prof.  H.  A.  Wilson,  F.R.S. 

The  distribution  in  intensities  in  the 
helium  spectrum,  when  excited  by  impacts 
between  electrons  and  atoms,  has  been 
studied  as  a  function  of  the  energy  of  im- 
pact of  the  electrons,  all  other  variables 
being  held  constant.  The  energy  of  impact 
varied  from  34  volts  to  210  volts. 

The  outstanding  result  of  the  work  is  that 
the  curve  showing  the  intensity  of  any  spec- 
trum line  as  a  function  of  the  energy  of  im- 
pact is  characteristic  of  the  series  to  which 
it  belongs.  The  intensities  in  the  Doublet 
System  all  decrease  rapidly  as  the  energy  of 
impact  is  increased  from  34  volts.  The 
rate  of  decrease  is  greatest  for  In -m<r  and 
least  for  ln-m8.  The  Principal  Series,  IS 
-mP,  of  the  Singlet  System  is  character- 
ised by  a  very  great  increase  in  intensity  as 
the  energy  of  impact  is  increased  from  34 
volts  up  to  about  80  volts,  beyond  which 
there  is  little  change.  The  lines  of  the 
Diffuse  Series,  IP-niD,  all  show  a  maxi- 
mum at  about  75  volts,  the  rise  to  maxi- 
mum being  progressively  greater  the  higher 
the  tenn  number  of  the  line.  The  lines  of 
the  Sharp  Series,  IP-wS,  after  a  small 
initial  rise  to  60  volts  decrease  sUghtly, 

A.  A.  Drk.  The  Effect  of  Quenching  from 
above  the  Carbide  Transition  Temperature 
upon  the  Magnetism  of  Steel.  Communi- 
cated by  Prof.  S.  W.  J.  Smith,  F.R.S. 

The  first  accurate  determination  of  a 
transition  point  in  iron  carbide  at  which 
the  ferromagnetism  disappears  during  heat- 
ing, in  a  similar  way  to  that  of  iron  at  the 
critical  temperature  of  the  latter,  was  made 
by  S.  W.  J.  Smith  in  1912.  It  has  recently 
been  suggested  by  Thompson  and  White- 
head that  this  carbide  transition,  described 
a©  from  a  to  /3  cementite,  is  such  that  the 
carbide  can  be  retained  in  the  ft  condition 
by    quenching  from     above  the    trnnsition 


TflE  CHEMICAL  NEWS. 


JtJLt  6,  1928. 


temperature.  The  experiments  described 
in  the  present  paper  show  that  the  magnet- 
ism of  steel  at  ordinary  temperatures  is  not 
materially  altered  by  quenching  of  the  kind 
above  described  and,  therefore,  that  the  re- 
turn of  the  carbide  to  the  ferromagnetic 
state  is  not  retarded  by  sudden  cooling 
from  above  the  transition  tem^perature. 

T.  S.  P.  Strangeways  and  H.  E.  H. 
Oakley.  The  Inunediate  Changes  observed 
in  Tissue  Cells  after  Exposure  to  Soft  X- 
Rays  while  growing  "  in  vitro."  Commu- 
nicated by  W.  B.  Hardy,  Sec.  R.S. 

Tissue  cultures  in  vitro  were  exposed  to 
soft  X-rays  for  gradually  increasing  periods, 
varying  from  5  minutes  to  2  hours. 

Four  cultures  were  exposed  at  a^  time  : 
two  of  these  were  stained  immediately,  and 
two  after  being  returned  to  the  incubator 
for  80  minutes.     It  was  found:  — 

(1)  That  there  was  a  latent  period  of 
about  15  to  20  minutes  before  the  changes 
produced  in  the  cells  by  irradiation  can 
be  recognised. 

(2)  That  after  5  minutes  irradiation  de- 
velopment of  new  dividing  cells  was  les- 
sened. After  exposure  of  20  minutes  or 
longer  the  formation  of  new  dividing  cells 
practically  ceased. 

(3)  After  exposure  of  5  niiuutes  granu- 
lar changes  and  fragmentation  of  the 
chromosomes  were  observed  in  some  cells 
in  mitosis  at  metaphase  and  anaphase. 
After  15  minutes'  in-adiation  the  majority 
of  cells  in  mitosis  showed  these  changes, 
and  also  a  definite  lag  in  the  passage  of 
some  chromosomes  to  the  poles  of  the 
spindle,  and  often  a  definite  lag  in  cell- 
division  itself,  but  in  spite  of  these 
changes  in  the  chromosomes  many,  if 
not  the  majority,  of  the  cells  passed 
through  the  various  phases  of  mitosis 
and  completed  division.  After  the  longer 
exposures,  however,  some  of  the  resulting 
daughter-cells  showed  abnormality. 

(4)  After  exposure  of  25  minutes  or 
longer  some  cells  in  mitosis  showed 
clumping  of  the  chromosomes  at  meta- 
phase. 

(5)  As  time  of  exposure  increased  there 
was  increase  in  size  and  alteration  in 
structure  of  cytoplasm,  nucleus  and  nu- 
cleolus of  some  fully  formed  cells. 

(6)  After  an  exposure  of  60  minutes  or 
longer,  definite  changes  occurred  in  cyto- 
plasm, nucleus  and  nucleolus  of  some 
cells.  These  affected  cells  became  dis- 
organised and  showed  irregular  and  vary- 


ing outline.  Eventually  cytoplasm  and 
nucleus  broke  up,  disintegrated  and  ap- 
peared to  go  into  solution  in  the  sur- 
rounding medium. 


ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

A  general  meeting  of  the  members    was 
held  on  Monday,  July  2,  1923. 


NATIONAL    ENGINEERS' 
ASSOCIATION. 

Address  by  W.  H.  Casmey,  C.E.,    at 
Wakefield,  June  25. 

Had  I  the  qualifications  of  an  artist  .in- 
stead of  being  a  critic  of  smoky  chimneys,  I 
should  paint  three  historical  pictures  which 
would  have  no  equal  in  the  National  Gal- 
lery, and  the  subjects  would  be : — 

First  picture,  entitled  The  Birth  of 
Power  687,  and  would  indicate  a  tall,  monk- 
ish figure,  with  a  basket  of  blackberries  on 
one  arm  and  a  lumip  of  coaj  under  the  other. 

The  second  picture  would  show  a  finely 
built,  solid-looking  Yorkshireman,  gazing  at 
a  smoky  chimney,  and  the  title  would  be 
Green's  Coinmon  Sense,  1845. 

My  third  artistic  effort  would  show  a  big 
pile  of  coals,  on  whtch  would  appear  in 
white  letters,  "  Thirteen  hundred  million 
tons,"  and  above  would  be  a  dense  mass  of 
black  clouds,  and  this  should  have  the  title 
of  Goals,  Clouds,  and  Wastage,  1923. 

The  first  picture  would  represent  the 
Monk  of  Glastonbury  Monastery,  who, 
whilst  gathering  blackberries  in  an  old 
quarry  in  the  year  687,  came  across  an  out- 
crop of  coal,  and,  not  having  seen  what  he 
terms  "black  stone"  before,  took  a  piece 
for  the  inspection  of  the  prior,  and  he,  after 
examination,  considered  it  of  no  conse- 
quence, and  told  hrs  man  to  throw  it  on  to 
the  fire.   Wood  was  the  only  fuel  then  used. 

The  black  stone,  helped  by  the  wood  fire, 
soon  made  the  principal  of  the  Monastery 
interested,  and  from  this  time,  coal  was  the 
only  fuel  used  there,  and  the  secret  of  its 
heating  power  was  kept  for  over  100  years, 
and  was  then  shared  with  a  monastery  in 
Northumberland,  and  it  is  probably  due  to 
this  that  Newcastle  coals  were  so  much  in 
demand  in  the  south  two  or  three  centuries 
later. 

If  we  now  make  a  leap  forward  of  1,000 
years,  we    are  in    the  company    of    James 


JULY  6,  1923. 


THE  CHEMICAL  NEWS 


Watt  and  others  in  Cornwall,  and  see  their 
efforts  in  constructing  a  steam  generator, 
which  finally  developed  into  the  Cornish 
boiler. 

Another  stride  of  50  years,  and  we  reach 
18(X),  in  which  year  the  first  steam  mill  in 
Bradford  was  started,  the  engine  of  which 
developed  15  horse  power. 

Mr.  Ed.  Green,  of  Wakefield,  recognising 
the  huge  wastage  of  coal  from  steam  boilers, 
conceived  the  idea  of  building  up  a  busi- 
ness by  utilising  the  waste  heat  for  heating 
the  water  before  passing  it  into  the  boiler, 
and  this  invention,  the  Green's  Economiser. 
is  now  a  household  word  wherever  steam 
boilers  are  in  use,  and  for  many  years  may 
be  considered  as  having  saved  steam  users 
eight  to  ten  million  tons  of  coal  per  year. 

Mr.  Brownlie,  in  his  tests  of  l.DOO 
boilers,  found  the  average  overall  efficiency 
was  60  iper  cent.,  the  maximum  being  over 
H<)  per  cent.,    the  minimum    under  50    per 


With     7  p.c.  CO,  Gases  per  lb.  of  coal  83.«  lbs 
8   p.c 20.8     ., 


9 
10 
11 


p^o. 
p.e. 
p.< 


12   f>.c 


13 


p.c. 


JO.;  I 

•il.H 

20  •_' 

IH.C, 


cent.  Now,  is  there  any  reason  in  allowing 
such  conditions'?  Twenty-two  boilers  out 
of  1,000  boilers  giving  over  80  per  cent., 
and  others  30  per  cent,  lower;  in  other 
words,  148.  worth  of  coal  in  one  case  doing 
the  work  of  20s.  in  another. 

Let  us  look  at  the  subject  more  closely, 
and  we  find  the  average  CO,  readings  were 
7  per  cent. ;  this  indicates  33  lbs.  of  air  per 
lb.  of  coal,  and  if  the  calorific  value  of  the 
coal  averaged  12,500  B.lTi.U.s,  the  average 
furnace  temperature  would  be  1,506  de- 
grees. 

By  decreasing  ihe  air  supply  to  18  lbs.  of 
coal,  the  CO,  readings  will  be  13  per  cenJb. 
and  the  furnace  temperature  2,797  degrees, 
a  difference  of  1,291  degrees  by  reducing 
the  air  suipply  per  lb.  of  coal  from  33  lbs.  to 
18  lbs.  A  difference  of  1  per  cent.  CO, 
shows  an  average  difference  in  furnace  tem- 
perature of  215  degrees.  The  actual  figuros 
per  1  per  cent.  CO,  are  as  follows: — 

Furnace    temperature  1,506  degrees. 

.,        1.748  „ 

1,962  ,, 

2,170  ,. 

2,390  ,. 

2,582  ,, 

2.797  .. 


il  ;.  liic  i»  at  its  be»t  and  pai  i  i»i  lue  hxi'l 
is  taken  off,  the  present-day    practice  is    t 
lower  the  damper  and  so  minimise  the  rale 
of  combustion,  but  the  effect  is  serious  from 
an  economical  point  of  view,  as  the  heat  of 
the  fire  rushes    into  the    boiler   due  to   th( 
lower  tcntperature    of  the  latter,    and  thus 
reduces    quickly    the  temperature    of    the 
fires,  so  that  when  the  load  is  put  on  again 
comparatively  cold    fires    are    found,     and 
these,  when  stoked,    being    below    the    gas 
ignition  point,  give  off  black  smoke.    Thre( 
minutes*  smoke  wastes  1  per  cent,  of  th« 
coal  used  per  hour. 

During  my  series  of  lectures  in  Wake- 
field. I  suggested  to  the  audience  one  night 
that  a  present-day  need  in  the  direction  of 
economy  was  a  movable  bridge  for  the  fur- 
naces, to  enable  the  quality  of  combut;tion 
to  be  maintained,  so  that  the  length  of  the 
fires  could  be  kept  suitable  to  the  steam  de- 
mands, and  one  of  the  class  tackled  the 
subject,  and  a  model  of  his  now  patented 
device  is  here  for  your  inspectiwi. 

In  another  invention  of  recent  date  for 
tank  boilers,    the  details  of  construction    I 


:uii  Uui  yil  cuiiv»  i>;iUt  With,  l)Ut  ihu  lael  of 
heating  the  air  before  it  enters  the  furnace 
must  of  necessity  be  an  economy,  and  one 
of  the  best  aids  in  preventing  the  formation 
of  smoke. 

For  many  years  1  have  studied  the  prob- 
lem, why  a  tank  boiler  was  so  ineflicient,  as 
in  some  cases  we  have  seen  the  boiler  is 
practically  dependent  on  the  economiser. 
lispocially  does  this  happen  when  the  air 
supply  is  much  too  high  and  more  so  when 
the  coals  used  have  a  big  proportion  of  hy- 
drocarbons (gas). 

In  an  attempt  to  assist  in  the  direction 
indicated,  a  patent  has  recently  been  taken 
out  for  fitting  up  a  furnace  in  such  a  way 
that  a  big  proportion  of  the  convccted  heat 
is  transformed  to  radiant  heat,  and  by  this 
arrangement  1  think  the  actual  boiler  effi- 
ciency can  be  increased  8  per  cent,  or  ten 
per  cent. 

It  may  interest  many  here  to  know  that 
27  years  ago,  Mr.  Michael  Longridge  car- 
ried out  some  tests  with  a  30'  0"  x  8'  6" 
Lancashire  boiler,  and  by  reducing  the 
grate  area  from  42  to  35  sq.  ft.  when  burn- 


10 


THE  CHEMICAL  NEWS. 


JtTLY  6,  1923. 


ing  35  lbs.  of  ooal  per  sq.  ft.  of  grate^  ;bihe 
overall  efi&ciency  of  boiler  and  economiser 
was  76  per  cent. 

The  subject  of  smoke  prevention  and  its 
natural  resultant  coal  economy  has  never 
been  so  seriously  considered  as  at  present, 
and  it  is  due-  more  to  the  medical  faculty 
than  to  the  engineer  that  the  stand  is  now 
being  made. 

We  engineers  and  manufacturers  burn 
coal,  and  in  doing  so  not  only  waste  a  large 
portion  of  it,  thereby  robbing  ourselves  and 
depriving  our  descendants  of  their  just 
rights,  but  we  create  conditions  responsible 
for  our  annual  fogs,  with  their  long  train  of 
losses  and  inconveniences,  depriving  our 
industrial  towns  of  nearly  two  hours'  sun- 
shine per  day,  and  contributing  in  no  small 
measure  to  our  high  death  rate  from  res- 
piratory troubles.  Our  annual  coal  wastage 
is  Kttle  short  of  50  million  tons. 

A  deputation  of  medical  men  and  others 
visited  the  Ministry  of  Health  a  few  days 
ago,  and  one  of  the  facts  laid  before  the 
Minister  was  that  six  days'  fog  in  Leeds  in- 
creased the  infantile  death  rate  from  50  per 
1,000  to  175,  and  in  the  case  of  a  four  days' 
London  fog  in  November  last,  the  death 
rate  in  the  City  increased  from  12.6  to  14.3 
per  thousand. 

Smoke  cannot  be  formed  with  properly 
proportioned  furnaces.  Hues  and  chimneys, 
as  given  these  and  ordinary  care  in  stoking, 
the  furnace  temperature  is  high  enough  to 
at  once  ignite  the  gases  as  liberated,  and 
heat  instead  of  smoke  is  produced. 

Boilers  sTiould  all  be  fitted  with  draught 
gauges,  CO2  indicators  and  water  meters. 
Without  them,  stoking  and  boiler  efficiency 
is  mere  guess  work,  and  only  leads  to  con- 
fusion. The  water  in  a  boiler  should  not 
be  any  higher  than  the  working  level.  Re- 
member 1"  above  working  level  in  a  30'  0" 
X  9'  0"  boiler  requires  i  cwt.  of  coal  extra 
per  hour. 

My  final  word  is,  we  spend  many  mil- 
lions sterling  per  year  in  providing  pure 
water  to  the  community,  and  it  is  quite 
right  that  this  should  be  done,  but  yet,  the 
senses  of  sight,  smell  or  taste  will  prevent 
us  from  drinking  impure  water,  _  but  in 
comparison,  we  waste  fully  50  million  tons 
of  ooal  per  year  in  fouling  the  atmosphere 
we  are  compelled  to  breathe,  and  directly 
cause  over  1,000  deaths  every  week  with 
our  floating  and  easily  prevented  aereal 
sewage ! 


THE  FAKADAY  SOCIETY. 

Monday,  July  2. 

Deterniination  of  the  Density  of  Charcoal 
by  Displace >ncnt  of  Liquids,  by  J.  B.  Firth, 
D.Sc,  F.I.C. 

In  two  previous  papers  Driver  and  Firth 
show  that  the  sorption  of  liquids  by  various 
types  of  charcoal  is  only  complete  after 
many  days.  Further  it  is  shown  that  the 
volume  of  liquid  sorbed  varies  with  the  dif- 
ferent charcoals;  and  also  for  any  given 
charcoal  varies  with  the  different  liquids. 

It  would  appear  from  these  results  that 
the  values  obtained  for  the  density  of  a 
given  specimen  of  charcoal  by  a  determina- 
tion of  the  displacement  in  a  given  liquid 
would  vary  continuously  until  the  sorption 
was  complete.  Again  since  the  volume  of 
liquid  sorbed  varies  with  the  different 
liquids  the  final  density  values  obtained 
would  likewise  vary. 

In  the  experiments  described  the  appar- 
ent densities  of  cocoanut  shell  charcoal  and 
sugar  charcoal  have  been  determined  after 
definite  intervals,  for  several  liquids. 

From  the  results  obtained  the  value  for 
the  density  of  the  charcoal  increases  with 
the  time  of  contact  between  the  liquid  and 
the  charcoal.  Further  the  final  density 
value  varies  with  the  different  liquids. 

From  the  previous  study  of  the  sorption 
of  liquids  by  charcoal  it  would  appear  that 
the  rate  of  change  in  the  density  value,  and 
also  the  final  density,  will  be  determined  by 
the  rate  of  sorption  and  sorptive  capacity 
respectively. 

Capillarity  is  an  important  factor :  with- 
out doubt,  the  capillarity  alone  will  not  suf- 
fice to  explain  the  present  results.  It  is 
the  opinion  of  the  author  that  an  additional 
force  of  a  chemical  nature,  which  is  respon- 
sible for  sorption  phenomena,  also  oper- 
ates, and  is  fundamental.  This  force  varies 
in  the  different  charcoals  also  between  the 
same  charcoal   and  different  liquids. 

In  the  case  of  benzene  and  water  with 
cocoanut  shell  charcoal,  since  the  density 
in  benzene  is  higher  than  that  in  water  in 
spite  of  the  fact  that  the  capillary  forces 
are  less  in  the  case  of  benzene,  it  follows 
that  the  sorption  attraction  between  the 
charcoal  and  benzene  is  considerably 
greater  than  that  in  the  case  of  charcoal  and 
water,  and  the  difference  between  the  capil- 
lary forces  is  more  than  counterbalanced. 
Hence  it  is  concluded  that  the  difference  in 
the  observed  densities  of  charcoal  in  the 
various  liquids  is  largely  determined  by  the 
sorption  attraction    between    the    charcoal 


JULY  6.  1923. 


THE  CHEMICAL  NEWS. 


11 


and  the  liquid,  and  to  a  much  lesser  degree 
by  the  capillary  forces  exerted  in  the 
system. 

A  further  factor  which  must  also  in- 
Huence  the  final  result  is  the  compressibil- 
ity of  the  liquids.  The  liquids  in  the  finer 
catpiilaries  are  highly  compressed,  and  the 
compression  will  vary  with  the  different 
liquids. 

Cunoentratiun  Cells  in  Methyl  Alcohol, 
by  J.  Grant  and  J.  li.  Partington. 

The  present  investigation  was  under- 
taken with  the  object  of  clearing  up  the  ap- 
parent deviation  from  Xernst's  formula. 
The  results  show  that  no  abnormalities, 
such  as  Wilson  (1906)  found,  exist  in  the 
case  of  silver  nitrate  in  methyl  alcohol,  the 
experimental  values  being  in  quite  satis- 
factory agreement  with  Nemst's  formula. 

The  theoretical  results  were  calculated 
on  the  formula 


2v 


E  = 


u  +  V 


R.T.        ^, 

log, 
N.F.        n. 


2v 


X  0.0002 


u  +  t) 


.  T  .  log, 

The  values  of  u  and  v  were  taken  from  a 
paper  by  Jones  and  Rouiller.  This  gives 
the  transport  number  of  the  anion  of  siivor 
nitrate  in  methyl  alcohol  as  0.561  at  0"  C. 
and  0.572  at  25°  C. 

The  values  of  /i,  and  /x^  at  0°  and  25°  C. 
were  taken  from  Jones  and  Bassett  {Amcr. 
Chem.  J.,  1904,  XXXll.,  409-445),  and 
were  given  earlier  in  the  ipresent  paper. 

Finally  the  observed  values  of  the 
E.M.F.'s  were  corrected  for  temperature, 
and  their  values  found  at  0°  and  25°  O.  so 
as  to  bring  them  into  line  of  comparison 
with  the  calculated  results.  The  E.M.F.'s 
were  taken  as  directly  proportional  to  the 
absolute  temperatures. 

The  Law  of  Definite  Proportions  in  the 
Light  of  Modern  Research,  by  Ulick  R. 
Evans. 

More  than  a  century  ago,  a  controversy 
took  place  between  Proust,  who  maintained 
that  homogenous  bodies  had  a  fixed  com- 
position, and  Berthollet,  who  believed  that 
the  composition  was  variable.  Since  the 
law  of  definite  proportions  occupies  an 
honourable  place  in  all  our  chemical  text- 
books, it  may  be  considered  that  the  view 
of  Proust  hits  prevailed,  at  least  in  the  ease 
of  crystnllin<'  bodies;  it  is  generally  ad- 
mitted that  glassy  bodies  have  no  fixed 
composition.  Of  course,  even  among  cry- 
stalline substances  the  existence    of  bodies 


("mixed  crystals"  or  "solid  solutions") 
having  variable  composition  is  recognised; 
for  insitance,  in  sodium  chloride,  part  of 
the  sodium  atoms  can  be  replaced  by  potas- 
sium, and  part  of  the  chlorine  by  bromine; 
but  the  mixed  crystal  (Na,  K)  (CI,  Br)  thus 
obtained  still  appears  to  obey  the  rule  that 
the  number  of  metallic  atoms  present  shall 
be  equal  to  the  number  of  halogen  atoms. 

When  we  consider  the  case  of  materials 
built  up  of  very  small  (ultra-microscopic) 
particles,  in  which  the  "surface  layers" 
cannot  be  neglected,  our  ideas  receive  some 
modification;  Quarteroli  has  calculated  that 
ultramicroscopic  crystals  of  iron  pyrites 
may  deviate  appreciably  from  the  proper 
composition  FeSj-  Gelatinous  precipitates, 
such  as  aluminium  hydroxide,  will  usually 
contain  more  water  than  corrcstponds  to  the 
formulae  commonly  applied  to  them,  since 
they  ocmtain,  besides  "combined"  water,  a 
great  deal  of  "capillary"  and  "free"  water; 
recently  Foote  and  Sax  ton  have  en- 
deavoured to  distinguish  between  the 
"  combined,"  "  capillarv,"  and  "free" 
water  by  observing  the  benaviour  of  the  gels 
on  freezing. 

But  even  if  we  exclude  cases  of  this  kind, 
and  confine  our  attention  to  dry,  clean  cry- 
stals of  ncrt-mal  size,  various  facts  arc  met 
with  which  suggest  that  Proust's  view  nuist 
be  modified.  In  certain  regions  of  niincnal- 
ogical  ehi'mistry  we  almost  lose  sight  of  the 
principle  of  fixed  composition.  The  com- 
mon minentl  plagioclase  felspar,  for  in- 
stance, is  assigned  a  formula 

m  NaAlbijO,  +  n  CaAlj,SijO„ 
although  it  is  a  homogeneous  crystalline 
body.  Such  cases,  which  are  very  common 
in  mineralogy,  are  seldom  considered  by 
the  advocates  of  the  law  of  definite  propor- 
tions. 

About  1913-1914  Kurnakow,  as  a  result 
of  his  study  of  alloys,  advanced  ^  views 
which  amount  practically  to  the  revival  of 
the  Berthollet  doctrine.  Since  that  time, 
further  work  on  alloys  hsus  served  to  throw 
new  light  on  this  question.  The  object  of 
the  present  paper  is,  firstly,  to  rotate  the 
present  metal  lographical  position  from  a 
standpoint  somewhat  different  from  that 
adopted  by  Kurnakow,  and,  secondly,  to 
show  that  Kurnakow 's  contention  is  not 
confined  to  intermetallic  compounds,  but 
extends  also  to  compounds  between  metals 
and  non-metals  {e.g.,  metallic  oxides,  sul- 
phides,  and  chlorides). 

From  a  study  of  solid  solutions  in  alloys; 
oxides,  chlorides,    and  suliphides;    and  the 


12 


THE  CHEMICAL  NEWS. 


JULY  6,  1923. 


hardness    of     mixed    crystals,    the    author 
draws  the  following  conclusions:  — 

1.  Many  of  the  series  of  solid  solutions 
met  with  in  alloys  show  a  maximum  melt- 
ing-point {i.e.,  a  maximum  thermal  stabil- 
ity) at  a  composition  indicated  by  a  simple 
atomic  formula  {e.g.,  AuMg);  it  is  custom- 
ary to  describe  this  member  of  the  series  as 
an  "  inter-metallic  compound,"  and  to  re- 
gard it  as  the  parent  of  the  series.  But  in 
cases  where  there  is  a  maximum  hardness 
{i.e.,  maximum  mechanical  stability)  at  a 
composition  indicated  by  a  simple  atomic 
formula  {e.g.,  AgAu),  or  where  there  is  an 
abrupt  change  of  chemical  behaviour  (a 
parting  limit),  it  is  not  at  present  custom- 
ary to  apiply  the  word  "  compound." 
Clearly  the  use  of  the  word  "compound" 
is  one  of  convenience;  there  is  no  definite 
distinction  between  a  compound  and  a 
mixed  crystal.  The  compound  is  in  many 
cases  merely  a  member  of  a  continuous 
series  of  solid  solutions  possessing  greater 
stability  and  therefore  greater  importance 
than  other  members;  the  fact  that  the 
maximum  stability  usually  occurs  at  a  com- 
position expressible  by  a  simple  formula  is 
often  capable  of  a  physical  exiplanation, 

2.  Many  of  the  oxides  of  those  metals 
which  possess  more  than  one  valency  have 
a  variable  composition;  the  decomposition 
pressure  varies  gradually  with  the  oxygen 
content,  thus  distinguishing  these  solid 
solutions  from  mechanical  mixtures.  There 
is  a  continuous  series  (or,  according  to 
some  chemists,  a  broken  series)  of  iron- 
oxygen  crystals  varying  in  composition  be- 
tween FcgO^  and  Fe^Og ;  pure  FcgO^  and 
FcaOg  may  be  regarded  as  the  "end-mem- 
bers" of  the  series.  Likewise  homogeneous 
bodies  of  variable  oxygen-content  occur 
among  the  oxides  of  platinum,  iridium, 
nickel,  molybdenum,  tungsten,  and  possi- 
bly silver,  lead,  and  thallium.  Among  the 
chlorides  we  have  a  series  of  homogeneous 
substances  with  TICI3  .  3T1C1  and  TICI3  as 
end-members,  whilst  crystals  of  variable 
composition  exist  in  sub-chlorides  and  sub- 
bromides  of  bismuth;  among  the  sulphides 
we  have  a  series  ranging  from  CUjS  to  CuS ; 
pyrrhotite  is  another  case  of  a  sulphide  of 
variable  composition,  whilst  mixed  crystals 
also  exist  in  the  sulphides  of  nickel  and 
cobalt. 

3.  The  cause  of  the  maximum  hardness 
of  metallic  mixed  crystals  at  the  equi- 
atomic  composition  is  discussed  in  an  ap- 
pendix. 

I  wish  to  thank  Mr.  A.  J.  Berry  for  his 
kindness    in  giving    me  early    information 


regarding    the  results    of  his    work  on    the 
oxides  of  thalTium. 

The  Formation  of  Anom,alous  Liesegang 
Bands,  by  F.  G.  Tryhorn  and  S.  C.  Black- 
tin. 

When  the  stratified  precipitates  known  as 
Liesegang  bands  are  produced  by  the  diffu- 
sion of  an  electrolyte  into  a  gel  containing  a 
second  electrolyte  of  low  concentration,  it 
is  found  in  general  that  the  distance  be- 
tween successive  strata  increases  as  diffu- 
sion proceeds. 

A  reaction  has  been  found  by  Hatschek, 
however,  which  presents  anomalies.  This 
is  the  production  of  lead  chromate  by  the 
interaction  of  lead  acetate  and  potassium 
chromate  or  dichromate.  Stratified  precipi- 
tates resulted  from  this  reaction  when  a  5 
per  cent,  solution  of  potassium  dichromate 
diffused  into  a  1  per  cent,  agar  gel  contain- 
ing 0.1  per  cent,  of  lead  acetate.  Under 
these  conditions  normal  bands  were  pro- 
duced fc«*  a  short  way  below  the  dichromate- 
agar  interface,  the  distance  between  succes- 
sive bands  increasing.  -As  diffusion  pro- 
ceeded, however,  a  second  series  of  bands 
was  observed.  These  secondary  bands 
formed  at  intervals  between  the  normal 
bands,  and  were  distinguishable  from  them 
by  greater  width,  and  the  distance  between 
consecutive  members  of  the  secondary 
series  decreased.  By  varying  the  concen- 
trations of  tln'  leactants  and  by  eliminat- 
ing temperature  changes  it  was  shown  that 
the  production  of  these  secondary  bands 
could  not  be  attributed  to  any  changes  of 
concentration  brought  about  by  unequal 
diffusion,  or  to  temperature  variations. 

The  time  of  diffusion  occupied  several 
days,  and  the  external  factor  which  natur- 
ally varied  over  this  period  was  the  light 
intensity.  Further  experiments  showed 
conclusively  that  the  secondary  bands  were 
to  be  attributed  to  the  variations  of  this 
factor. 

The  mechanism  of  the  production  of 
these  anomalous  bands  was  obscure.  A 
chemical  origin  in  the  reducing  action  of 
the  gel  under  the  influence  of  light  was 
ruled  out  on  the  grounds  that  although  re- 
duction has  been  recorded  by  gelatin  and 
gum  arable,  agar  is  not  known  to  possess 
reducing  properties.  A  second  possible 
action  of  the  light  would  be  upon  the  rate 
of  diffusion  of  the  electrolyte  in  the  colloid 
medium.  This  was  investigated  by  observ- 
ing the  limits  of  diffusion,  under  varied 
conditions  of  illumination,  of  potassium  di- 


JULY  6.  1923. 


THE  CHEMICAL  NEWS. 


13 


cbromate  into  an  agar  sol  free  from  lead 
acetate.  No  variation  in  the  limits  of  diffu- 
sion could  be  detected.  An  investigation  of 
the  size  of  the  granules  of  the  precipitates 
threw  no  light  on  the  mechanism  of  the 
phenomenon. 

In  seeking  an  explanation  of  the  influence 
of  light  on  the  formation  of  Liesegang 
bands,  several  factors  must  be  considered. 
In  addition  to  temperature  changes,  varia- 
tions in  diffusion  velocity?  or  concentration, 
and  chemical  effects,  a  change  in  the  velo- 
city of  crystallisation  may  be  effected  by 
incident  light.  With  the  exception  of  the 
last  effect,  these  possibilities  are  negatived 
by  the  experiments  of  Hatschek.  The  only 
experimental  evidence  bearing  on  the  last 
alternative  is  to  be  found  in  some  results  of 
Trniitz  and  Anschiitz,  and  is  inconclusive. 

An  apparent  increase  in  velocity  of  cry- 
stallisation would  be  caused  by  an  increase 
in  either  of  the  two  factors,  rate  of  nucleus 
formation  and  rate  of  growth  of  the  nuclei. 
Considering  the  work  of  Trautz  and  An- 
schiitz, it  would  seem  that  evidence  is 
afforded  for  the  acceleration  bv  light  of 
nucleus  formation  in  the  cases  of  particular 
salts,  but  that  there  is  no  evidence  for  any 
effect  of  light  on  the  ratt^  of  growth  of  the 
nuclei  once  they  are  formed.  It  will  be 
shown  later  that  the  former  effect  would 
account  for  the  formation  of  an(»nalous 
bimds  in  the  Liesegang  phenomenon. 

The  present  investigation  was  under- 
taken to  determine  whether  the  production 
of  anomalous  bands  of  lead  chromate  is  a 
unique  case,  or  whether  the  effect  is  a 
general  one,  and  further  to  determine 
whether  the  influence  of  the  light  could  he 
attributed  to  a  change  in  the  rate  of  nucleus 
formation  in  the  precipitation  (process. 

Two  further  examples  of  the  production 
of  anomalous  Liesegang  hands  were  cit<>d 
in  addition  to  the  case  of  lead  chromate  in 
agar  gels  first  noticed  by  Hatschek. 

It  is  further  shown  that  the  substances 
formed  in  these  three  reactions  crystallise 
from  the  respective  gels  more  readily  in  the 
light  than  in  the  dark. 

Such  an  effect  is  sufficient  to  explain  the 
formation  of  anomalous  bands  in  these  in- 
stances, and  a  tentative  suggesticm  of  the 
mechanism  of  the  process  is  advanced. 

Papers  read :  — 

On  a  Relation  between  Surface  Tension 
and  Density,  by  Allan  Ferousox,  M.A.. 
D.Sc. 

In  a  paper  read  recently  before  the  Fara- 


day Society,  Dr.  Macieod  has  shown  em- 
pirically that,  for  a  number  of  unassooiated 
liquids 

where  y  is  the  surface  tension  of  the  liquid 
at  any  temiperature,  p,  -  p^  the  difference 
between  the  orthobaric  densities  of  the 
liquid  and  Tho  vapour  at  that  temperature, 
and  C  a  constant  which  is  independent  of 
the  temperature.  The  relation  holds  with 
considerable  accuracy  over  a  wide  range  of 
temperature,  and  it  becomes  a  matter  of 
interest  to  examine  the  exactness  and  the 
physical  meaning  of  the  relation,  and  espe- 
cially to  determine  the  connection  of  the 
constant  C  with  other  physical  constants  of 
the  liquid. 

There  exists  an  almost  endless  variety  of 
such  empirical  formulae. 

For  the  purpose  of  this  paper  the  power 
law  and  the  Eotvos  equation  are  sutticii'ut 
guides. 

The  power  law  is  by  no  means  so  widely 
used  as  it  should  be. 

Some  little  time  ago,  desiring  a  form  of 
equation  which  should  more  accurately  re- 
present the  results  of  experiment  than  the 
evergreen 

y  =  70(1  -  «0. 
I  tried  independently  the  formula    next  in 
order  of  complexitv,  namely: 

y  =  Yo(«  -  ^0' 
If  we  do  not  attempt  to  force  the  value  of 
the  constants  b  and  n,  but  determine  the 
values  appropriate  to  each  liquid  from  a 
few  measurements  of  y  and  t  made  at  ordi- 
nary temperatures,  it  will  be  found  that  the 
value  of  b  represents  the  reciprocal  of  the 
critical  temperature  with  an  accuracy  com- 
parable with  that  of  the  experimental  deter- 
mination of  ^c- 

The  agreement  between  the  observed  and 
values  calculated  by  a  development  of  this, 
is  as  close  as  can  be  expected,  and  the 
author  feels  justified  in  stating  that  the  re- 
lation between  the  surface  tension  and  den- 
sity of  any  unassociated  liquid  is  given  very 
fairly  by  the  equation:  — 

y    =    A  .  {px    -   pr)* 

M|p„io 
where  A  is  a  constant  independent  of  the 
nature  of  the  liquid. 

URUGUAY. 

Tenders  Invited  for  Lubricatino  Oils. 

The  British  Vice-Consul  at  Montevideo 
reports     that     the     State     Electric     Light 


14 


THE  CHEMICAL  NEWS. 


JULY  6,  1923. 


Works  at  Montevideo  are  calling  for  tenders 
to  be  presented  by  August  22  for  various 
lubricating  oils.  A  copy  of  the  specifica- 
tion, general  conditions  of  tender,  etc.  (in 
Spanish)  can  be  seen  at  the  Department  of 
Overseas  Trade  (Room  52),  35,  Old  Queen 
Street,  Westminster,   S.W.I. 


In  the  House  of  Commons  recently.  Sir 
John  Simon  asked  the  President  of  the 
Board  of  Trade  whether  he  was  aware  that 
Messrs.  A.  E.  &  E.  Becker,  of  Howden 
Clough  Mills,  Birstall,  near  Leeds,  applied 
on  April  16  last  to  the  Dyestuffs  Advisory 
Licensing  Committee  for  a  licence  to  im- 
port one  ton  of  Diamond  Black  P.V.,  and 
that  the  licence  was  refused  on  the  ground 
that  Diamond  Black  P.V.  was  available 
under  the  reparation  arrangements;  that 
the  lowest  price  at  which  this  dye  could  be 
supplied  from  reparation  stock  was  2s.  8d. 
per  lb.,  and  that  this  price  was  fixed  by  the 
Board  of  Trade,  whereas  this  firm  could 
have  obtained  this  dye  under  an  import 
licence  at  2s.  per  'lb. ;  and  whether  he 
would  take  steps  to  enable  the  British  dye- 
ing industry  to  obtain  the  best  dyes  at  thie 
lowest  price,  in  order  that  it  might  not  be 
handicapped  in  competing  with  the  pro- 
ducts of  other  countries. 

Sir  PhiUp  Lloyd-Greame  rephed :  The 
application  for  a  licence  was  refused  on  the 
ground  that  large  quantities  of  the  dye- 
stuff  mentioned  were  available  in  repara- 
tion stock.  As  regards  the  price  charged, 
the  ordinary  procedure  has  been  followed, 
and  the  matter  referred  to  the  Price  Com- 
mittee which  advises  the  Board  of  Trade; 
but  that  Committee,  which  consists  of  two 
representatives  each  of  the  dye-users  and 
dye-makers,  has  not  up  to  the  present  re- 
commended any  change  in  the  price 
charged  for  this  particular  dyestuff. 


The  Department  of  Mines,  Canada,  has 
issued  a  Summary  Report  of  Investigatwns 
made  hy  the  Mines  Branch,  1921. 

This  Report  contains  much  information 
of  scientific  interest,  especially  concernmg 
the  possibilities  of  using  the  vast  natural 
resources  of  this  Dominion. 

Brief  accounts  are  given  of  the  following : 

Coalmont  amber  (Alfred  W.  G.  Wilson  . 
The  iron  industry  (A.  H.  A.  Robinson). 
Iron  oxide    pigments    in  Ontario    (Howells 


Fi'echette).  Investigations  of  miscellane- 
ous non-metallic  minerals  (H.  S.  Spence). 
Alkali  deposits  of  Western  Canada  (L.  H. 
Cole  and  F.  M.  MacNiven),  Cretaceous 
shales  of  Manitoba  and  Saskatchewan : 
their  economic  value  as  a  possible  source  of 
petroleum  (S.  C.  Ells).  Oil  shales  of  Can- 
ada (S.  C.  Ells).  Chemical  products  from 
natural  gas  (R.  T.  Elworthy).  In  the 
Chemical  Division,  the  possibility  of  pro- 
ducing methanol  (methyl  alcohol)  and 
formaldehyde  from  natural  gas,  is  dis- 
cussed by  R.  T.  Elworthy;  and  chemical 
and  physical  characters  of  bentonite,  by  E. 
A,  Thompson  and  A.  Sadler. 

In  his  paper,  Mr.  Elworthy  shows  the 
possibilities  of  natural  gas  as  a  raw  material 
for  chemical  products  of  great  value.  This 
is  a  sufficient  argument  for  the  expenditure 
of  time  and  money  for  the  conservation  and 
development  of  this  natural  resource.  The 
Mines  Branch  laboratories  are  well 
equipped  to  carry  out  much  of  this  work, 
though  the  successful  solution  of  these 
problems  will  be  obtained  only  by  the 
widest  exchange  of  opinions  and  by  co- 
operation with  the  natural  gas  and  chemi- 
cal industry. 

A  general  review  of  ore-dressing  occvi- 
pies  over  100  pages.  Other  reports  from 
the  Fuels  and  Fuel  Testing  Division,  Cera- 
mic Division,  and  Road  Materials  Division. 

The  report  is  illustrated  with  photo- 
graphs,  drawings,   and  diagrams. 


CORRESPONDENCE. 
To  the  Editor  of  The  Chemical  News. 

Sir, — My  attention  has  been  called  to 
Science  Abstracts,  No.  305,  of  May  25,  in 
which  an  extract  is  given  under  No.  648, 
page  261,  Micro-Telescope  and  Super- 
Microscoipe. 

In  reading  this  extract,  I  would  like  to 
point  out  that  a  very  serious  misstatement 
is  made,  one  quite  at  variance  with  what 
was  actually  said  by  me,  I  refer  to  the 
fourth  sentence,  in  which  I  am  made  to  say 
that  the  "collector"  forms  an  image  of  a 
microscopic  object  at  a  position  of  the  stage 
of  the  microscope.  This  should  read,  "  at 
a  position  beyond  the  stage  of  the  micro- 
scope," quite  a  different  thing  altogether. 

The  article  referred  to  appeared  in  The 
Chemical  News,  Vol.  CXXV.,  pages  353  to 
355,  December  15,   1922.— Yours,   &c., 

F.  Davidson. 

29,  Gt.  Portland  Street,  London,  W. 
June  25,  1923. 


JULY  6,  1923. 


THE  CHEMICAL  NEWS. 


15 


NOTICES  OF  BOOKS. 

Therniudynauiica  and  the    Free  Enenjij 

of  Chemical  Substances,  by  G.  M.  Lewis 

and    M.    Randall.       Pp.  'XXIV.  +  653. 

•Messrs.     McGraw-Hill      Publishing    Co., 

Ltd.,  6  and  8,  Bouverie  Street,   Ijondon, 

E.C.4.     1923.     Price  25s.  net. 

This    book     contains     a    great    deal     of 

material,  which  is  presented  in  an  attractive 

and    useful  form,    the  main   idea  being    to 

treat  the  science    of  thermodynamics  so  as 

to  make  it  readily  applicable  to  quantitative 

and  numerical  calculations.       The    authors 

develop  a  variety  of  methods    of  treatment 

owing  to  the  requirements  of  the  cases,  and 

thus  the  reader  will  find  chemical,  algebraic, 

arithmetical     and       graphical     troatmenis, 

which  should  be  helpful  to  him. 

The  book  is  up-to-date.  For  example, 
the  entropy  of  "electron  gas"  is  indicated, 
also  the  thermal  ionisation  of  metals. 
Saha's  work  in  connection  with  8t<'llar 
spectra  is  briefly  noted.  On  page  464  the 
atomic  entropies  per  gram-atom  of  76  ele- 
mentary substances  are  tabulated.  Carbon 
(diamond)  has  the  lowest  numerical  value, 
while  iodine,  xenon,  caesium,  mercury  and 
niton,  as  gases,  are  almost  equal  to  one  an- 
other, and  the;y  have  the  highest  values 
listed. 

The  aipplications  of  thermodynamics  to 
chemical  reactions  an>  treated  at  length, 
and  it  is  profitable  to  study  these,  as  they 
may  afford  a  means  of  determining  the 
limits  to  theoretical  yields  so  that,  in  com- 
mercial developments  contemplated,  errors 
need  not  be  made.  Thus  a  saving  of  us<^- 
less  expenditure  may  be  avoided.  The  booK 
shoiild  prov(>  of  great  value  to  the  advancdl 
student  and  the  practical  worker  requirin;: 
fimdamental  knowledge  of  the  thertnwlyna 
mies  of  chemical  reactions,  and  as  a  work 
of  reference  and  study  it  is  a  moAt  valuable 
one. 

As  regards  diction,  there  is  aclearness  of 
statement  we  admire.  For  example,  on 
page  6()6  the  authors  state  that  "  If  a  sub- 
stance is  capable  of  undergoing  a  spontane- 
ous change,  and  if  by  this  change  the  sub- 
stance is  heated  so  that  the  process  acceler- 
ates itself  after  once  starting,  the  substance 
belongs  to  the  class  of  exiplosives."  It  is  of 
interest  to  note  here  that  the  radio-atoms 
are  not  explosive  in  this  sense. 

There  is  one  minor  fault  which  we  think 
should  be  observed  generally  in  connection 
with  books  intended  for  reference,  and  that 
is  the  use  of  special  words  having  a  particu- 


lar meaning  peculiar  to  the  author,  as  the 
reader  is  apt  to  forge  their  significance,  and 
he  has  then  to  road  back  to  find  out  whatJ 
they  mean.  It  should  be  realised  that  any- 
thing that  saves  time  in  reading  enhances 
the  value  of  a  book.  An  example  will  illus- 
trate our  meaning  here.  On  page  50  it  is 
stated  that  "  the  deviations  from  whole 
numbers  of  the  atomic  weights  of  pure  iso- 
topes (referred  to  hydrogen)  measure  the 
energy-  changes  in  the  synthesis  of  the  ele- 
ments." The  italics  are  ours.  Not  know- 
ing the  authors'  use  of  the  word  pure,  the 
reader  is  apt  to  ask  himself — What  are  im- 
pure isotopes?  The  definition,  however,  of 
pure  substances  and  solutions  is  given  on 
page  10,  which  shows  that  the  authors  have 
been  thorough  in  their  work ;  but  still  we 
think  that  a  few  extra  words  in  cases  of  this 
kind  would  be  helpful  to  the  reader.  It  is 
true  that  the  index  is  useful  in  this  respect, 
but  it  is  doubtful  whether  it  would  always 
bo  of  assistance. 


The  Chemistry  of  the  Inorganic  Com- 
plex Compounds,  by  Dr.  Robert 
ScnwARZ.  Authorised  Translation  by 
Lawukxce  W.  Bass,  Ph.D.  Pp.  X.  + 
82.  London:  Messrs.  Chapman  &  Hall, 
11.  Henrietta  St..  Covent  Garden,  W.C.2. 
1923.     8s.  6d.  net. 

The  fact  that  numerous  double  salts  and 
complex  inorganic  compounds  have  been 
prepared,  which  do  not  easily  accord  with 
the  simple  conceptions  of  valency  as  origin- 
ally defined,  has  led  numerous  authors  to 
extend  and  alter  these  conceptions. 

Probably  the  greatest  advance  in  this 
direction  is  that  of  Werner,  who  put  for- 
ward in  1908  his  Co-ordination  Theory  to 
account  for  the  existence  of  double  and 
complex  salts,  basing  his  theory  on  some 
classical  researches  on  the  Cobaltamines, 
etc. 

His  volume,  Neuere  Anschauungen  anf 
dem  Qebiete  der  Anorganischcn  Chemie 
(the  second  edition  of  which  was  translated 
into  English  by  Hedley.  1911),  gave  a  full 
account  of  the  co-ordination  theory,  but 
possesses  the  disadvantage,  from  the  stu- 
dents' viewipoint,  of  being  difficult  to  fol- 
low. It  is  for  such  students  that  Prof. 
Schwarz  has  written  this  present  volume, 
which  is  intended  as  an  intrinluction  to  the 
study  of  complex  inwganic  compounds. 

It  is  shown  how  the  valency  theory, 
which  hold  for  the  explanation  of  the  for- 
mation and  behaviour  of  all  simple  chemi- 


16 


THE  CHEMICAL  NEWS. 


JULY  6,  1923. 


oal  compounds,  does  not  hold  for  com- 
pounds of  higher  order,  i.e.,  compounds 
fonned  by  the  union  of  two  or  more 
saturated  molecules. 

These  are  divided  by  Prof.  Schwarz  into 
addition  co^npounds  and  penetntion  coin- 
pounds  (Einlagerungsverbindungen).  The 
former  include  true  double  salts,  like 
KaPtClg,  cobaltinitrites,  etc.  Such  sub- 
stances as  the  metal  ammines  and  hydrated 
salts  are  examples  of  penetration  com- 
pounds. 

The  book  concludes  with  a  useful  his- 
torical survey  of  the  subject,  and  consti- 
tutes a  further  interesting  contribution  to 
the  literature  of  this  subject. 

Electrons,    Electric  Waves,    and  Wire- 
less Telephomj,  by  J.  A.  Fleming.       Pp. 
VIII.  +  326.     The  Wireless  Press,    Ltd., 
12  &  13,  Henrietta  Street,  Strand,    Lon- 
don, W.C.2.      New  York,    Sydney,  Mel- 
bourne, Madrid,  Genoa,  and  Amsterdam. 
1923.     Price  7s.  Gd.  net. 
Addressing      ourselves      particularly      to 
chemists,  they  will    find  in  this  book    that 
Wireless  is  not  so  far   removed  from  chemi- 
cal problems  as  they  might  suppose.     Prof. 
Fleming  devotes  a  considerable    portion  of 
his  book  to  atomic  theory.       Much    funda- 
mental science  whether,  for  example,  it  be 
the  chemical  reaction,  the  dynamo,    or  the 
thermionic  valve,  as  used  in  wdreless,  have 
in  common  one  agent    of  great  and  wonder- 
ful activity,  namely,  the  electron.     In  this 
book  the  reader    will  find    many    scientific 
lines  of  research    and    study  blended    in    a 
most  fascinating  manner.       We  cannot    do 
better  than    list  the  main    contents: — Sur- 
face waves  and  wave  production;    waves  in 
air;  architecture  of  atoms;  electro-magnetic 
fields,  forces  and  radiation;  production  and 
detection  of  long  electric  waves;    telephony 
and  speech  transmission;  principles  of  wire- 
less telephony;  index. 

As  a  striking  instance  of  the  practical  side 
which  is  evident  throughout  the  book,  the 
following,  from  page  305,    will  serve  as  an 
example:— "A    still  more    important    im^ 
provement,  however,    has    come  from    the 
United  States,  in  the    form  of  a  thermionic 
valve,  of  which  the  greater  part  of  the  bulb 
is  formed  of  sheet  copper.     The  copper  not 
only  forms  part  of  the  bulb,  but  also  consti- 
tutes the  anode  cylinder,    and  can    be  kept 
cool  by  cold  water.     The  foundation  of  this       j 
improvement  is  the  technical  discovery  of  a       i 
method  of    sealing  copper    to  glass    m  such       | 
fashion  that  it  does  not  crack  away  on  cool- 
ing  or  subsequent  heating.     The  reason  the       | 


expensive  metal,  platinum,  has  hitherto 
been  used  for  wires  which  must  be  sealed 
ail-tight  through  the  wall  of  the  glass  bulb 
is  that  it  possesses  three  essential  qualities 
for  this  purpose.  First,  it  has  nearly  the 
same  coefficient  of  expansion  with  heat  as 
lead  glass.  In  the  second  place,  hot  plati- 
num is  "wetted"  by  molten  glass;  that  is, 
it  sticks  to  it;  and  lastly,  platinum  is  not 
oxidised  when  heated  in  a  blowpipe  flame, 
but  retains  a  bright  and  clean  metallic  sur- 
face. No  other  metal  has  been  found  which 
possesses  all  these  properties,  but  the  dis- 
covery was  made  some  years  ago  that  if 
copper  is  kept  unoxidised  in  a  flame  con- 
taining reducing  gas,  it  is,  when  very  hot, 
"wetted"  by  molten  glass,  which  sticks  to 
it.  Copper,  however,  has  not  the  same  co- 
efficient of  thermal  expansion  as  glass,  and 
the  only  way  to  attach  a  copper  tube  to  a 
glass  tube  of  the  same  size  is  to  give  thie 
copper  a  sharp  knife  edge.  If.  then,  a  sort 
of  copper  thimble  is  made,  closed  at  one 
end,  but  with  the  edge  of  the  open  end  made 
sharp  like  a  knife,  this  thimble  can  be 
sealed  airtight  to  a  glass  tube  of  the  same 
diameter  as  the  thimble,  and  the  joint  will, 
not  crack  away  in  cooling,  and  can  be  made 
vacuum-tight.  The  glass  tube  terminates 
in  a  re-entrant  portion  through  which  are 
sealed  wires,  to  which  are  sealed  the  wires 
which  carry  the  ends  of  the  filament  of  the 
valve  and  also  the  leading-in  wire  for  the 
grid." 

Much  of  this  book  will  appeal  to  the 
general  reader  having  interest  in  modern 
scientific  developments.  The  book  is  not 
without  interesting  theoretical  matters  of 
fundamental  importance.  A  short  but 
lucid  account  of  the  quantum  theory  is 
sketched.  All  chemists  should  possess  the 
book  and  study  it  carefully,  for  it  makes 
clear  many  things  which  enter  into  modern 
chemical  and  physical  problems. 


i'His  lisi,  is  specially  compiled   for    The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chance "y  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 
Latest  Patent    Applications. 
14663— Rhenania     Verein     Chemisclier      Fabriken 
Akt-Ges.— Production     of  salts    of     barium 
and  strontium  soluble  in  water.     June  4. 
14954— Urfer,     C. — Synthetic     production     of     am- 
monia.   June  7. 

Specifications   Published   this    Week. 
198287  -Barnes,  E.   A.— Method     of  manufacturing 
fulminate  of  mercury. 


JULY  13,  1923. 


THE  CHEMICAL  NEWS. 


17 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3300. 


SULPHUR  DYES. 
By  R.  F.  Hunter,  F.C.S. 

The  first  of  this  important  class  of  dyes 
was  preipnred  by  Croissant  and  Bretonniere 
in  1873  by  heating  various  kinds  of  organic 
matter  such  as  sawdust,  bran,  straw,  etc.. 
with  sulphur  and  alkaline  polysulphides. 
This  dye  was  called  Cachou  de  Laval,  and 
received  quite  a  large  application  as  a  cot- 
ton dye,  despite  its  unpleasant  odour.  The 
substance  dyes  cotton  green  and  yellow 
shades — these  on  exposure  to  atmosphere 
unflcrgo  oxidation  to  brown  shades.  These 
brown  colours  are  exceedingly  fast,  both  to 
light  and  to  soap. 

This  dye  remained  the  solo  representa- 
tive of  its  class  until  some  twenty  years 
lat.er  a  French  chemist,  Raymond  Vidal. 
prepared  the  famous  Vidal  Black.  He  ob- 
taincnl  it  by  fusion  of  sodium  "Vjulphide  and 
sulphur  with  p-aminophenol. 

The  dye  by  far  surpassed  any  other  cotton 
dye  of  its  kind,  save  anilino  black,  in  fast- 
ness to  light,  washing  and  boiling  witii 
acids,  and  aroused  considerable  interest ;  so 
much  so  that  various  organic  bases  were 
fusi'd  with  sulphur,  and  hence  arose  tin 
sulphur  dye  industry-.  The  extreme  fast 
ness  of  the  first  two  members  gave  the  im- 
pression that  the  remaining  members  of 
the  family  would  possess  similar  ipropt  r- 
ties,  but  bitter  disappointment  doomed  tbi< 
hope. 

There  are  at  present  two  methods  f.f  pn- 
paration  employed,  viz. : 
d)  Baking, 
(2)  Refluxing  of  boiling  solution. 

The  latter  yields  the  l)est  results.  The 
usual  method  of  procedure  is  to  dissoKv 
Na.S  crystals  in  water,  add  sulphur  flowers. 
th<>n  the  base,  and  boil  under  a  reflux  con- 
denser until  the  desired  stage  is  reached  : 
then  filter,  wash  and  dry.  The  process 
must  be  watched,  since  sulphur  dyes,  it 
shoiild  hv  remembered,  are  complex  enn- 
densation  products,  and  if  heating  is  carnCI 
too  far,  weird  results  appear.  During  the  n  - 
action,  torrents  of  H,R  and  NH,  ar<> 
evolved,  and  hence  the  preparation  should 
be  carried  out  in  a  good  draught. 

Very  little  is  known  as  to  the  chemienl 
constitution    and  composition,    even  of  the 


sulphur  dyes,  and  w^  can  only  surmise  that 
they  probably  contain  a  large  number  of 
thiazine  rings  and  possibly  mereaptan 
groups. 

Blue  and  black  dyes  are  usually  derived 
from  thiodiphenylamine,  whilst  yellow  and 
brown  are  obtained  from  thiazoles.  Imme- 
dial  yellow  is  produced  by  fusion  of  dehy- 
drothiotoluidin  with  sulphur,  and  probably 
consists  of  complex  mixture  of  the  higher 
primulins. 

NH3C„H/        etc. 

\n 

The  red  type  of  dyes  are  mostly  unsatis- 
factory, and  are  derived  from  azines,  and 
have  been  shown  to  contain  an  unchanged 
azinc  ring. 

Vidal  regarded    his  black    from     atmos- 
phere as 
C.H,(0H).NH.S.(CH),8NH(CH)2 

NHSC„H,0H 
and  further  by  carrying  out  th»^  reaction  nt 
a  lower  temperature  he  obtained  dehvdro- 
thiodiphenvlamine. 

-  C.H,(0TI)NHS  C.  H,rOH). 

Immedial  pure  blue  on  oxidation  and 
bromination  gives 

C.Ht Br),N(CH  ),NSC.HBr, : O. 
(tetra  bromodimethyl  aminothiazine). 

The  fomiula 

C.H,(CTT,)NH,NSC,H,S. 
has  been  assigned    to  Immedial  Indone  ob- 
tained from  a  mixture  of  o-fcoluidin    and  p- 
aminophenol. 

A  point  worthy  of  note  is  that  Green,  by 
oxidising  a  mixture  of  p-diamine  or  p-ami- 
dophenol  with  a  large  excess  of  NajSjO, 
and  solid  KjCr^O,,  obtained  di  or  tetra  sul- 
phonic  acids. 

A  few  of  the  commoner  sulphur  dyes 
might  now  be  described  : 

Immedial  Yrlhnr  is  prepared  from  NajS 
and  m-tolylene  diamine.  If  heating  is  car- 
ried tf)0  far.  orange  shades  result. 

Thional  Brmni  is  prepared  by  condensa- 
tion of  ar>lamino  derivatives  of  b-naphtho- 
quinone  with  sodium  polysulphide,  tem- 
peratures 2-10-280°  C. 

Cnffnn  Brmvn  is  obtained  from  nitro  di- 
phenylamine  and  sodium  polysulphide. 

Erlipsr  Brown  is  made  by  heating  toly- 
lene  diamine  and  oxalic  acid  with  polysul- 
phide. 

Immedinl  Blork  is'  obtained  from  p-hy- 
dr()-o-;)-dinitrndii>benylamine.  which  re- 
sults from  condensation  of  p-aminophenol 
and  dinitroehlorbenzene. 


18 


THE  CHEMICAL  NEWS. 


JULY  13,  1923. 


Sulphur  Black  T  Extra  made  from  dini- 
trophenol. 

Thiophenol  Black  T  Extra  from  dinitro- 
phenol. 

Immedial  pure  blue  C  is  made  from  p- 
dimethylamine  p-hydroxydiphenylamine. 

Immedial  blue  C  from  p-hydroy-o-p- 
dinitrodiphenylamine. 

Imm,edial  Indone  from  the  indone 
NH3CeH,N:NCeH,:0. 

Indo.  carbon  SSF  is  by  far  the  most  im- 
portant blue,  and  is  prepared  from  the  indo- 
phenol  produced  by  condensation  of  carba- 
zole  and  nitro  phenol. 

Italian  Green  is  produced  by  adding  c0ip- 
per  sulphate  to  the  melt  obtained  from  p- 
nitrophenol  and  sulphur  (Vidal's  black). 

hnmedial  Green  is  prepared  in  the  same 
manner  from  the  indophenol.  A  red  sul- 
phide dyestuff  is  obtained  from  amino 
hydroxy  phenazine. 


AN  EXPLANATION    OF  THE  THEORY 

OF   THE  ROTATION  OF    THE  ATOMIC 

NUCLEUS. 

Part  III. 

By  Herbert  Hen  stock. 

The  hydrides,  halides  and  hydroxides  de- 
scribed in  Part  II.  of  this  series  were  chiefly 
concerned  with  simple  co-valencies  or  elec- 
tro-valencies where  single  bonds  came  into 
iplay,  and  consequently  did  not  present  the 
difficulties  which  will  be  met  with  in  oxy 
compounds,  where  not  only  double  bonds, 
but  even  distortion  of  the  octet  are  encoun- 
tered. 

A  double  bond  might  occur  as  described 
in  Part  I.  of  this  series,  but  it  might  also 
occur  as  shown  in  Fig.  1. 

/  2 


cLcuJytz.  -ircsYiCi 

Most  double  bonds  would  probably  be 
formed  in  this  fashion.  Cube  No.  1  has  its 
nuclear  poles  in  the  plane  of  the  paper,  No. 
2  has  them  almost  at  right  angles  to  the 
plane  of  the  paper.  A  double  bond,  as  here 
shown,    is  composed  of    two  positive    and 


two  negative  edges  in  each  atom,  so  that 
when  such  a  bond  Qpens  into  a  single  bond 
it  may  do  so  at  any  edge. 

Here  the  double  bond  is  not  formed  on 
the  faces  of  the  cube,  which  lie  at  right 
angles  to  the  nuclear  poles,  but  on  any  of 
the  four  faces,  which  are  parallel  with  the 
poles :  as  a  consequence  of  this  there  can- 
not be  more  than  four  such  double  bonds 
operating  from  any  atom,  which  has  an  un- 
distorted  octet. 

In  double  bonds  one  or  more  electron? 
may  be  displaced  and  may  occupy  different 
corners  of  the  octet  from  those  which  they 
normally  occupy  in  the  atom :  the  same 
thing  will  also  occur  in  a  treble  bond. 

Distortion  of  the  octet  will  be  considered 
here  only  as  from  the  cube  to  the  tetrahe- 
dral  form,  either  partly  or  wholly  as  a 
shrinkage,  but  it  is  possible  that  the  octet 
may  exhibit  other  forms  of  distortion  in 
shrinkage  or  expansion,  as,  for  instance,  to 
the  octohedron.  In  shrinking  from  the 
cube  to  the  tetrahedron,  one  or  more  cor- 
ners of  the  cube  disappear,  leaving  triangles 
which  will  constitute  tetrahedral  faces. 


K,0 


Oxides. 
Group  I. — General     Types   Li20,     Na^O, 
etc.,  are  shown  in  Fi?.  2. 


F. 


Na^Og    will  be  constituted    like  H^Og    (see 
Part  II.)  thus:  — 

+         -        + 

Na  -  O  -  0— 

I 
+Na 
the  molecule  having  the  same  weakness  in 
one  of    the  oxygen  atoms    (Rule  2)    which 
occurs  in  that  compound,  Kfi^  will  have  a 
somewhat  similar  construction,   as:  — 
+         -        + 
K - O - O— 

I 

+   - 

0-0+ 


K 


JULY  13,  1923. 


THE  CHEMICAL  NEWS. 


19 


weakness.  Copper  is  one  of  those  elements, 
which  may  have  varying  numbers  of  elec- 
trons in  its  octet,  see  Bury  (J.  Amer. 
Chcm.  Soc,  1021,  XLIIL,  1G02),  so  tha^ 
its  three  oxides  will  be  constituted  differ- 
ently. CujO  will  conform  with  Fig.  2 
where  it  has  only  one  electron  in  its  octet: 
CuO  with  Fig.  3  with  two  electrons,  and 
CuOj  with  Fig.  5  with  four  electrons :  its 
chlorides  and  other  salts  will  likewise  have 
nonnal  structures. 

Gold  has  similar  properties  to  copper 
with  respect  to  its  octet,  so  that  AuO  will 
conform  with  Fig.  3,  and  Au^Og  with  Fig.  4. 

The  reasons  for  the  instability  of  the 
cuiprous  salts  and  also  of  most  of  the  salts 
of  gold  do  not  seem  clear;  it  is  possible 
that  the  cause  may  be  due  to  the  change  in 
the  numbers  of  electrons  in  the  octets  of 
these  elements,  which  brings  about  stable 
or  unstable  arrangements  in  their  atoms. 
Silver  peroxide,  Ag^O,,  will  probably  have 
a  composition  similar  to  that  of  sodium  or 
hydrogen   peroxides,   since  when  AgjO,    is 


slowly  acted  upon  by  water  it  yields  H^Oj. 
The  instability  of  Ag202  is  therefore  ac- 
counted for. 

Group  //.—General  types,  BeO,  MgO, 
CaO,  ZnO,  etc.,  are  represented  by  Fig.  3. 

In  the  octet  of  the  metal  the  electron  at 
(b)  hjis  travelled  from  its  normal  position 
(a)  and  a  similar  action  has  occurred  in  the 
oxygen  octet. 

The  stability  of  these  oxides  to  heat  is 
very  great,  but  the  bond  is  only  stable  to 
heat  and  not  to  the  electricity  of  other 
atoma,  for  it  is  weak  enough  to  be  attacked 
by  such  a  neutral  substance  as  water, 
which  fact  is  a  good  demonstration  of  the 
difference  between  the  actions  of  these  two 
ff>rce8. 

The  peroxides  of  the  tyipes  CaO,,  BaOj, 
etc.,  will  have  a  somewhat  analagous  con- 
stitution to  that  of  hydrogen  pt^roxide,  since 
they  can  l)e  fonned  by  its  action  upon  the 
hydroxides  of  thest^  metals :  their  instabil- 
ity is  thus  accounted  for.  They  will  be 
constituted  as  follows:  — 

-\-^ O 

Ca    V       I  + 

+  0 
Mercurous  salts  will  be  abnormally 
ff>rnied.  Mercurous  chloride,  as  an  ex- 
ample, is  not  so  stable  as  the  mercuric  salt; 
since  its  vapour  density  agrees  with  the 
formula  Hg,CI,  (see  Smith  and  Menzies, 
./.  Atnrr.  Ch'rm.  .Soc,  1910,  XXXIl.,  1434, 
nnd  Ann.  Physik,  1010,  XXXIII.,  979)  it 
will  be  represented  by 

-         +  - 

CI  -  Hg  -  Hg 

Qrnup  III. — General  types,  B,0,,  AljO,, 
etc.,  are  constituted  as  shown  in  Fig.  4. 


CCcvovu  -WTTfaf, 


20 


THE  CHEMICAL  NEWS. 


JULY  13,  1923. 


where  three  oxygen    atoms  show  the  same 
and  are  all  quite  regular. 


Group  IV. — General    types,    CO2,    SiOj, 
TiOo,  SnOg,  etc.,  are  represented  by  Fig.  5.* 


crjoiLQ^^^ 


obruMx        -Hjna 


Fi^.^. 


The  great  stability  of  silica  is  not  appar- 
ent from  the  theory  of  nuclear  rotation. 

The  case  of  carbon  monoxide  presents 
more  difficulty  than  that  of  the  di  oxide, 
but  an  explanation  may  be  found  by  taking 
into  account  the  partial  distortion  of  the 
carbon  octet.  If  the  uncombined  carbon 
atom  be  taken  as  possessing  the  form  of  the 
tetrahedron  and  the  uncombined  oxygen 
atom  that  of  the  cube,  then  when  two  such 
atoms  approach  one  another  under  suitable 
conditions  for  union,  we  should  have  a  pos- 
tulation  somewhat  after  the  manner  con- 
templated in  Fig.  6. 


There  is  in  this  case  no  edge  or  face  for 
union,  which  will  correspond  in  each  atom : 
if,  however,  the  carbon  octet  begins  to  form 
itself  around  the  tetrahedron,  but  on  one 
side  only  where  one  edge  of  the  tetrahedron 
expands  into  a  cube  face,  we  have  a  state 
of  things  as  shown  in  Fig.  7. 

The  dotted  lines  indicate  the  alteration 
in  shape  which  the  figure    will  take.       We 


F-j7 


can  now  write  the  complete  formula  of  car- 
bon mon  oxide  as  follows  :  — 


ctcruAnA.  vtrrLoC 


F'cj.^ 

There  are  here  no  free  valencies  in  either 
the  carbon  or  the  oxygen  atoms  until  the 
rest  of  the  distorted  cube  is  opened  out, 
which  would  occur  when  another  group  or 

^  The  reason  for  the  inclusion  of  the 
tetrahedron  will  appear  later. 


JULY  13,  1923. 


THE  CHEMICAL  NEWS. 


21 


atom,  say,  of  oxygen,  came  in  contact  with 
the  carbon  junder  suitable  conditions  for 
union ;  the  result  would  be  as  shown  in  Fig. 
5,  in  which  the  dotted  Unes  represent  the 
new  lines  of  force  brought  into  play;  these 
pass  out  through  the  middle  of  the  two 
tetrahedral  faces.  The  tetrahedron  has 
been  retained  in  Fig.  5,  in  order  to  show  its 
bearing  on  the  whole  thing.  The  new  lines 
of  force  may  be  taken  to  be  halves  of  tiio 
old  lines  of  force  running  to  the  electrons 
(c)  and  (d)  in  Fig.  8. 

When  lines  of  force  run  out  to  the  comers 
of  the  octet  of  an  atom  to  positions  where 
there  are  no  electrons,  and  when  no  union 
occurs  with  another  atom,  the  first  atom 
will  be  in  the  activated  or  nascent  condi- 
tion ;  if  union  occurs,  these  lines  of  force  re- 
main in  position,  but  when  union  does  not 
take  place  they  may  shrink  into  the  nucleus 
or  they  may  coalesce  with  the  lines  of  fwce 
running  to  neighbouring  electrons,  in  which 
case  di8torti<m  would  occur. 

This  view  of  the  matter  may  seem,  at 
first  sight,  a  little  bizarre,  but  when  it  is 
remembered  that  a  transition  of  this  kind 
is  only  a  passage  from  hemihedral  to  holo- 
hedral  types,  well  known  in  crystal lo- 
gr.ipliy,  there  seems  no  reason  why  it 
should  not  occur  in  such  ca^es  as  this,  the 
only  difference  l)eing  that  it  might  take- 
place  in  stages.  It  explains  both  the  pos- 
sibility of  the  existence  of  carbcm  mon 
oxide,  as  well  as  its  instability  to  certain 
reagents  such  as  oxygen,  chlonne,  etc.  (see 
rule  7),  since  the  opening  up  of  the  second 
cube  face  in  the  carbon  atom  will  take 
place  more  readily  after  the  first  has  been 
formed.  At  the  same  time  the  double  bond 
in  CO  is  a  normal  one,  and  this,  together 
with  the  likelihood  that  a  small  quantity  of 
electrical  energy  or  effort  would  be  neces- 
sary to  open  up  the  distorted  carbon  octet, 
gives  CO  enough  stability  to  exist,  al- 
though only  half  of  the  normal  valencies  of 
the  carbon  are  saturated.  This  substance 
is  another  instance  of  great  stability  to  heat 
but  not  to  the  electricity  of  other  atoms. 

C3O3  will  be  normally  formed  like  CO,, 
thus: — 

-»--»-        -f        -I-        + 

0  =  C  =  C  =  C  =  0 

Each  double  bond  is  composed  of  both 
nogaiivo  and  positive  edges,  as  shown  in 
Fig.  1. 

\h  analagous  cases  to  CO,  in  this  group, 
might  be  cited  those  of  the  stannous  and 
plumbous  salts.     The  example  of  stannous 


chloride,  which  will  be  seen  in  Fig.  9,  is  a 
representative  one. 


This  configuration  explains  the  readiness 
with  which  the  compound  absorbs  oxygen, 
since  the  second  half  of  the  cube  is  easily 
ojKjned. 

The  tendency  of  the  octets  of  the  ele- 
ments of  this  group  towards  distortion 
seems  to  be  greater  than  those  of  most  of 
the  other  groups :  also  quadrivalence  seems 
to  become  less  pronounced  with  increase  of 
atomic  weight,  the  greater  number  of  inter- 
nal electrons  in  the  atoms  of  the  members 
of  higher  atomic  weight  evidently  weaken 
the  lines  of  force  to  the  electrons  of  their 
octets,  thus  encouraging  distortion. 

It  cannot  be  thought  that  every  atom  has 
a  full  cube  octet;  as  examples,  hydrogen, 
the  alkali  metals,  the  alkaline  earths,  and 
the  boron  group  have  not  enough  electrons 
in  their  outer  layers  to  warrant  us  in  sup- 
posing that  an  imaginary  cube,  having  only 
one  or  two  comers  occupied  by  electrons, 
surrounds  the  nucleus;  these  elements 
must  naturally  have  distorted  octets,  and 
it  is  therefore  more  than  likely  that  those 
I'lements,  having  larger  numbers  of  elec- 
trons in  their  octets,  may  also  exhibit  dis- 
tortion, even  in  the  combined  state. 

Chemical  Research  Laboratory, 
School  Gardens, 
Shrewsbury. 


GENERAL  NOTES. 


THE  STRUCTURE  OF  THE  ATOM. 

The  issue  of  Nature  for  July  7  contains  a 
special  Ifi-page  supplement,  in  which  Prof. 
Niels  Bohr,  professor  of  physics  in  the  Uni- 
versity of  Copenhagen,  gives  a  comprehen- 
sive and  striking  account  of  the  present 
state  of  knowledge  of  the  structure  of  the 
atom. 


.22 


THE  CHEMICAL  NEWS. 


JULY  13,  1923. 


Prof.  Bohr  has  taken  a  leading  part  in 
the  development  of  modem  conceptions  of 
atomic  structure;  and  he  devotes  particu- 
lar attention  in  his  paper  to  the  interpreta- 
tion of  spectra,  and  the  main  features  of 
the  properties  of  atoniical  elements  on  con- 
siderations of  the  manner  in  which  an  atom 
can  be  imagined  to  be  built  up  by  the  cap- 
ture and  binding  of  electrons  to  the  nucleus, 
one  by  one. 


NEED  FOE  SETTLEMENT  OF 
EUEOPEAN  SITUATION. 

In  the  course  of  his  speech  at  the  Brad- 
ford meeting  of  the  Federation  of  British 
Industries,  Sir  Eric  Geddes  said:  — 

"  The  general  upward  trend  of  trade 
which  goes  on  through  the  centuries  is, 
therefore,  checked  because  of  the  disturbed 
condition  of  Europe,  and  while  I  see  fair 
reason  to  hope  for  an  upward  trend  in  the 
cycle  of  trade,  I  can  at  present  see  nothing 
but  blackness  when  I  look  for  a  resumption 
of  the  upward  progression  in  the  general 
level  of  trade  shown  during  the  last  centuiy. 
Therefore,  as  first  and  foremost  of  all 
measures  which  can  be  taken  for  the  im- 
iprovement  of  trade,  and  the  reduction  of 
unemployment  in  this  country,  I  would  put 
the  settlement  of  the  European  situation. 
We,  as  a  great  exporting  country,  are  worst 
hit  of  all  by  the  present  state  of  affairs  in 
Europe.  Our  unemployment  is  caused  by 
that,  and  I  do  not  think  that  the  working, 
trading,  and  banking  community  of  the 
country  can  too  insistently  bring  before  His 
Majesty's  Government  the  conviction 
which  I  feel — and  which  I  believe  is  gener- 
ally felt — that  the  great  problems  of  this 
country  would  melt  as  mist  melts  before 
the  sun,  if  a  stabilised  condition  could  be 
brought  about  in  Europe.  It  is  not  only 
the  direct  influence  on  trade  that  is  felt; 
but  it  has  an  influence  on  taxation,  and  tax- 
ation is  one  of  the  great  burdens  against 
trade  to-day." 


In  a  pamphlet  issued  by  the  United 
States  Geological  Survey*  some  interesting 
particulars  are  given  of  the  occurrence  of 
diamonds  in  Arkansas. 

Stones  found  within  the  exposures  of 
peredotite  and  have  been  mined  to  a  depth 
of  20  feet,  and  the  deposit  is  thought  to  ex- 
tend to  great  depths.    Dr.  G.  F.  Kunz  con- 


siders that  the  peridotite  is  the  source  of 
the  diamonds.  The  production  so  far  does 
not  appear  to  be  very  great,  although  it  is 
stated  that  it  is  difficult  to  obtain  comiplete 
figures  of  production,  some  5,300  stones 
are  known  to  have  been  obtained. 

The  method  of  separating  the  stones  is 
the  same  as  is  now  practised  in  Kimberley, 
viz.,  working  the  material  in  circular  pans 
having  a  revolving  vertical  shaft  to  which 
radiating  arms  are  attached,  at  stated  inter- 
vals the  concentrates  are  removed  and 
passed  over  grease  tables  to  which  the  dia- 
monds adhere  while  the  other  minerals  are 
washed  off.  The  stones  are  said  to  be 
mostly  small,  and  to  vary  in  colour  from 
white  to  yellow  and  brown,  some  very  fine 
crystals  have  been  found. 

*  Diamond-bearing  Peridotite  in  Pike 
County,  Arkansas,  by  Hugh  D.  Miser  and 
Clarence  S.  Ross.     Bulletin  735,  I. 


The  current  number  of  the  Analyst  con- 
tains a  paper  by  H.  Droop  Richmond  on 
the  action  of  potassium  carbonate  upon 
lead  glass.  It  was  found  that  the 
apparently  dry  salt  had  an  appre- 
ciable action  on  the  glass,  and  _  that 
the  action  increased  rapidly  as  moisture 
was  absorbed.  Both  lead  and  arsenic  were 
found  in  potassium  carbonate  that  had  been 
stored  in  bottles  containing  these  sub- 
stances, and  the  danger  of  the  use  of  such 
bottles  as  containers  for  this  salt  is  pointed 
out. 


LABORATORY    EQUIPMENT. 

The  Council  of  the  Society  of  Chemical 
Industry  have  received  from  the  Depart- 
ment of  Scientific  and  Industrial  Research 
a  request  to  nominate  three  or  four  mem- 
bers to  furnish  information  with  regard  to 
the  quality  and  technical  range  of  British 
production  ,  of  optical  glass  and  instru- 
ments, laboratory  glass  and  porcelain,  syn- 
thetic organic  chemicals,  analytical  re- 
agents, and  other  fine  chemicals.  The  De- 
partment had  already  sought  the  opinions 
of  a  large  number  of  professors  of  chemis- 
try, physicists,  and  others,  but  appeared  to 
have  addressed  enquiries  to  very  few  prac- 
titioners in  chemistry.  The  Council  sug- 
gested, therefore,  that  useful  opinions 
might  be  obtained  from  such  practitioners, 


JtJLY  13,  1923. 


TfiB  CHEMICAL  NfiWS 


23 


and  they  have  forwarded  the  names  of  Mr. 
W.  T.  Burgess,  Dr.  J.  T.  Dunn,  Dr.  Ber- 
nard Dyer,  Mr.  E.  W.  Voelcker  (Hon. 
Treasurer),  together  with  that  of  Mr.  H. 
W.  Cremer,  who  is  responsible  for  supplies 
in  the  chemical  deipartment  of  King's  Col- 
lege, London. 

The  Council  have  also  appointed  a  Com- 
mittee to  consider  the  proposal  from  the 
National  Physical  Laboratory  that  the 
work  of  the  Joint  Committee  for  the  Stan- 
dardisation of  Scientific  Glass-ware  should 
be  brought  under  the  aegis  of  the 
Institute  of  Chemistry,  The  Coun- 
cil hold  that  the  proposal  is  desir- 
able on  general  grounds,  but  in  order  to  ob- 
tain more  detailed  information  with  regard 
to  the  probable  and  possible  activities  ex- 
pected of  the  Institute  in  this  connection, 
they  have  appointed  a  Sub-Committoc 
consisting  of  the  President,  with  Dr.  Brady, 
Dr.  Bernard  Dyer,  Dr.  J.  J.  Fox,  Sir  Her- 
bert Jackson,  and  Mr.  E.  W.  Voelcker 
(Hon.  Treasurer),  to  confer  with  represen- 
tatives of  the  National  Physical  Labora- 
tory, the  Department  of  Scientific  and  In- 
dustrial Research,  and  of  such  other  bo<lie8 
as  the  Sub-Committee  may  deem  desirable, 
and  to  report  to  the  Council  on  the  pro- 
position. 

Till-  Special  Purposes  Committee  hnve 
appointed  a  Sub-Conmiitteo,  consisting  of 
Messrs.  E.  R.  Bolton,  O  L.  Brady,  F.  H. 
Carr.  P.  H.  Kirkaldy,  and  K.  H.  Pick-ird. 
to  consider  and  investigate  the  present 
British  production  of  filter  paper. 


SMOKE  PRODUCTION  AND  THE 
POTTERY  INDUSTRY. 

By  Cuthhrrt  Bailey,  of  the  Pottery 
Manufacturers'  Federation. 

The  man  has  yet  to  rise  who  will  teach 
industry  the  means  to  extract  full  value 
from  the  coal  it  burns;  invention  after  in- 
vention has  been  recorded  at  the  Patent 
Office,  but  still  our  industrial  centres  lie 
under  their  black  mantles. 

That  the  past  has  been  wholly  blanjcless 
few  manufacturers  would  contend,  but  bit- 
ter and  costly  experience  has  taught  the 
wisdom  of  caution. 

But,  oblivious  of  past  and  present  en- 
deavours, there  is  arising  a  type  of  legisla- 
tor who  hesitates  not  to  impeach  every  in- 
dustry of  reckless  waste,  and  manufac- 
turers generally  of  wallowing  in  content  and 


inaction,  and  who    roundly    accuses    local 
governing  authorities  (in  the  words  of  a  re- 
cent public  speaker)  of  being    "  influenced 
too  much  by    the  selfish  considerations    of 
their  manufacturing  friends."     These  men, 
with  their  perambulating  minds,  with  their 
power  of  generalisation  and  reducing  masses 
of  evidence  to    mere    paradoxical    phrases, 
are  active  to-day  with  an  interrogative  eye- 
glass, and,  as  a  consequence,  legislation  is 
now  proposed  that  threatens    the  very  life 
of  some  of  the  nation's  industries. 

As  a  few  years'  dissipation  will  break  the 
cwitinuity  of  will  and  the  sequence  of  intel- 
lect of  any  man,  so  would  premature  legis- 
lation react  on  industry. 

Industry  invites  investigation  —  though 
investigation  by  duly  qualified  experts — 
under  the  sure  conviction  that  any  unpre- 
judiced enquiry  would  dispel  ^le  insinuat- 
ing delusions  now  being  broadcasted. 

Every  industry  has  its  essential  processes 
and  its  own  inherent  limitations;  all  carry 
their  own  signals  and  the  expert  alone 
knows  the  cyphers.  Of  all  industries  the 
manufacture  of  pottery  may  be  claimed  to 
be  the  most  complicated  and  intricate,  and 
it  is  prol)abIy  realised  by  few  outside  the 
pottery  areas  that  the  great  bulk  of  the 
smoke  emitted  is  not  made  in  raising  the 
necessary  power  to  drive  the  machinery  for 
its  production,  but  is  made  in  the  various 
"baking"  stages  to  which  all  pottery  must 
of  necessity  be  subjected  in  the  process  of 
its  manufacture. 

The  first  "baking"  stage  is  that  which 
reduces  the  formed  clay  to  a  durable  and 
stable  state  such  as  will  permit  general 
handling,  and  the  subsequent  glazing  and 
decorating.  But  the  mixture  of  the 
various  clay  ingredients  that  form  the 
final  composition  of  the  ware,  after  being 
brought  to  a  dry  state,  poesesses  a  water  of 
(>r>mbination  that  varies  from  6  per  cent,  to 
12  per  cent,  of  the  total  weight  of  the 
articles  themselves,  and,  as  a  "Kiln"  may 
contain  each  time  it  is  fired  from  ten  to 
thirty  tons  of  pottery,  according  to  the  type 
of  articles  being  manufactured  (placed  in 
thi"  fireclay  "saggars"  that  are  piled  up  in 
bungs),  it  follows  that  from  approximately 
10-30  cwts.  of  water  is  to  be  dispersed  dur- 
ing the  initial  stages  of  the  "  baking." 
This  dispersal,  if  cracking,  warping,  stain- 
ing, and  even  general  collapse  of  the 
articles,  is  to  be  avoided  is  essentially  a 
gradual  process,  and  occupies  the  first  20- 
30  hours  of  the  "baking" — and  woe  betide 
the    manufacturer    whose    fireman    unduly 


24 


THE  CHEMICAL  T^EWS, 


JULY  13,  1923. 


expedites    what    is  technically    called    this 
"  smoking  period." 

Suppose  an  oven  holds  20  tons  ot  clay- 
ware  carrying  10  per  cent,  of  combined 
water  two'  tons  of  water  is  to  be  dispersed, 
which  at  500°  will  occupy  roughly  one- 
quarter  of  a  million  cubic  feet.  As  this 
rushes  into  the  cold  air  outside  it  is  natur- 
ally condensed,  and,  stained  by  the  pro- 
ducts of  combustion  from  the  burning 
coal  forms  a  cloud  of  what  the  man  m  the 
street  would  call  "  smoke."  Similar  re- 
marks apiply  to  the  water  in  the  moist 
croods  in  the  earliest  stages  of  the  tiring 
(below  200°  C.)  during  the  so-called  water- 
smoking  period— and  all  this  steam  is  fur- 
ther supplemented  by  that  produced  by  the 
combustion  of  the  hydrogen  compounds  of 
the  fuel  itself. 

During  these  "smoking'  penods  what  is 
called  smoke  is,  therefore,  in  the  main  only 
discoloured  steam;  after  their  completion 
little  smoke  is  emitted  from  a  modem  overt. 

But  smoke  itself  is  an  essential  concomi- 
tant in  the  manufacture  of  the  famous 
Staffordshire  blue  bricks,  blue  roofing  tiles, 
and  many  grades  of  pottery.  So  far  as  our 
present  knowledge  goes  it  is  not  a  mere  re- 
ducing atmosphere  that  is  in  question; 
decomposing  hydrocarbons  are  reqmred  to 
produce  the  required  effect.  There  are  fur- 
ther what  mifvht  be  called  "  quahties  ot 
smoke,"  for  the  results  obtained  with  some 
types  of  smoke  produce  better  results  .with 
than  others.  The  old  potters  knew  this, 
and  in  the  production  of  lustre  effects,  red 
"  sang-de-boeuf,"  and  other  types  of  de- 
corative effects,  one  will  find  in  the  old 
literature  that  they  attached  a  special  vu-- 
tue  to  smoke  derived  from  particular 
shrubs,  ete.  Thus  Piccolpassi  favoured 
"  the  branches,  etc.,  of  green  broom  ; 
another  recommended  "rice  husks,  and 
so  on.  English  Potters,  under  the  lead  of 
Mr.  Bernard  Moore,  have  during  the  last 
twenty  years  rediscovered  the  secrets  of 
the  old  lustre  glazes,  and  Chinese  red 
glazes,  and  are  to-day  producing  decorative 
effects  that  are  universally  acclaimed  as 
surpassing  in  genral  beauty  any  of  the 
works  of  the  old  potters— but  tet  rt  be 
realised  that  the  one  essential  conddion  for 
their  production  is  a  reducing  atmosphere. 

Pottery  manufacturers  are  not  mdit- 
ferent  to  the  progress  of  public  op^^ioi^^^^ 
this  smoke  question,  but  let  not  that 
opinion  be  formed  on  a  mendicant  truth 
Essential  conditions  of  manufacture  must 
be  conformed  to;  while  the  pressure  of  in- 
ternational competition  is  always  sufficient 


to  ensure  that  all  unnecessary  waste  of  fuel 
will  be  constantly  subjected  to  the  closest 
investigation. 

Fuel  Economy  Review,  June,  1923. 


BRITISH  V.  GERMAN  GOODS  IN 
NORWAY. 

Chemicals. 

There  is  a  good  market  for  British  heavy 
chemicals,  such  as  bleaching  powder,  salt 
cake  and  soda.  Good  business  may  be 
done  in  alum  for  the  paper  trade,  and  there 
are  also  good  prospects  in  aniline  dyestuffs. 
GtM-many  is  showing  signs  of  being  unable 
to  deliver  the  goods,  and  there  is  therefore 
every  chance  of  a  good  opening  for  British 
dyestuffs.  This     also     applies     to     fine 

chemicals. 

—Bulletin  of  the  Federation  of  British 

Industries. 


NEW  RAPID-REGENERATING 
"  PERMUTIT.' 

One  of  the  interesting  features  of  the 
Textile  Exhibition  at  Nottingham  is^  the 
exhibit,  for  the  first  time,  of  the  new  Per- 
mutit"  Rapid-Regenerating  material  tor 
water  softening,  which  marks  a  great  ad- 
vance in  the  technique  of  water  purification 

by  zeolites.  i    «.  -r.  i-t^ 

The  new  material  is  named  Permutit 
B."  Its  principal  difference  from  the  ordi- 
nary Permutit  lies  in  the  time  taken  for  re- 
generation. Previously  a  Permutif  unit  was 
designed  to  soften  water  for  10  to  12  hours 
continuously.  It  then  required  an  equal 
time  for  regeneration.  Where  day  and 
night  working  was  the  rule,  this  involved 
the  use  of  two  units. 

A  "  Permutit  B."  plant  softens  tor  a 
shorter  period,  ranging  from  3  to  6  hours, 
and  is  then  exhausted.  It  can,  however  be 
completely  ronegeratcd  and  put  to  work  in 
under  one  hcjur.  The  advantages  of  this  are 
obvious.  One  unit  only  is  required  tor  day 
and  night  working,  as  the  plant  is  continu- 
ously in  operation  except  during  the  one- 
hour  periods  in  which  it  is  regenerated.  All 
that  is  necessary  is  sufficient  soft  water 
storage  to  pn.vide  for  one  hour's  require- 
ments, to  enable  one  unit  to  be  used 
throughout  the  24  hours. 

"  Permutit  B."  uses  less  salt    than  ordi- 


JULY  13,  1923. 


THfi  CHEMICAL  NEWS 


25 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


nary  Pennutit,  thus  efifecting  saving  in  the  ■ 
cost  of  treatment.  It  will  be  seen  that  the  j 
new  material  brings  down  the  cost  of  the  ; 
Permutit  process  considerably,  by  saving 
one  unit  where  continuous  working  is  re- 
quired, and  by  reducing  the  salt  consump- 
tion. 

Formerly  the  standard  and  universal  pro- 
duct employed  in  connection  with  iJie  eli- 
mination of  calcium  and  magnesium  from 
water  by  the  base-exchange  principle  was 
produced  synthetically,  either  by  fumacing 
or  by  precipitation.  The  "Ptrmutit"  pro- 
duced in  this  way  was  always  subject  to 
certain  limitations. 

The  latest  class  "  Permutit,"  which  has 
now  been  in  commercial  service  in  water 
.softening  for  close  on  three  years,  and  which 
is  a  non-«ynthetic  material  sipecially  treated 
to  increase  its  activity,  and  t^)  stabilise  its 
qualities,  has  the  following  advantages  as 
against  all  previously  emplov<'d  zeolites : 

(1)  Free  carbonic  acid,  which  exists  to  a 
greater  or  lesser  degree  in  all  water  sup- 
pliers, has  no  destructive  efT<et  upon  it. 

(2)  It  is  to  a  much  greater  degree  immune 
from  depreciation  in  structure  and  activity 
by  reason  of  iron  in  the  water. 

(3)  A  rate  of  exchange,  and.  therefore,  a 
permissible  rate  of  flow  through  any  given 
plant,  of  upwards  of  ten  times  that  of  pre- 
vious Permutit  materials,  can  be  effected. 

(4)  A  siinilarly  rapid  regeneration  of  the 
material  as  and  when  the  point  of  exhntis- 
tion  has  l)een  reached  at  the  end  of  n  day's 
run,  is  feasible. 

(5)  With  the  new  material  a  reduction  •  f 
from  25  per  cent,  to  33J\  per  cent,  in  the  re- 
quisite weight  of  salt  for  regenerati<Mi  is 
effected. 

(0)  Lastly,  and  this,  perhaps,  may  be  nv 
garded  as  the  most  important  advance  in 
the  art.,  the  "commercial"  phrase  of  "zerf»- 
hardness"  which  has  always  \yoon  employed 
in  reganl  t^)  waters  softene<l  by  the  bnst^- 
exchange  method,  is  literally  and  actually 
borne  out  by  the  new  material. 

The  new  softening  material  is  put  on  the 
market  by  United  Water  Softeners,  T^td.. 
sole  proprietors  of  the  Permutit  patents  in 
the  country. 


James  Crichton-Browne,  Treasurer  and 
Vice-President,  in  the  chair.  The  death  of 
Sir  James  Keid,  Bart.,  was  reported  to  tne 
meeting,  and  a  resolution  of  condolence 
with  the  family  was  passed.  Mr.  R.  N. 
Lennox  was  elected  a  member. 


TFTE    HOYAL    INSTITUTION. 
A  general  meeting  of  the  members  of  the 
Royal  Institution  was  held  on  July  2,    Sir 


THE  INSTITUTE  OF  METALS. 

Autumn    Meetino. 

The  annual  autunm  meeting  of  the  In- 
stitute of  Metals  will  be  held  this  year  in 
Manchester,  on  September  10-13,  and  pro- 
mises to  be  an  exceptionally  interesting 
gathering.  The  meeting  will  open  with  the 
second  annual  autumn  lecture,  to  be  de- 
livered by  Lt.-Col.  Sir  Hbnry  Fowler, 
K.B.E.,  on  The  Use  of  Non-Ferroua  MctaU 
in  Engineering.  The  lecture  will  be  a 
p(M)ular  one,  and  is  ctpen  to  the  public, 
tioketft  being  obtainable  from  Mr.  G.  Shaw 
Scott,  M.Sc.,  36,  Victoria  Street,  London, 
S.W.I. 

The  mornings  of  September  11  and  12 
will  be  devoted  to  the  reading  and  discussion 
of  papers.  After  an  official  luncheon  on 
September  11,  visits  will  be  paid  to  several 
large  works  in  the  vicinity  of  Manchester, 
ana  in  the  evening  there  will  be  a  reception 
at  the  University,  when  the  new  metallur- 
gical lal)oratories  will  be  officially  opened. 
Following  the  conclusion  of  the  business 
side  of  the  programme  on  September  12, 
the  afternoon  of  that  day  will  be  devoted  to 
a  trip  along  the  Manchester  Ship  Canal, 
and  in  the  evening  there  ^will  be  a  smoking 
concert  at  the  Midland  Hotel.  A  trip  to 
Chester  has  been  arranged  for  September 
13,  this  excursion  also  including  a  launch 
trip  up  the  river  Dee.  For  those  persons 
intending  to  proceed  to  the  British  Asso- 
ciation meting  at  Liverpool  the  same  even- 
ing, the  trip  to  Chester  will  be  very  con- 
venient, Chester  being  within  easy  reach  of 
Liverpool. 

Reduced  fare  facilities  have  been  ar- 
ranged with  the  railway  companies  in  con- 
nection with  the  Manchester  meeting,  and 
the  necessary  vouchers  for  obtaining  these 
facilities  can  bo  obtained  on  applieation  to 
the  Secretary,  Mr.  G.  Shaw  Scott,  who  will 
be  glad  to  send  a  detailed  programme  of  the 
meeting  to  those  interested. 


26 


THE  CHBMICAL  NEWS. 


JtJLY  13,  1928. 


THE  CHEMICAL  SOCIETY  OF  JAPAN. 
Papers  communicated  to  the   Society :  — 

On  the  Quantitative  Sejmration  of  Plati- 
num and  Iridium,  by  Shin-ichi  Aoyama. 

On  Contact  Potentials,  by  Shiro    Take- 

GAMI. 

On  a  New  Method  for  the  Determination 
of  Sulphur  Contained    in    Iron,    by    Teruo 

ASHIDA. 


THE  GEOLOGICAL  SOCIETY  OF 
LONDON. 

June  20,  1923,  Prof.  A.  C.  Seward,  Sc.D., 
F.E.S.,  President,  in  the  Chair. 

Miss  P.  de  B.  F.  Bowen-Coulthurst  pre- 
sented a  geological  hammer,  chisel,  and 
satchel  formerly  belonging  to  George  Bellas 
Greenough,  first  President  and  one  of  the 
founders  of  the  Society.  She  also  presented 
a  number  of  valuable  documents  and 
minute-books  of  great  historical  and  scien- 
tific 'nterest,  forming  part  of  the  earliest 
records  of  the  Society's  activities. 

Dr.  Herbert  H.  Thomas,  M.A., 
V.P.G.S.,  gave  a  demonstration  of  the 
Source  of  Origin  of  the  Stones  of  Stone- 
henge,  illustrated  by  lantern-slides. 


The  following  communications  were 
read :  — 

The  River-Gravels  of  the  Oxford  District, 
by  Kenneth  Stuart  Sandford,  B.A., 
F.G.S. ;  with  an  Appendix  on  the  Non- 
Marine  Mollusca,  by  Alfred  Santer  Ken- 
nard,  F.G.S. ,  and  Bernard  Barham  Wood- 
ward, F.L.S.,  F.G.S. ;  and  an  Appendix  on 
the  Mineral  Analyses  of  the  Clay-  and 
Sand-Deposits  of  Wolvercote,  by  R.  C. 
Spiller,  B.A. 

A  discussion  followed. 

The  Deposits  of  Paleocene  Mammalia  in 
Belgium,  by  Prof.  Louis  Dollo,  Sc.D., 
For.Mem.G.S.,  and  Prof.  P.  Teilhard  de 
Chardin,  D.Sc. 

Dr.  G.  T.  Prior,  M.A.,  F.R.S.,  ex- 
hibited a  meteoric  stone  which  fell  at  Ash- 
don,  near  Saffron  Walden  (Essex),  on 
March  9,  1923. 


Dr.  L.  L.  Fermor  exhibited  microsco(pic- 
slides  of  cordierite  from  Indian  "  para- 
lavas,"  pleochroic  in  thin  section,  in  illus- 
tration of  his  remarks  on  Dr.  C.  E,  Tilley's 
paper  read  on  June  6. 

Mr.  K,  S.  Sandford  exhibited  mamma- 
lian remains  and  implements,  in  illustra- 
tion of  his  paper. 

The  next  meeting  of  the  Society  will  be 
held  on  Wednesday,  November  7,  1923. 


PETROLEUM— A  SHORT  HISTORY. 
By  J.  Norman  Taylor,  M.S. 

Petroleum  and  its  products  are  in  greater 
use  to-day  than  at  any  other  time  in  the 
world's  history.  When  we  consider  that  at 
present  there  are  millions  of  motor  cars, 
hundreds  of  thousands  of  motor  boats,  to 
say  nothing  of  a  steadily  increasing  number 
of  other  internal-combustion  engines  de- 
pending for  their  usefulness  upon  gasoline, 
kerosene  and  lubricating  oils,  the  necessity 
of  insuring  an  adequate  supply  of  petroleum 
is  obvious.  Another  petroleum  product, 
fuel  oil,  is  being  consumed  in  increasing 
quantities  both  upon  land  and  on  the  sea. 
Yet,  while  the  demand  for  petroleum  and 
its  products  is  growing,  the  supply  of  crude 
oil  is  being  rapidly  depleted.  No  wonder 
that  our  statesmen  and  scientists  are 
searching  for  a  solution  of  the  oil  problem — 
a  situation  that  can  only  be  reheved  by 
finding  new  supplies,  eliminating  waste, 
and  adopting  imjproved  methods  in  refining 
processes. 

The  increasing  importance  of  this  com- 
modity in  our  national  economy  makes  the 
story  of  petroleum  a  most  interesting  one 
indeed,  not  only  to  those  who  are  pursuing 
the  study  of  chemistry  and  the  allied 
sciences,  but  to  all  who  have  contact  with 
modern  civilisation. 

Petroleum  is  a  complex  mixture  of  hy- 
drocarbons varying  in  physical  state  from 
solid  to  gaseous,  and  in  colour  from  coal- 
black,  through  brown,  greenish,  red  and 
yellow,  to  colourless.  The  chemical  nature 
of  its  constituents  varies  with  the  locality 
in  which  it  is  found,  the  chain  bodies  pre- 
dominating. 

Although  the  petroleum  industry  of  the 
United  States  is  of  comparatively  recent 
origin,  the  crude  oil  has  been  known  from 
the  earliest    historical    period    and  in    this 


JULY  13,  1923. 


THE  CHEMICAL  NEWS. 


27 


country  had  undoubtedly  been  long  used  by 
the  Indians. 

It  occurs  in  rocks  of  ail  ages,  "  from  the 
lower  yilurian  to  the  most  recent  "  (Mer- 
rill), and  as  a  rule  in  sandstone  formations. 
Occasionally  it  is  found  in  limestones  and 
shales.  Geologic  relations  indicate  petro- 
leum to  be  of  organic  origin — a  product  de- 
rived from  the  slow  physical  and  chemical 
alteration  of  ancient  deposits  of  vegetable 
and  animal  material  under  the  influence  of 
heat  and  pressure. 

For  convenience,  the  sources  of  petro- 
leum in  the  United  States  may  be  classified 
as  follows: — 

The  Appalachian  field  (centreing  in  Penn- 
sylvania), the  Lima-Indiana  field  (in  In- 
diana and  Ohio),  the  Illinois  field,  the  mid- 
continent  field  (centreing  in  Oklahoma),  the 
Gulf  coast  field  (in  south  Texas  and  Louisi- 
ana^, the  Colorado- Wyoming  field,  and  the 
California  field.  In  the  midcoatineut  field 
lie  various  pools,  groups  of  pools,  or  dis- 
tricts, the  distinguished  ones  being  called 
the  Gushing  pool  (Oklahoma),  the  Heald- 
ton  (pool  (Oklahoma),  the  Caddo  district 
(north-wcHicrn  Louisiana),  and  the  north 
Texas  district. 

There  are  about  as  many  varieties  of 
crude  petroleum  as  there  are  oil  fields. 
However,  the  refiner  recognises  three  dis- 
tinct types,  noted  below,  each  of  which 
must  l>e  handled  by  diffcnnt  methods.  The 
paraffin  base  crude  similar  to  that  found  in 
Pennsylvania  and  West  Virginia  is  cssenli- 
ally  a  light-coloured  crude  containing  p.ira- 
ffin;  the  asphalt  base  crude,  similar  to  tiiat 
found  in  Texas  and  California,  contains  no 
paraffin,  and  is  generally  dark  coloured,  al- 
most black;  mixed  base  crudes,  similar  to 
thow'  found  from  Ohio  to  Oklahoma,  are 
essentiallv  mixtures  of  paraffin  and  asphalt 
base  crudes.  California  oils  contain  nitro- 
gen and  ring  compounds. 

Professor  Charles  E,  Munroe,  in  his  well- 
known  monograph  on  "  Potrofeum  Kcfin- 
ing,"  states  that  it  is  not  surprising  that 
ipi'troleum  obtained  in  Texas,  Califcmiia 
and  Ohio  should  differ  in  appearance  and 
properties  from  each  other  and  from  the 
iK'tter  known  Pennsylvania  oil  and  from 
that  obtained  from  other  parts  of  the  coun- 
try. He  attributes  this  difference  in  apponr- 
nnce  not  only  to  the  fact  that  petrolenni 
consists  of  a  mixture  of  various  hydrocar- 
bons from  difforcnt  acyclic  and  cyclic  8(>ries 
and  of  hydrocarbon  derivatives  contnininfj 
sulphur  or  oxygen  or  nitrogen  or  other  ele- 
ments   which  tnemaelves    differ    widelv    in 


properties  and  aippearance,  but  also  to  the 
varying  conditions  under  which  the  petro- 
leum is  produced  and  to  the  effect  due  to 
migration. 

Crude  petroleum  has  a  limited  applica- 
tion and  owes  its  great  value  to  the  products 
derived  from  it.  It  is,  therefore,  treated  at 
the  pcnnt  of  origin  or  is  transported  to  an 
industrial  centre  by  tank  car,  tank  ship, 
barge,  or  pipe  line.  This  latter  mode  of  car- 
riage is  remarkable  for  its  ingenuity,  and  we 
have  to-day  the  remarkable  achievement 
whereby  vast  quantities  of  oil  are  made  to 
flow  under  rivers  and  through  mountains  to 
great  refineries  on  the  seaboard  such  as  are 
found  at  Philadelphia,  Bayonne,  and  Balti- 
more. Upon  arrival  at  its  destination  the 
crude  oil  is  freed  from  water  and  other  sedi- 
ment by  allowing  it  to  settle  in  storage 
tanks,  after  which  it  is  pumped  into  retorts 
where  it  is  submitted  to  fractional  distilla- 
tion. 

This  operation  depends  upon  the  principle 
that  different  liquids,  at  the  same  pressure, 
have  different  boiling  points.  The  mixture 
of  various  hydrocarbons  when  submitted  to 
gradually  increasing  temperature  might  be 
supposed  to  assume  the  vapour  condition  at 
the  temperature  of  their  respective  boiling 
points  and  upon  condensation,  the  indi- 
vidual constituents  of  the  petroleum  would 
be  in  their  pure  state.  But  such  simple 
conditions  do  not  obtain,  since  the  boiling 
points  of  mixtures  varv  inversely  as  the 
vapour  pressures.  Although  the  comiN)Bi- 
tion  o(  the  vapour  given  off  from  such  mix- 
tures bears  no  close  relation  to  the  composi- 
tion of  the  mixture,  the  vapour  contains  a 
preponderating  amount  of  the  most  vola- 
tile constituent.  Hence  it  is  to  be  expected 
that  when  the  crude  oil  is  subjected  to 
gra<iually  increasing  heat,  the  constituents 
are  successively  converted  into  vapour  sub- 
stantially in  the  order  of  their  volatilities, 
but  that  the  separation  thus  effected  would 
not  b<^  perfect,  as  the  oils  of  the  higher  boil- 
ing points  are  to  some  extent  carried  over  by 
the  vapour  of  those  of  lower  boiling  points. 

It  is  evident  from  this  that  difficulties 
arise  in  the  distillation  of  petroleum  attri- 
butable to  one  or  other  of  three  causes :  (a) 
<o  the  presence  of  two  substances,  the  boil- 
ing points  of  which  are  very  close  together; 
(b)  to  thi'  presence  of  one  or  more  compo- 
nents relatively  in  very  small  quantity;  (c) 
to  the  formation  of  mixtures  of  constant 
boiling  point.  These  difficulties  have  to  a 
great  extent  b(>en  obviated  by  the  use  of  de- 
phlegmators  similar  to  the  Hempel  column, 


28 


THE  CHEMICAL  NEWS. 


JULY  13,  1923. 


in  which  the  dephlegmating  column  con- 
sists of  a  drum  filled  with  cobble  stones, 
surmounted  by  a  number  of  tubes.  A  large 
surface  is  thus  presented,  and  a  more  com- 
plete separation  of  the  constituents  of  the 
crude  obtained. 

The  distillation  retorts,  known  as  stills, 
are  of  cylindrical  form,  constructed  of  boiler 
plate,  and  are  set  horizontally  in  brick-work 
furnaces  arranged  in  batteries.  Stills  sur- 
mounted by  dephlegmators  such  as  de- 
scribed above  are  known  as  "  tower  stills." 
Upon  the  application  of  heat  the  crude  oil 
is  converted  into  vapour  and  the  vapourised 
oil.  upon  passing  into  the  condensers,  is 
thus  brought  into  the  liquid  condition.  In 
practice  it  is  usual  to  divide  the  distillation 
into  two  operations,  the  more  volatile  pro- 
ducts, naphtha  and  kerosene,  being  ob- 
tained in  the  first  part  and  the  residue  be- 
ing transferred  to  the  tar  stills  and  heated 
to  a  higher  temperature  with  the  object  of 
separating  the  lubricating  oils  and  paraflin. 
By  the  use  of  "tower  stills"  the  entire  dis- 
tillation may  be  conducted  without  transfer 
to  the  tar  stills,  as  the  tower  is  supplied 
with  three  traps,  from  the  first  of  which 
may  be  collected  heavy  distillate,  inter- 
mediate distillate  from  the  second,  and 
light  distillate  from  the  third,  and  the  still 
run  to  "maltha"  or  coke  as  desired.  The 
streams  of  distillate  are  from  time  to  time 
diverted  into  various  tanks  by  the  stillman. 
When  the  still  temperature  reaches  about 
325°  F.,  the  crude  naphtha  ceases  to  come 
over,  and  the  stream  is  directed  into  the 
lamp  oil  tank.  When  that  portion  of  the 
oil  from  which  the  high  test  oils  of  120°  to 
150°  F.  fire  test  are  prepared,  is  distilled  off 
(the  still  temperature  being  about  600°  F.), 
the  fires  are  slackened,  and  if  it  is  desired  to 
produce  a  maximum  amount  of  light  pro- 
ducts in  preference  to  a  maximum  amount 
of  the  heavy  lubricating  oils  and  petroleum 
asphalts,  the  "cracking"  process  will  be 
used. 

The  "cracking"  process,  whereby  a  con- 
siderable quantity  of  the  oil  which  is  inter- 
mediate between  kerosene  and  lubricating 
oil  is  converted  into  hydrocarbons  of  lower 
density  and  boiling  points,  is  one  of  great 
scientific  and  technical  interest.  This  dis- 
sociation into  simpler  molecules  may  be 
brought  about  by  pyrolytic  distillation  and, 
unless  a  catalytic  agent  is  used,  is  due  to 
puper-heating  of  the  boiling  liquid.  A  con- 
siderable number  of  processes  have  been 
brought  forward  for  effecting  the  transfor- 
mation of  heavier  hydrocarbons  into  gaso- 


line hydrocarbons,  the  most  widely  used 
one  being  that  of  Dr.  Burton,  in  which  the 
pressure  which  obtains  is  greater  than  the 
atmospheric  pressure.  Other  processes 
operate  at  atmospheric  pressure  and  some, 
as  in  the  McAfee  patent,  use  a  catalytic 
material  such  as  anhydrous  aluminium 
chloride. 

The  products  obtained  on  separating 
petroleum  into  its  commercial  fractions  are 
usually  purified  by  treatment  successively 
with  sulphuric  acid  and  ammonia  or  soda, 
the  lightest  distillates  being  treated  with 
about  5  per  cent,  by  volume  of  the  concen- 
trated acid  and  the  intermediate  distillates 
with  about  1.5  per  cent.  The  treatments 
with  acid  and  with  alkali  are  conducted  in 
agitators  lined  with  lead  and  provided  with 
an  air  blast  and  outlets  for  the  spent  chemi- 
cals and  treated  oils.  These  agitators  hold 
from  50,000  to  150,000  gallons  of  oil  at  one 
charge.  Concentrated  sulphuric  acid  is 
thoroughly  mixed  with  the  oil  by  means  of 
the  air  blast,  and  after  settling  the  acid 
sludge  is  drawn  off,  the  oil  washed  with 
water,  then  with  alkali  and  finally 
brightened  with  fuller's  earth.  This  treat- 
ment improves  the  colour  and  odour  of  the 
oil,  and  removes  the  aromatic  and  unsatu- 
rated hydrocarbons,  phenols,  tarry  pro- 
ducts, and  other  substances  which  lower  its 
quality. 

The  acid  sludge  is  diluted  with  water  to 
separate  the  oil  dissolved  in  it,  and  usually 
is  treated  to  regain  the  acid  used  in  the 
manufacture  of  fertilisers,  or  it  is  concen- 
trated for  re -use  in  the  refinery.  The  oil 
which  separates  on  treating  this  acid  sludge 
is  called  "  acid  oil,"  and  is,  after  appro- 
priate treatment,  used  to  some  extent  as  a 
substitute  for  ichthyol. 

Oils  high  in  sulphur,  like  the  Ohio  oils, 
receive  a  special  treatment  devised  by 
Frasch.  The  first  distillation  is  conducted 
in  the  ordinary  way,  and  the  distillate  sub- 
sequently pumped  into  another  still  pro- 
vided with  a  mechanical  stirrer  and  redis- 
tilled in  the  presence  of  an  excess  of  finely 
divided  oxide  of  copper,  the  contents  being 
kept  thoroughly  mixed  by  the  revolving  ap- 
paratus. The  second  distillate  is  practi- 
cally free  from  sulphur,  and  is  treated  in  the 
usual  way  with  acid  and  alkali.  The  resi- 
due in  the  still,  consisting  of  a  mixture  of 
tar  and  copper  oxide,  is  drained  and  pressed 
and  the  pressed  copper  compound  is  revivi- 
fied through  roasting  and  used  over  again. 

The  residue  from  the  kerosene  distillation 
is  worked  up  into  lubricating  oil  and  para- 


JULY  13,  1923. 


THE  CHEMICAL  NEWS. 


29 


ffin  by  distilling  with  superheated  steam  to 
prevent  dissociation  of  the  hydrocarbons. 
This  steam  distillate  is  then  treated  with 
successive  portions  of  sulphuric  acid  and  of 
alkali,  then  cooled  by  passing  through  a 
tubular  cooler,  when'thc^  paraffin  crystal- 
lises out  and  is  soiparatod  from  the  oil  by 
means  of  filter  presses.  Both  the  lubricat- 
ing oil  and  paraffin  are  further  refined  by 
filtering  through  fuller's  earth  or  animal 
charcoal. 

Petrolatum  (known  also  as  cosmoline  and 
vaseline)  is  obtained  by  the  careful  distilla- 
tion of  selected  grade  petroleum  carried  on 
in  vacuum  stills.  Liquid  petrolatum  may 
be  prepared  from  the  lubricating  oil  of  frac- 
tion of  certain  oils  and  is  composed  essenti- 
ally of  the  naphthene  hydrocarbons. 

A  large  number  of  physical  and  chemical 
tests  are  applied  to  the  raw  materials  and 
manufactured  prwlucts.  The  determina- 
tion of  the  specific  gravity  is  one  of  the  tests 
that  is  considered  important  in  every  pro- 
duct from  the  lightest  to  the  heaviest.  This 
is  generally  determined  by  means  of  the  hy- 
drometer and  is  expressed  in  degrees 
Baume. 

The  specific  gravity  and  range  of  boiling 
points  are  the  tests  chiefly  applied  to  the 
light  petroleum  products,  some  of  which 
are  commercial  "  pentane,"  used  exten- 
sively as  a  standard  of  light  in  (photometric 
work;  petroleum  ether  and  ligroin,  both  of 
which  are  used  as  solvents  for  fats,  oils, 
waxes,  and  certain  resins ;  76"  gasoline ;  de- 
odorised naphtha;  stove  naphtha;  varnish 
makers'  and  painters'  naphtha,  and  motor 
spirit.  The  boiling  point  limits  of  these 
light  products  are  being  extended  from 
time  to  time,  so  that  it  is  impossible  to 
define  them  accurately. 

Kerosene  is  examined  as  to  colour,  odour, 
flash  pcMnt  and  fire  test,  as  well  as  to  burn- 
ing qtiality,  viscosity,  composition  (as  as- 
certained by  fractional  distillation)  and 
suliphur  content.  The  flash  point  is  deter- 
mined for  the  purpose  of  ascertaining  the  in- 
flammability of  the  oil.  There  are  several 
instruments  in  use  for  this  determination, 
chief  among  them  being  the  Abel  tester. 
Savholt's  electric  tester,  Tagliabue's  open 
and  closed  cups,  the  Elliott  cup,  and  fho 
Bureau  of  Mines  tester. 

Lubricating  oils  are  of  great  variety,  and 
the  requirements  vary  with  the  purpose  for 
which  they  are  used.  All  should  have  high 
burning  points.  Viscosity  is  the  most  im- 
portant index  in  evaluating  a  lubricating  oil 


and    for  those  used    in  internal-combustion 
engines    the    "carbonising    number"    is    a 
valuable  consideration.       The    "  chill,"    or 
temperature    at  which    solid    hydrocarbons 
are  deposited,  is  also  imiportant. 

Petrolatum  and  paraffin  are  examined 
principally  for  their  melting  points.  Petro- 
latum is  used  extensively  as  a  basis  for  oint- 
ments. Liquid  petrolatum  is  used  as  a 
laxative  and  as  a  vehicle  for  substances 
used  in  the  treatment  of  mucous  mem- 
branes. Paraffin  is  used  for  a  number  of 
purposes,  as  in  the  arts  and  in  the  manu- 
facture of  candles,  and  is  sold  in  several 
grades.  The  tarry  residual  products,  oer- 
taln  types  of    which  are    sometimes    calleil 

maltha,"  are  used  extensively  in  road 
building.  Petroleum  ooke  is  used  for  fuel, 
but  sinc<^  it  contains  very  little  ash  and 
much  "  fixed  carbon,"  it  is  used  more  ex- 
tensively in  the  manufacture  of  electric 
light  carbons. 

These  art^  but  a  few  of  the  products  which 
ipetroleum  is  furnishing  us  to-day.  Upon 
the  establishment  of  this  industry  only  a 
few  generations  ago,  the  main  product  was 
illuminating  oil,  and  remained  so  for  three 
decades.  Materials,  such  as  gasoline,  fuel 
oil  and  lubricating  oils,  which  were  then 
considered  as  by-products — in  the  sense 
that  by-pr()<lucts  are  defined  by  Professor 
Munroe.  namely,  as  "substances  or  results 
obtained  in  the  operation  of  a  specific  pro- 
cess in  a<ldition  to  the  result  mainly 
sought  " — .have  since  risen  to  the  rank  of 
main  products.  To-day,  petroleum  by-pro- 
flucts  are  counted  by  the  hundreds,  and  are 
increasing  in  number  and  in  importance, 
and  it  seems  quit<^  likely  that  the  romance 
of  the  conl-tar  derivatives  industry  will,  in 
the  not-distant  future,  be  paralleled  by  a 
great  chemical  inrlustry  hiving  its  basis  in 
petroleum. 

— Abstract  from  "  The  American  Journal 
of  Phannani,"  1923,  XCV.,  292-298. 


LITERARY  INTELLIGENCE. 

An  important  new  book  entitled  Chuds 
and  Swoken :  the  Properties  of  Diaperse 
8}f/item8  in  Gascn,  will  shortly  be  published 
by  Messrs.  J.  k  A.  Churchill.  The  author 
js  Dr.  W.  E.  Gibbs,  Chief  Chemist  to  The 
Salt  Union  lit^l.,  Liverpool.  There  will  bo 
about  30  illustrations. 

The  investigation    of  matter  in  a  highly 


30 


THE  CHEMICAL  NEWS. 


JULY  13,  1923. 


dispersed  or  "conoidal"  condition  has  been 
large Ij  directed  towards,  those  disperse 
systems  in  which  the  dispersion  medium  is 
a  liquid  or  a  solid.  Less  research  has  been 
made  in  fog,  smoke,  flame,  cloud  and  the 
atmosphere  itself.  They  are  disperse  sys- 
tems in  which  a  liquid  or  a  solid  substance 
exists  in  a  highly  dispersed,  or  colloidal, 
condition  in  a  gas. 

The  author  describes  the  various  ways  in 
which  such  disperse  systems  in  gases  can 
be  formed,  and  deals  fully  with  their 
mechanical,  thermal,  optical  and  electrical 
jiroperties,  and  the  conditions  which  deter-  i 
mine  their  stability.  This  information  is 
then  applied  to  the  practical  problems  of 
meteorology,  fume  condensation,  gas  fil- 
tration, the  manufacture  of  substances  in  a 
finely  powdered  condition,  and  the  use  of 
smoke  in  warfare ». 


NITROGEN  AND  OTHER  SUBSTANCES 
IN  RAIN  AND  SNOW. 

By  John  IT.  Woehlk. 

It  seems  important  to  gain  a  knowledge 
of  the  various  substances  that  come  down 
in  the  rains  and  snows  on  account  of  the 
agricultural  and  hygienic  significance. 
Similar  work  has  been  carried  on  for  some 
time  in  the  chemical  lalwratories  of  Cornell 
College,  and  in  many  other  places. 

Our  special  purpose  is  to  determine  the 
amounts  of  nitrogen  compounds,  chlorine 
and  sulphates  in  the  rains  and  snows  of  this 
locality. 

The  work  was  carried  on  under  ordinary 
laboratory  conditions.  There  is  included  a 
period  of  eight  months,  October  1,  1922,  to 
June  1,  1923.  The  samples  were  collected 
in  two  granite  pans,  each  20  inches  in  dia- 
meter. The  place  is  an  open  space  near  the 
centre  of  Mount  Vernon,  Iowa,  which,  in- 
cluding the  college,  has  a  population  of 
about  2,500,  without  manufacturing  enter- 
prises. This  condition  eliminates  excessive 
smoke  contamination  of  the  atmosphere. 
In  the  work  every  possible  precaution  was 
taken  to  avoid  contamination.  The  samples 
were  always  collected  soon  after  the  pre- 
oiipitation,  and  the  determinations  were 
made  as  soon  thereafter  as  possible. 

Altogether  forty-one  samples  were  ana- 
lysed, of  which  twelve  were  snow  and 
twenty-nine  were  rain.  There  were  70 
inches  of  snow  and  11.2  inches  of  rain.  This 
represents  17.21  inches  of  rain  considering 
twelve  inches  of  snow  the  equivalent  of  one 
inch  of  rain. 

We  found  in  the  aggregate  of  the  precipi- 


tations 20.35  pounds  of  chlorine,  0.57 
pounds  of  sulphate  as  SO3,  and  3.93  pounds 
of  nitrogen  per  acre.  Phosphates  were 
sometimes  found,  but  only  as  a  trace,  never 
in  sufficient  quantity  to  be  determined. 

Expressed  in  parts  per  million,  the  chlor- 
ine varies  from  3.54  to  28.1.  The  precipita- 
tions in  this  section,  both  the  rain  and 
snow,  seem  to  come  from  the  east,  and  the 
salt  particles  doubtless  come  from  the  At- 
lantic Ocean.  The  spraj-  on  the  shore  may 
1)0  caught  by  the  wind  and  is  borne  across 
the  continent,  until  it  descends,  in  solu- 
tion in  the  precipitations.  The  chlorine 
was  determined  with  hundredth  normal  sil- 
ver nitrate,  using  neutral  potassiimi  chro- 
mate  as  the  indicator. 

The  total  nitrogen  shows  an  average  of 
0.896  parts  iper  million,  and  is  quite  con- 
stant. Electrical  storms  seem  to  have  been 
responsible  for  some  of  the  higher  averages. 

The  average  parts  per  million  of  free  am- 
monia is  0.34,  abluminoid  ammonia  0.264, 
nitrogen  in  nitrates  0.346  and  in  nitrites 
0.397,  and  sulphates,  SO3,  0.147. 

The  amount  of  the  precipitation  deter- 
mines largely  the  number  of  pounds  of  ni- 
trogen supplied  per  acre;  but  an  examina- 
tion of  tbe  pounds  of  nitrogen  supplied  by 
each  of  the  41  precipitations  reveals  quite  a 
variation.  This  is  due  to  the  difference  in 
the  amount  of  rainfall,  namely,  0.05  of  an 
inch  to  1.8  inches,  and  it  shows  a  marked 
degree  of  concentration  in  the  smaller  pre- 
cipitation. The  same  standard  reveals  the 
fact  that  during  continuous  precipitation, 
such  as  occurred  from  November  5-27,  the 
total  nitrogen  gradually  diminished. 

We  determined  the  various  substances  in 
each  precipitation  on  the  basis  that  one 
inch  of  rain  on  an  acre  weighs  226,875 
pounds. 

We  desire  to  express  our  thanks  to  Dr.  N. 
Knight  for  aid  and  encouragement  in  carry- 
ing on  this  work. 

Cornell  College, 

Mount  Vernon,  Iowa. 
June  27,  1933. 


THE  PROSPECTS  OF  A  REVIVAL 

IN  TRADE. 
I  think  the  President  of  the  F.B.I. ,  ad- 
dressing the    members  in  Bradford    at  the 
present  time,  could  hardly  choose  any  sub- 
ject for  his  address    other  than  the    condi- 
tion of  trade  and  its  prospects. 
Twofold  Meaning  of  "Trade  Expansion." 
An  examination  of    the  trade  figures    of 
the  country  over    the  past  century,    shows 


JULY  13,  1923. 


THE  CHEMICAL  NEWS. 


31 


two  main  features.  Firstly,  that  trade 
moved  in  cycles  of  from  5  to  10  years;  and, 
secondly,  that  trade  as  a  whole  moved 
steadily  upwards,  that  is  to  say,  that  the 
lowest  points  and  the  peaks  of  the  cycles  of 
trade  consistently  showed  a  general  up- 
ward tendency.  The  years  of  war  upset 
both  the  regularity  of  the  cycles  and  the 
regularity  of  their  upward  progression.  At 
the  present  time,  so  far  as  I  can  see,  in  spite 
of  the  handicaips  which  the  aftermath  of 
war  has  left  us,  we  are  emerging  from  the 
bottom  of  a  cycle,  and  even  in  spite  of  those 
handicaps  I  think  that  a  mild  form  of  opti- 
mism is  possibly  justified.  It  is  difficult  to 
account  for  the  cycles  in  trade,  but  prob- 
ably the  principal  reason  is  this.  Finished 
goofls  take  some  time  to  produce,  and  the 
manufacturer  looking  ahead  has  to  pro- 
I)he8y  as  to  the  results  of  his  sales.  As  a 
rule  a  Sales  Department  is  a  little  optimis- 
tic— if  they  were  not  they  would  not  be  a 
good  Sales  Department — and  the  manufac- 
turing power  of  the  country,  anticipating 
the  demand  several  months  hence,  t^nds  to 
over-produce ;  that  is  to  say,  to  produce 
more  in  prospect  than  the  realised  con- 
sumption. Free  and  imemployed  money  is 
used  to  finance  this  manufacture,  and  a 
point  is  reached  when  the  over-production 
l)egins  to  show,  and  money  becomes  dearer 
because  there  is  a  shortage  of  money  out  of 
employment.  Then  the  trade  slump  begins; 
prices  break  on  account  of  over-production : 
manufacturers  cut  down  their  mill  specifi- 
cations ;  bankers,  short  of  free  cash,  raise 
their  credit  rates;  lack  of  confidence  creeps 
in,  and  the  trade  depression  is  established. 
Consumption  overtakes  production,  dear 
money  means  liquidation  of  stocks,  and 
trade  only  begins  to  improve  when,  owing 
to  conservative  (production,  consumption 
has  again  exceeded  it. 

How  TO  Prevent  Cyclical  Fluctuations 
OF  Trade. 
It  is  difficult  for  anyone  to  dogmatise  in 
these  matters,  but  I  hold  the  view  that  the 
cyclical  depressions  and  heights  of  trade 
are  really  the  outcome  of  the  psycholc^  of 
the  manufacturer  and  the  banker,  but  prin- 
cipally of  the  manufacturer.  Without  opti- 
mism and  hope,  this  world  would  be  a  poor 
place,  and  we  would  effect  little,  but,  as  I 
see  it,  the  principal  cause  of  the  cyclical 
fluctuations  in  trade — which  are  very  un- 
desirable— are  caused  by  lack  of  accurate 
knowledge  as  to  what  the  world  can  con- 
sume. It  would  be  idealistic  to  hope  that 
in  this  imiperfect  and  competitive  world  we 
could  estimate  exactly  what  we  could  sell, 


partitioning  the  demands  among  the  vari- 
ous producers,  but  I  feel  sure  much  can  be 
done  by  the  collation  and  collection  of  in- 
formation by  the  great  trade  and  industrial 
organisations,  to  enable  their  members  to 
forecast  more  accurately  what  the  demand 
will  be,  and  what  production  will  be.  In 
this,  I  think,  the  great  nation  of  the  United 
States  of  America  is  probably  ahead  of  us. 


NOTICES  OF  BOOKS. 
Ubrr  Naturprodulde,  Festschrift  zum 
70  Geburtstage  Max  Honig,  Herausgege- 
l)en  von  Prof.  Dr.  B.  M.  Margosches 
und  Priv.  Doz.  Dr.  W.  Fuchs.  Pp.  X. 
+  181,  with  7  figures  and  a  portrait. 
Dresden  and  Leipzig:  Verlag  von  Theo- 
dor  Steinkopff.  1923.  Price  4s.  4d.  un- 
bound. 

The  recent  celebrations  of  the  Jubilee  of 
Prof.  Max  Honig  by  his  colleagues,  friends 
and  students  of  the  German  Technical  In- 
stitute at  Rrunn  (Brno)  have  led  the  pro- 
mot^'rs  to  publish  this  collection  of  papers 
by  various  authors  under  the  title  of  a 
chemical  treatise  on  the  knowledge  and 
valuation  of  different  natural  products. 

This  Jubilee  volume  includes  the  con- 
tributions communicated  on  the  occasion  of 
the  celebrations.  Mnny  were  naturally 
from  Honig's  stud<'nts  either  still  working 
at  the  Deutsche  Teehnische  Hochschule, 
Brunn.  or  in  other  countries. 

Mr.  C.  F.  Cross.  F.R.S.,  communicated 
the  first  paper.  On  Crilulose  with  lirfrrcncr 
io  StfHtematic  Chcwigtry  and  Natural 
Scirner. 

Drs.  Fischer  and  Tropsch,  of  Mulheim, 
gave  a  eontribtition,  Comparative  Distilla- 
tion in  vacuo  of  CcUulose,  Lignin  and  har- 
dened Wood. 

Prof.  P.  Klason.  Stockholm,  described 
Synthetic  Uesearches  on  the  Lignin  of 
Pinewood;  Prof.  E.  Hagglund,  Lignin  Hy- 
drochlorides: Dr.  K.  Kursohner.  The  Pento- 
san Content  of  Pine  Lignin;  Dr.  B.  Eis- 
ner. The  Methylation  of  Natural  Products -, 
P.  Ehrenstein,  Honig's  Extract  as  used  in 
Tanning:  Prof.  E.  Jalowetz.  Vienna,  The 
Bahing-Power  of  an  old  Wheat  Flour;  F. 
Tempiis.  The  Quantitative  Estimation  of 
Starch ;  Prof.  Margosches  and  Dr.  F.  Stein- 
dler.  On  the  Hindering  of  Reduction  by  Re- 
ducing Sugars  caused  bif  Trichloracetic 
Acid:' Dr.  6.  Wohryzek,  Raw-Sugar  Refin- 
ing: Prof.  E.  Zemer,  Vienna,  The  Oxida- 
tion of  Stearic  and  other  Acids  unth  Oxy- 
gen; Prof.  J.  Marcusson,  Berlin,  The 
Honig-Spitz  Procedure  for  separating 
Sapo'nifiable  and   Unsaponifiable   Oils;     Dr. 


32 


THE  CHEMICAL  NEWS. 


JULY  13,  1923. 


W.  Fuohs,  The  Humic  Acid  Problem;  P. 
Stamberger,  Buda^pest,  Synthetic  Humic 
Acids;  Prof.  A.  Lissner,  The  de -sulphuris- 
ing of  Coke;  Prof.  E.  Donatli,  Estimation 
of  the  Combustibles  in  the  Firing -residues 
of  Coals;  H.  Rath,  The  Honig-Spitz  Esti- 
mation of  Boric  Acid;  Dr.  A.  Kurtenacker, 
Estimation  of  Bismuth  in  Ores  and  Indus- 
trial Products;  F.  Abt,  The  Purification  of 
the  Water  of  Briinn;  Prof.  G.  Ullrich,  The 
Water  conditions  in  the  Textile  Industries 
of  Briinn;  O.  Kyas,  The  Technique  of 
Manuring  Experiments ;  Prof.  C.  Frenzel 
and  Dr.  E.  Klamiann,  Eontgen  Bays  and 
their  Application  in  Chemistry  and  Tech- 
nology. 

The  volume  will  appeal  especially  to 
those  who  have  been  connected,  in  some 
way,  with  Prof.  Honig  or  his  work. 


BOOKS  RECEIVED. 

Supplementary  Notes  on  Gravimetric 
Analysis  for  Beginners,  by  W.  Lowson, 
B.Sc,  F.I.C.  Pp.  54.  1923.  Messrs. 
Longmans,  Green  k  Co.,  39,  Paternoster 
Row,  E.C.4.     2s.  6d. 

Sum.mary  Report  of  Investigations  made 
by  the  Mines  Branch  during  the  Calendar 
Year  ending  December  31,  1921.  Pp.  346. 
1923. 


iHis  lisL  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chance fy  Lane.  London,  from  whom 
all  information  relating  to  Patents,  Tradft  Marks, 
and  Designs  can  be  obtained  gratuitously. 


Latest  Patent   Applications. 

15634 — Chemische  Fabrik  vorm-Sandoz.— Manu- 
facture of  oardiao  glucoside  of  bulbus 
scillse.    June  15. 

15645 — Perceira,  H. — Process  for  manufacturing 
I>eryl6ne  vat-dyes.    June  15. 


15644— Perceira,     H.— Process     of    manufacturing 
aminoperylenequinones.    June   15. 


Specifications  Published  this   Week. 

198385— Nielsoa,  H.,  and  Laing,  B.— Manufacture 
and  utilisation  of  formic  acid. 

198423— Wild,  R.,  and  Wild,  A.  H.— Manufacture 
of  ferro  alloys,  particularly  ferro-chro- 
miuni  alloys. 

198545— Hechenbleikner,  U.,  and  Oliver,  T.C.— 
Treatment  of  acids. 

196576— Elektrizitatwerk  Lonza. — Manufacture  or 
preparation  of  mctaldehyde. 

198615— Chemische     Werke     Altstetten    Akt-Ges.— 
Process   for   the   manufacture  of   1-phenyl- 
2-3-<limethyl-4t-dimethylamino-5-pyrazolon©. 


Abstract  Published  last  Week. 


196672—2  ;4-Diamidophenol ; 
velopors. — King,   O., 
Kensington,   London. 


photographic        de- 
of  35,  Russell  Road, 


A  compound  of  2 :4r-diamidophenol  with  tin 
chloride,  of  good  keeping  qualities  and  suitable 
for  use  as  a  photographic  develoi>er,  is  prepared 
by  treating  2 :4-dinitroplicnol  with  sufficient  tin 
and  liydrmhloric  acid  or  bi^  boiling  2  : i-diamido- 
phenol  with  stannous  chloride  and  hydrochloric 
acid,  and  precipitating  with  concentrated  hydro- 
chloric acid;  the  product  may  further  be  dissolved 
in  water,  sulphiir  dioxide  passed  in,  and  a  pro- 
duct containing  sulphur  dioxide  in  addition  to 
the  tin  chloride  obtained. 


Abstract  Published  this  Week. 


196431 — Organic-mercury  compounds.  —  Wolve- 
kamp,  M.  E.,  of  1116,  2nd  Avenue,  Oak- 
land,  California,   U.S.A. 

Mercurv  derivatives  of  aurintricarboxylic  acid 
and  alkali  salts  thereof  are  obtained  by  heating 
with  mercury  compounds  a  solution  of  an  alkali 
\salt  of  the  acid,  or  a  suspension  of  the  acid  in  a 
solution  of  sodium  chloride.  The  products, 
which  may  contain  one,  two,  or  three  atoms  of 
mercury  in  the  niolecule,  are  substitiites  for  mer- 
cury salicylate;  the  free  acids  are  insoluble  in 
water,  but  soluble  in  sodium  chloride  solution. 
According  to  examples,  products  containing 
sodium  chloride  are  prepared  by  boiling  aurintri- 
carboxvlic  acid  ith  sodium  bicarbonate,  mercuric 
chloride  and  water,  filtering,  and  evaporating; 
products  not  containing  sodium  chloride  are  ob- 
tained bv  replacing  the  mercuric  chloride  by  mer- 
curic oxide,  the  mercuric  aurintricarboxylates 
b?ing  precipitated  by  acidifying  with  sulphuric 
acid. 

Messrs.  Rayner  &  C<).  will  obtain  printed  copies 
of  the  published  specification  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  le.  6d. 
each. 


JULY  20,  1923. 


THE  CHEMICAL  NEWS. 


83 


THE    CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3301. 


NOTE  ON  THE  CHEMISTRY  OF 
HAFNIUM. 

By  G.  Hevesy. 

The  near  relation  between  the  chemical 
properties  of  hafnium  and  zirconium  is 
clearly  exhibited  by  the  fact  that  all  zir- 
conium minerals  contain  hafnium,  in  an 
amount  varying  between  1  to  30  per  cent,  of 
their  zirconium  content.  The  relationship 
between  hafnium  and  its  higher  homologue, 
thorium,  on  the  other  hand,  is  much  less 
conspicuous.  The  most  typical  thorium 
mint'ials,  such  as  orangite,  thorite,  and 
thoriiinite,  were  found  to  be  free  from 
hafnium. 

The  above  conclusimis,  drawn  from  roo- 
chemical  data,  were  fully  confirmed  by 
comparing  the  chemical  properties  of  the 
principal  zirconium  and  hafnium  com- 
pounds. This  investigation  included  com- 
pounds with  hydrochloric,  hydrofluoric, 
nitric,  sulphuric,  oxalic,  carbonic,  phos- 
phoric and  salicyclic  acids,  etc.  Attempts 
to  achieve  a  wparation  of  hafnium  from  zir- 
conium, based  on  the  different  solubility  of 
the  corresponding  compounds,  showed  that 
the  most  successful  method  of  separation 
was  by  the  crystallisation  of  the  potassium 
double  fluoride.  This  compound  can.  as  is 
well  known,  easily  be  prepared  by  melting 
the  zirconium  mineral  with  potassium  hy- 
drogen fluoride.  The  zirconium  and  hafnium 
doiiblo  fluoride  is  then  extracted  with  the 
aid  of  boiling  wat^r,  which  dissolves  as 
miu'h  as  25  per  cent,  of  K.ZrF,.  When 
cooling  down  the  solution  the  greatest  part 
of  the  salt  crystallises  out,  the  Bolubility  at 
20°  amounting  only  to  1.8r>  per  cent,  (in  one- 
eighth  normal  hvdrofluoric  acid  solution). 
The  solubility  of  the  hafnium  double 
fluoride  (amounting  to  about  8  per  cent.) 
being  larger  than  the  solubility  of  the  cor- 
responding zirconium  compound,  the  haf- 
nium concentrates  in  the  mother-liquor. 
The  efficiency  of  this  method  is  shown  by 
the  following  data  :  — 

1000  grams  of  KjZrF,,  containing  0  p  r 
cent,  of  KjHfFft.  were  crystallised  from  a  10 
per  cent.  HF  solution.  After  repeating  this 
operation  ff>nr  times  the  remaining  ir,0 
grams  of  the  double  fluoride  contained  only 
2  per  cent.  KjHfF,,    and  the  hafnium  con- 


centration of  the  mother  liquor  was  corres- 
pondingly raised. 

The  above-mentioned  method  of  separa- 
ticm  can  also  be  replaced  by  a  crystallisation 
of  the  corresponding  ammonium  compound 
or  successfully  combined  with  the  partial 
precipitation  of  zirconium  hafnium  com- 
pounds with  ammonia,  or  by  boiling  the 
solution  with  sodium  thiosulphate,  and  so 
on.  Hafnium  being  more  basic  than  zir- 
conium, the  first  precipitate  accordingly 
contains  relatively  less,  the  last  relatively 
more  hafnium    than  the  original    material. 

The  phosphate  of  hafnium,  on  the 
other  hand,  was  found  to  be  appreciably 
less  soluble  in  concentrated  acids  than  the 
phosphate  of  zirconium,  but  this  method<>f 
separation  was  rather  tedious  considering 
the  difficulties  attending  the  resolution  of 
the  phosphate.  A  partial  separation  was 
further  achieved  by  distilling  the  tetra- 
chloride at  about  250"  C.  but  this  method 
also  was  found  much  less  successful  than 
the  crystallisation  of  the  double  fluoride. 
The  hafnium  content  was  in  all  cases  l^ont- 
gen-spectroscopically  determined.  A  de- 
tailed description  of  this  method  by  Dr. 
Coster  will  be  given  in  a  subsequent  issue  of 
The  Chemical  Ncwh. 

By  using  the  above  described  method  of 
separation,  large  amounts  of  hafnium  still 
containing  5  to  0  per  cent,  of  zirconium 
were  obtained.  A  preliminary  atomic 
weight  determination,  carried  out  with  the 
aid  of  this  material,  gave  a  value  for  the 
atomic  weight  of  hafnium  lying  between 
178.4  and  180.2.  (Concerning  further  de- 
tails of  this  determination,  see  the  July, 
1028.  issue  of  the    Ber.  d.    devtsrh.    Chrw. 

GCH.) 

The  properties  of  KjZrF„  and  a  large 
number  of  other  double  fluorides  were  in- 
vestigated in  detail  by  the  French  chemist, 
Marignac.  and  described  in  a  most  fascinat- 
ing contribution  to  the  ArtnalcH  de  Chhnie  et 
dr  Phynique  in  1860.  He  purified  his  zir- 
•  niuili  by  crystallising  the  KoJ^rF,  and  cal- 
culated the  atomic  weight  of  zirconium 
KjZrF. 

from  the  ratio 

ZrO, 

It  is  of  interest  to  note  that  Marignac,  to 
prove  the  homogenity  of  the  olfnicnt  zir- 
fonium  doubtod  by  Svanberg  and  others, 
determined  th(>  solubility  of  different  KjZrF, 
fractions.  No  difference  was  found.  Marig- 
nac prepared  his  double  fluoride  from  a 
nearly  colourless  zircon,  "presumably" 
from  Ceylon,  which  was  found  by  us  to  have 
a    rather     low    hafnium     content.         The 


m 


34 


THE  CHEMICAL  NEWS. 


JULY  20,  1923. 


accuracy  of  Marignac's  solubility  measure- 
ments amounted  to  about  1  per  cent.,  which 
was  not  sufficient  to  detect  the  presence  of 
hafnium  in  his  material  with  the  help  of 
solubility  measurements. 

Copenhagen,     Univensitetets    Institut    fur 
Teoretisk  Fysik. 
June,  1923. 


THE   COLOKATIONS  OF  CERTAIN 
QUAKTZ    AND    THEIIi    MUTABILITY 

By  Geokg  0.  Wild  and    K.  E.  Liesegang. 

To  the  older  observations  on  the  changes 
of  colour  produced  by  the  influence  of  Heat, 
Light,  and  Rontgen-rays,  Uoelter  has  re- 
cently added  others.  Still  more  may  be 
noted. 

Many  reddish  amethysts  become  colour- 
less when  heated  to  500-600°  C.  On  cool- 
ing, a  yellow  colour  suddenly  develops  at 
about  275°  C. 

These  stones  are  colourless,  light  yellow, 
Hght  violet,  brownish  violet,  or  reddish 
brown.  Some  may  be  colourless  with  ame- 
thyst coloured  seams  running  across.  All 
these  varieties  became  yellow  at  500-600° 
C.  Below  this  the  light  violet  stones  be- 
came brownish  or  reddish  yellow.  The 
others  changed  slightly  at  temperatures 
below  500°  C,  the  colourless  ones  re- 
mained partly  colourless.  Many  of  these 
ambers  appear  exactly  similar  to  the  yellow 
quartz  oi  Brazil  and  Madagascar.  In  fact, 
the  latter  became  colourless  when  heated. 

An  improvement  of  the  colour  shades  of 
amethysts  by  the  application  of  short  or 
long-waved  Rontgen  rays  has  now  been  at- 
tempted by  us. 

From  the  work  of  Doelter,  the  hypothesis 
that  the  change  of  colour,  which  certain 
characteristic  minerals  exhibit  under  the 
action  of  light,  Rontgen,  and  the  different 
radium  rays,  arises  from  the  changing  of 
the  degi'ee  of  dispersion  of  the  admixed 
colouring  bodies. 

Doubtless,  such  changes  in  the  degree  of 
dispersion  make  big  changes  in  the  colour. 
One  o  us,  e.g.,  has  shown  that  the  same 
amount  of  metallic  silver  in  a  layer  of  gela- 
tine can  be  so  dispersed  that  this  layer  be- 
comes colourless  and  transparent  like  glass 
or  the  layer  becomes  absolutely  opaque. 

Between  these  two  extremes  are  all 
stages  from  light  yellow,  orange  deep  red, 
brown,  olive,  green;  very  deeip  blue  can  also 


appear  by  transmitted  light.  From  the 
colourless,  through  the  yellow  to  the  black, 
the  size  of  the  silver  pai-ticles  increases, 
and  yet  it  is  to  be  admitted  that  it  is  diffi- 
cult for  us  to  abandon  Doelter's  views.  The 
colloid  particles  of  the  colouring  matter  can 
undergo  coagulation  in  the  solid  crystal  lat- 
tice, or  in  a  crystal  aggregate  a  kind  of  co- 
agulation (or  peptisation). 

This  is  comparable  with  Zsigmondy's  ex- 
periments, in  which  red  gold  sols  turn  lu 
blue  when  electrolytes  are  introduced. 

It  is  also  comparable  with  the  gel  forma- 
tion in  aqueous  albumin  and  cerium  oxide 
sols  under  the  influence  of  Radium  Rays,  as 
was  studied  by  A.  Fernau  and  W.  Pauli.  In 
the  latter  case,  the  tendency  to  coagulate 
is  not  hindered  by  the  presence  of  protec- 
tive colloids,  gel-media,  or  by  the  crystal 
lattice  structure  of  the  body. 

On  the  other  hand,  Marc's  results  from 
studies  of  effect  of  traces  of  special  organic 
dyestuffs  in  ipreventing  actual  crystal  lat- 
tice formation,  point  in  another  direction. 
The  movement  of  colloid  particles  has  been 
shown  not  to  occur  in  gels  which  are  not 
quite  set,  how  then  can  the  coagulation  be 
hindered  inside  a  solid  crystal?  The  col- 
loid particles,  then,  must  be  regarded  as 
not  movable. 

The  coagulation  theory  completely  fails 
to  explain  this. 

There  are  other  possibilities  which  admit 
of  the  change  of  degree  of  dispersion  in  a 
rigid  system,  namely,  in  the  case  where 
inetrmediate  solution  comes  in.  For  in- 
stance, silver  chloride  should  be  very  finely 
dispersed  in  a  gelatin  gel,  so  that  the  cloudi- 
ness is  very  small. 

When  sodium  nitrate  diffuses  with  this 
gel  a  great  increase  of  the  cloudiness  oc- 
curs. A  part  of  the  silver  chloride  has  dis- 
solved to  form  an  intermediate  solution. 

The  other  particles  of  the  silver  chloride 
then  increase  in  size  from  this  solution. 
This  may  well  occur  in  minerals. 

The  Rontgen  Rays  make  amethyst  darker 
but  the  heating  makes  it  lighter  again. 
Diffusion  would  take  a  long  time  in  this 
medium,  and  the  changes  by  heating  are 
too  quick  for  this.  Our  ultra-microscopic 
experiments  with  heated  and  vmhcated 
amethyst  have  not  shown  any  support  for 
the  theory  of  the  change  of  dispersion.  The 
purely  chemical  hypothesis  seem  to  offer 
the  most  satisfactory  explanation. 

(From  the    Centralblatt    f.    Min.,    1922 
XVI.,  481.) 


JULY  20,  1923. 


THE  CHEMICAL  NEWS. 


35 


EMPIRE  COTTON  AND  RE  SEARCH. 

£5,000  Donation  to    Imperial  College. 

The  Empire  Cotton  Growing  Corporation 
has  recently  been  considering  the  necessity 
for  organised  research  at  the  Universities 
and  Colleges  of  Great  Britain,  and  has  de- 
cided to  oflfer  retaining  grants  to  certain 
Universities  where  highly  specialised  re- 
search is  alrendy  going  on.  The  Cotton 
Corporation  has  offered  to  the  Imperial,  Col- 
lege of  Science  and  Technology,  South  Ken- 
sington, the  sum  of  £1,000  a  year  for  a 
period  of  five  years  from  October  1,  10*23, 
the  money  to  be  devoted  to  Plant  Physio- 
logy and  Plant  Pathology  in  the  Depart- 
ment of  Botany.  This  generous  offer  has, 
we  understand,  been  accepted  by  the  G<)v- 
erning  Body,  and  the  research  work  will  be 
undertaken  in  the  new  Botany  Building 
which  was  recently  opened  by  tne  Duke  of 
Devonshire,  and  to  which  the  Rubber 
Growers'  Association  of  the  City  of  London 
subscribed  approximately  £30,000  about 
two  years  ago.  This  donation  is  tangible 
eviflenc4'  of  the  value  which  tropical  agri- 
culturists attach  to  the  important  research 
work  which  is  being  undertaken  ut  the  Im- 
perial College,  especially  in  connection  with 
plant  physiology  and  pathology  under  the 
direction  of  Professor  J.  B.  Farmer,  F.R.S.. 
and  Professor  V.  H;  Blackman,  F.R.S.  Wc 
have  nf>  doubt  tha(|  other  groups  interested 
in  research  work  will  continue  to  su|^ort 
undertakings  of  this  character. 

The  United  States  Department  of  Agri- 
culture has  issued  a  Department  Bulletin. 
No.  1J47.  entitled  Chemical,  Physical,  ami 
Inaccticidal  Properties  of  Arsenicals,  by  F 
C.  Cook  and  N.  E.  McIndoo. 

This  study  of  the  chemical,  physical,  and 
inseoticidal  properties  of  arsenicals  on  the 
market  was  undertaken  in  order  to  gain  a 
better  understanding  of  them,  to  be  able,  if 
possible,  to  improve  thefn,  and  to  produc(^ 
new  arsenicals  for  inseoticidal  punposes. 
The  results  of  this  investigation,  which  was 
conducted  by  the  Bureau  of  Chemistry  and 
the  Bureau  of  Entomology  of  the  United 
States  Department  of  Agriculture,  %re  here 
repotted. 

Paris  green  and  lead  arsenate,  which  have 
been  standardised  snd  found  reliable  for 
many  years,  have  constituted  the  principal 
inseotioides  used  against  external  chewing 
\nsects.  However,  during  the  past  few 
vears,  the  use  of  calcium  arsenate  has 
steadily  increased,  owing  in  part  to  the  dis- 
covery that  it  is  effective  in  combating  the 


boll  weevil.  The  manufacture  of  calcium 
arsenate,  although  well  beyond  the  experi- 
mental stage  in  most  factories,  probably 
will  not  be  completely ,  standardised  for 
several  years.  Because  of  the  importance 
and  recent  large-scale  production  of  cal- 
cium arsenate,  many  of  the  results  in  this 
bulletin  deal  with  comparisons  of  calcium 
tirsenate  and  acid  lead  arsenate. 

Chemical  Properties  of  Arsenicals. 

Arsenious  oxide  (As-O,),  commonly 
called  white  arsenic  w  simply  arsenic,  is 
the  basis  for  the  manufacture  of  all  arseni- 
cals. Arsenious  oxide  is  a  by-product  from 
the  smelting  of  lead,  copper,  silver,  and 
gold  ores,  being  recovered  from  the  flue 
dust  and  fumes.  The  arsenious  oxide  first 
sublimed  is  impure,  owing  to  the  presence 
of  carbon  and  sometimes  of  sand.  The  im- 
pure oxide  may  then  be  resublimed  to  give 
a  relatively  pure  one.  consisting  of  approxi- 
mately 99  per  cent,  of  arsenious  oxide  and 
a  trace  of  arsenic  oxide  (AsjO^).  Between 
11,000  and  P2.0()0  tons  of  arsenious  oxide 
were  produced  in  the  United  States  in 
1920,  more  than  half  of  which  was  used  for 
insecticide  purposes.  Canada,  Mexico,  Eng- 
land, Germany,  France,  Japan,  and  Portu- 
gal produce  large  quantities  of  arsenious 
oxide. 

There  are  three  forms  of  arsenious  oxide : 
(a)  The  amorphous,  vitreous,  or  glassy 
form;  (b)  the  ordinary  crystalline  ('  octa- 
he<lrar')  form;  and  (c)  the  orthorhombic 
crystalline  form.  The  amorphous  form 
changes  spcMitaneously  into  the  crystalline 
form  on  standing.  The  trade  usually  recog- 
nisi>8  two  grades,  the  light  and  the  heavy 
fonns.  although  they  are  the  same  chemic- 
ally. 

'The  literature  contains  conflicting  state- 
ments concerning  the  solubility  of  arsenious 
oxide  in  water.  Because  of  the  slowness 
with  which  it  goes  into  solution,  many 
weeks  being  required  to  dissolve  even  a 
small  sample  of  the  solid,  it  is  probable 
that  in  all  of  ^he  reported  results  equili- 
brium heul  not  been  reached.  The  varying 
oercentages  of  crystalline  and  amorphous 
material  present  in  the  samples  tested,  the 
amorphous  form  being  more  soluble  than 
the  crystalline  forms,  may  possibly  help  to 
account  for  these  discrepancies. 

With  the  exception  of  Paris  green,  the 
arsenites  are  prepared  by  combining  arseni- 
ous oxide  and  the  base. 

As  a  rule,  arsenates  are  made  by  the 
direct  action  of  arsenic  acid  in  solution  on  a 
metallic  oxide.      The  arsenic  acid  used  for 


36 


THE  pHEMICAL  NEWS. 


JULY  20,  1923. 


this  purpose  is  manufacture^    from  arseni- 
ous  oxide  by  oxidation,    usually  by    means 
of  nitric  acid. 
Bases  Used  in  Preparing  Arsenicals. 

The  oxides  of  lead,  zinc,  calcium,  and 
magnesium  are  the  bases  most  used  in 
manufacturing  arsenicals.  Litharge  is  the 
commercial  calcium  oxide.  Zinc  oxide 
(ZnO)  and  lead  oxide  (PbO),  cwdinarily  em- 
ployed in  the  manufacture  of  zinc  arsenite 
and  lead  arsenate,  are  more  expensive  than 
calcium  oxide  (CaO)  and  magnesium  oxide 
(MgO)  used  in  manufacturing  calcium  ar- 
senate and  magnesium  arsenate. 

The  principal  lead  arsenate  is  acid  lead 
arsenate  (PbHAsO^),  an  acid  salt,  so-called 
because  of  the  presence  of  hydrogen  (H)  in 
its  molecule.  It  has  the  following  theore- 
tical composition,  AS2O5  (33.13  per  cent.), 
PbO  (64.29  per  cent.),  and  water  of  con- 
stitution (2.58  per  cent.). 

In  the  early  procedure  for  preparing  acid 
lead  arsenate,  solutions  of  lead  acetate  or 
of  lead  nitrate  were  precipitated  by  sodium 
hydrogen  arsenate  (Na2HAsO^).  The  ten- 
dency is  to  produce  acid  lead  arsenate  when 
lead  nitrate  is  used,  and  the  more  basic 
form  when  the  acetate  is  used.  McDonnell 
and  Smith  obtained  acid  lead  arsenate  of 
practically  theoretical  composition  by  pre- 
cipitating lead  nitrate  or  lead  acetate  by  an 
excess  of  monopotassium  arsenate.  A 
method  frequently  employed  in  manufac- 
turing this  arsenate  is  to  mix  arsenic  acid 
(H3ASOJ  and  litharge  (PbO)  in  the  pre- 
sence of  a  small  amount  of  nitric  acid.  The 
fact  that  acid  lead  arsenate  is  a  compara- 
tively stal)le  compound  and  is  but  slightly 
soluble  in  water,  offers  an  extplanation  as  to 
why  it  burns  foliage  only  very  slightly  when 
properly  applied. 

Basic  Lead  Arsenate. 

The  early  investigators  recognised 
"basic,"  or  "  sub,"  arsenate  of  lead,  and 
applied  the  term  "neutral  lead  arsenate"  tf> 
PbHAsO^,  which  is  the  present  commercial 
acid  lead  arsenate.  They  also  applied  the 
term  "neutral  lead  arsenates"  to  lead  pyro- 
arsenates,  which  are  not  commercial  pro- 
ducts, and  therefore  will  not  be  discussed 
here. 

"Basic  lead  arsenate  may  be  prepared  as 
follows :  Produce  basic  lead  acetate  by  the 
action  of  acetic  acid  on  lead  or  lead  oxide, 
usually  litharge.  Then  mix  it  with  arsenic 
acid,  thus  forming  basic  lead  arsenate. 
Basic  lead  arsenate  may  also  be  made  by 
the  reaction  of  sodium    arsenate,    litharge, 


and  nitric  acid,  or  by  the  action  of  ammo- 
nia on  acid  lead  arsenate.  It  has  the  fol- 
lowing theoretical  composition :  As^O^  (23.2 
per  cent.),  PbO  (75  per  cent.),  and  water  of 
constitution  and  crystallisation  (1.8  per 
cent.).  The  specific  gravity  of  this  sub- 
stance was  found  by  McDonnell  and  Smith 
to  be  6. 80. 

Calcium    Arsenates. 

Pickering,  in  1907,  stated  that  calcium 
arsenate  had  already  been  used  in  the 
United  States  as  an  insecticide.  He  gave 
the  proportions  of  a  calcium  salt  and  an 
arsenate  to  be  united  in  preparing  calcium 
arsenate,  recommending  the  use  of  an  ex- 
cess of  lime  in  order  to  produce  a  calcium 
arsenate  with  all  the  arsenic  precipitated 
and  therefore  containing  no  appreciable 
amount  of  water-soluble  arsenic. 

As  many  of  the  early  commercial  sam- 
ples of  calcium  arsenate  contained  exces- 
sive amounts  of  water-soluble  arsenic,  fre- 
quent scorching  of  foliage  resulted  from  its 
use,  thus  retarding  its  general  introduction. 
Since  1907,  many  experiments  to  devise  a 
method  for  making  a  commercial  calcium 
arsenate  have  been  performed.  It  is  now 
being  produced  by  many  American  manu- 
facturers, and  its  sale  is  constantly  increas- 
ing. The  quality  of  the  commercial  pro- 
duct has  been  much  imtproved  during  the 
past  few  years,  but  its  course  of  manufac- 
ture has  not  yet  been  standardised  as  has 
that  of  lead  arsenate. 

Dicalcium  arsenate  (CaHAsO^(H20))  con- 
tains theoretically  28.3  per  cent,  of"  calcium 
oxide  and  58  per  cent,  of  arsenic  oxide.  It 
breaks  down  easily  in  water,  yielding  a 
large  quantity  of  water-soluble  arsenic,  and 
is  not  suitable  for  commercial  spraying  pur- 
poses. 

The  following  simple  method  of  preparing 
calcium  arsenate  commercially,  as  out- 
lined by  Haywood  and  Smith,  calls  for  the 
direct  mixing  of  calcium  hydroxide  and  ar- 
senic acid,  the  only  by-product  being 
water :  Slake  the  lime  to  a  smooth  paste  by 
using  from  3  to  3|  times  as  much  warm 
water  (by  weight)  as  lime,  and  allow  it  to 
stand  until  the  lime  is  completely  slaked. 
Then  mix  it,  add  the  cold  arsenic-acid  solu- 
tion at  room  temperature  as  rapidly  as  pos- 
sible, and  stir  the  mixture  well  until  +he 
liquid  becomes  alkaline  to  phenolphthalein. 
Lastly,  filter,  dry,  and  grind  the  resulting 
compound. 

The  lime  and  arsenic  acid  should  be 
mixed  in  such  proportion  that  the  actual 
weight  of  calcium  oxide  used  will  be  equiva- 


JULY  20,  1923. 


THE  CHEMICAL  NBWS. 


d7 


lent  to  that  of  the  arsenic  oxide  employ  iii. 
This  method  produces  a  reasonably  lif^ht 
(bulky)  material,  which  is  easily  pulverised. 
The  finished  product  should  contiun  ap- 
proximately 44  per  cent,  of  calcium  oxide, 
from  40  to  42  per  cent,  of  arsenic  Cixidj, 
.md  from  14  to  16  per  cent,  of  water  and 
impurities,  which  approaches  the  rati.). 
4  CaO:  1  As^O^.  The  excess  of  lime  is  used 
to  kiH'p  any  soluble  calcium  arsenate  f  >ni 
remaining  in  the  product. 

Pakis  Green. 

Paris  green,  originally  used  as  a  paint  pig- 
ment, is  said  to  have  first  served  as  an  in- 
secticide in  the  western  United  States.  It 
is  a  comiprnrnd  of  arsenic,  acetic  acid,  and 
copper,  known  as  aceto-arsenite  of  copper. 
The  theoretical  composition  of  Paris  green 
is  copper  oxide  (31.39  per  cent.),  arsenious 
oxide  (58.55  per  cent,),  and  acetic  anhy- 
dride (10.06  per  cent.) 

The  manufacture  of  Paris  green,  which 
hiw  become  standardised,  may  be  briefly  de- 
scribed thus :  Solutions  of  sodium  carbon- 
ate nnl  arsenious  oxide  arc  heated  together, 
forming  sodium  arsenite.  Crystalline  cop- 
per sulphate  is  dissolved  in  warm  water  in 
a  separate  container.  The  sodium  arsenitc 
mixture  is  poured  into  a  mixing  tank,  the 
copper  sulphate  solution  is  added,  and  the 
mixture  is  stirred.  Acetic  acid  is  added, 
and  after  a  little  stirring  the  olive-coloured 
mixture  becomes  green.  The  Paris  green  is 
washed  with  water,  after  which  it  is  allowed 
to  settle,  and  all  the  water  that  can  be 
drained  off  is  so  removed.  This  washing 
should  be  repeated  as  often  as  necessary  to 
remove  practically  all  the  sodium  sulphate. 
The  Paris  green  Is  then  dried.  The  dried 
product  is  passed  through  a  '*  breaker." 
and  finally  through  a  fine  sieve  or  a  boltini; 
machine.  The  "tailings"  are  mixed  with 
the  next  batch  of  Paris  green.  The  finely 
divided  Paris  green  is  now  ready  to  be 
placed  in  containers. 

The  conclusions  that  may  be  drawn  from 
this  investigation  are  that  a  chemical  analy- 
sis of  an  arsenical  does  not  jjive  sxifiieient 
data  to  judge  satisfactorily  its  insecticidal 
(properties,  and  a  toxicity  study  alone  doe-- 
not  show  that  an  arsenical  is  suitable  for 
general  insecticidal  purposes,  but  both  a 
chemical  analysis  and  a  thorough  toxicity 
study  nre  required  in  order  to  judge  whether 
or  not  an  arsenical  is  a  satisfactory  insecti- 
cide. 


GENERAL  NOTES. 


TRADE  CATALOGUES  REQUIRED  IN 
NICARAGUA. 

Mr.  T.  J.  Rees,  H.M.  Consul  at  Mana- 
gua, has  informed  the  Department  of  Over- 
seas Trade  that  although  the  supply  of 
catalogues  and  price  lists  available  at  the 
Consulate  is  very  limited,  he  has,  never- 
theless, been  able  to  divert  orders  to  the 
United  Kingdom  through  their  use.  Simi- 
lar conditions  obtain  at  Leon  and  Granada. 

The  Consul  suggests,  therefore,  that 
there  are  good  prospects  of  increasing  Brit- 
ish trade  by  supplying  him,  and  the  Con- 
sular Officers  at  Leon  and  Granada,  with 
catalogues  and  price  lists  of  manufacturers 
of  the  following  (among  others):  — 

Novelties,  cutlery,  ironmongery,  pottery 
and  glassware,  stationery,  fine  and  pharma- 
ceutical chemicals,  patent  medicines,  drug- 
gists' sundries,  toys,  firearms,  and  of  any 
other  articles  in  general  demand. 

Further,  should  samples  be  supplied,  the 
Consul  would  be  pleased  to  use  them  to  the 
best  possible  advantage. 

Firms  desiring  to  take  advante^e  of  the 
poftsibilities  offered,  should  forward  three 
copies  (for  use  at  the  three  ports  named)  of 
their  catalogues,  etc.,  directly  to  His 
Majesty's  Consul,  British  Consulate,  Mana- 
gua, >^icaragua. 

GERMANY'S  TRADE  AND    INDUSTRY 
IN  JUNE. 

Mr.  J.  W.  F.  Thelwall,  Commercial  Sec- 
retary at  Berlin,  has  forwarded  to  the  De- 
partment of  Overseas  Trade  a  review  of 
Germany's  trade  and  industrj'  during  June. 
From  the  report  it  is  seen  that  the  month 
was  noteworthy  for  a  further  extraordinary 
depreciation  of  the  mark.  On  the  one  hand 
this  led  to  a  strong  revival  of  trade,  with 
the  result  that  an  miprovement  occurred  in 
many  branches  of  industry,  e.g.,  in  the  tex- 
tile, leather,  paper,  india-rubber  and  glass 
industries.  The  potash,  machinery,  and 
chemical  industries  were  also  able  to  record 
better  sales.  On  the  other  hand,  the  cur- 
rency depreciation  led  to  quite  exceptional 
advances  in  prices.  The  wage  increases  in 
the  first  half  of  June,  to  55-60  per  cent,  as 
compared  with  May,  and  in  the  second  half 
of  June  to  about  60  per  cent,  as  compared 
with  the  first  half  of  the  month.  The  mar- 
ket conditions  in  occupied  territory  con- 
tinued to  develop  unfavourably.  The  pres- 
sure   of    occupation     became     increasingly 


38 


THE  CHEMICAL  NEWS. 


JULY  20,  1923. 


greater.  The  deliveries  of  coal  and  coke 
did  not  increase  in  quantity,  while,  as  re- 
gards quality,  they  became  still  worse.  Coke 
was  produced  only  to  meet  the  in  mediate 
requirements  of  the  foundries  and  gas- 
works. The  coal  supplies  also  diminished 
constantly.  The  time  is  not  far  distant, 
therefore,  when  deliveries  will  have  to  cease. 

Potash.  —  The  general  situation  in  the 
potash  industry  was  favourable.  Sales, 
which  had  declined  heavily  in  March  and 
April,  revived  in  May  under  strong  calls 
from  home  and  abroad.  These  calls  con- 
tinued throughout  June.  As  a  result,  shifts 
which  had  previously  been  dropped  were  re- 
sumed, so  that  ^he  works  in  June  were,  in 
general,  fully  employed.  The  fuel  supply 
was  adequate.  The  quality  of  the  coal  de- 
livered left,  however,  much  to  be  desired. 
Chemical  Industry. 

The  strong  home  demand  was  maintained 
owing  to  the  heavy  currency  depreci;;tion 
which  occurred  in  the  course  of  the  mcnth, 
and  it  was  not  always  possible  to  carry  out 
orders  promptly.  The  raw  material  supply 
from  abroad  proceeded  without  interruption 
or  difficulty. 

Paper  Industry. 

Owing  to  the  depreciation  of  the  mark, 
the  prices  of  paper  wood  rose  considerably. 
The  small  quantities  still  available  on  the 
inland  market  from  the  last  fellings  fetched 
prices  two  to  three  times  higher  than  those 
in  the  previous  m.onth.  Inland  sales  in- 
creased somewhat  and  foreign  trade  con- 
tinued very  brisk.  Production  equalled  that 
in  the  preceding  month.  The  labour  supply 
was  adequate.  In  the  paiper  wholesale 
trade  the  demand  continued  satisfactory, 
and  the  factories  were  again  better  em- 
ployed. 

India-Ruhber  Industry. 

The  india-rubber  industry  was  probably 
everywhere  very  actively  employed,  as  the 
home  demand  was  very  lively.  A  consider- 
able clearance  of  the  accumulated  stocks 
was,  in  part,  effected.  Price  increases  were 
not  nearly  able  to  follow  the  movement  of 
foreign  exchanges.  The  fuel  supply  still 
caused  the  gravest  anxiety. 


BOAED  OF  TEADE  ANNOUNCEMENT. 

Dyestuffs  (Import  Eegulation)  Act,  1920. 
Applications  for  Licences  in  June. 

The  following  statement  relating  to  appli- 
cations   for  licences    under    the    Dyestuffs 


(Import  Eegulation)  Act,  1920,  made  dur- 
ing June,  has  been  furuished  to  the  Board 
of  Trade  by  the  Dyestufts  Advisory  Lict'us- 
ing  Committee. 

The  total  number  of  applications  received 
during  the  month  was  512,  of  which  893 
were  from  merchants  and  dealers.  To  these 
should  be  added  the  21  cases  outstanding 
on  June  1,  making  a  total  for  the  month  of 
533.  These  were  dealt  with  as  follows  :  — 
Granted— 872  (of  which  828  were  dealt 
with  within  seven  days  of  receipt). 

Eef erred  to  British  makers  of  similar 
products — 96  (of  which  78  were  dealt 
with  within  seven  days  of  receipt). 

Eeferred  to  Eeiparation  supphes  avail- 
able— 41  (all  dealt  with  within  two  days 
of  receipt). 

Outstanding  on  June  30 — 24. 
Of  the  total  of  583  applications,    430,  or 
80  per  cent.,    were  dealt    with  within    four 
days  of  receipt. 
Board  of  Trade. 
July  11,   1028. 


CHEMICALS  EEQUIEED  IN  U.S. 

Mr,  L.  E.  Bernays,  H.M.  Consul  at  New 
York,  reports  that  a  local  firm  are  desirous 
of  purchasing  the   undermentioned    chemi- 
cals in  England,  primarily  for  sale  in  Cuba  : 
Eef.  Pyridine, 

Ammonium     Carbonate,       Jjump     and 
Powdered. 

Castor  oil    of  the    No.  1    or   medicinal 
grade. 

Whiting  (Blanco  Espana). 
Tartaric  and  Citric  Acid. 
Naphthalene  Hakes  and  l)alls, 
British  firms  desirous    of  receiving    fur- 
ther    particulars     regarding     this     enquiry 
should  apply  to    the  Department  of    Over- 
seas Trade,  85,  Old  Queen  Street,    London, 
S.W.I,      quoting     reference    20f)39/F.\\    /- 
C.C.2. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 

THE  FAEADAY  SOCIETY. 


A  GENEEAL  DISCUSSION    ON    "  THE 

ELECTEONIC  THEOEY  OF  VALENCY," 

HELD  AT  CAMBEIDGE  ON  JULY 

13-14,  1923. 

Valency  and  the  Electrons,  by    Gilbert 
N.  Lewis. 


JULY  20,  1923. 


THE  CHEMICAL  NEWS 


39 


As  it  is  the  purpose  of  this  discussion  to 
secure  a  better  uuderstan-ling  of  divergent 
points  of  view,  I  have  chosen  a  few  ques- 
tions which  seem  likely  to  arise  and  which 
concern  the  application  of  the  newer 
theories  of  valence  to  the  problems  of 
chemistry.  I  should  like  to  express  my 
belief  that  the  two  views  of  the  structure  of 
the  atom,  derived  respectively  from  chemi- 
cal and  phjrsical  researches  which  a  few 
years  ago  seemed  so  incompatible,  are  now 
reconcilable. 

While  Bohr,  in  his  development  of  quan- 
tum theory,  has  accounted  for  the  general 
characteristics  of  the  periodic  table  by  as- 
suming groups  of  energy  levels,  of  which 
the  first  may  contain  two,  the  second  eight, 
the  third  eighteen,  the  fourth  thirty-two 
electrons,  etc.,  there  is  nothing  to  show 
why  the  group  of  two  electrons  and  that  of 
eigfit  play  so  imiportant  a  role  in  the  outer 
shells.  Thus  the  rare  gases  from  neon  to 
niton  possess  eight  electrons  in  the  outer 
shell,  the  same  is  true  for  all  stable  elemen- 
tary ions  such  as  K  +  ,  A1  +  +  +  ,  S--. 

Prof.  Lewis  went  on  to  discuss  the  elec- 
tron pair  as  the  chemical  bond,  nomoncln- 
ture,  multiple  bonds,  conjugation  and 
polarisation. 

Bohr'g  Atom  in  Relation  to  the  Problem 
of  Covalency,  by  R.  H.  Fowleh,  M.A. 

Considerable  atlvances  have  been  made  in 
our  views  on  at«;mic  structure  since  the  idea 
of  nuclear  structure  was  put  forward  by 
Kutherford  in  lOlL  From  Bohr's  work  the 
main  features  now  seem  to  have  been 
worked  out. 

Prof.  Fowler  considered  the  physical  in- 
terpretatif;n  of  covalence  from  a  study  of 
the  hydrides  of  boron,  sulphur  hexa- 
fiuoride,   and  the    co-ordinated    compotmds 

of  (-01)81 1. 

The  Nature  of  the  Non-Polar  Link,  by  N. 

V.    SiDOWICK. 

No  theory  of  the  phvsical  nature  of 
valency  can  take  us  very  far  unless  founded 
on  some  definite  conception  of  atomic 
structure.  In  the  remarks  that  follow  T 
have  assumed  the  truth  of  Bohr's  theory  of 
the  atom,  based  on  the  apjplication  of  dy- 
namics (under  the  quantum  restriction)  to 
electrons  which  are  held  in  their  orbits  h\ 
the  balance  between  their  mutual  electro- 
static repulsions  and  the  attraction  of  the 
nucleus,  and  centrifugal  force. 

It  is  generally    admitted    that  the    non- 
polar  (as  opposed  to  the  polar)  link  consists 


in  the  "sharing"  of  two  electrons  between 
the  two  linked  atoms.  The  only  new  as- 
sumption which  I  make  is  that  the  orbit  of 
each  "shared"  electron  includes  both  of  the 
attached  nilclci.  This  assumption  has  been 
found  by  Professor  Nicholson  to  be  the  only 
one  which  will  account  for  the  spectrum  of 
molecular  hydrogen;  and  it  has  also  been 
put  forward  by  Dr.  N.  P.  Campbell  as  a 
more  or  less  self-evident  extension  of  Bohr's 
theory  to  non-tpolar  linkages.  The  author 
considered  the  results  obtained  by  applying 
this  conception  to  chemical  facts. 

There  are  two  obvious  differences  be- 
tween such  binuclear  orbits  and  the  simple 
orbits  of  Bohr.  One  is  that  the  presence  of 
a  second  nucleus  in  the  orbit  makes  pre- 
cession of  the  orbit  impossible,  unless  in- 
deed the  same  orbit  successivelv  includes 
s<neral  niJcIei.  The  second  is  t)iat  all  the 
electrons  shared  by  any  one  atom  have  to 
pass  through  their  perinuclea  in  due  succes- 
sion, and  hence  their  periods  musf  agree; 
moreover  in  a  chain  of  atoms  the  periods  of 
all  the  binuclear  orbits  must  be  the  same, 
or  must  differ  rationally. 

The  theory  exf)1ains  why  the  groups  at- 
tached, say,  to  a  carbon  atom  retain  their 
relative  positions,  in  spite  of  the  fact  that 
each  of  the  electrons  holding  them  goes 
roimd  the  carbon  nucleus ;  and  these  posi- 
tions may  be  expected  to  have  the  t^trahe- 
dral  symmetry  which  Bohr  finds  in  the  4 
orbits  of  an  electron  sub-group. 

It  also  satisfies  the  condition  of  permit- 
ting the  free  rotation  of  singly  linked  car- 
bon atoms. 

Coordination. 

What  Werner  calls  the  co-ordination 
number  of  an  atom  is  the  number  of  non- 
polar  links  that  it  is  able  to  form.  This  is 
proved  by  the  occurrence  of  optical  activity 
among  the  6-co-nrdinated  compounds  under 
conditions  parallel  to  those  which  hold 
among  asymmetric  carbon  compounds. 
Werner's  substances  can  be  formulated 
without  asstiminp  any  kind  of  valency 
other  than  polar  and  non-polar  linkages,  if 
we  realise  that  while  a  monovalent  group 
(like  -CI  or  -XOj)  contributes  one  electro- 
nic orbit  to  the  central  atom,  a  group  which 
can  exist  as  nn  independent  molecule  (such 
as  ammonia  or  water)  contributes  two.  the 
nitrogen  or  oxygen  assuming  a  higher 
valency  by  the  loss  of  an  electron,  or,  if  you 
will,  supplying  both  electrons  for  the  link. 
If  the  resulting  complex  is  an  ion,  its  elec- 
trovalencv  must  he  added  or  subtracted. 
Thus  you  get  a  vnlue    for  the  number  of  or-. 


40 


ME  CHEMICAL  T^SWS. 


JULY  20,  1923. 


bits  added  to  the  atom  in  the  compound, 
and  by  adding  this  to  the  atomic  number 
you  arrive  at  what  may  be  called  the  effec- 
tive atomic  number. 

The  Electronic  Theory  of  Valency.  Part 
II. — Intramolecular  lonisation  in  Organic 
Compounds,  by  Professor  T.  Martin  Low- 
RY,  C.B.E.,  M.A..  D.Sc,  F.E.S. 

1. — Intfamolccular  lonisation  in  Inor- 
ganic Compounds. 

In  the  preceding    paper    of  this    series    I 
directed  attention  to  the  fact  that  the  elec- 
tronic theory  of  valency  permits    of  a  very 
wide  extension  of  Thomson's  theory  of  in- 
tramolecular    lonisation,     and     that    polar 
bonds  may  be  detected    in  a  large  range  of 
inorganic    con)ipounds    where    it  has    been 
generally  assumed   hitherto  that  the     link- 
ages are  all  of  a  non-polar  or  covalent  type. 
In  particular,  a  study  of  the  electronic  for- 
mulae of  Langmuir  reveals    the  fact    that, 
whilst  there  is  usually  a  perfect  balance  be- 
tween the  nuclear  charge  of  each  atom  and 
the  enveloping  shell  of  electrons,     in  other 
cases    the  negative    charge  of    the  shell    is 
either    too  large    or  too    small    to    balance 
exactly  the  positive  charge  of  the  nucleus. 
2, — Application   to   Organic   Compounds. 
An  extensive  application  of  the-  theory  of 
intramolecular    ionisation    to  organic    com- 
pounds is  rendered  possible    by  taking  ad- 
vantage of  a  more  recent  conception  of  Sir 
J.  J.  Thomson.       He  suggests  that  the  re- 
activity of  double  bonds  in  organic  chemis- 
try may  be  attributed  to  the  fact  that  it  is 
easier  to  open  the  hinge  between  two  cubi- 
cal octets  sharing  a  common    face  than  to 
break  the  huge  which    holds    together    two 
octets  sharing  only  a  common  edge.     This 
view  can    scarcely  be  accepted  as    an  ade- 
quate    explanation     of     the     reactivity     of 
double  bonds,  since  fluorine    is  in  fact    far 
more  reactive  than  oxygen;    but  if    the  as- 
sumption be  made  that  the  rupture    of  the 
double  bond  takes  place    unsymmetrically, 
so  as  to    leave  2  L- electrons  on  one    atom 
and  only  6  on  the  other,    a  very  suggestive 
system  of  formulae  is  arrived  at,    in  which 
ethylene     is  reipresenetd     as     containing     a 
"  mixed  double    bond,*'    whilst    acetylene 
can  be  represented  in  a  similar  way  as  con- 
taining a  "  mixed  triple  bond." 

The  theory  of  intramolecular  ionisation 
can  thus  be  extended  to  organic  com- 
pounds, if  it  be  assumed  that  double  bonds 
can  assume  a  form  in  which  one  carbon 
atom  carries  eight  L-electrons,  but  the 
other  only  six,  one  pair  of  electrons  only 
being  shared.      Since  the  former    atom    is 


then  negatively  and  the  latter  positively 
charged,  this  type  of  double  bond  may  be 
represented  as  made  up  of  one  co-valency 
and  one  electrovalency. 

This  extension  of  the  theory  of  intra- 
molecular ionisation  brings  the  reactivity  of 
organic  compounds  into  line  with  the  well- 
recognised  activity  of  inorganic  ions,  and 
makes  it  possible  to  regard  all  chemical 
action  as  ultimately  ionic  in  character. 

The  resting  forms  of  the  molecules  need 
not  be  identical  with  their  ionised  or  re- 
active forms.  Examples  are  given,  how- 
ever, of  organic  compounds  which  probably 
have  a  permanently-ionised  structure,  com- 
jjarable  with  that  of  metallic  salts.  In  other 
cases  evidence  is  quoted  to  show  that  this 
condition  results  from  a  definite  process  of 
activation. 

Attention  is  directed  to  several  pheno- 
mena which  receive  a  simple  explanation  in 
the  "crossed  polarities"  of  compounds 
which  have  hitherto  been  classed  as  "con- 
jugated." 

The  properties  of  "multipolar  ions"  are 
referred  to  as  furnishing  a  basis  for  a  novel 
theory  of  tautomeric  ions,  and  an  explana- 
tion of  their  readiness  to  yield  co-ordination- 
compounds. 

Part  III. — The  Transmission  of  Chemical 
Affinity  by  Single  Bonds. 

It  is  shown  that  the  reactivity  of  the 
methyl-group  in  ethyl  crotonate  is  in  har- 
mony with  the  theory  of  polar  double  bonds. 
It  cannot  be  used  as  a  proof  of  the  exist- 
ence of  polarised  single  bonds  (polar  co- 
valencies),  since  it  receives  a  simple  inter- 
pretation in  terms  of  Thiele's  theory  of  con- 
jugation. 

The  small  fluctuations  which  are  ob- 
served in  the  strength  of  unsaturated  acids 
as  the  double  bond  is  moved  along  the 
chain  may  be  attributed  to  steric  influences 
such  as  those  which  Pickard  has  discovered 
in  optically  active  compounds. 

The  fact  that  amino-acids  are  sometimes 
stronger  than  the  acids  from  which  they 
are  derived  is  attributed  to  the  acylous 
haracter  of  the  amino-group;  this  is  usu- 
^lly  masked  by  the  direct  neutralising 
action  of  the  basic  group. 

The  conclusion  is  drawn  that  alternate 
polarities  are  characteristic  of  conjugated 
systems,  and  are  not  developed  in  chains  of 
single  bonds,  where  both  acylous  and  basyl- 
ous  groups  produce  effects  of  constant  sign. 

Remarks  on  Some  Recent  Contributions 
to  the  Theory  of  Induced  Alternate  Polari- 


JULY  20,  1923. 


THE  CHEMICAL  NEWS 


41 


ties  in  a  Chain  of  Atoms,    by  Arthur  Lap- 
woRTU  and  Kobert  Robinson. 


The  deductions  of  the  Principle  of  In- 
duced Alternate  Polarities  put  fc«:ward  by 
Lapworth  and  by  Kermack  and  Robinson, 
though  having  little  superficial  resem- 
blance in  some  respects,  are,  on  critical 
examination,  found  to  be  identical  in 
others,  and  suggest  very  similar  applica- 
tions of  the  rule.  The  range  of  phenomena 
embraced  by  the  theories  is  very  wide,  but 
a  complete  exposition  of  the  subject  in  re- 
lation to  reactivity,  orientation,  mechanism 
of  reactions,  intramolecular  rearrange- 
ments, tautomerism,  co-ordination,  tri- 
phenylmethyl,  and  tphysical  properties  of 
substances  could  only  be  attempted  in  a 
monograph,  and  such  a  work  we  are  en- 
gaged in  preparing  for  publication.  In 
broad  outline  the  principle  may  be  said  to 
have  developed  as  a  common  expression  of 
such  well-known  rules  93  those  of  M»u-k- 
ownikoff,  Michael,  and  Crum  Brown;  in 
particular,  the  regularities  observed  in  the 
course  of  substitutions  in  aromatic  com- 
pounds had  a  specially  noteworthy  import- 
ance in  revealing  the  wider  generalisation. 
It  is  therefore  not  a  little  surprising  to  find 
that  some  recent  contributions  to  the  sub- 
ject reverse  the  order,  and,  employing  the 
general  theory  as  a  basis,  proceed  to  point 
out  that  certain  groups  of  facts  are  in  li|u- 
m<Miy  with  the  principle.  For  example. 
Fraser  and  Humphries  (The  Chemical 
News,  1923,  CXXVI..  257)  find  that  the 
theories  mav  be  applied  to  the  manifold 
problems  of  orientation  in  the  benzene 
series. 


Lowry's  theory  of  mixed  double  bonds 
fails  to  suggest  any  explanation  whatever 
of  the  most  important  facts  which  led  to 
the  recognition  of  the  "Principle  of  In- 
duced Alternate  Polarities,"  n  few  of  which 
facts  have  been  mentioned  above,  and  it  in- 
admisnible  as  an  explanation  of  the  Prin- 
ciple, since  it  introduces  theoretical  limita- 
tions where  no  distinctions  are  in  practice 
to  be  perceived.  There  are  theoretical  diffi- 
culties also.  The  remark  that  a  double 
bond  in  organic  chemistry  usually  reacts  as 
if  it  contained  one  co-valency  and  one  elec- 
trovalrncji  is.  with  its  double  qualification, 
unexceptionnble,  being  no  more  than  ji  re- 
statement f)f  the  fact  that  unsaturated  com- 
pounds undergo  polar  additive  reactions. 


Octet  Stability  in  Relation  to  Orientation 
and  Reactivity  in  Carbon  Compounds,  by 
Robert  Robinson. 

The  explanation  of  the  alternating  polar 
effect  advanced  by  Kermack  and  Robin- 
son has  apparently  been  misunderstood  in 
some  quarters,  and  further  remarks  on  the 
subject  may  not  be  out  of  place.  Two  de- 
ductions from  the  octet  theory  were  made, 
and  the  second  was  an  interpretation  of  the 
mechanism  of  addition  to  conjugated  sys- 
tems, a  precise  translation  in  electronic 
terms  of  earlier  representations  by  means  of 
partial  valency  symbolism.  Here  it  was 
shown  that  the  a-y-rule  is  in  part  a  conse- 
quence of  the  preservaticm  of  octets  in  the 
intermediate  atoms  of  the  chain,  and  the 
schemes  given  are  fundamentally  identical 
with  some  of  the  cases  presented  by  Jjap- 
worth  in  a  more  general  form.  Some  time 
before,  the  writer  had  suggested  that  the  re- 
sidual or  additional  partial  valencies  of 
'J'hiele  should  be  replaced  by  real  partial 
valencies,  which  in  the  sum  are  equivalent 
to  the  normal  valency,  and  the  interest  of 
the  translation  in  electronic  terms  partly  re- 
sided in  the  fact  that  it  was  possible  only 
when  this  real  partial  valency  theory  was 
adopted.  So  natural  does  this  suggestion 
appear  that  in  several  recent  text-books  and 
memoirs  the  theory  is  ascribed  to  Thiele, 
although  this  author  did  not  adoi()t  a  par- 
tial valency  symbol  derived  by  splitting  a 
nonnal  valency,  and  his  benzene  formula 
was  not,  as  nuiny  writers  now  assume,  more 
.symmetrical  than  that  of  Kekule. 

In  connection  with  the  first  deduction 
from  the  octet  theory,  which  concerns  what 
may  be  called  static  alternate  polarity,  mis- 
oanoeption  has  arisen.  The  octet  theory 
was  employed  in  a  more  cm-  less  symbolic 
fashion,  nuiking  no  assumptions  in  regard 
to  the  position  of  electrons  or  the  precise 
.significance  of  covalency.  The  views  ad- 
vanced arc  considered  to  be  just  as  sound 
on  the  basis  of  the  Rutherford-Bohr  atom 
as  on  the  Lewis-Langmuir  atom.  The  es- 
sential point  is  that  there  are  certain  stable 
electronic  configurations  associated  with  in- 
dividual atoms  and  termed  for  convenience 
octets;  although  if  they  are  duplets,  sex- 
tets, decets,  or  dodecets  the  argument  is 
unaffected.  The  second  stage  is  that  there 
must  be  some  f>ctct -stability  factor  which 
is  not  wholly  the  outcome  of  the  equili- 
brium of  eiectrostatie  forces.  It  should  be 
remarked  that  the  words  stnble  and  un- 
stable are  used  in  reference  to  behaviour  in 
the  course  of  reactions. 


42 


THE  CHEMICAL  NEWS. 


JULY  20,  1923. 


THE    SEPAEATION  AND   DETERMI- 
NATION OF  SODIUM  AND  LITHIUM 
BY  PRECIPITAITON  FROM  ALCO- 
HOLIC PERCHLORATE   SOLUTION.^ 

By  H.  H.  Willard  and  G.  Frederick 
Smith. 

[Contribution  from    the   Chemical    Labora- 
tories of  the  University  of  Michigan  and 
the  University  of  Illinois.] 

A  review  of  the  literature  on  the  separa- 
tion of  sodium  and  lithium  shows  that  none 
of  the  methods  so  far  suggested  is  entirely 
satisfactory.  The  solubiHty  corrections  are 
usually  large  and  the  separation  must  be 
repeated  one  or  more  times. 

Most  of  the  methods  proposed  involve 
the  extraction  of  lithium  chloride  from  the 
anyhdrous  mixed  chlorides  of  the  metals 
involved,  using  an  organic  solvent  or  mix- 
ture of  solvents  in  which  the  chlorides 
other  than  lithium  chloride  are  insoluble. 
Another  general  type  of  procedure  consists 
in  dissolving  the  mixed  chlorides  in  the 
least  quantity  of  water  necessary  for  their 
solution,  followed  by  the  precipitation  of 
the  chlorides  other  than  lithium  chloride, 
by  the  addition  of  an  organic  solvent  or 
mixture  of  solvents  in  which  the  chlorides 
precipitated  are  but  slightly  soluble,  a  cor- 
rection being  aipplied  for  this  slight  solu- 
bility. 

A  full  and  critical  discussion  of  the 
papers  relating  to  this  subject  up  to  the 
year  1912  is  given  l^y  Skinner  and  Collins.^ 
Of  the  more  recent  work,  that  of  Winlcler'' 
employs  tsobutyl  alcohol  in  an  extraction 
emthod,  more  than  one  extraction  being 
required  in  each  analysis.  The  method  is 
tedious  in  operation  and  subject  to  errors, 
because  of  the  ntimber  of  manipulations  in- 
volved. In  the  method  of  Palkin*  a  con- 
centrated aqueous  solution  of  the  mixed 
chlorides  is  precipitated  by  the  addition  of 
anhydrous  alcohol  followed  by  ether.      The 


^  The  work  done  in  connection  with  this 
paper  was  suggested  by  H.  H.  WiUnrd  and 
th  epreliminary  u'orlc  was  carried  out  at  the 
University  of  Michigan.  The  final  work 
was  done  at  the  University  of  Illinois. 

2  Skinner  and  Collins,  tf.S.  Dept.  Agr., 
Bur.  Chem.  Bull.,  1912,  CLIII. 

»  Winkler,  Z.,  anal.  Chem.,  1913,  LIT, 
628. 

*  Palkin,  Jour.  Amer.  Chew.  Soc,  1916, 
XXXVIII. ,  2326. 


chlorides  thus  precipitated  are  filtered  and 
the  small  amount  remaining  in  solution  is 
recovered  by  evaporating  to  dryness  and 
extracting  with  alcohol  and  ether.  The 
method  is  an  imiprovement  over  the  others, 
since  it  eliminates  the  solubility  correction, 
but  the  use  of  the  volatile  ether  is  a  dis- 
advantage. 

The  methods  in  which  chlorides  are  pre- 
cipitated rather  than  extracted  most  closely 
approximate  the  usual  analytical  processes 
and  are  theoretically  more  accurate.  How- 
ever, Palkin's  process  is,  strictly  speaking, 
not  really  such,  as  the  precipitant  does  not 
carry  a  component  which  enters  into  the 
composition  of  the  precipitate  formed ; 
moreover,  the  method  is  applied  to  satur- 
ated rather  than  dilute  solutions. 

The  object  of  the  present  paper  is  the 
development  of  a  method  for  the  separa- 
tion and  determination  of  lithium  and 
sodium,  based  upon  precipitation  of  the 
material  separated,  in  a  manner  analogous 
to  the  usual  analytical  practice. 

The  Method. 

The  process,  in  brief,  consists  in  the  pre- 
cipitation and  separation  of  sodium  chloride 
from  a  solution  of  the  mixed  perchlorates  of 
sodium  and  lithium  in  n-butyl  alcohol  by 
the  addition  of  a  butyl  alcohol  solution  of 
hydrogen  chloride  according  to  the  reaction, 
NaClO,  +  HCI  =  NaCl  +  HCIO,.  The  re- 
agent is  added  to  the  solution  of  the  iper- 
chlorates  until  a  6  per  cent,  acid  concen- 
tration is  attained.  The  precipitated 
sodium  chloride  is  filtered  on  a  weighed 
Gooch  crucible,  washed  with  a  6-7  per 
cent,  solution  of  hydrogen  chloride  in  butyl 
alcohol,  dried  at  250°  and  ignited  for  a  few 
minutes  at  600°.  The  lithium  chloride, 
after  removal  of  the  organic  matter  by  eva- 
poration, is  determined  by  conversion  to 
lithium  sulphate,  a  correction  being  applied 
for  the  almost  negligible  amount  of  sodium 
chloride  remaining  in  the  filtrate.  In  some 
cases  the  reagents  give  a  slight  blank.  Po- 
tassium cannot  be  present  since  its  per- 
chlorate  is  insoluble  in  alcohol. 

Preparation  of  Materials. 

Normal  Butyl  Alcohol. — This  material  is 
readily  obtainable  on  the  market  at  the 
present  time  at  a  moderate  price.  The 
alcohol  used  in  this  research  had  a  boiling 
range  of  112-118°  and  a  density  of  0.8065  at 
25°/4°;  60  per  cent,  of  this  product  boiled 
within  a  range  of  1°  of  the  true  boiling 
point.     This  fraction,  when  dried  by  reflux- 


JULY  20,  1923. 


THE  CHEMICAL  NEWS. 


43 


ing  \\  ith  a  slight  excess  of  metallic  calcium, 
perLuients  were  also  carried  out  usiqg  alco- 
had  a  boiling  range  of  116.2-116.7°  and  a 
density  of  0.8060  at  25°/ 4°.  Half  of  this 
fraction  boiled  within  a  range  of  0.05°.  In 
most  of  the  work  the  60  per  cent,  fraction, 
obtained  as  described  above,  was  used.  Ex- 
hol  of  widely  different  constants,  the  data 
concerning  which  will  be  recorded  later. 

Perchloric  Acid. — The  method  of  Willard^ 
was  used  for  the  preparation  of  the  per- 
chloric acid.  It  was  twice  distilled  under  a 
pressure  of  from  5  to  15  mm.  and  c<Mitained 
about  72  per  cent.  HCIO..  Ten  g.  of  this 
mati-nal  when  eva|>orated  in  a  platinum 
crucible  gave  an  almost  unweighable  resi- 
flue  after  ignition. 

Sodium  Chloride. — An  imported  product 
of  hightst  purity  was  used. 

Sodium  Ferchloratc. — This  material  was 
prepared  by  treatment  of  the  purest  sodium 
carb<>nat<'  with  a  slight  excess  of  dil.  per- 
chloric acid.  The  anhydrous  sodium  per- 
chlorate  was  obtained  by  crystallisation 
above  50®,  using  centrifugal  drainage.  The 
pimluct  thus  obtained  was  dried  in  a  cur- 
rent of  dry  air  at  a  temperatruc  of  250°,  To 
obtain  samples  of  sodium  tp<rchl<M^te  for 
the  imai^tical  separations,  pure  sodium 
chloride  in  weighed  portions  was  evnjmr- 
ated  on  a  hot  plate    with  a  slight  '  '< 

perchloric    acid  until    fumes    of    [x  . 

acid  were  no  longer  evolved. 

Lithium  Chloride. — This  material  was 
prepared  from  a  product  which  contained 
some  sodium  chloride.  It  wa«  freed  from 
the  latter  by  solution  in  hot  butyl  alcohol 
under  a  reflux  condenser.  The  solution  was 
cooled  and  the  sodium  chloride  filtered  ()flf. 
The  lithium  chloride  in  the  filtrate  was  n- 
covered  by  evaporation  in  a  platinum  dish 
to  a  party  mass  which  wjvs  dried  in  an  elec- 
tric oven  at  100".  It  was  further  heated  in 
a  muffle  at  500°,  and  finally  fused  in  a  ciir- 
r«'nt  of  hydrogen  chloride  dried  with  sul- 
phuric acid.  The  product  thus  obtained 
was  cooled,  crushi-d.  and  powdered  under 
conditions  which  insured  no  contact  with 
atmospheric  moisture.  It  was  used  only  in 
the  solubility  determinations. 


*  Wiflord,  .lour.  Awcr.  Cheni.  Soc,  1912 
XXXIV..   1480. 


Lithium  Pcrchlurate. — The  method  em- 
ployed in  the  propai-ation  of  this  material 
was  that  described  by  Richards  and  Wil- 
lard.*  Lithium  nitrate  was  purified  by  re- 
crystallisation  and  then  precipitated  by  the 
additicm  of  hydrotluoric  acid.  The  lithium 
tluoride  was  converted  to  perchlorate  by 
evaporation  wilh  pure  perchloric  acid.  This 
was  then  recrystallised  from  water  with 
centrifugal  drainage,  platinum  vessels 
Ih-ing  used  throughout.  The  lithium  per- 
chlorate' trihydrate  thus  obtained  was  de- 
hydrated by  fusion  in  a  current  of  dry  air  at 
250°. 

Sam()les  of  this  anhyrdous  lithium  per- 
chlorate were  weighed  into  platinum  cru- 
cibles contained  in  glass-stoppered  weigh- 
ing bottles  and  again  fused  by  placing  the 
crucibles  in  a  drying  tube  at  250°,  through 
which  passed  a  current  of  dry  air.  The  cru- 
cibles and  contents  were  then  replaced  in 
their  weighing  Imttles,  cooled,  and  re- 
wiighed.  The  original  weight  was  usually 
lowered  a  fraction  of  a  milligram  due  to  the 
very  slight  hygroscopic  nature  of  anhydrous 
lithium  perchlorate. 

The  Solution  of  Hydrogen  Chloride  in 
lilityl  Alcohol. — Butyl  alcohol  wAs  treated 
with  hydrogen  chloride  generated  in  the 
usual  way  by  the  action  of  cone,  sulphuric 
acid  on  sodium  chloride  or  cone,  hydro- 
chloric acid;  200  cc.  of  20  per  cent,  solu- 
tion could  be  pntpared  in  two  or  three 
hours.  For  testing  the  strength  of  these 
solutions  an  hydrometer  serves  admirably. 
For  use  in  this  connection  a  density- 
concentration  curve  was  construct<>d  be- 
tween the  limits  of  0  and  20  per  cent,  hy- 
drogen chlcride. 

Conditions  Affkctino  the  Precipitation 

OF    iH)DIUM   CHLoKIDK   FttoM   A    SOLUTION  OF 

Sodium  Pbrchlokatk  in  Butyl  Alcohol. 

Several  fjujtors,  some  unexpected,  were 
found  to  influence  the  quantitative  separa- 
tion of  sodium  and  lithium  from  solution  in 
anhydrous  butyl  alcohol  by  the  addition  of 
the  solution  of  hydrogen  chloride  in  butyl 
alcohol. 

(To  he  Continued.) 


•  Richards    and     ]Villard,    Jour.     Amer. 
Chem.  Soo.,  1910,  XXXII.,  4. 


44 


CORRESPONDENCE . 


THE  CHEMICAL  NEWS. 


JULY  20,  1923. 


ISOTOPES  OF  COPPEE. 

To  the  Editors  of  The  Chemical  News. 

Gentlemen,  —  Readers  of  this  Journal 
niay  remember  that  I  made  an  attempt  to 
prove  that  copper  was  composed  of  whole- 
number  isotopes  in  such  proportion  as  to 
give  a  mean  value  as  the  atomic  weight  of 
this  element,  viz.,  63.57.  The  values  sug- 
gested in  this  Journal  of  March  20,  1914, 
page  143,  were  63  and  67. 

W.  D,  Harkins,  in  The  Journal  of  the 
American  Chemical  Society  for  June,  1923, 
on  page  1429,  predicts  the  values  63  and  65. 

Now,  A.  J.  Demipster,  in  Nature  of  Jul^ 
7,  1923,  records  having  obtained  positive 
rays  of  copper  by  means  of  a  molybdenum 
furnace  heated  with  a  coil  composed  of 
molybdenum  wire  embedded  in  alundum 
cement.  Three  isotopes  were  observed,  hav- 
ing provisionally  the  values  62,  64,  66. 

Should  Dempster's  values  be  confirmed 
by  further  experiments,  it  will  show  the 
utter  futility  of  attempting  precise  predic- 
tions based  uipon  rather  meagre  evidence, 
but  the  general  result  indicated  as  far  back 
as  1914  will  have    been  confirmed. — Yours, 

&C.,  F.   H.   LOHING*. 


NOTICES  OF  BOOKS. 

Atomic  Strxictvre  and  Spectral  Lines, 
by  A.  Sommerfeld,  Translated  from  the 
third  German  Edition  (1922)  by  H.  L. 
Brose.  Pp.  XIII.  +  626  and  125  Figures 
in  text.  London :  Messrs.  Methuen  & 
Co.,  Ltd.,  36,  Essex  Street,  W.C.2. 
1923.    32s.  net. 

It  is  one  thing  to  possess  a  book  and  an- 
other thing  to  understand  all  that  is  in  it. 
Prof.  Sommerfeld 's  book,  now  a  classic, 
contains  much  that  requires  very  special 
study  to  understand  fully,  but  there  is  a 
great  deal  of  information  clearly  presented, 
thanks  to  the  translator;  and  all  who  are  in- 
terested in  the  fundamental  characteristics 
of  the  atom,  as  studied  and  investigated 
more  particularly  by  the  physicist,  should 
add  this  volume  to  their  library,  and  study 
it. 

In  order  that  the  reader  may  form  some 
idea  in  advance  of  the  scope  of  this  work, 
the  following  sub-headings  have  been 
selected  out  of  a  total  number  of  about  100 : 
Atomicity  of  electricity ;  ions  and  electrons ; 


photo-electric  effect  and  its  converse; 
glimpses  of  the  quantum  hypothesis;  radio- 
activity; nuclear  charge  and  atomic  num- 
ber; the  atom  as  a  planetary  system;  laws 
of  radio-active  displacement'  and  the  theory 
of  isotopes;  peripheral  and  central  proper- 
ties of  the  atom ;  visible  and  Kontgen  spec- 
tra; configurations  of  the  inert  gases;  Lane's 
discovery ;  survey  of  the  K,  L,  and  M  series; 
corresponding  limits  of  excitation;  K  series 
and  its  bearing  on  the  periodic  system;  L 
and  M  series;  doublet  relationships;  intro- 
duction to  the  quantum  theory ;  empirical 
data  about  the  spectra  of  hydrogen ; 
principle  of  combination;  Bohr's  theory  of 
the  Balnier  series;  elliptic  orbits  in  the  case 
of  hydrogen;  quantising  the  spatial  position 
of  Kepler  orbits ;  iTieory  of  the  magneton ; 
spherical  wave  and  its  propagation;  conser- 
vation of  energy  and  momentum ;  principje 
of  selection  and  rule  of  polarisation ;  orbits 
of  hydrogen  in  the  Stark  effect;  Zeeman 
effect;  quantum  theory  of  the  series 
scheme;  principle  of  selection  for  the  azi- 
muthal  quantum ;  testing  the  series  scheme 
by  the  method  of  electronic  impact ;  spec- 
troscopic law  of  displacement  and  law  of 
exchange ;  visible  bands ;  meaning  of  the 
head  of  the  band;  law  of  the  edge  of  the 
band;  many  lines  spectra;  preliminaries 
concerning  the  theory  of  relativity;  vari- 
ability of  mass  and  inertia  of  energy ;  rela- 
tivistic  Kepler  motion;  fine  structure  and 
the  relativity  correction;  doublets  of  the 
Rontg^  spectra;  spectroscoipic  confirma- 
tion of  the  theory  of  relativity,  Bohr's  prin- 
ciple of  correspondence,  &c. 

Prof.  Sommerfeld,  as  we  all  know,  has 
developed  a  theory  of  the  fine  structure 
based  upon  Bohr's  classical  work  in  ex- 
planation of  the  spectra  of  hydrogen  and 
helium,  but  the  theory  in  seme  respects 
extends  to  all  elements.  In  the  "  theory  of 
the  fine  structures  there  is  a  confluence  of 
the  three  main  currents  of  modem  research 
in  theoretical  physics,  namely,  the  theory 
of  electrons,  the  theory  of  quanta,  and  the 
theory  of  relativity.  This  is  exhibited  in  a 
particularly  vivid  way  in  the  way  our  fine- 
structure  constant  a  is  built  up: — a  = 
^ne^jhc.  Here  c  is  the  representative  of 
the  theory  of  electrons,  h  is  the  ivorthy  re- 
presentative of  the  quantum  theory,  and  c 
comes  from  the  theory  of  relativity  and,  in- 
deed, characterises  it  in  comparison  with 
the  classical  theory." — Page  525. 

From  the  foregoing  it  will  be  seen  that  in 
developing  a  theory  of  the  atom  based  upon 
electron  movements,  much  of  modem  phy- 


JULY  20,  1923. 


THE  CHEMICAL  NEWS. 


45 


sics  has  been  brought  into  the  problem,  and 
on  this  account  the  book  becomes  a  treatise 
of  considerable  sco|>e. 

Apart  from  the  more  rigorous  treatment, 
there  are  ideas  introduced  in  a  suggestive 
way  which  will  afford  food  for  those  in 
search  of  advance  information.  As  an  ex- 
ample, the  question  of  two  kinds  of  electri- 
city is  not  made  so  evident  by  current  elec- 
tricity, which  is  a  flow  of  electrons,  for  in 
terms  of  electrons  the  unity  idea  is  promi- 
nent. In  atomic  physics,  however,  a  posi- 
tive charge  signifies  more  than  the  absence 
of  a  negative  charge,  since  "  positive  elec- 
tricity is  always  associated  with  ordinary 
matter."  The  difference,  therefore,  im- 
plies "  types  of  electricity  that  differ  not 
only  in  sign  but  also  in  nature,"  which  are 
individualised  in  the  electron  and  the  posi- 
tively charged  H  atom.  Quoting  from  pnge 
22,  "  We  can  picture  an  atom  (or  a  body) 
as  highly  charged  negatively  as  we  like,  that 
is,  we  cnn  a<id  to  it  any  number  of  negative 
electrons";  whereas,  we  can  only  incrense 
the  positive  charge  "  to  a  certain  maximum 
jimount  so  long  as  we  do  not  considtrably 
alter  the  mass."  We  can  remove  from  the 
atom  only  as  many  electrons  as  it  possesson 
at  the  outset.  According  to  the  theory  uf 
relativity,  no  inherent  or  relative  change  in 
charge  can  take  place.  Electricity  thus  be- 
comes a  Hubstance,  but  there  are  two  such 
substances,  "  The  charge  and  the  mans 
arc  hereby  indissolnbly  associated  with  one 
another,  the  negative  charge  with  the  elec- 
tronic mass,  the  positive  charge  with  fhe 
hydrogen  mass." 

In  discussing  polarisation,  Prof.  Sommer- 
feld  states  that  "  it  signifies  that  a  ray 
favours  a  certain  plane  passing  through  it 
more  than  the  one  perpendicular  fo  this 
plane."  The  early  idea  that  Hontgen  ray-* 
were  longitudinal  vibrations  involves  (he 
scheme  of  symmetry,  and  therefore  polari- 
sation becomes  impossible,  since  Barkla 
discovered  that  primary  Rcintgen  rays  are 
partly  polarised,  and  that  secondary    Hone- 

Sen  rays  are  wholly  ipolarised  in  certain 
irections.  The  longitudinal  vibration 
theory  thus  breaks  down,  and  we  are  left 
with  the  interpretation  that  the  direction  of 
vibration  does  not  correspond  with  the 
direction  of  motion  of  matter,  but 
that  the  vibration  is  that  of  elec- 
tric force  which  "  participates  in  the 
wave-radiation."  In  wireless  telegraphy 
the  emission  is  zero  in  the  direction  of  the 
alternating  current,  corresponding  to  its 
component    of    acceleration,    but    at    right 


angles  to  the  antenna  the  emission  becomes 
a  maximum. 

The  theory  of  fine -structure,  which  Prof. 
Sonimerfeld  has  developed  with  great 
mathematical  skill,  follows  when  the  Bohr 
Cheory  of  stationary  states  involving  the 
quantum  theory  is  analysed  by  means  of 
relativity  mechanics  involving  the  change 
of  mass  of  the  electron  with  a  change  in  its 
(H-bital  velocity,  so  that  those  lines  which 
were  regarded  as  coincident  become  separ- 
ated into  a  configuration  of  closely  asso- 
eiatcd  lines  owing,  as  is  evident,  to  the 
relativity  effect  involved.  The  velocity  of 
the  electron  is  less  at  the  aphelion  than  at 
the  perihelion,  and  this  difference  becomes 
greater  as  the  eccentricity  of  the  orbit  in- 
creases. Quoting  from  page  475:  "  Thus 
the  observation  of  the  fine-structures  dis- 
cloees  the  whole  mechanism  of  the  intra- 
atomic  motions  as  far  as  the  motion  of  the 
perihelion  of  the  elliptic  orbits.  The  com- 
plex of  facts  contained  in  the  fine-structures 
has  just  the  same  importance  for  the 
special  theory  of  relativity,  and  for  the 
atomic  structure  as  the  motion  of  Mercury's 
perihelioo  for  the  general  theory  of  relativ- 
ity." It  is  important  to  note  that  without 
the  theory  of  relativity  it  would  have  Ix'en 
impossible  to  develop  the  theory  of  fine 
structure. 

In  a  work  of  this  magnitude  errors  are 
bound  to  occur  in  the  first  translated  edi- 
tion. These  do  not,  however,  de- 
tract frr  m  the  value  of  the  book.  On  p. 
12,  5th  line  from  top,  captivity  would  be  a 
better  word  than  "  capacity."  Two  lines 
further  down,  on  the  same  page,  the  word- 
ing, "  Although  they  here  also  soon,"  could 
be  improved.  On  p.  23,  the  expression, 
"  soup-plate,"  seems  to  imply  a  shape  not 
strictly  accurate,  and  it  is  not  in  dignified 
ke<'ping  with  the  subject. 

On  p.  84  it  is  stated  that  "isotopic  ele- 
ments cannot  be  separated  from  one  another 
by  chemical  means  at  all,  and  exhibit  iden- 
tical physical  properties  throughout." 
Atomic  mass  is  a  physical  property  and.  in 
the  case  of  some  isotopes  of  a  given  ele- 
ment, it  varies  to  the  extent  of  eight  units, 
as  stated  in  the  same  paragraph.  The  above 
stmtenoe  is  faulty  in  two  respects;  for  (I), 
there  are  some  physical  properties  which 
are  not  identical,  and  (2)  the  word  element 
is  more  correctly  used  in  a  collective  sense, 
and  it  should  not  be  used  synonomously 
with  the  word  atom  in  this  connection.  An 
element  is  a  collection  of  atoms  of  the  same 
<'hemical  kind  with  one  common  atomic 
numl)er,  except    in  the  case    of  radio-active 


46 


TH£1  CHEMICAL  NEWS. 


JULY  20,  1923. 


elements  which  receive  different  names 
owing  to  their  radio-active  properties,  oi 
radio-active  origins,  differing. 

On  p.  101,  7th  line  from  bottom,  "inner" 
should  read  outer.  On  p.  102,  20th  line  from 
top,  "elements"  should  read  electrons.  On 
the  same  page,  and  on  p.  86,  the  practice 
of  placing  mass-numbers  partly  below  the 
type  line  should  be  discouraged ;  they  should 
be  above  it,  or  level  with  it,  otherwise  con- 
fusion with  chemical  notation  arises:  The 
meagre  reference  to  Sir  J.  J.  Thomson's 
pioneer  work  on  the  atom  is  a  serious  omis- 
sion in  a  book  of  this  scope.  The  general 
get-up  and  printing  of  the  book  leaves  no- 
thing to  be  desired.  The  up-to-date  and 
complete  X-ray-spectra  tables  in  Chapter 
III.  will  be  appreciated. 


The  CoHfiiitutio)!  of    M after,    bv    Max 
BoKN,  translated  bv  E.  W.  Blair,  D.I.C, 
B.Sc,  A. I.e..  andT.  S.  Wiieelek,  B.Sc, 
A.R.C.S.I..  A. I.e.   Pp.  VII.   +  80,  Lon- 
don: Methuen  &  Co.,  Ltd.,  36,  Essex  St., 
W.C.2.     1923.     Price  6s. 
This  volume  is  based    upon  three  impor- 
tant essays  which  Prof.  Born  has  amplified 
and  published  in  book  form.      The  import- 
ance of  the  subject  matter  may  be  inferred 
from  the  fact  that  a  second  edition  was  soon 
demanded,  and  upon  it  the  present  transla- 
tion is  based. 

An  outline  is  given  of  the  knowledge  of 
atomic  structure  gained  during  the  last  few 
years,  esipecially  as  the  result  of  much 
patient  investigation  in  the  field  of  Atomic 
Physics.  •* 

The  methods  of  measuring  the  charge  and 
mass  of  an  electron  and  the  various  models 
of  atomic  structure  are  described,  together 
with  such  matters  as  the  X-ray  diffraction 
by  crystals,  and  recent  work  on  X-ray  spec- 
tra. 

Reference  is  made  to  the  general  theoreti- 
cal development  of  the  subject  by  Som- 
merfeld  and  by  Kossel. 

Prof.  Born  further  develops  his  outline  of 
the  constituti  u  of  matter  from  a  study  of 
the  inter-at  mic  forces  in  solids. 

There  is  no  index,  but  an  extensive  biblio- 
graphy is  appended  to  each  section. 

It  will  be  realised  that  little  more  than  a 
critical  examination  of  the  results  of  physi- 
cal investigations  in  Atomic  Science  is  pos- 
sible in  Prof.  Bom's  admirable  survey  of 
the  subject,  which  does  not  prefend  to  be  an 
exhaustive  account  of  all  the  Atomic 
Theories. 


The  Department  of  Scientific  and  Indus- 
trial Reseai'ch  has  issued  a  Report  of  the 
Fuel  Research  Board  for  the  Years  1928-1^3. 
— First  Section :  The  Production  -of  Air 
Dried  Peat.  Pp.  VII.  +  146.  Price  5s.  4d. 
post  free. 

The  investigations  made  since  1919  by 
Prof.  Pureed  and  his  assistant,  Mr.  E.  J. 
Duffy,  B.Sc,  on  the  production  and  utili- 
sation of  air-dried  peat  are  contained  in  this 
valuable  report. 

In  1921,  the  report  of  the  Irish  Peat  In- 
quiry Committee  was  published,  together 
with  recommendations  and  other  docu- 
ments showing  why  it  was  not  found  pos- 
sible to  carry  out  the  large  experimental 
scheme  of  peat  winning  recommended. 

Peat,  as  found  in  undrained  Irish  bogs, 
contains  as  much  as  92  to  95  per  cent,  of 
water.  Draining  reduces  it  to  between  88 
and  91  per  cent. 

Peat  cannot  be  usefully  employed  as  a 
fuel  until  the  moisture  content  is  below  30 
per  cent.  No  economic  method  of  drying 
by  artificially  generated  heat  is  yet  avail- 
able, and  where  peat  is  used  commercially 
it  has  been  air-dried.  The  report,  there- 
fore, deals  only  with  air-dried  peat. 

Mr.  Duffy  has  investigated  the  proper- 
ties of  air-dried  peat  and  the  factors  which 
govern  the  rate  of  drying  of  both  hand-cut 
and  machine-formed  blocks.  His  report  is 
given  in  an  ajppendix. 

Professor  Purcell  visited  Canada  in  1920, 
to  see  the  work  the  Canadian  Peat  Commit- 
tee was  carrying  out  for  the  Federal  and 
Provincial  Governments  on  the  mechanical 
production  of  peat,  and  in  1921  and  1922  he 
visited  Germany  and  Sweden  for  the  pur- 
pose of  studying  the  latest  practices  in  these 
countries.  His  reports  are  also  given  in 
appendices. 

The  winning  of  peat  on  a  small  scale  has 
been  successfully  practised  from  time  im- 
memorial, but  the  problem  of  large  scale 
production  is  far  more  difficult. 

Professor  Purcell  has  dealt  with  these 
difficulties  and  has  visualised  possible 
schemes  for  peat  winning  on  a  scale  of 
100,000  tons  per  annum  from  one  bog  area 
over  a  period  of  years. 

This  report,  which  is  very  fully  illus- 
trated, may  be  had  from  H.M.  Stationery 
Office,  Imperial  House,  Kingsway,  W.C.2, 
and  also  from  the  provincial  and  colonial 
offices  and  agencies. 


JULY  20,  1923. 


THE  CHEMICAL  NEWS. 


47 


Alcoholic  Fermentation,  by  Arthur 
Harden,  Ph.D.,  D.Sc,  F.K.S.  Pp.  194. 
London :  Messrs.  Longmans,  Green  & 
«o.,  39,  Paternoster  Row,  E.C.4.  19*23. 
6s.  6d.  net. 


The  subject  of  alcoholic  fermentation  has 
been  of  interest  and  importance  from  the 
earUest  times. 

Periodically  in  the  development  of  scien- 
tific knowledge  some  great  advance  has 
been  made  towards  the  elucidation  of  the 
true  mechanism  of  the  chemical  changes  in- 
volved in  this  process. 

One  of  the  earliest  discoveries  was  that  of 
van  Helmont  who,  in  the  17th  century;, 
distinguished  the  evolution  of  carbcMi  di- 
o.xide  (gas  sylvestre)  in  the  course  of  alco- 
holic fermentaticm. 

The  next  real  step  forward  was  made  al- 
most simultaneously  (1837)  but  inde{)on- 
(lently  by  three  observers,  Cagniard-Latour. 
Theodor  Schwann,  and  Kiit/inp;,  who  de- 
monstrated that  the  yeast  which  performed 
the  fernuntation  was  a  living  organism. 
This  paved  the  way  for  Pasteur's  re- 
searches, which  mark  the  next  advance, 
since  he  conclusively  showed  that  there 
could  be  no  fermentation  without  Hfe. 

Finally  there  is  Buchner's  discovery 
(1897)  of  the  enzyme,  zymase.  This  auth- 
ority showed  that  the  action  of  the  yeast  is 
due  to  ferments  secreted  by  the  cells  of  the 
yeast  plant. 

It  is  now  further  known  that  zymase, 
which  is  essential  for  the  fermentation  of 
sugar,  only  docs  so  in  the  presence  of  a 
second  body,  called  for  want  of  a  better 
term,  the  co-enzvme.  The  nature  of  this 
mysterious  co-adjutor  is  at  present  un- 
known. 

It  withstands  heating  to  100°  C,  and  is 
also  dialysable  and  may  be  simpler  in  con- 
stitution  than  zymase. 

Another  essential  condition  for  the  fer- 
mentation of  sugar,  as  Prof.  Harden  him- 
self has  proved,  is  the  (presence  of  a  phos- 
phate. The  way  in  which  this  substance 
enables  the  decomposition  of  the  carbohy- 
drate into  carbon  dioxide  and  alcohol  fand 
other  substances)  to  occur  is  very  ably  de- 
scribed. 

Prof.  Harden 's  monograph  constitutes  a 
most  important  contribution  to  Organic 
Chemistry,  and  the  border  subject  of  Bio- 
chemistry. J.G.F.D. 


Supplementary  Notes  on  Gravimetric 
Analysis,  by  W,  Low^soN,  B.Sc,  F.I.C 
Pp.  54.  London :  Messrs.  Longmans, 
Green  &  Co.,  39,  Paternoster  Row,  E.C.4. 
1923.     2s.  6d. 

In  this  little  volume  the  author  has  col- 
lected t(^ether  those  important  points  in 
manipulative  work,  which  are  seldom  given 
in  ordinary  laboratory  manuals. 

It  is  just  these  essential  hints  that  enable 
the  average  student  to  acquire  skill  and 
accuracy  in  conducting  quantitative  analy- 
ses. 

This  section  of  practical  chemistry  is  apt 
to  become  tedious  to  some  students,  especi- 
ally if  through  lack  of  supervision  or  help 
thev  unconsciously  neglect  some  appar- 
ently trivial  operation,  or  accidentally  in- 
tnjduce  an  errt>r  into  their  work,  thus  feel- 
ing discouraged  by  poor  results. 

The  book  should  therefore  be  of  service 
to  demonstrators.  It  includes,  in  spite  of 
its  title,  a  chapter  on  the  calibration  of 
volumetric  apparatus,  as  well  as  others  on 
some  tyfiical  Estimations  and  Occlusion. 

Thf  intro«luct<)ry  section  on  Apparatus 
and  Manipulation  contains  much  useful  in- 
fonnation  for  beginners. 


BOOKS  liECElVEJ). 

A  Trent inc  on  Chemistry,  by  The  liight 
Honourable  Sir  H.  E.  Roscob,  F.R.S., 
and  C.  ScHOHLKMMKK,  F.R.S.  Pp.  XII.  + 
829.  Vol.  11..  Part  I.  1923.  Messrs. 
Macmillan  k  Co..  Ltd.,  St.  Martin's  St., 
W.G.2.     508.  net. 

A  Treatise  on  Chemistry,  by  The  Right 
Hrmourable  Sir  H.  E.  Roscoe,  F.R.S., 
and  C.  SciioRLKMMBR,  F.R.S.  Pp.  VIII.  + 
1.568.  Vol.  II..  Part  II.  1928.  Messrs. 
Macmillan  A  Co.,  Ltd.,  St.  Martin's  St., 
W.C.2.    60b.  net. 

Orijanic  Chemistry,  by  Ira  Rbmsen,  Re- 
vised and  Enlarged  by  W.  R.  Orndorff, 
Il^r.D.  Pp.  XI.  +  567.  1923.  Messrs. 
Macmillan  A  Co.,  Ltd.,  St.  Martin's  St., 
VV.C.2.     lOs.  net. 

The  Structure  of  the  Atom,  by  E.  N.  da 
C.  Andrade,  D.Sc.  (Lond.),  Ph.D.  (Hei- 
DKLBKRo).  Pp.  XIV.  +  814.  1928.  Messrs. 
Bell  A  Sons.  Ltd..  York  House,  Portugal 
Street,  W.C.2.     16s.  net. 


48 


THE  CHEMICAL  NEWS. 


JULY  20,  1923. 


Quantitative  Chemical  Analysis  and  In- 
organic Preparations,  by  R.  M.  Gaven, 
D.Sc.  (LoND.),  F.I.C.  Pp.  VI.  +  156. 
1923.  Messrs.  Blackie  &  Sons,  Ltd.,  50, 
Old  Bailev,  E.G.    3s  6d.  net. 


The  Paper-Makers'  Directory  of  AU 
Nations.  Pp.  XLIX.  +  971.  Thirty-second 
Edition.  1923.  Messrs.  Dean  &  Son,  Ltd., 
Debrett  House,  29,  King  Street,  Govent 
Garden,  W.G.2.     21s. 


SYNTHESIS  OF  a-DIKETONES  BY 

MEANS  OF  ORCtANO-ZING 

DERIVATIVES. 

By  E.  E.  Blaise. 


The  author  has  previously  shown  that 
the  condensation  of  zinc  propyl  iodide  with 
oxalylbisoxyisobutyryl  chloride  gave  a  mix- 
ture containing  propyl-glyoxal  and  dibuty- 
ryl  biscycloacetatoxyisobuty  rates.  After 
alcoholysis  of  the  mixed  products  the  latter 
remains  alone.  This  formed  a  crystalline 
substance,  which  melted  at  55-80°,  and  was 
a  mixture  of  the  internally  compensated 
and  the  racemic  isomers.  These  were  only 
separated  by  slow  crystallisation  from 
methyl  alcohol,  followed  by  mechanical 
separation  of  the  two  kinds  of  crystals  iso- 
lated. The  pure  substances  melted  at  72° 
and  82°  respectively,  and  boiled  at  168°  C. 
under  a  pressure  of  13  mm.  The  hydroly- 
sis of  the  mixed  isomers  by  means  of  hy- 
driodic  acid  was  accompanied  by  reduc- 
tion, and  propyl  n-butyl  ketone  was 
formed,  which  boiled  at  163°  and  gave  a 
semicarbazone.  This  melted  at  96°  C.  Hy- 
drolysis by  means  of  a  mixture  of  hydro- 
chloric and  acetic  acids  gave  a  60  per  cent, 
yield  of  dibutyryl.  It  is  a  yellow  liquid, 
b.ip.  61.5°  G.  under  a  pressure  of  14  mm. 
The  dioxime  melted  at  181-182°,  and  the 
disemicarbazone  not  below  250°. 


{From  Compt.    rend., 
1148-1160.) 


1923,     GLXXVI., 


XH18  lisi.  is  specially  compiled  for  The  Chemical 
News,  by  MessrB.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chanoeoy  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Maxks, 
and  Designs  can  be  obtained  gratuitously. 


Latest  Patent  Applications. 


16138— Coley,     H.     E.— Reduction     of       sulphides. 
June  21. 


Specifications  Published  this  Week. 

198705— Plauson,  Dr.  H.— Process  and  apparatus 
for  the  recovery  of  oils,  bituminous  mat- 
ter, tar  and  resin  from  bituminous  shale, 
oil-bearing  sands,  bleaching-earths,  peat, 
brown  ooal,  coal  and  wood. 

198825— Chemische  Fabriken  vorm.  Weiler-ter- 
Meer. — Process  for  impregnating  wood. 

198829— Soc.  of  Chemical  Industry  in  Basle.— 
Manufacture  of  a  new  derivative  of  pyra- 
sM>lone  and  of  new  dyestuffs  therefrom. 

198855— Royal  Baking  Powder  Co.— Apparatus  for 
effecting  chemical  reactions  by  means  of 
amalgams. 

19897.5— Vains,  A.  R.  De.— Processes  for  dissolving 
the  organic  products  obtained  by  the 
chlorination  of  cellulose  material. 


Abstract  Published  this  Week. 

197223— .Sodium  chromate.— Baumgartner,  E.,  of  6, 
Kamstrupsti,  Roskilde,  Denmark. 


Sodium  bhromate  is  obtained  by  heating  in  a 
current  of  hot  air  in  a  mxiffle,  a  mixture  of  chro- 
mium ore  with  sodium  carbonate  with  or  without 
lime  or  calcium  carbonate.  The  materials  are 
formed  into  briquettes  and  are  arranged  in  the 
muffle,  for  instance,  in  rows  with  spaces  between 
Ko  as  to  allow  contact  with  the  current  of  air. 
Stirring  or  turning  of  the  charge  is  unnecessary 
and  undesirable  and  the  operation  is  complete  in 
one  burning. 


Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each, 


JULY  27.  1923. 


THE  CHEMICAL  NEWS. 


49 


THE    CHEMICAL  NEWS, 


VOL.  OXXVII.      No.  3302. 


BRIDGING  THE  GAP  IN  THE 
SPECTKUM.* 

Hertz's  classical  experiments  with  elec- 
tric waves  in  1888  not  only  paved  the  way 
for  the  develoipment  of  wireless  communi- 
cation, but  showed  that  these  waves,  as  in- 
dicated by  Maxwell's  electromagnetic 
theory  of  light,  were  waves  of  the  same  kind 
as  light,  for  they  could  he  bent  by  prisms 
and  shown  to  be  a  part  of  a  spectrum.  The 
electric  waves  which  Hertz  produced  in  his 
laboratory  were  60  cms.  lonj^. 

It  was  not  until  1895  that  Lebedew  ob- 
tained electric  waves  which  had  a  length  of 
6  mms.  Lampa,  about  the  same  time,  had 
produced  waves  of  4  mms.  in  length. 
Mobius,  in  1918,  confirmed  the  general  re- 
sults of  the  two  foregoing  investigators,  but 
he  came  to  the  conclusion  that  their  waves 
were  respectively  10  and  7  mms.  Icmg. 
Mobius,  from  experimental  considerations, 
deduced  evidence  that  in  this  case  anything 
shorter  than  the  above  were  ripples  as  dis- 
tinct froTn  regular  waves. 

At  this  time,  following  Langley's  re- 
searches on  the  solar  spectrum,  Rubens  and 
Pasohen  investigated  the  infra-red  end  of 
the  stpectrum  and  detected  waves  9.4/x. 
which  is  Ifi  times  longer  than  the  wave- 
length of  yellow  light. 

In  1807  Rubens  and  Nichols,  by  means  of 
a  multiple-reflection  method,  succeeded  in 
extending  the  boundaries  of  the  infra-red 
spectrum  ten-fold.  Then  the  former  inves- 
tigator obtained  a  further  extension  by  em- 
ploying Wood's  metho<l  of  focal  isolation. 
Following  on  this,  Rubens  and  von  Bayer, 
in  1911,  measured  infra-red  waves  up  to 
0.320  mm.  in  length. 

There  remained  a  gap  between  the  heat 
waves  and  those  produced  by  electrical  ap- 
paratus, but  this  gap  Nichols  and  Tear  have 
now  bridged  by  electrical  waves,  using  a 
metho<l  which  is  briefly  described  in  the 
Proceedings  of  the  National  Academy  of 
Sciences  of  U.S.A.,  Vol.  IX.,  No.  6,    June, 

*  Compihd  from  Nichols  and  Tear's  paper 
in  the  "  I'mceeditKis  of  the  National  Acn- 
detny  of  Sciences  of  U.S.A.,"  Vol.  IX.,  No. 
6,  June,  1923. 


Rev.,  1896-7,  Vol.  IV.,  ip.  297),  which  re- 
ceived the  waves.  The  usual  blackened 
vaneg  in  this  radiometer  were  replaced  by 
mica  strips,  on  which  were  deposited  bright 
metallic  platinum.  By  shielding  the  vanes 
on  one  side,  their  rotation  was  obtained,  as 
the  action  of  the  electric  waves  produced 
oscillating  currents  in  the  metal,  which  per- 
ceptibly heated  it  owing  to  its  ohmic  re- 
sistance, and  thus  gave  rise  to  the  well- 
known  radiometer  action.  The  short  elec- 
tric waves  were  generated  by  means  of  a 
Hertzian  doublet  with  minute  tungsten 
cylinders  substituted  for  platinum.  The 
wave-length  measurements  involved  the  use 
of  a  new  form  of  reflecting  echelon  analyser. 

By  means  of  the  equipment  briefly 
sketched  above,  Nichols  and  Tear  were  able 
to  produce  and  measure  electric  waves 
down  to  0.220  mm.  in  length,  which  is 
"  shorter  than  the  longest  known  heat 
waves  emitted  by  matter  at  high  tempera- 
tures." In  a  check  exiperiment  on  the  ap- 
paratus, these  investigators  exposed  their 
electric- wave  receiver  to  Rubens'  and  von 
Bayer's  heat  waves  of  0.320  mm.  in  wave- 
length, and  obtained  "  results  identical 
with  those  recorded  by  these  earlier  investi- 
gators." 

The  range  represented  by  the  shortest 
wave-length,  that  of  gamma  rays  (y  rays) 
from  radioactive  matter,  to  that  of  the 
loQgcst  Hertz  waves,  is  now  practically  ex 
piored  throughout.  The  ratio  of  the  short- 
est wave-length  to  the  longest  wave-length 
is  about  1  to  20  million  billion. 
"  Matter  under  the  action  of  heat  is  capable 
of  giving  off  radiations  in  the  so-called  infra- 
red, visible,  and  ultra-violet  spectra ; 
gamma  rays  are  the  natural  accompaniment 
of  radio-active  disintegration,  and  there  are 
various  electric  phenomena  in  the  atmos- 
phere giving  rise  to  pulse-like  disturbances 
resembling  fragments  of  very  long  electric 
waves.  But  X-rays  and  the  old  and  new 
short  electric  waves  we  may  still  regard  as 
artificial,  or  purely  products  of  laboratory 
manufacture." 


THE  INSTITUTE  OF  PHYSICS. 
At  the  last  meeting  of  the  Board  the  fol- 
lowing Corporate  Members    were  elected:  — 
Fellows:  C.  H.  Desch,  M.  Fishendon,    W. 
M.  Jones,    S.  Marsh;    Associates:     R.    P. 
Black,  M.  Brotherton,    J.  F.  Congdon, 
E.  Jolin.  H.  Lowery,    S.  P.  Peters,    L. 
Sutton,    N.  W.  Turnell,    A.  Whitaker, 
Wright. 


D. 
J. 
L. 


50 


THE  CHEMICAL  NEWS. 


JULY  27,  1923. 


THE  BRITISH  DYE  INDUSTRY. 

During  a  recent  debate  on  the  Board  of 
Trade  vote  in  the  House  of  Commons,  Mr. 
Clayton,  the  Unionist  member  for  Widnes, 
refen-ing  to  British  dyes,  said  that  we  had 
all  the  raw  materials  for  the  dye  industry  in 
this  country,  and  there  was  no  reason  why 
those  dyes  which  were  made  before  the  war 
in  Germany  could  not  be  made  here.  Enor- 
mous progress  had  already  been  made,  and 
the  dye-users  agreed  that  under  the  help 
and  guidance  of  the  present  Board  of  Trade 
they  would  yet  establish  a  dye  industry  in 
this  country  which  could  hold  its  own  with 
any  other.  The  intermediates  for  these 
dyes  were  necessary  for  explosives,  and  if 
the  dye  industry  was  maintained  in  this 
country  we  should  have  valuable  materials 
at  our  disposal  in  .case  of  emergency?.  Be- 
fore the  war  in  Germany  it  was  part  of  the 
Army  manoeuvres  to  turn  the  dye-works  in- 
to explosive  factories.  He  maintained  that 
the  chief  opposition  to  this  subsidy  came 
from  the  merchants  who  supplied  German 
dyes. 


Sir  P.  Lloyd-Greame,  President  of  the 
Board  of  Trade,  said  that  the  value  of  the 
dye  industry  to  the  textile  industry  of  this 
country  was  greater  than  ever  before.  The 
occupation  of  the  Ruhr  had  taken  place,  and 
great  uncertainty  existed  as  to  whether  the 
dyes  would  come  forward  at  all.  He  knew 
one  company  which  had  been  manufactur- 
ing day  and  night  almost  since  the  occupa- 
tion to  supply  the  things  that  were  needed. 
The  textile  trade  would  have  been  in  a  very 
anxious  position  in  the  last  six  months  if  it 
had  existed  entirely  on  dyes  coming  from 
the  Continent.  It  had  been  said  that  the 
dyes  that  were  being  used  in  Lancashire 
were  bad,  but  the  Chairman  of  the  Dye- 
Users'  Association  had  paid  a  tribute  of  ad- 
miration to  the  makers  for  the  progress 
achieved  in  the  production  of  dyestuffs  in 
the  last  few  years.  Our  ipre-war  consump- 
tion of  German  and  other  foreign  colours 
was  70  to  80  per  cent,  of  the  total,  and  last 
year  we  used  70  to  80  per  cent,  of  British 
dyes,  this  change  having  been  effected  with- 
out in  any  way  reducing  our  standards. 


STUDIES   ON   THE   PHYSICAL 

FOUNDATIONS    OF    DEEP    THERAPY 

TREATMENT. 

By  Prof.  Dr.  Friedrich  Dessauer 

{Director  of  the  Institution  for  the  Study  of 

Physical  Laws    of  Medicine,     University  of 

Frankfort,  Frankfort-on-the-Main, 

Germany.) 

Study  of  the  Pyhsical  Conditions. 

The  paper  dealt  first  with  the  physical 
laws  of  irradiation  and  the  exact  knowledge 
of  the  distribution  of  the  rays  within  the 
tissues . 

The  second  line  of  study  covered  the 
technical  requirements  for  a  practical  solu- 
tion of  the  problem.  I  have  been  working 
in  Germany  on  the  development  of  the  ap- 
paratus, and  have  spent  many  years  of 
thought  on  producing  one  that  would  gene- 
rate very  high  voltages  and  would  operate 
continuously  without  change  under  condi- 
tions of  absolute  safety  and  within  small 
dimensions;  that  is,  an  apparatus  which 
could  be  used  by  the  medical  man  without 
danger  and  without  great  expense  for 
operation  and  upkeep.  In  the  meantime 
my  friend  and  co  worker.  Dr.  W.  D.  Cool- 
idge,  has  still  further  developed  his  wonder- 
ful tube,    with    which    I  could    obtain    the 


most  accurate  results,  and  with  which  I 
could  bring  to  their  best  effect  the  high 
voltages.  This  subject  will  be  covered  in 
my  second  paper. 

Before  arriving  at  my  last  results,  I  shall 
briefly  touch  upon  the  history  of  how  the 
problem  started.  In  1904,  nearly  seventeen 
years  ago,  I  first  formulated  the  problems. 
At  that  time  superficial  skin  diseases  were 
being  treated  with  Rontgen  rays.  The  re- 
sults were  not  satisfactory,  and  Professor 
Perthes  published  interesting  experiments, 
coming  to  the  conclusion  that  an  insufficient 
quantity  of  rays  penetrate  to  a  depth.  I 
naturally  approached  the  problem  from  lh(- 
physicist's  point  of  view. 

The  Laws  pf  Hotnogeneous  Irradiaiion 
were  the  foundation  for  the  development  of 
deep  therapy,  and  have  to-day  proven  to  bo 
true.  To-day  it  is  very  simple  and  natural, 
but  it  was  not  so  seventeen  years  ago,  when 
the  nature  of  Rontgen  rays  was  unknown 
and  their  laws  could  not  have  been  known. 
Amongst  those  who  had  grasped  at  the  first 
the  importance  of  the  physical  laws  of  deep 
therapy  and  had  made  use  of  them  con- 
sciously, I  should  like  to  mention  Beclero 
of  Paris  and  Wetterer  of  Mannheim. 

The  laws  of  homogeneous  irradiation  are 
in  abbreviated  form  the  following  : 

First  Law. — The  foundation  of  Rontgen- 
otherapy   is  formed  by    the  biological    ex- 


JULY  27,  1923. 


THE  CHEMICAL  NEWS. 


51 


perience  that  different  cell  forms  show  dif- 
ferent sensitiveness  to  the  same  Rontgen 
rays. 

Second  Law. — Rays  of  different  penetra- 
tion arc  to  be  regarded  as  different  medica- 
ments, so  long  as  the  contrary  is  not  proven. 
The  difference  in  sensitiveness  of  different 
cells  appears  more  marked  if  hard  rays  are 
applied. 

Third  Law. — In  order  to  determine  and 
utilise  precise  differences  in  sensibility,  the 
homogeneity  of  the  field  of  radiation  is  n 
required  condition. 

Fourth  Law. — The  non-homogeneity  of  a 
treated  field  detracts  from  the  effect.  The 
conditions  for  a  favourable  influence  upon 
the  disease  are  not  fulfilled  when  the  non- 
homogeneitj^  of  the  field  is  greater  than  the 
difference  in  sensitiveness  between  the  dis- 
eased cells  and  the  healthy. 

This  law,  the  law  of  the  limit  of  effect, 
can  easily  be  expressed  by  algebraic  formu- 
la. 

Fifth  Law. — There  is  a  homogeneity  of 
space  or  quantiative  homogeneity  and  a  spe- 
cific homogeneity,  cw  qualitative  homoge- 
neity. The  aim  must  be  to  dose  the  dis- 
eased zone  throughout  its  extent  with  ihv 
needed  quality  or  dose  of  irradiation,  and  to 
have  this  dose  of  the  same  quality  throu«jh- 
out. 

Sixth  Law. — The  condition  of  qualitative 
or  specific  homogeneity  is  fulfilled  when  the 
irradiation  in  the  coniplet<>  zone  during  its 
course  through  the  body  does  not  change  its 
composition  or  consistency.  The  reaction 
on  the  different  cells  is  then  (physically  onl\ 
dependent  on  the  intensity  and  the  time. 

Seventh  Law. — The  intensity  of  effect 
may  not  differ  more  than  the  degree  of  sen- 
sitiveness. This  is  only  a  moee  precise 
statement  of  the  fourth  law,  the  limit  of  ef- 
fect, but  one  may  try  to  increase  the  inten- 
sity on  the  diseased  zone  in  the  depth  and 
to  raise  it  above  the  intensity  on  the  surface, 
and  in  the  vicinity  of  diseased  cells. 

Having  a  well-ixnown  composition  of  rays 
we  have  measured  the  distribution  of  the  in- 
tensity of  irradiation  within  a  body.  These 
measurements  have  been  made  with  four 
kinds  of  rays — the  most  penetrating  which 
up  to  then  could  have  been  produced  con- 
tinuously. Five  focal  distances  were  studied 
each  for  three  different-sized  treatment 
fiflds — small,   medium,   and  large. 

(From  "  The  American  Journal  of  Rnevt- 
genoJogy,"  Vol.  VIII.,  No.  10,  October. 
1021,  pages  r)78-588.) 


AGRICULTURAL    MACHINERY 
EXHIBITION  AT  PARIS. 

The  Department  of  Overeeas  Trade  is  in 
receipt  of  information  that  the  Third  Agi'i- 
cultural  Machinery  Exhibition  will  be  held 
in  Paris  in  January,  1924. 

This  exhibition,  like  those  held  in  1922 
and  1923,  will  include  agricultural  machines 
and  implements  manufactured  in  France  or 
in  countries  which  were  allied,  associate  or 
neutral  during  the  war. 

Applications  for  space  will  be  received  up 
to  October  15  next,  by  the  Commissariat 
General,  8  rue  Jean  Goujon,  Paris  (Be). — 
(From  the  "  Board  of  Trade  Journal," 
July  12,  1923.) 


INTERNATIONAL  SAMPLES  FAIR 
AT  ZAGREB. 

The  Department  of  Overseas  Trade  is  in- 
formed that  the  Third  International 
Samples  Fair  is  to  be  held  at  Zagreb 
(Agram),  Jugo-Slavia,  from  April  27  to 
May  5,  1924.— (From  the  "  Board  of  Trade 
Journal,"  July  12,  1923.) 


CANADA. 

SimmcAL  Instruments    and  Hospital 
Supplies  for  Vancouver,  B.C. 

II. M.  Trade  Commissioner  at  Vancouver 
reports  that  a  firm  in  that  city  is  desirous 
of  receiving  from  United  Kingdom  firms, 
catalogues,  prices,  etc.,  relative  to  surgical 
instruments  and  hospital  supplies.  Fur- 
ther particulars  can  be  obtained  on  appli- 
cation to  the  Department  of  Overseas 
Trade  (Room  53).  35,  Old  Queen  Street, 
Tifrtidon,  S.W.I. 


RAPESEED  OIL  REQUIRED  IN  IJ.S. 

Mr.  G.  Campbell,  H.M.  Consul-General 
at  San  Francisco,  reports  that  a  local  firm 
of  import  and  export  merchants  are  de- 
sirous of  n^ceiving  c.i.f.  quotations  for  lin- 
seed and  refined  deodorised  rapeseed  oil. 
In  the  case  of  the  former,  the  company 
wish  to  deal  with  London  exporters  alone, 
and  in  the  case  of  the  latter  only  with 
manufacturers. 

British  firms  desirous  of  receiving  further 
particulars  of  this  enquiry  should  apply  to 
the  same  Department.  (Reference  2(K)0fi/ 
F.W./C.C.2.). 


52 


THE  CHEMICAL  NEWS. 


JULY  27,  1923. 


OBSEEVATIONS  UPON  AND 

DEDUCTIONS    FROM    THE    FIGURES 

GIVEN  IN  THE  INTERNATIONAL 

TABLE  OF  ISOTOPES,  1923. 

By  Hawks  worth  Collins. 

In  this  paper  it  is  inferred  that  all  the 
figures  given  in  the  International  Table  of 
Isotopes,  1923  (which  appeared  in  The 
Chemical  News,  1923,  CXXVL,  147),  are 
results     obtained    by    independent    exiperi- 


Atomic  Dominant 

Element  Weight     Isotope  Remark 

He       4.00  4  even 

Li       6.94  7  odd 

Gl       9.1  9  odd 

B       10.9  11  odd 

C       12.005  12  even 

N       14.008  14  even 

0       16.000  16  even 

F       19.0  19  odd 

Ne       20.2  20  even 

Na      23.00  28  odd 

Mg       24.32  24  even 

Al       27.0  27  odd 

Si        28.1  28  even 

P       31.04  31  odd 

S        32.06  32  even 

CI     35.46  35  odd 

A       39.9  40  even 

K       39.10  39  odd 

Ca        40.07  40  even 

Pe       55.84  56  even 

Ni       58.68  58  even 

As       74.96  75  odd 

Br       79.92  79  odd 

Rb      86.45  86  odd 

1       126.92  127  odd 

Cs       132.81  133  odd 


ments,  and  that  no  one  of  them  is  merely 
the  result  of  hypothesis;  e.g.,  18  has  beeu 
obtained  by  independent  experiment  as  the 
atomic  number  of  Argon.  If  it  has  not  been 
so  obtained,  it  would  not  have  appeared  in 
the  table,  for  the  duty  of  the  new  Commit- 
tee is  "to  keep  chemists  informed  of  ihe 
various  advances  made  each  year  in  this 
field,"  and  the  word  "advances"  evidently 
does  not  include  anything  of  the  nature  of 
hypothesis. 


Table  I. 


Atomic 
Number 

2 

3 

4 

5 

6 

7 

8 

9 
10 
11 
12 
13 
14 
15 
16 
17 
18 
19 
20 
26 
28 
33 
35 
37 
53 
55 


Remark 
even 
odd 
even 
odd 
even 
odd 
even 
odd 
even 
odd 
even 
odd 
even 
odd 
even 
odd 
even 
odd 
even 
even 
even 
odd 
odd 
odd 
odd 
odd 


Maximum 

Valency  Remark 
2  even 


odd 

odd 

odd 

even 

odd 

even 

odd 

even 

odd 

even 

odd 

even 

odd 

even 

odd 

even 

odd 

even 

even 

odd 

odd 

odd 

odd 

odd 

odd 


Observation  1. 

When  the  atomic  number  is  even,  tho 
masSes  of  the  isotopes  are  even  whole  num- 
bers; and  when  the  atomic  number  is  odd, 
the  masses  of  the  isotopes  are  odd  whole 
numbers;  with  a  few  exceiptions. 

There  are  70  numbers  given  for  the 
masses  of  the  isotopes  (not  including  the 
doubtful  ones  in  brackets,  and  excluding 
also  the  mass  of  hydrogen  which  is  not 
given  as  a  whole  number),  and  of  these,  12 
are  exceptions  to  the  above  general  rule.  If 
we  wish  to  know  whether  this  general  rule 
contains  a  truth,  we  must  proceed  in  the 
following  manner:  — 

The  probability  that,     when  the    atomic 


number  is  even,  the  mass  of  the  isotope 
would  accidentally  also  be  even  is  1  :  2. 
and  that  when  the  atomic  number  is  odd, 
the  isotope  would  also  be  odd,  is  1  :  2. 
Therefore  •  the  probability  that  the  above 
regularity  would  happen  accidentally  in  58 
cases  out  of  70  is  1  :  2^"  -'-'-f  ^^^  =  1  :  2" 
=  1   :  70  billion. 

So,  the  probability  that  this  state  of  af- 
fairs has  not  happened  by  accident  is  70  bil- 
lion to  one,  that  is,  it  is  absolutely  certain 
that  a  truth  is  contained  therein. 

Deduction  1. — Therefore,  with  the  ad- 
vance of  knowledge,  the  exceptions  will 
probably  diminish;  e.g.,  the  single  odd  iso- 


JULY  27,  1923. 


THE  CHEMICAL  NEWS. 


58 


tope  of  tSe  may   be  found  later  to  be  an  im- 
purity and  not  Se  at  all. 

Deduction  2. — There  is  some  fundamen- 
tal and  uniform  connection  between  the 
atomic  number  of  an  element  and  its  iso- 
topic  masses,  and  this  connection  must  be 
expressible  by  whole  numbers. 

In  the  case  of  Li,  whose  atomic  weight  is 
given  as  6.94,  and  whose  isotopes  are  7  and 
6,  it  is  evident  that  the  majority  of  the  iso- 
topes must  have  masses  of  7.  A  similar  re- 
mark can  be  made  in  the  cases  of  several 
other  elements.  Omitting  those  to  which 
such  a  remark  cannot  be  applied,  the  figures 
for  dominant  isotopes  (given  in  Table  1.) 
are  obtained. 

Observation  2. 

When  the  atomic  number  is  even  (or  odd) 
the  dominant  isotope  is  correspondingly 
even  (or  odd)  in  24  cases  out  of  26. 

The  probability  that  this  contains  a 
truth  is  2^*  — 'x*  :  1  =  four  milUon  to  one. 

Deduction  3. — There  is  some  fundamental 
and      unifc«rm     connection      between      the 
atomic  number  of  an  element  and  the  him  - 
of  its  dominant  isotope,    and    this  coniit  <• 
ti  )n  must  be  expressible  by  whole  numbers. 

The  maximum  valences  given  in  Table  I. 
are  univcFBally  recognised  as  such. 
Observation  3. 

When  the  atomic  number  is  even  (or 
odd),  both  the  dominant  isotope  and  also 
the  maximum  valency  arc  correspondingly 
even  (or  odd^  in  23  cases  out  of  26. 

The  probaoility  that  this  contains  a  truth 
is  4"  _iy   :  1  =  17  billion  to  one. 

This  can  be  seen  to  be  correct  by  the  fol- 
lowing consideration.  If  it  were  merely  a 
matter  of  accident,  only  one  out  of  every 
four  elements  would  be  likely  to  have  3 
evens  or  8  odds.  Therefore,  in  26  elements, 
6.5  (  =  26/4)  \<'ould  be  likely  to  satisfy  this 
condition;  so  that  there  would  be  19.6  ex- 
ceptions. (The  fact  that  19.5  is  not  a  whole 
number  does  not  affect  the  reasoning,  of 
course).  The  probability  would  then  be 
tae  _  1215X1    ;  1    =    4°  :  1    =    1  :  1,  which 

3 

is  evidently  correct. 

Deduction  4. — There  is  some  fundamen- 
tal and  uniform  connection  between  the 
atomic  number  of  an  element,  the  mass  of 
its  dominant  isotope,  and  its  maximum 
valency,  and  this  connection  must  be  ex- 
ipressible  by  whole  numbers. 

The  following  observation  applies  exactly 
to  all  but  throe  of  the  first  19  elements  in 
Table  I.,  i.e.,  to  the  great  majority  of  the 
common  elements. 


Observation  4. 

The  atomic  number  gives  the  number  of 
3's  and  I's  into  which  the  mass  of  the  domi- 
nant isotope  can  be  split  up,  always  com- 
mencing with  a  3,  and  taking  the  3's  and  I's 
alternately. 

E.g.,  the  atomic  number  of  B  is  5,  and 
its  dominant  isotope  can  be  split  up  into  5 
parts,  3+1+3+1+3;  the  atomic  number  of 
-Mg  is  12,  and  its  dominant  isotope  can  be 
split  up  into  6(3+1),  i.e.,  into  12  parts. 

This  state  of  affairs  continues  as  far  as 
Ca,  when  there  is  an  abrupt  change,  and 
occurs  no  more  at  all  in  the  elements  of 
atomic  weight  greater  than  40. 

The  probability  that  there  is  a  truth  in- 
volved in  this  observation  is  infinitely 
greater  than  2'»  -«x»  :  1  =  8000  :  1,  be- 
cause it  is  a  complex  regularity. 

Observation  5. 

If  the  mass  of  the  dominant  isotope  is  an 
even  number,  the  atomic  number  is  ob- 
tained by  halving  it.  And,  if  the  mass  of 
the  dominant  isotope  is  odd,  the  atomic 
number  is  obtained  by  subtracting  one  and 
then  halving  the  result. 

This  state  of  affairs  continues  again  as  far 
as  Ca,  when  there  is  an  abrupt  change,  and 
occurs  no  more  at  all  in  the  elements  of 
atomic  weight  greater  than  40. 

The  probability  that  there  is  a  truth  con- 
tained in  this  observation  is  2"  —  *  x  '  :  1  = 
130,000  :  1,  for  there  is  only  one  exception, 
viz.,  Arg(Mi. 

Deduction  5. — It  follows  from  the  last 
two  observations  that  the  majority  of  the 
common  elements  of  atomic  weight  less 
than  41  are  differentiated  absolutely  from 
all  other  elements  by  some  fundamental 
property  or  {properties.  Either  this  is  the 
case,  or  the  atomic  numbers  from  Fe  up- 
wards are  wrong.  But  since  chemists  are 
convinced  that  the  properties  of  all  ele- 
ments are  periodic  functions  of  their  atomic 
weights,  they  cannot  admit  that  there  is 
any  fundamental  regularity  which  belongs 
solely  to  those  elements  which  happen  to 
have  atomic  weights  less  than  41.  There- 
fore the  atomic  numbers  from  Fe  upwards 
must  be  wrong. 

It  is  not  merely  extraordinary,  but  it  is 
also  quite  absurd,  that  a  complex  general 
rule  connecting  the  atomic  weight  with  the 
atomic  number  should  apply  only  to  those 
elements  which  happen  to  have  atomic 
weight  less  than  41,  and  which  also  happen 
to  include  nearly  all  the  common  elements. 


54 


THE  CHEMICAL  NfiWS. 


JULY  27,  1923. 


Deduction  6.  —  The  fourth  observation 
evidently  contains  the  fundamental  and 
uniform  connection,  which  has  been  proved 
to  exist  between  the  atomic  number  of  an 
element  and  its  dominant  isotope,  for  there 
is  no  other  uniform  arrangement  of  whole 
numbers  possible;  and  this  is  especially 
suitable,  since  it  is  known  that  one  electro- 
positive force  emanates  from  a  mass  of 
1(1.008),  also  one  from  a  mass  of  3(H3), 
also  two  from  4(He). 

Observation  6. 

If  helium,  with  its  two  electro-positive 
forces,  could  be  given  off  from  the  hetptad 
CI  (35),  a  pentad  would  be  left  with  atomic 
weight  31.     The  pentad  P  has  at.  wt.  31. 

If  helium  were  given  off  from  the  pentad 
P,  there  would  be  left    a  triad  with  at.  wt. 

27.  The  triad  Al  has  at.  wt.  27. 

If  helium  were  given  off  from  the  triad 
Al,  a  monad  would  remain  of  mass  23.  The 
monad  Na  has  at.  wt.  23. 

If  helium  were  given  off  from  the  hexad 
S  (32),  there  would  be  left  a  tetrad  of  mass 

28.  The  dominant  isotope  of  the  tetrad  Si 
has  mass  28. 

If  helium  were  given  off  from  the  tetrad 
Si  (28),  a  dyad  of  mass  24  would  remain. 
The  dominant  isotope  of  the  dyad  Mg  has 
mass  24. 

If  helium  were  given  off  from  the  domi- 
nant isotope  (11)  of  B,  a  monad  of  mass  7 
would  be  left.  The  dominant  isotope  of  the 
monad  Li  has  mass  7. 

Observation  7. 

In  all  the  above  six  examples,  which  are 
exact,  the  element  which  is  supposed  to  be 
disintegrated  has  2,  4,  or  6  electro-positive 
valences,  which  always  act  in  pairs,  and 
which  cause  these  elements  to  be  classed  as 
non-metallic. 

The  discovery  involved  in  the  last  two  ob- 
servations was  first  published  in  an  adver- 
tisement in  Nature  on  June  14,  1906,  long 
before  chemists  admitted  that  the  atomic 
weights  were  whole  numbers,  or  that  the 
elements  could  be  disintegrated,  also  seve- 
ral years  before  it  was  known  that  helium 
possessed  two  electro-positive  valences. 
This  new  chemical  law  was  worded  as  fol- 
lows:  "  The  non-metallic  nature  of  an  ele- 
ment is  always  due  to  a  pair  or  pairs  of 
electro-positive  forces,  each  pair  emanat- 
ing from  a  portion  of  the  element  of  which 
the  mass  is  4,  taking  the  mass  of  an  atom 
of  hydrogen  as  unity." 


If  any  chemist  were  asked  to  name  three 
elements  which  are  especially  similar  to 
one  another,  considering  only  the  33  given 
in  the  International  Table  of  Isotopes,  there 
is  not  much  doubt  that  he  would  choose 
either  CI,  Br  and  I,  or  K,  Eb  and  Cs.  It 
was  shown  in  The  Chemical  News,  Jan.  10, 
1914,  and  Oct.  1,  1920,  that  Na  (23)  takes 
a  prominent  part  in  the  formation  of  all 
elements  of  greater  atomic  weight  than  it- 
self. This  was  done  at  a  time  when  chem- 
ists objected  to  the  mathematical  proof 
that  the  atomic  weights  were  whole  num- 
bers; but  now  that  this  difficulty  has  been 
almost  entirely  removed,  the  demonstration 
of  the  matter  is  much  simplified. 


Observation  8. 


Element 
CI 
Br 
I 
K 
Kb 

Cs 


Isotopes 

35 

81 
127 
39;     41 

85;     87 

133 


Observation 


81  =  2x23+35 
127  =  4x23+35 

85  =  2x23+39 

87  =  2x23+41 

133  =  4x23+41 


Deduction  7 :  — 

Br  =  Na^Cl 
I  =  Na^Cl 
Kb  =  Na^K 
Cs    =   Na,K 

All  these  observations  are  matters  of 
fact.  There  is  no  hypothesis,  speculation, 
or  guesswork  involved  in  them.  Also  there 
is  no  arbitrary  choice  of  facts;  for  all  avail- 
able data  are  employed,  whether  favourable 
or  unfavourable. 

There  can  be  no  valid  objection  to  ex- 
ceptions to  general  rules  with  respect  to 
the  structure  of  the  elements,  for  there  is 
no  reason  why  all  elements  should  be  built 
up  in  exactly  the  same  manner. 

When  a  state  of  affairs  has  been  proved 
to  be  due  to  cause  and  not  to  chance,  it  is 
evident  that  no  future  discoveries  or  addi- 
tions to  knowledge  (such  as  isotopes,  e.g.) 
can  ever  contradict  the  general  truth  ob- 
tained, for  it  is  impossible  for  scientists  to 
unconsciously  evolve  a  state  of  affairs 
which  can  be  proved  to  be  due  to  cause  and 
not  to  chance,  and  yet  for  it  not  to  contain 
an  absolutely  incontrovertible  truth. 

The  explanation  of  the  odd  and  even  ob- 
servations evidently  is :  that  if  an  even 
number  of  3's  and  I's  be  added  together 
the  result  is  even,  and  if  an  odd  number  of 


JULY  27,  1923. 


THE  CHEMICAL  NEWS 


55 


3'8  and  I's  be  added  together  the  result  is 
odd. 

From  the  above  and  additional  observa- 
tions, other  deductions  leading  to  the  defi- 
nite demonstration  of  the  Constitution  and 
Structure  of  the  Elements  were  given  in 
papers  published  in  The  Chemical  News, 
Dec.  19  and  26,  1919,  April  9,  June  4,  Oct. 
1  and  15,  1920,  etc. 


THE    ANNUAL    MEETING      OF    THE 

ASSOCIATION    OF    BKITISH 

CHEMICAL    MANUFACTURERS. 

The  Seventh  Annual  General  Meeting  of 
the  Association  was  held  at  the  Chemical 
Society's  rooms  on  July  12.  Sir  Max  Mus- 
pratt,  Bart,,  Chairman  of  the  Association, 
presided. 

In  proposing  "  That  the  report  and  ac- 
counts of  the  Association  be  and  they  are 
hereby  ad()pted,"  the  Chairman  said  the 
Association's  sphere  of  usefulness  is  con- 
stantly increasing. 

In  spite  of  being  chemical  manufacturers, 
we  have  in  recent  years  somewhat  overcrmie 
the  modesty  of  previous  eras  of  chemical 
itidustry,  Jind  we  believe  that  we  have  a 
nu'ssagu  of  a  two-fold  nature  to  give  to  the 
nation.  We  have  a  duty  to  perform  in  in- 
structing Ministers  and  other  members  of 
the  Government  and  the  Civil  Service  as  to 
what  they  ought  to  know  about  this  most 
important  industry.  We  have  also  to  im- 
press upon  the  nation  at  large  that  in  Great 
liritain  tiu;  chemical  industry  is  a  very  im- 
portant national  asset,  and,  like  every  other 
important  national  asset,  it  has  to  go  for- 
ward or  go  back.  We  intend,  bv  every 
means  in  our  power,  to  further  the  pro- 
gress of  this  industry. 

The  British  Industries  1  air  of  1928  is 
dealt  with  in  the  report,  but  I  might  accen- 
tuate the  fact  that  in  the  British  Industries 
Fair,  both  this  year  and  on  previous  occa- 
sions, we  have  tried  to  carry  out  the  policy 
of  showing  the  close  interlocking  of  the 
various  brandies  of  the  chemical  industry, 
and  1  believe  at  the  recent  British  Indus- 
trios  Fair  we  carried  that  out  to  no  small 
extent.  The  British  Industries  Fair  is,  we 
hope,  an  annual  factor,  but  next  year  when 
the  British  Empire  Exhibition  also  takes 
place,  we  felt  that  it  would  be  calling  too 
innch  upon  our  members  to  make  an  ade- 
quate chemical  section  on  both  those  occa- 


sions, and  so  we  are  not  taking  part  in  the 
Fair  of  next  year.  In  the  British  Emipire 
Exhibition  of  1924  we  are  taking  a  verj' 
great  part.  We  intend  the  Chemical  Sec- 
tion of  the  British  Empire  Exhibition  to  be 
a  complete  survey  of  Britain's  services  to 
chemistry,  from  the  smallest  chemical 
manufacturer  to  the  most  brilliant  and 
epoch-making  discovery  by  scientific  men  in 
chemistry.  It  will  be  one  of  the  most  com- 
plete exhibitions  of  chemistry  in  its  broad- 
est sense  that  has  ever  been  brought  before 
the  British  public — greater  than  has  been 
presented  anywhere  before.  When  I  tell 
you  that  the  Royal  Society  is  going  to  take 
part  in  an  exhibition,  I  think  you  will  admit 
that  we  are  bringing  even  the  academic 
section  of  chemistry  into  the  services  of 
mankind  and  the  Empire.  The  Chemical 
Society  is,  of  course,  assisting  us;  the  So- 
ciety of  Chemical  Industry;  the  Society  of 
Petroleum  Technologists;  the  Pharmaceuti- 
cal Society ;  the  Society  of  Dyers  and 
Colourists  are  all  assisting,  and,  from  the 
Royal  Society,  Sir  Herbert  Jackson  is 
liaison  (^cer  in  conjunction  with  our 
General  Manager,  to  see  that  the  most  com- 
plete linking  up  in  absolute  harmony  of 
every  aspect  of  chemistry  is  duly  and  pro- 
perly carried  out  at  the  British  Empire 
ExmbitioQ  next  year. 

With  regard  to  the  Continental  situation, 
I  believe  that  a  few  words  will  be  said  about 
that  in  another  place  to-day,  and  by  one 
(the  Prime  Minister),  who  was  a  guest  at 
our  dinner  last  year.  I  need  only  deal  with 
it  purely  from  the  aspect  of  chemical  in- 
dustry. The  whole  position  of  the  Ruhr  is 
one  which  the  chemical  industry,  especially 
the  fine  chemicals  and  the  dyestuff  branches 
of  the  industry,  has  to  look  upon  with  great 
apprehension.  There  are  superficial  advan- 
tages in  having  competitors  closed,  but  I 
am  sure  that  nobo<ly  with  the  broad  train- 
ing of  a  chemist  will  for  a  moment  take  that 
aspect.  On  the  purely  material  side,  it  is 
even  better  to  have  the  chemicals  in  the 
hands  of  a  competitive  manufacturer  than 
to  have  them  in  the  hands  of  an  irrespon- 
sible Government  Department,  and  when 
that  irresponsible  Government  Department 
is  not  even  in  this  country,  I  need  hardly 
say  that  what  is  going  to  happen  to  those 
(lyes  and  other  chemicals  which  have  been 
taken  by  the  French  Government  is  causing 
grave  doubt  and  grave  uneasiness  in  the 
minds    of     everyone    connected    with    the 


56 


THE  CHEMICAL  NEWS. 


JULY  27,  1923. 


Council  of  the  Association  of  British  Chemi- 
cal Manufacturers. 

I  will  not  elaborate  the  paragraph  in 
which  the  Dyestuffs  Act  is  dealt  with  exceipt 
to  refer  to  the  agitation  for  the  repeal  of 
that  Act,  and  to  ask  if  the  real  trouble  of 
the  textile  industry  is  not  the  high  price  of 
cotton.  I  know  I  am  speaking  for  every- 
one occupied  with  the  heavy  chemical  in- 
dustry in  assuring  him  and  his  colleagues 
in  other  branches  of  the  dye  industry  that 
the  heavy  chemical  industry  does  desire  to 
assist  and  co-operate  with  them  in  every 
possible  way. 

Turning  to  the  question  of  alcohol,  which 
has  been  discussed  for  years,  and  especially 
for  months  past,  I  should  like  to  say  how 
deeply  we  are  indebted  to  Mr.  Carr  for  the 
way  in  which  he  has  handled  this  problem 
in  conjunction  with  the  Committee.  It 
would  be  absolutely  invidious  to  mention 
names,  but  I  know  that  everyone  of  you 
will  wish  to  add  in  your  vote  on  this  written 
report  a  vote  of  aippreciation  to  the  able 
staff  who  manage  our  affairs. 

Mr.  R.  G.  Perry,  C.B.E.,  in  the  absence, 
owing  to  illness,  of  the  Vice- Chairman,  Sir 
William  Pearce,  seconded  the  resolution. 
He  said  there  was  only  one  point  to  which 
he  would  like  to  refer.  It  was  the  para- 
graph in  the  report  which  read :  ' '  The 
Council  records  with  satisfaction  and  ap- 
preciation the  honour  which  has  been  con- 
ferred by  His  Majesty  the  King  upon  its 
Chairman,  Sir  Max  Muspratt,  Bart."  They 
all  wished  to  congratulate  their  Chairman 
upon  that  honour.  They  were  all  quite  sure 
that  never  had  an  honour  fallen  upon  more 
worthy  shoulders,  and  never  would  an 
honour  be  more  worthily  borne. 

Tihe  Treasurer  (Mr.  C.  A.  Hill),  in  com- 
menting on  the  accounts,  said  that,  in  case 
it  should  be  thought  they  were  working  on 
too  narrow  a  margin,  he  would  like  to  put 
forward  the  view  that  that  was  a  matter  for 
congratulation  to  the  administrative  staff 
who  were  responsible  for  the  working  of  the 
Association. 

Mr.  A.  T.  Smith  said  there  was  one  mat 
ter  of  which  they  should  make  a  special 
note,  and  that  was  the  remarkable  result 
which  has  followed  their  efforts  as  an  asso- 
ciation to  better  the  chemical  trade.  They 
had  one  very  particular  instance  to  record, 
and  it  arose  from  the  speech  by  Sir  William 
Alexander,  as  Chairman  of  the  British  Dye- 
stuffs  Corporation.  He  (Mr.  Smith)  did  not 
pretend  that    the  results    were    due  to    the 


efforts  of  the  Association,  but  he  did  say 
that  the  fact  that  the  Association  lived  and 
existed  and  did  co-operate  and  help  in  every 
possible  way,  must  'have  been  of  the  utmost 
assistance  to  Sir  W^illiam  Alexander  in  the 
very  arduous  work  he  had  undertaken.  He 
might  be  perfectly  certain,  as  far  as  the 
heavy  chemical  industry  was  concerned, 
that  he  would  have  the  same  co-operation 
in  the  future  as  he  has  had  in  the  ipast,  and 
he  hoped  the  results  would  be  quite  as 
good. 

Dr.  E.  F.  Armstrong,  F.B.S.,  said  that 
the  Association  had  certainly  done  well 
during  the  year,  but  it  was  desirable  that 
chemical  industry  should  try  to  stand  on  its 
own  feet.  He  did  not  mean  to  criticise  the 
policy  of  the  Association  in  the  past.  Sir 
William  Alexander,  in  the  few  words  which 
he  addressed  to  the  shareholders  of  the 
British  Dyestuffs  Corporation,  mentioned 
that  a  sum  of  £400,000  had  been  spent  on 
research.  The  fact  that  it  has  been  spent 
showed  that  one  firm  in  this  country  real- 
ised the  enormous  importance  of  making  it- 
self strong  on  the  scientific  side  as  a  ])re- 
liminary  to  its  success  financially.  It  was 
only  by  research  and  by  its  technical  work 
that  they  could  get  an  advantage  in  the 
future.  Whatever  the  Association  did  as 
its  primary  object,  in  the  representation  of 
the  chemical  industry  as  a  whola,  the  Gov- 
ernment must  never  lose  sight  of  its  second- 
ary object,  namely,  the  encouragement, 
first  to  co-operation,  because  that  is  the 
secret  to  other  things,  as  Mr.  Smith  had  in- 
dicated; and  secondly,  the  encouragement 
of  technical  progress  within  their  industry. 

Sir  William  Alexander,  K.B.E.,  C.B.. 
C.M.G.,  D.S.O.,  said  his  company  had  re- 
ceived from  the^large  members  of  the  heavy 
chemical  industry  in  recent  times  very  real 
and  concrete  assistance  in  bringing  down 
the  prices  of  their  products.  In  every  case 
where  it  had  been  at  all  possible  for  them 
to  meet  the  company  they  had  done  so,  and 
in  every  case  where  it  has  been  possible  for 
the  company  to  pay  a  higher  price,  they  had 
paid  it.  He  felt  certain  that  their  industry 
was  going  to  pull  through.  He  hoiped  that 
their  industry  would  be  of  assistance  to  the 
other  large  industries  which  were  embraced 
in  the  Association  of  British  Chemical 
Manufacturers,  and  that  as  time  went  on 
they  would  find  that  they  merited  the  con- 
fidence which  was  being  placed  in  them. 


JULY  27,  1923. 


THB  CHEMICAL  NEWS 


57 


The  lit.  Hon.  J.  W.  Wilson  alluded  to 
the  last  two  paragraphs  in  the  report  with 
regard  to  transport. 

Mr.  F.  H.  Carr,  C.B.E.,  F.I.C.,  referred 
to  the  alcohol  question.  The  importance  of 
alcohol  to  the  fine  chemical  industry  had 
perhaps  never  been  stated,  and  yet  he 
thought  that  chemical  manufacturers  and 
fine  chemical  manufacturers  in  jiarticular 
were  coming  to  realise  that  it  was  a  sub- 
stance, as  a  chemical,  which  they  could  use, 
whereas  hitherto  it  has  always  been  re- 
garded as  a  substance  which  was  beyond 
their  reach.  Many  still  believed  that  the 
chief  use  of  alcohol  was  as  a  beverage. 
Choinists  and  Americans  did  not  believe 
that.  It  was  the  raw  material,  the  coal  tar, 
of  the  pharmaceutical  chemical.  The  ethyl 
group  entered  ifato  a  large  propOTticm  of  the 
synthetic  compounds  used  in  medicine,  and 
hitherto  the  manufacture  of  such  com- 
pounds had  been  practically  impossible  ow- 
ing to  the  difficulties  which  had  been  met 
with  in  the  early  stages  of  mnnufjicture  in 
getting  satisfactory  arrangements  with  the 
Excise  Authorities.  The  work  that  had  been 
(lone  by  the  Committee  had  cmly  been  poe- 
siblo  because  of  an  entirely  new  state  of 
iffairs  at  the  Board  of  Customs  and  Excise, 
md  it  was  to  such  people  as  Sir  Horace 
Hamilton  and  Sir  Robert  Robertson  that 
I  heir  thanks  must  be  chiefly  given.  They 
had  in  the  concessions  which  they  hud 
given  shown  that  we  are  at  the  dawn  of  a 
new  era  ah  regards  the  iis<'  of  alcoliol  in 
chemical  manufacture.  The  concessions 
which  had  been  made  i|)erniitted  manufac- 
turers who  are  commencing  to  use  alcohol 
to  use  quantities  up  to  1(X)  gall(Mi8  without 
any  restrictions  as  regards  their  receivers 
without  the  necessity  of  an  officer  being  on 
the  spot;  and  provided  adequate  figures 
were  shown  as  regards  the  destination  of 
the  alcohol  that  was  being  used,  they  were 
quite  satisfied  to  leave  it  with  fairly  moder- 
ates restrictions.  He  urged  all  those  in- 
terested in  fine  chemical  manufacture  to 
iruike  use  of  these  privileges  and  to  lay  be- 
fore the  Association  «uch  difficulties  as  they 
might  meet  with  in  order  that  the  Commit- 
tee might  go  on  with  this  work  until  they 
got  every  possible  fsioility  required  for  their 
manufacture. 

Mr.  Kenneth  Chanoe,  M.A.,  associated 
himself  with  the  remarks  of  Mr.  Wilson  as 
to  the  question  of  transport. 

Mr.  E.  V.  Evans.  O.B.E.,  F.I.C.,  ex- 
pressed on  behalf  of  the  Society  of  Chemi- 


cal Industry  its  appreciation  of  the  help 
and  contributions  made  by  the  Association 
to  its  Journal. 

Dr.  H.  Levinstein,  M.Sc,  referred  to  a 
sentence  in  the  report  stating:  "  The  Coun- 
cil has  been  asked,  and  has  agreed,  to  or- 
ganise the  Chemical  Section  of  the  Exhibi- 
tion to  be  held  at  Wembley  next  year." 
That  was  a  remarkable  testimony  to  the 
Association.  The  mere  fact  that  when  they 
had  a  British  Empire  Exhibition  the  whole 
of  the  chemical  exhibit  could  be  dealt  wifli 
by  one  organisation  of  this  kind  showed 
what  an  enormous  stride  the  chemical  in- 
dustry (had  nuide  in  organisation  since  the 
last  exhibition  of  the  same  kind  was  held. 
He  had  not  the  slightest  doubt  that  this 
chemical  exhibit  would  make  the  same  im- 
pression on  chemists  visiting  the  British 
Empire  Exhibition  as  the  wonderful  ex- 
hibit shown  by  the  Germans  in  Paris  in  the 
year  1900,  which  no  doubt  many  of  them 
remembered. 

Mr.  Bernard  Hickson  endorsed  the  rc- 
luiu-ks  with  regard  to  transport. 

Mr.  T.  D.  Morson  said  that  as  a  back- 
bencher he  hoped  that  publicity  would  re- 
main in  the  fore-front  of  the  policy  of  the 
.'Vssociation. 

The  Chairman,  having  briefly  replied, 
then  put  the  motion  to  the  meeting,  and 
declared  the  report  and  accounts  unani- 
mously a^lopted. 

The  Ordinary  Meeting  was  followed  by  a 
S(>ecial  General  Meeting,  when  the  amount 
of  the  annual  subscription  payable  by  mem- 
bers of  the  Association  for  the  year  1923- 
1924  was  fixed  at  four-fiths  of  the  sums 
laid  down  in  .Vrticle  17  of  the  Articles  of 
Association. 

Sir  John  Brunner,  Bart.,  proposed,  and 
Mr.  li.  G.  Perry,  O.B.E.,  seconded,  a  vote 
of  thanks  to  the  Chairman,  which  was  car- 
ried mianimously,  and  the  proceedings  then 
terminated. 


THE    SEPAH.\T10N     AND    DETERMI- 
N.\TI()N    OF  SODIUM  AND    LITHIUM 
BY     PRECIPITATION      FROM     ALCO- 
HOLIC PERCHLORATE    SOLUTION.* 
By  H.  H.  Willard  and  G.  Frederick 
Smith. 
[Contribution  from  the    Chemical    Labora- 
tories   of  the    University  of    Michigan    and 
the  University  of  Illinois.] 
[Continued  from   Page   43.) 
It  was  found  to  be  sufficiently  close  to   a 
straight  line  function    so  that    values    be- 


58 


THE  CHEMICAL  NEWS. 


JULY  27,  1923, 


tween  those    given  in    the  following    table 
could  be  obtained  by  interpolation. 

Table  I. 

Density  of  Solutions  of  Hydrogen  Chloride 
in  Dry  Normal  ISutyl  Alcohol. 


HCl 

Density 

HCl 

Density 

% 

% 

0 

0.8060 

11 

0.8685 

1 

0.8180 

12 

0.8930 

2 

0.8195 

13 

0.8770 

3 

0.8255 

14 

0.8810 

4 

0.8315 

15 

0.8855 

5 

0.8370 

16 

0.8895 

6 

0.8425 

17 

0.8935 

7 

0.8485 

18 

0.8960 

8 

0.8540 

19 

0.9010 

9 

0.8590 

20 

0.9050 

10 

0.8635 

These  values  were  obtained  by  using  a 
pycnometer  and  thermostat  and  refer  to 
25°/4°  corrected  to  vacuum.  The  hydro- 
chloric acid  was  determined  by  titration 
with  standard  alkali. 

The  factors  in  the  order  of  their  import- 
ance are :  (1)  temperature  of  precipitation ; 
(2)  concentration  of  hydrochloric  acid,  giv- 
ing minimum  solubility  of  of  sodium  chlor- 
ide; (3)  conditions  favouring  ease  of  filtra- 
tion ;  (4)  prerequisites  or  drying  and  ignition 
of  the  sodium  chloride  obtained ;  (5)  physi- 
cal constants  of  butyl  alcohol  used  in  the 
method;  (6)  treatment  of  filtrates  from 
sodium  chloride  for  recovery  of  lithium. 
These  factors  will  be  taken  up  in  the  order 
given. 

Temperature  of  Precipitation. — Sodium 
chloride  precipitated  from  boiling  solutions 
of  sodium  perchlorate  in  butyl  alcohol  when 
filtered  on  asbestos,  washed,  and  dried  at 
250^  for  a  long  time,  is  perfectly  white,  but 
upon  ignition  to  500-600°  it  becomes  dark 
grey,  and  when  then  dissolved  in  water  a 
black  deposit  of  carbon  is  obtained.  This 
results  from  occlusion  of  solvent  in  the  pre- 
cipitated sodium  chloride.  The  error  in 
weight  of  the  precipitated  sodium  chloride, 
due  to  this  cause,  is  variable  and  too  large 


^  The  work  done  in  connection  with  this 
paper  was  suggested  by  H.  H.  Willard,  and 
the  preliminary  work  was  carried  out  at  the 
University  of  Michigan.  The  final  ^vork 
was  done  at  the  University  of  Illinois. 


to  be  neglected.  Precipitation  at  room 
temperature  gave  a  similar  result,  but  much 
less  carbon  was  obtained.  Wash  solutions 
such  as  acetone,  ether  and  carbon  tetra- 
chloride, are  incapable  of  removing  the  oc- 
cluded solvent  from  the  precipitate.  Igni- 
tion of  the  sodium  chloride  containing  car- 
bon in  a  stream  of  oxygen  did  not  remove 
the  impurity.  The  lower  the  temperature 
of  the  solution  from  which  sodium  chloride 
is  precipitated,  the  less  the  tendency  it 
shows  to  occlude  solvent.  When  iprecipi- 
tated  at  —15°  to  —20°  the  dried  and  ignited 
salt  contains  no  carbon  but  is  pure  sodium 
chloride. 

Effect  of  Acid  Concentration  Upon  the 
Solubility  of  Sodium  C/tionde.— Solutions 
of  sodium  perchlorate  of  known  content 
were  precipitated  by  the  addition  of  butyl 
alcohol  containing  20  per  cent,  of  hydrogen 
chloride.  A  definite  excess  of  hydrogen 
chloride  was  then  added  over  that  required 
for  precipitation.  After  being  heated  to 
boiling,  the  precipitated  samples  were 
cooled  to  room  temiperature,  filtered 
through  asbestos,  and  washed  with  solu- 
tions of  hydrogen  chloride  in  butyl  alcohol 
o  the  same  strength  as  those  from  which 
the  sodium  chloride  was  precipitated.  The 
precipitate  was  dried  at  250°,  ignited  at  500- 
600°  and  the  sodium  chloride  found,  cor- 
rected for  its  carbon  content,  was  compared 
with  the  amount  present.  The  concentra- 
tion of  hydrogen  chloride  was  gi-adually  in- 
creased, until  at  6  per  cent,  to  7  per  cent, 
the  solubility  of  sodium  chloride  reached  a 
mmimum  of  0.6  mg.  per  100  cc.  This  ex- 
cess of  hydrogen  chloride  can  be  obtained 
closely  enough  by  adding  to  the  solution  of 
the  perchlorate  half  as  many  cc.  of  20  per 
cent,  solution  of  hydrogen  chloride  in  butyl 
alcohol,  as  there  are  grams  of  the  solution. 
The  wash  solution  is  made  in  the  same  way. 

The  solubilities  of  the  various  salts  in- 
volved are  shown  in  the  following  tables : 

Table  II. 

Solubilities  in  Anhydrous  Normal  Butyl 
Alcohol  at  25°. 


G.  iper  100  g. 
solution. 

LiClO^        44.23 

NaClO,       1.83 

LiCI        11.49 

NaCl       0.014^ 

^  0.0116  g.  per  100  cc. 


Density 

25°/4°. 

1.1341 

0.8167 

0.8713 

0.8060 


JULY  27,  1923. 


THE  CHEMICAL  NEWS. 


59 


Table  III. 

Solubility  of  Sodium  Chloride  Precipitated  from  Anhydrous  Butyl  Alcohol  Goniainirnj 

6  per  cent,  of  Hydrogen  Chloride. 


Vol.  fil- 

Free 

Solubility  ol 

NaCl 

NaCl 

trate  and 

HCIO. 

LiCIO^ 

NaCl  in  100 

taken 

found 

washingsf 

present 

prtjeeut 

cc. 

G. 

G. 

Cc. 

% 

G. 

G. 

1 

0.3021 

0.3007 

102 

— 

— 

0.0014 

2 

0.3004 

0.2989 

110 

— 

0.1720 

0.0014 

3 

0.3031 

0.3020 

102 

— 

— 

0.0011 

4 

0.3510 

0.3493 

87 

— 

0.0350 

0.0019 

5 

0.1549 

0.1546 

52 

0.6 

— 

0.0000 

6 

0.1593 

0.1590 

55 

0.6 

— 

0.0006 

7t 

0.1034 

0.1027 

43 

0.5 

— 

0.0016 

8 

0.3505 

0.3481 

98 

1.6 

— 

0.0024 

acid 


1i  Consisting  of  butyl  alcohol  containing  hydrogen  chloride    and  a  little  perchloric 


f  Alcohol  as  received,  not  dried  or  distilled. 


It  is  evident  froui  the  above  data  that  the 
solubility  of  sodium  chloride  is  greatly  re* 
duced  by  the  presence  of  hydrogen  chlor- 
ide. That  of  lithium  chloride  is,  however, 
much  less  affected.  The  addition  of  4.9 
per  cent,  of  hydrogen  chloride  reduced  it 
from  11.49  g.  to  9.60  g.  per  100  g.  of  solu- 
tion. No  lithium  chloride  was  precipitated 
when  a  20  iper  cent,  solution  of  hydrogen 
chloride  in  butyl  alcohol  was  added  to  a  40 
per  cent,  solution  of  lithium  perchlorate  in 
the  eame  solvent.  The  solubility  of  sodium 
chloride  is  reduced  from  11.6  mg.  per  100 
cc.  in  pure,  drv  butyl  alcohol  to  1.4  mg.  by 
the  addition  of  6  per  cent,  hydrogen  chlor- 
ide and  to  0.6  mg.  per  100  cc.  by  the  fur- 
ther addition  of  0.5  per  cent,  of  70  per  cent, 
perchloric  acid.  The  rea.son  for  this  latter 
decrease  is  not  evident.  Moro  than  0.5  per 
cent,  of  perchloric  acid  increases  the  solu- 
bility. In  untpurified  and  undried  6  per 
cent,  hydrogen  chloride — alcohol  contain- 
ing 0.5  per  cent,  of  perchloric  acid,  the 
solubility  rises  to  1.6  mg.  per  100  cc. 

Conditions  Favouring  Filiraiion.  —  The 
higher  the  temperature  of  precipitation,  the 
greater  the  ease  of  filtration.  From  a  boil- 
ing sodium  perchlorate  solution  in  butyl 
alcohol,  the  sodium  chloride  precipitated  is 
perchlorate  solution  in  butyl  alcohol,  the 
sodium  chloride  precipitated  is  coarse, 
settles  rapidly,  and  filters  easily.  From  the 
same  solution  precipitated  at  room  tempera- 
ture, the  precipitate  is  more  gelatinous, 
settles  slowly,  and  is  difficult    to  filter    and 


wash.     The  same    soIuti<Mi  precipitated    at 
—IS*  to  —20"  cannot  be  filtered. 

Since  it  is  desirable  to  utilise  cold  precipi- 
tation to  prevent  occlusion  of  solvent  by  the 
sodium  chloride,  solutions  precipitated  at 
— 15®  to  — ^20°  were  heated  to  boiling  and 
allowed  to  cool  to  room  temperature  before 
filtration.  The  precipitate  of  sodium 
chloride  should  be  formed  by  adding,  drop 
by  drop,  to  the  cold  solution,  1-1.5  cc.  of 
the  hydrogen  chloride — butyl  alcohol  re- 
agent, the  remainder  to  f<»*m  a  6  per  cent, 
acid — butyl  alcohol  solution  being  added 
rapidly.  Under  these  conditions  the  pre- 
cipitated sodium  chloride,  after  boiling, 
settles  rapidly,  and  after  cooling  to  room 
temperature  can  be  filtered  clear,  using  a 
Ooooh  crucible.  It  is  washed  with  a  6-7 
per  cent,  solution  of  acid  in  butyl  alcohol. 
If  the  concentration  of  acid  is  over  6  per 
cent.,  coagulation  of  the  sodium  chloride  is 
less  effective. 

Physical  Constants  of  the  Butyl  Alcohol 
Used  in  the  Method. — In  view  of  the  results 
obtained  by  Winkler^  in  the  use  of  iso- 
butyl  alcohol,  a  rather  carefully  purified  n- 
butyl  alcohol  was  employed  in  most  of  the 
work  recorded  in  this  paper.  Winkler  used 
t«obutyl  alcohol  dehydrated  over  caustic 
potash  and  which  had  a  boiling  range  of  one 
degree,  106-107*.  It  was  further  specified 
that  this  fraction  of  the  dried  sanjiple  was 
necessary  for  good  results.  It  will  be 
shown  later  that  drying  only  and  no  frac- 
tionation is  required. 


60 


THE  CHEMICAL  NEWS. 


JULY  27,  1923. 


Treatment  of  Filtrates  from  Sodium 
Chloride  for  Recovery  of  Lithium. — The  fil- 
trates from  the  sodium  chloride  precipitate 
consisted  of  a  butyl  alcohol  solution  of  hy- 
drogen chloride  and  perchloric  acid,  lithium 
and  a  slight  amount  of  sodium  as  perchlor- 
ate  or  chloride,  the  latter  resulting  from  the 
almost  negligible  solubility  of  sodium 
chloride.  The  salts  were  recovered  by 
evaporation  of  the  solvent  and  volatile 
acids,  converted  to  lithium  and  sodium  sul- 
phates, ignited  and  weighed.  From  this 
weight,  corrected  for  the  known  amount  of 
sodium  sulphate,  the  amount  of  lithium 
was  calculated. 

Although  the  dilute  solution  of  anhy- 
drous perchloric  acid  and  lithium  iperchlor- 
ate  could  be  boiled  without  trouble,  eva- 
poration to  dryness  without  first  adding 
water  resulted  in  a  violent  deflagration;  30 
to  50  cc.  of  water  was  added  to  50-100  cc.  of 
the  cold  alcoholic  solution  and  2  immiscible 
layers  were  obtained.  The  under  layer  of 
water  extracted  most,  if  not  all,  of  the  pro- 
ducts of  solution  from  the  upper  alcoholic 
layer.  When  this  mixture  was  evaporated 
on  a  steam-bath  the  alcoholic  layer  evapo- 
rated completely,  leaving  the  greater  part 
of  the  water  solution  of  lithium  and  sodium 
perchlorates  and  perchl(»-ic  acid.  Tho  or- 
ganic matter  remaining  was  eventually  oxi- 
dised, and  after  the  addition  of  suliphuric 
acid  the  evaporation  was  continued  to  dry- 
ness. The  lithium  sulphate  was  then  dis- 
solved in  a  little  water,  washed  into  a 
weighed  platinum  crucible,  covered  and 
heated  over  a  ring  burner  to  remove  excess 
of  sulphuric  acid.  The  conversion  of 
lithium  perchlorate  to  lithium  sulphate  is 
more  easily  carried  out  without  loss  than 
conversion  of  lithium  chloride  to  sulphate. 
The  lithium  sulphate  was  ignited  in  a 
muffle  at  600°  for  5  to  10  minutes,  or  to 
constant  weight  in  case  of  large  amounts. 
Samples  thus  treated  were  neutral  and 
could  be  fused  without  loss  in  weight. 
Separation  of  Sodium  and  Lithium. 

When  free  from  potassium,  the  mixed 
chlorides  (free  from  sulphate)  obtained  by 
the  J.  Lawrence  Smith  or  other  method, 
are  evatporated  to  dryness  with  excess  of 
perchloric  acid.  A  second  evaporation  is 
desirable  if  the  amount  is  large.  If  potas- 
sium is  present  it  is  first  separated  by  the 
usual  perchlorate  method  and  the  filtrate, 
after  addition  of  water,  to  avoid  explosion, 
is  evaporated  to  dryness.  Since  a  definite 
amount  of  perchloric    acid  should    be    pre- 


sent, it  is  desirable  to  remove  first  all  ex- 
cess of  acid. 

The  mixed  perchlorates  of  sodium  and 
lithium  free  from  perchloric  acid  are  dis- 
solved in  anhydrous  n-butyl  alcohol  using 
at  least  15  g.  or  18.5  cc.  for  each  100  mg.  of 
sodium  chloride  present.  The  containing 
beakei's  may  be  conveniently  weighed  upon 
a  small  platform  balance.  The  mixture 
dissolves  readily  if  the  alcohol  is  heated  to 
boiling,  which  can  be  done  with  a  burner 
over  a  wire  gauze;  0.1  cc.  of  70  per  cent, 
perchloric  acid  is  added  and  the  solution  is 
cooled  to  — 15°  by  means  of  a  freezing 
mixture.  The  sodium  chloride  is  precipi- 
tated by  adding  from  a  buret,  drop  by  drop, 
with  constant  stirring,  1-1.5  cc.  of  a  20  per 
cent,  solution  of  hydrogen  chloride  in  an- 
hydrous butyl  alcohol,  after  which  the 
amount  necessary  to  form  a  6  per  cent. 
solution  is  ra^pidly  added  (half  as  many 
cubic  centimetres  as  there  are  grams  in  the 
solution  to  be  precipitated).  The  precipi- 
tate of  sodium  chloride  is  then  coagulated 
by  heating  the  solution  to  boiling  on  a  wire 
gauze  with  a  free  flame.  After  cooling  to 
room  t'Cmperature  the  sodium  chloride  is 
filtered  on  a  weighed  Gooch  crucible  and 
washed  8  or  10  times  with  a  6-7  per  cent, 
solution  of  hydrogen  chloride  in  butyl  alco- 
hol. (A  rubber-tipped  rod  can  be  used  in 
transferring  the  precipitate  from  beaker  to 
crucible.  It  is  well  to  preserve  it  by  wash- 
ing with  a  little  acetone  after  use.)  The 
sodium  chloride  is  dried  for  one  hour  at  250° 
and  ignited  for  5  to  8  minutes  at  600°  in  a 
muffle  furnace  (a  free  flame  may  be  used 
but  a  very  dull  red  must  not  be  exceeded). 
A  correction  of  0.6  mg.  for  the  sodium 
chloride  remaining  in  each  100  cc.  of  fil- 
trate and  washings  is  added  to  the  weight  of 
sodium  chloride  found,  to  obtain  the  total 
sodium  chloride  present. 

The  filtrate  and  washings  from  the 
sodium  chloride  are  diluted  with  one-third 
their  volume  of  water  (to  avoid  subsequent 
deflagraticfn)  forming  2  layers,  and  the 
whole  is  evaporated  on  the  steam-bath  in 
such  a  way  as  to  avoid  any  condensation  on 
the  upper  part  of  the  beaker,  which  causes 
loss  by  "  creeping."  It  is  well  to  add  5  to 
10  cc.  of  water  at  the  end  to  make  the  re- 
moval of  organic  matter  more  complete  be- 
fore the  perchloric  acid  takes  effect.  By 
such  treatment  a  colourless  residue  of 
lithium  perchlorate  and  perchloric  acid  can 
be  obtained.  If  a  slight  brown  colouration 
is  present,    remove    the  watch    glass    sup- 


JULY  27.  1923. 


THE  CHEMICAL  NEWS. 


61 


iports  from  the  beaker  and  lieat  the  covered 
beaker  on  a  wire  gauze  tf>  fumes  of  per- 
chloric acid.  If  any  brown  colour  remains 
adhering  to  the  beaker  walls  after  this 
treatment,  it  can  be  removed  by  brushing 
the  walls  o  the  beaker  with  the  flame.  If 
not  enough  perchloric  acid  is  present  to 
oxidise  the  last  traces  of  organic  matter,  a 
few  drops  are  to  be  added.  When  the 
brown  colouration  is  removed,  0.5  cc.  of 
cone,  sulphuric  acid  is  added,  the  watch 
glass  replaced,  and  the  acid  fumed  oft,  using 
either  a  hot  plate  or  low  Hame  and  wire 
gauze.  The  beaker  is  then  cooled,  5  to  10 
cc.  of  water  is  added,  and  the  cover  glass 
and  beaker  walls  washed.  The  Uthium  sul- 
phate is  then  transferred  to  a  platinum  cru- 
cible previously  ignited  and  weighed  with 
its  lid.  The  solution  is  cautiously  evapo- 
rated to  dryness  and  the  covered  crucible  is 
heated,  (preferably  by  a  ring  burner,  until 
every  trace  of  acid  is  removed,  after  which 
it  is  heated  to  600°  in  a  muffle  for  5  to  10 
minutes.  When  the  same  treatment  is  car- 
ried out  using  a  free  flame  and  a  very  dull 
red  heat,  some  reduction  to  sulphide  often 
takes  place,  due  to  diffusion  of  the  flame 
gases  through  the  platinum.  Fusing  with  a 
free  flame  to  oheck  the  weight  obtained  by 
the  above  treatment  is  possible  if  the  tem- 
perature is  not  too  high  or  the  treatment 
too  long. 

The  weight  of  lithium  sulphate  is  to  be 
corrected  for  its  sodium  sulphate  content 
by  subtracting  the  weight  of  the  solubility 
correction  calculated  as  sodium  sulphate, 
or  0.7  mg.  per  100  cc.  of  filtrate  and  wash- 
ings. A  further  correction  to  be  applied  is 
a  blank  for  the  reagents  ermployed.  This 
correction  in  found  by  precipitating  a 
weighed  sample  of  sodium  chloride  in  the 
manner  above  described.  One  cc.  of  per- 
chloric acid  is  ample  for  any  ordinary  quan- 
tity of  salts  to  be  converted,  and  the  sub- 
sequent additions  of  0.5  cc.  each  of  sul- 
phuric acid  and  perchloric  acid  are  enough 
to  provide  excess.  The  weight  of  material 
obtained  at  the  end  of  this  process  should 
bo  less  than  1  mg,    when  corrected  for  the 


sodium  chloride  solubility. 

Gooch  crucibles  with  0.5  mm.  holes  are 
nmch  better  than  those  with  large  holes. 
Platinum  Gooch  crucibles  with  their  much 
smaller  perforations  are  still  better.  A 
heavy  mat  of  asbestos  is  essential,  and  a 
perforated  porcelain  disc  should  be  placed 
on  it  to  prevent  disturbance  of  the  mat.  If 
platinum-sponge  filtering  crucibles  are  used, 
weighing  of  the  empty  crucible  should  be 
made  after  the  sodium  chloride  has  been 
washed  out  with  water,  since  spongy  plati- 
num is  slightly  attacked.  Asbestos  for  use 
in  filtrations  with  solutions  of  hydrogen 
chloride  in  butyl  alcohol  should  be  refluxed 
with  some  of  this  material  in  preparation 
for  its  use.  The  same  crucible  should  be 
used  many  times  over,  and  in  such  a  case 
previous  treatment  of  the  asbestos  with  the 
acid-alcohol  solution  is  not  necessary.  To 
show  the  effect  of  the  solvent  upon  asbes- 
tos, the  same  crucible  was  used  repeatedly, 
starting  with  untreated  asbestos.  The  so- 
dium chloride  was  washed  out  each  time. 
The  following  successive  weights  weie 
obtained:  26.6413,  26.0405,  26.6401, 
26.6401.  26.6401.  In  order  to  avoid  an 
additional  operation  the  filtration  with  suc- 
tion can  be  made  directly  from  the  crucible 
to  a  beaker  by  using  a  vacuum  desiccator  of 
the  usual  fonn  but  with  a  hole  pz'ovided  in 
the  cover  for  the  passage  of  a  filtering  tube 
and  rubber  stopper.  In  this  way  the 
beaker  to  receive  the  filtrate  can  be  placed 
in  the  bottom  of  the  desiccator.  The  filter- 
ing tube  should  have  a  small  perforation  in 
its  side  about  an  inch  from  the  bottom  to 
prevent  spattering. 

The  filtrates  were  rapidly  evaporated  on 
the  steam-bath  by  immersing  the  beaker 
in  a  C(:»pper  capsule  flanged  at  the  top  and 
fitt<»d  to  the  rings  of  the  steam-bath  so  that 
condensation  did  not  take  place  on  the 
walls  of  the  boakor  or  cover  glass.  This  is 
very  important  because  the  alcoholic  solu- 
tion shows  a  strong  tendency  to  "  creep." 

The  value  of  the  methcxi  was  tested  by  a 


I       series  of  analyses  of  known  mixtures,  with 
the  results  recorded  in  the  following  table. 
Table  IV. 
Separation  and  Estimation  of  Sodium  and  Lithium. 


NaCl 

NaCl 

xpt. 

taken 

found 

Error 

G. 

G. 

G. 

1 

0.1521 

0.1510 

-0.0002 

"2 

0.1481 

0.1478 

-0.0003 

3 

0.1017 

0.1017 

0.0000 

4 

0.2027 

0.2024 

-0.0003 

5 

0.1016 

O.IOIC) 

0.0000 

6 

0.0217 

0.0218 

+0.0001 

7 

omoQ 

0.0503 

+0.0001 

8§ 

0.1017 

0.1019 

+0.0002 

LiClO^ 

LiCI 

LijSO, 

LiCl 

taken 

calc. 

found 

found 

Error 

G. 

G. 

G. 

G. 

G. 

0.481  n 

0.1920 

0.2488 

0.1919 

-0.0001 

0.5,'>34 

0.2205 

0.2860 

0.2206 

+0.0001 

0..')205 

0.2110 

0.2736 

0.2110 

0.0000 

0.3004 

0.1197 

0.1558 

0.1202 

+0.0005 

0.4455 

0.1775 

0.2315 

0.1785 

+0.0010 

1.6354 

0.6118 

0.7929 

0.6116 

-0.0002 

62 


THE  CHEMICAL  NEWS. 


JULY  27,  1923. 


§  Alcohol  dried  but  not  fractionated;  b 
oiling  range  112-118°. 

The  separation  of  sodium  from  very  large 
amounts  of  lithium  is  accomplished  by  one 
precipitation  (Expt.  7). 

In  case  it  is  desired  to  avoid  a  cold  pre- 
cipitation (a  step  which  requires  but  one 
short  additional  operation),  the  method  can 
be  applied  exactly  as  described,  omitting 
cooling  to  — 15°  before  precipitation,  and 
adding  the  precipitant 'to  the  mixed  per- 
chlorate  solution  at  nearly  its  boiling  tem- 
perature. In  this  case  the  solubility  of  so- 
dium chloride  was  found  to  be  1.6  mg.  in 
100  cc.  of  solvent.  The  carbon  occluded  by 
a  precipitate  of  about  0.5  g.  of  sodium 
chloride  is  approximately  1.6-1.0  mg.  under 
these  conditions.  The  weight  of  sodium 
cKloride  in  the  precipitate  can  be  deter- 
mined by  dissolving  it  in  water,  drying  the 
crucible  with  its  carbon  impurity,  and 
weighing  after  filtration  rather  than  before. 
Summary. 

1.  A  method  is  described  for  the  separa- 
tion of  sodium  and  lithium  based  upon  thi^ 
precipitation  of  sodium  chloride  from  a  solu- 
tion of  the  perchlorates  in  anhydrous  n- 
butyl  alcohol  by  the  addition  of  an  alcoholic 
solution  of  hydrogen  chloride. 

2.  Conditions  affecting  the  accuracy  of 
the  process  were  studied  and  the  accom- 
panying errors  eliminated. 

3.  The  solubilities  of  the  anhydrous  per- 
chlorates and  chlorides  of  lithium  and  so- 
dium in  anhydrous  n-butyl  alcohol  at  25° 
are  given. 

4.  A  table  is  given  showing  the  density 
and  composition  of  solutions  of  hydrogen 
chloride  in  butyl  alcohol. 

5.  Test  analyses  show  that  one  separa- 
tion gives  accurate  results  even  in  the  pre- 
sence of  large  amounts  of  lithium. 

Ann  Arbor,  Michigan  and  Urhana, 

Illinois. 
(From     the    "Journal    of    the    American 
Chemical  Society,"  p.  2816,  1022.) 


GENERAL  NOTES. 


BRITISH  STANDARDS  FOR 
ELECTRICAL  MACHINERY. 
The  British  Engineering  Standards  Asso- 
ciation announces  the  withdrawal  of  Brit- 
ish Standard  Specification  72-1917,  from 
circulation.  This  document  is  now  under 
revision,  and  will  be  divided  into  the  follow- 
ing section<?,  each  of  which  will  be  issued  as 
a  separate  publication. 


(a)  Industrial  machines  (B.S.S.  168- 
1923)  has  already  been  published,  whilst 
(b)  Large  machines,  (c)  Transformers,  (d. 
Rotary  Converters,  and  (e)  Traction  motors 
are  in  course  of  preparation.  —  (From  the 
"  Board  of  Trade  Journal,"  July  12,  1923.) 


CONDENSED  MILK    INVESTIGATION. 

The  Food  Investigation  Board  of  the  De- 
partment of  Scientific  and  Industrial  Re- 
search has  issued  Special  Report  No.  13. 
under  the  title  of  "  Studies  in  Sweetened 
and  Unsweetened  (Evaporated)  Condensed 
Milk,"  by  W.  G.  Savage,  M.D.,  B.Sc,  and 
R.  F.  Hunwicke,  B.Sc,  A.I.C. 

The  Report  has  been  prepared  by  the 
Canned  Foods  Committee  of  the  Food  In- 
vestigation Board,  and  deals  chiefly  with 
the  bacteriological  problems  involved  in  the 
successful  condensation  and  canning  of 
milk. — {From  the  "  Board  of  Trade  Jour- 
nal," July  12,  1923.) 


CANADIAN  NATIONAL  EXHIBITION. 
In  a  recent  dispatch,  H.M.  Trade  Com- 
missioner at  Toronto  rqports  optimistically 
of  the  probable  British  participation  in  the 
Canadian  National  Exhibition,  to  be  hold 
in  that  city  from  August  25  to  September  8 
next. 

The  British    displays    may  be    classified 
under  three  headings  :  — 

(i)  Private  exhibits,  which  are  far  more 
numerous  this  year  than  previously. 

(ii)  The  collective  exhibit  organised  by 
the  Federation  of  British  Industries, 
which  is  understood  to  have  been  well 
supported. 

(iii)     The     Propaganda     and    Samples 
Bureau,    maintained  for  the  Department 
of  Overseas  Trade    by  H.M.  Trade  Com- 
missioner,  on  which    firms    will    disiplay 
trade  catalogues  and  table  samples.       It 
is    understood    that    at    least  40    British 
firms  will  avail  themselves  of  the  oppor- 
tunity offered  by  this  Bureau. 
In  connection  with    the  rapid  growth  of 
the  Canadian  National  Exhibition,  it  is  re- 
ported that  the    Cuban  Government  is  con- 
sidering a  recommendation    to  vote  a   sum 
of  50, (KX)  dols.  fo  rthe  erection    of  a  perma- 
nent pavilion    to  house    an  annual    Cuban 
exhibit  at  Toronto. — {From  the    "  Board  of 
Trade  Journal,"  July  12,  1923,) 


JULY  27,  1923. 


THE  CHEMICAL  NEWS. 


63 


In  the  House  of  Commons,  recently,  Mr. 
Attlee  asked  the  President  of  the  Board  of 
Trade  whether  he  was  aware  that  the  Brit- 
ish Dyestuiis  Gorporatiou,  Limited,  charged 
10  iper  cent,  commission  ou  reparation  dye- 
stuffs,  whereas,  when  the  distribution  wat 
undertaken  by  the  central  importing  agency, 
only  2i  per  cent,  was  charged;  and  for 
what  reason  was  this  high  rate  of  oonmiis- 
sion  permitted? 

Sir  i'.  Lloyd-Greame  repUed:  I  am  not 
aware  that  the  British  Dyestuffs  Corpora- 
tion charge  10  per  cent,  commission  on  re- 
paratiwi  dyestuffs,  and  would  refer  to  an 
answer  which  1  gave  on  this  matter  on 
December  4  last,  to  the  effect  that  the  Cor- 
poration receives  a  commission  of  6^  per 
cent,  on  the  actual  turnover  plus  a  further 
1  per  cent,  for  guaranteeing  accounts,  and 
a  grant,  which  is  limited  ui  amount,  to- 
wards the  charges  which  they  incur  relating 
to  the  importation  of  the  dyestuffs.  The 
Central  Importing  Agency  undertook  the 
duty  of  importing  and  distributing  the  dye- 
stuffs  for  a  commission  of  3^  per  cent.,  the 
rate  to  be  adjusted  if  prices  fell,  but  this 
charge  proved  to  be  inadequate,  and  was 
considerably  increased  with  the  approval  of 
the  Treasury  by  various  allowances  made 
to  the  Central  Importing  Agency  upon  the 
final  adjustment  of  their  accounts. 

Mr.  Attlee  further  asked  the  President 
of  the  Board  of  Trade  whether  he  was 
aware  of  the  high  prices  charged  for  repara- 
tion dyestuffs  by  tlie  British  Dyestuffs  Cw- 
i{)oratiou,  Limited;  that  the  price  of  diamine 
last  yellow  F.h\,  a  dye  for  which  there  was 
no  satisfactory  British  substitute,  had  been 
raised  from  4s.  per  lb.  to  7s.  6d.  per  lb..,  and 
to  lOs.  per  lb.,  although  this  dye  oould  be 
imported  from  Germany  for  4s.  6d.  per  lb. ; 
and  of  the  discontent  aroused  by  this  action 
among  colour  users ;  and  what  action  he  was 
prepared  to  take  in  the  matter? 

Sir  1*.  Lloyd-Greame  said  :  No  complaint 
about  the  price  of  this  dyestuff  has  been 
received  by  the  Board  of  Trade,  but  the  ar-' 
rangements  as  to  the  pricing  of  reparation 
dyes  are  being  reconsidered,  and  the  ()rice 
of  this  particular  dye  will  come  under  re- 
view. 

Major-General  Sir  Robert  Hutchinson 
asked  the  President  of  the  Board  of  Trade 
whether  he  was  aware  that  British  impor- 
ters of  lithopone  from  Germany  who  made 
contracts  before  February  1  found  it  almost 
impossible  to  get  delivery  of  their  goods,  be- 
cause   the  French    authorities    would    not 


issue  export  licences,  even  after  the  pay- 
ment of  the  French  7  per  cent,  duty,  and 
that  although  the  Freuch  authorities,  under 
pressure,  agreed  to  issue  export  licences, 
they,  in  fact,  put  every  obstacle  in  the  way 
of  British  traders  receiving  these  licences; 
and  what  could  he  do  in  the  matter  to  pro- 
tect British  trade  interests? 

Sir  P.  Lloyd-Greame  said :  The  answer 
to  the  first  ()art  of  the  question  is  in  the 
negative.  If  the  lion,  and  gallant  member 
will  furnish  me  with  particulars  of  the  cases 
which  he  has  in  mind  I  will  make  inquiry. 


COHHESPONDENCE. 


THE  COLOURING  OF  POISONS. 

To  the  Editors  of  The  Chemical  News. 
Sir, — In  the  interests  of  pubUc  safety,  it 
will  be  unfortunate    if  a  recent  decision  of 
the  General  Medical  Council  be  accepted  as 
the  final  wotd  in  the  highly  important  ques- 
tion of  colouring  deadly  poisons.     The  facts 
are  simple.    After  careful  experimenting  by 
British    dyemakers    and    pharmacists,    the 
Pharmaceutical    Society    of    Great    Britain 
reconuneuded  Brilliant  Green    to  the  Privy 
Council  as  a  colouring  for  a  preparation  of 
strychnine.     The  Privy  Council    forwarded 
the     suggestion    to    the    General    Medical 
Council  as  the  body  who  could  say  whether 
Brilliant  Green    would    interfere  with    the 
healing    properties  of    the  strychnine    pre- 
paration    in     question.        Thereupon     the 
General  Medical  Council  unanimously  con- 
demned the  proposal,    and  that  for  six  rea- 
sons, only  two  of  which  can  be  said  to  have 
a  remote  connection    with  the  curative  as- 
pect of  the  question,  namely,  that,  in  cer- 
tain mixtures,    Brilliant    Green    undergoes 
colour  changes  which  "might  be  objection- 
able" to  patients,  and  that  a  coloured  solu- 
tion "would  be  objectionable"  for  hypoder- 
mic injection. 

The  four  other  points  made  were :  (1) 
that  it  was  only  proposed  to  colour  one 
strychnine  preparation;  (2)  that  risk  would 
arise  from  keeping  coloured  solutions  side 
by  side  with  uncoioured;  (3)  that,  the  pre- 
paration being  uncoioured  in  other  coun- 
tries, difficulties  of  an  international  kind 
would  arise;  and  (4)  that  the  question  was 
a  general  one  and  should  not  be  determined 
in  the  case  of  a  single  preparation  of  a  single 
poison. 


64 


THE  CHEMICAL  NEWS. 


JULY  27,  1923. 


These  four  objections  may  be  just  or  they 
may  not.  What  I  do  submit  is  that  they 
are  matters  of  policy  to  be  determined  by 
Parliament  in  open  debate  rather  than 
settled  autocratically  by  the  most  conser- 
vative of  our  trade  unions. — Yours,  &c. , 

James  Sexton. 
House  of  Commons,  S.W'.l. 
July  16,  1923. 


NOTICES  OF  BOOKS. 

Quantitative  Cheviical  Analysis  and  In- 
organic Preparations,    by  E.    M.  Caven, 
D.Sc.  (LOND.),  F.I.C.     Part  I.     Pp.  VI. 
+  156.      London:    Blackie  &  Sons,  Ltd., 
50,  Old  Bailey,  E.C.    1923.    3s.  6d.  net. 
The  author  has  aimed  at  including  in  one 
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least  in  the  first  part  now  under  review. 

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gravimetric  analysis,  followed  by  exercises 
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tion of  preparations. 

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have  been  found  most  suitable  in  present- 
ing the  subject  to  students.  It  possesses, 
however,  one  or  two  features  that  call  for 
special  mention.  The  introductory  instruc- 
tions are  particularly  well  presented,  and  it 
is  to  be  hoped  that  all  students  using  the 
book  will  master  them  at  the  beginning  of 
the  course. 

Another  point  of  interest  is  the  use  of 
standard  oxalic  acid  as  the  basis  of  stan- 
dardisation in  acidimetry  and  alkalimetry. 
By  following  this  procedure,  the  teacher 
has  a  good  opportunity  to  press  home  a 
number  of  interesting  theoretical  and  prac- 
tical points.  It  might  be  pointed  out  here 
that  the  short  note  on  the  Use  and  Theory 
of  Indicators  does  not  go  very  far  and  seems 
inadequate. 

Also,  whilst  most  of  the  matter  in  the 
section  on  preparations  is  good,  the  method 
suggested  for  ferrous  ammonium  sulphate 
could  be  much  improved. 

The  book,  as  a  whole,  fulfils  its  intention 
for  the  use  of  students  who  have  passed  the 
elementary  stage,  and  it  will  prepare  such 
students,  in  practical  work,  up  to  degree 
standard. 


LITERARY    INTELLIGENCE. 

Volume  II.,  Part  II.  of  Molinari's  "  Or- 
ganic Chemistry  "  will  shortly  be  ready. 
This  volume  completes  the  whole  section  of 
the  work,  thus  making  available  a  compre- 
hensive treatise  covering  the  whole  ground 
of  Industrial  Chemistry,  both  Inorganic  and 
Organic. 

The  new  part  contains  over  300  illustra- 
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drates, Cyclic  Comipounds,  Dyestuffs,  Tex- 
tile Fibres,  Proteins,  etc. 

The  publishers  are  Messrs.  J.  &  A. 
Churchill. 


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solutions.    July  2. 

17466— Soc.  Chimique  des  Usines  du  Rhone.— Pre- 
paration of  diethvlchloracetamide.  July   5. 

17388  Soc.  of  Chemical  Industry  in  Basle.— 
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Abstract  Published  this  Week. 
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of    Oakhurst,     Church     Road.     Edgbaston, 

Birmingham. 
Phosphorus  i)entoxide  made  by  burning  phos- 
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AUGUST  3.  1923. 


THE  CHEMICAL  NEWS. 


THE  CHEMICAL  NEWS, 


VOL.  CXXVII.     No.  3303. 


X-RAY  SPECTROSCOPY    AS  A  MEANS 

OF  QUALITATIVE  AND 

QUANTITATIVE  CHEMICAL 

ANALYSIS. 

By  D,  Coster. 

The  X-ray  omission  from  the  anticathode 
of  an  X-ray  tube  consists  of  two  essentially 
different  parts  :  (1)  The  heterogeneous  radia- 
tion, or  the  "white"  X-ray  light,  the  nature 
of  which  depends  only  on  the  tension  used 
and  not  on  the  material  of  the  anticathode ; 
(2)  The  characteristic  radiation,  or  the 
"  line  spectrum,"  which  characterises  the 
el(.ii,.'nt«  present  on  the  anticathode.      The 


65 


X-ray  Ime  spectra  have  a  much  simpler 
structure  than  the  optical  line  spectra.  The 
characteristic  X-ray  spectra  of  the  different 
elements  are  built  uip  in  nearly  the  same 
way,  which  is  due  to  the  great  similarity  of 
the  inner  groups  of  electrons  of  the  atom 
for  the  different  elements.  They  consist  of 
but  very  few  strong  lines  and  a  relatively 
small  number  of  weaker  lines.  For  the  X- 
ray  lines  the  following  simple  relation 
holds :  the  square  root  of  the  frequency  of  a 
definite  line  is  to  a  first  approximation  pro- 
portional to  the  atomic  number  of  the  emit- 
ting element.  Roughly  speaking,  we  could 
say :  If  the  X-ray  spectrum  of  a  definite 
element  is  known,  those  for  the  next  ele- 
ments with  higher  atomic  number  Ore  found 
by  shifting  the  whole  group  of  lines  a  cer- 
tain amount  to  the  short  wave-length  side 
This  fact  may  be  illustrated  by  the  follow- 
mg  figures. 


Pig.    1. 


m 


THE  CHEMICAL  NEWS 


AUGUST  3,  1923. 


wave:     length    X  lOCms 


SQUARE 


10  12 

ROOT 


14  16  18 

OF     FREQUENCY 
Fig.    2. 


QO 

X  10- 


22 


24 


AUGUST  3,  1928. 


THE  CHEMICAL  NEWS. 


67 


Fig.  2  gives  the  square  roots  of  the  fre- 
quences of  some  Hues  of  the  K-series  (ordi- 
nates)  as  a  function  of  the  atomic  number 
(abscissa;).  Fig.  1  gives  the  photographs 
of  the  lines  for  the  same  series  for  some 
Hghter  elements  (both  figures  have  been 
taken  from  a  paper  by  Moseley^).  As  ap- 
pears from  the  above,  the  atomic  number  of 
an  element  is  strictly  determined  by  its  X- 
ray  spectrum.  As  we  know,  Moseley,  in  his 
fundamental  investigations  of  the  high  fre- 
quency spectra,  was  able  to  determine  in 
this  way  the  number  of  elements  between 
Ba  and  Ta.  Whereas,  in  consequence  of 
the  exceptional  behaviour  of  the  rare  earth 
metals,  no  direct  information  in  this  mat- 
ter could  be  obtained  from  Mendelejeff's 
table. 

Due  especially  to  the  work  done  in  the 
laboratory  of  Prof.  Siegbahn,  the  X-ray 
spectra  of  the  elements  Na-U  are  known 
rather  completely.  Following  Barkla's  no- 
menclature of  the  characteristic  X-radiati()n 
the  lines  have  been  classified  in  different 
groups  or  series  which  are  called  K-,  L-,  M-, 
and  N-series.  The  range  of  wave-lengths 
which  can  be  measured  in  the  present  state 
of  X-ray  spectroscopy  lies  between  18.5  and 
0.1  A-units.  As  a  consequence  of  this,  the 
K-series  of  the  lighter  elements  could  only 
be  measured  as  far  down  as  Na,  the  L-series 
is  only  known  for  the  elements  of  higher 
atomic  number  than  Co,  whereas  the  M- 
series,  as  yet,  has  been  found  only  for  the 
elements  of  higher  atomic  number  than  Dy, 
and  the  N-series  only  for  Bi,  Th,  and  U.* 

As  a  chemical  element  is  unambiguously 
determined  by  its  X-ray  spectrum,  X-rny 
spectroscopy  may  be  used  as  woll  as  optical 
spectroscopy,  as  a  means  of  identification 
of  elements.       For  this  purpose  the  former 


'  Phil.  Mag.,  1018,  XXVI.,  1024;  1011. 
XXVII.,  703.  Though  in  Fig.  1  the  nonini- 
clature  of  the  elements  60-72  j«  not  wholly 
up-to-date,  I  thought  it  of  great  hi«toricof 
interest  to  reproduce  the  figures  as  they  are 
found  in  the  original  papers. 

^  See  M.  Siegbahn.  Jahrbuch  filr  Radio- 
ahlivifdt.  1922,  XVIII.,  240.  PuhUcations 
of  later  date  which  arc  not  mentioned  in 
Sieghahn's  summarising  article  are:  M. 
Siegbahn  and  V.  Dolcjsek,  Zeitschrift  fiir 
Vhysih,  1022,  X.,  159;  D.  Coster,  Phil. 
Mag.,  1922,  XLIII.,  1070  anJ  1022,  XLIV.. 
546;  Hjalntar,  Zeitschrift  fiir  Physik,  1923, 
XV.,  65. 


has  even  some  important  advantages :  (1) 
As  the  X-ray  spectra  are  much  simpler 
than  the  optical  spectra,  the  identification 
of  the  lines  meets  with  less  difficulties;  (2) 
In  X-ray  spectroscopy  it  is  of  no  import- 
ance in  what  mixtures  or  compounds  the 
element  in  question  occurs;  (3)  One  per 
cent,  of  a  certain  element,  in  a  preparation 
of  which  only  1  milligram  is  available,  is 
enough  to  be  detected.' 

It  may  be  pointed  out,  however,  that  in 
general  some  faint  X-ray  lines  do  not  suffice 
to  determine  a  certain  element,  even  if  their 
position  nearly  coincides  with  that  expected 
for  the  element  in  question.  Though, 
as  is  stated  above,  the  number  of 
X-ray  lines  is  very  limited,  in  the  last  few 
years  several  investigators  have  succeeded 
in  establishing  the  existence  of  a  rather 
large  number  of  fainter  lines.  Moreover, 
as  usually  rather  high  tensions  are  used, 
not  Mily  the  spectrum  of  first  order,  but 
also  that  of  second  and  third,  and  in  some 
cases  even  of  still  higher  order  may  appear.* 
As  also  very  small  impurities  of  the  anti- 
cathode  material  and  of  the  substance 
under  examination  give  their  characteristic 
X-ray  spectrum,  in  most  cases  there  are 
several  possibilities  for  the  identification  of 
a  given  line.  In  order  to  avoid  erroneous 
conclusions,  regard  must  therefore  be  taken 
not  only  to  the  wave-lengths  of  the  lines, 
but  also  to  their  typical  behaviour,  especi- 
ally as  regards  the  relative  intensity  of  the 
lines  belonging  to  the  same  element. 

In  one  respect,  however.  X-ray  spectro- 
scx>py  might  be  of  more  use  for  chemistry 
than  optical  spectroscoipy,  in  that  it  may 
also  be  applied  successfully  to  quantitative 
analysis.  It  was  used  for  the  first  time  for 
this  purpose    by    Hevesy    and    the    author 


•'•  Mitlioda  and  apparatus  have  been  thor- 
oughly diitcmsed  by  M.  Siegbahn  Jahrbuch 
de'r  liadioahtivitdt,  1916,  XIII.,  296,  and 
1022,  XVIII.,  240. 

*  According  to  Bragg' s  relation :  n\  = 
2  d-sin  (here  is  the  glancina  angle,  d  the' 
grating  cionstant,  A  the  reflected  wave- 
length, and  n  an  integer)  corresponding  to 
different  values  of  n  different  values  of  A 
are  related  to  a  definite  glaneing  angle,  n  = 
1  corresponds  to  the  first  order  spectrum, 
n  =  2  to  the  second  order  spectrum,  etc. 
Hoiv  far  the  spectra  of  higher  order  appear 
depends  on  the  tension  used  and  the  analys- 
ing crystal. 


68 


THE  CHEMICAL  NEWS. 


AUGUST  3,  1923. 


during  an  examination  of  the  occurrence  of 
the  new  element  hafnium^  in  zirconium 
minerals  and  the  investigation  of  its  chemi- 
cal properties.  The  main  feature  of  the 
method  is  the  addition  to  the  substance  to 
be  examined  of  a  known  quantity  of  an  ele- 
ment with  an  atomic  number  in  the  neigh- 
bourhood of  that  of  the  element  under  con- 
sideration and  the  determination  of  the  X- 
ray  spectrum  of  the  mixture.  By  compari- 
son of  the  intensity  of  the  lines  of  the 
added  element  to  that  of  the  corresponding 
lines  of  the  element  under  investigation  an 
estimation  of  the  concentration  of  the  latter 
element  may  be  obtained.  The  reliability 
of  the  method  appears  from  the  following 
considerations.  The  energy  of  an  X-ray 
line  is  proportional  to  the  number  of  atoms 
of  the  corresponding  element  in  the  anti- 
cathode  spot.  In  the  case  of  two  elements 
adjacent  in  the  periodic  table,  the  configu- 
ration of  the  inner  electrons  of  the  atom  is 
very  nearly  the  same.  We  may,  therefore, 
assume  that  the  ratio  of  the  energies  of  two 
corresponding  lines  of  such  elements  in  first 
approximation  is  the  same  as  that  of  the 
numbers  of  radiating  atoms  belonging  to 
each  of  them. 

Two  objections  could  be  raised  against 
the  method.  (1)  The  critical  exciting  ten- 
sion of  a  definite  line  is  not  the  same  for 
different  elements.  Using  a  tension  which 
is  much  higher  than  the  critical  tension  of 
the  lines  for  the  elements  in  question,  this 
difference  may  be  neglected".  (2)  Another 
objection  could  be  made  against  the  practi- 
cal application  of  the  method.  By  sputte- 
ring or  evaporation,  part  of  the  atoms  pre- 
sent in  the  anticathode  spot  will  disappear 
during  the  course  of  an  exposure.  In  gene- 
ral this  will  give  rise  to  a  change  in  the 
ratio  of  the  quantities  of  the  different  ele- 
ments present  on  the  anticathode.  Errors 
due  to  this  circumstance,  however,  may  be 
avoided  by  a  suitable  choice  of  the  condi- 
tions of  experiment  (small  current  densities 
in  the  anticathode  spot).  Only  in  a  few  ex- 
ceptional cases,    e.g.,  if  mercury  or  iodium 


■'  Nature,  Feb.  10,  1923.  See  also  G. 
Hevesy,  The  Chemical  News. 

*  In  this  connection  it  may  be  pointed  out 
that  the  intensity  of  the  characteristic  X- 
ray  speetrum  is  in  first  approximation  pro- 
portional to  the  second  power  of  the  dif- 
ference of  the  tension  used  and  the  critical 
tension. 


compounds     are    to    be    investigated,     the 
method  would  not  lead  to  the  right  results. 


Figure  3  shows  how  the  hafnium  content 
in  zirconium  minerals  was  determined. 
The  figure  represents  a  photometer  curve  of 
the  blackening  of  the  photographic  plate 
taken  with  the  MoH  microphotometer^  of 
the  firm  Kipp  (Delft,  Holland).  The  uipper- 
most  curve  is  taken  from  a  plate  of  a  zir- 
conium mineral  from  the  Ural.  The  haf- 
nium content  appears  to  be  a  little  more 
than  5  per  cent.  The  copper  lines  are  due 
to  the  copper  anticathode.  The  zirconium 
Ka  lines  which  in  second  order  lie  nearly  on 
the  same  place  as  the  hafnium  La  lines, 
could  not  aippear  on  the  plate,  as  the  ten- 
sion used  during  the  exposure  was  less  than 
the  critical  tension  for  the  zirconium  lines, 
i.e.,  18,000  volts.  The  other  curve  repre- 
sents the  blackening  of  a  photograph  of  a 
zirconium  mineral  from  Brazil.  The  haf- 
nium content  appears  to  be  a  little  smaller 
than  2  per  cent. 

In  the  same  way  the  chemical  properties 
of  hafnium  were  studied.  Our  former  in- 
vestigations had  already  shown  that  in 
nearly  all  zirconium  minerals  a  rather  large 
percentage  of  hafnium  is  present.  From 
this  we  might  conclude  that  the  chemcial 
properties  of  hafnium  are  closely  related  to 
those  of  zirconium.  This  conclusion  was 
firmly  established  by  a  further  investiga- 
tion. The  method  used  may  be  illustrated 
in  the  following  example.  In  order  to  de- 
termine   the  solubility    of  hafnium    phos- 


^  W.  J.  H.  Moll,  Proceedings  Phys.  8oc. 
London,  1921,  XXXIII. ,  207. 


AUGUST  3,  1923. 


THE  CHEMICAL  NEWS. 


phate  compared  with  that  of  zirconium 
phosphate,  a  solution  of  a  mixture  of  zir- 
conium and  hafnium  was  precipitated  with 
sodium  phosphate  in  11  equal  fractions. 
The  original  mixture  contained  about  4  per 
cent  hafnium ;  10  per  cent  Ta  was  added 
to  each  of  the  different  fractions,  and  then 
the  X-ray  spectra  were  investigated.  Figure 

Cu  KcK 


Fig.    4. 

4  givL'8  the  photometer  curves  of  the  flpeo- 
tra  of  the  Ist,  4th,  and  8th  fractiwi.  These 
curvcH  clearly  show  that  the  solubility  of 
hafnium  phosphate  is  considerably  less 
than  even  that  of  zirconium  phoephate. 


SbZa, 


-Co/fouoj 


Fig.  5  gives  an  idea  of  the  sensibility  of 
the  method.  Two  artificial  preparations 
were  made  of  CaSO^  mixed  with  SnCla  and 
SbjOj.  Both  preparations  contained  10  per 
cent,  antimony.  To  the  first  12  per  cent, 
ten  was  added,  to  the  other  8  per  cent.  The 
photometer  curves  express  very  well  the 
real  state  of  things.  It  may  be  pointed  out 
that  the  above  example  was  not  at  all 
chosen  so  that  it  should  give  a  too  favour- 
able impression  of  the  reUability  of  the 
method.  Indeed,  antimony  oxide  subli- 
mates very  socHi,  and  when  the  preparation 
was  heated  in  the  Bunsen  flame  before  the 
exposure,  the  antimony  appeared  to  have 
decreased  by  about  30  per  cent,  relatively 
to  the  amount  of  ten.  Therefore,  in  expos- 
ing the  plates,  a  rather  small  current  was 
used  and  the  anticathode  was  cooled  effec- 
tively. 

Evidently  it  is  possible  to  improve  the 
sensibility  of  the  method.  We  will  discuss 
some  sources  of  error  which  were  to  be 
taken  into  consideration  for  obtaining  a 
larger  accuracy.  (1)  The  photographic 
plate  has  not  the  same  sensibility  at  differ- 
ent places.  Errors  of  this  origin  could  be 
avoided  by  determining  the  photometer 
curves  at  different  heights  of  the  plate  and 
eventually  by  taking  more  than  one  iplate 
of  the  same  preparation.  (2)  The  different 
lines  appearing  on  the  photographic  plate 
are  reflected  by  different  parts  of  the  crys- 
tal and  in  general  the  reflecting  power  of 
the  crystal  will  not  be  the  same  at  different 
places.  (8)  The  different  lines  correspond 
to  different  parts  of  the  anticathode  spot 
for  which  in  general  the  intensity  of  radia- 
tion will  not  be  the  same.  The  last  two 
errors  could  be  avoided  for  the  greater  part 
by  constructing  the  apparatus  in  such  a 
way  that  only  a  very  small  angle  was  ex- 
posed at  the  same  time.  In  this  case  only 
a  definite  part  of  the  crystal  is  used,  the 
radiaticu  coming  from  a  definite  part  of  the 
anticathode  spot.  As  it  is  necessary  to 
photograph'  more  than  one  hne  on  the  s£kme 
plate  the  crystal  was  to  be  turned  during 
the  exposure. 

In  order  to  obtain  a  greater  accuracy  it 
would  also  Ik  desirable  to  make  the  amount 
of  the  comparison  clement  as  exactly  as 
possible  equal  to  that  of  the  investigated 
element,  which,  of  course,  can  only  be 
done  by  repeated  trials.  In  proceeding  in 
this  way,  however,  we  should  miss  one  of 
the  greatest  advantages  of  X-ray  analysis, 
i.e.,  its  rapidity.  Therefore  in  this  form  it 
should  only  come  into  consideration  for 
elements  like  zirconium  and  hafnium,  for 
which  quantitative  analysis  meets  with 
great  difficulties.    But  if  a  great  accuracy  is 


Fig.    5. 


70 


THE  CHEMICAL  NEWS. 


AUGUST  3,  1923 


not  wanted  in  the  first  place,  e.g.,  in  the 
case  of  investigations  of  minerals,  the 
method  as  it  was  used  in  our  hafnium  in- 
vestigation works  very  quickly,  having  at 
the  same  time  a  high  reliability.  In  this 
connection  it  may  be  pointed  out  that  it  is 
not  at  all  necessary  to  take  photometer 
curves  of  all  the  plates.  After  some  experi- 
ence, it  is  not  difl&cult  to  estimate  rather 
accurately  the  relative  intensity  of  lines 
with  the  eye.  Moreover  a  relatively  small 
difference  in  the  blackening  of  the  lines  re- 
veals itself  clearly  as  a  phase-difference  in 
the  appearance  of  the  lines  during  the  de- 
velopment of  the  plate. 

As  is  shown  above,  X-ray  analysis  gives 
a  means  of  rapid  determination  of  the 
nature  and  the  amount  of  the  elements 
occurring  in  a  preparation.  It  may,  how- 
ever, also  be  used  in  an  investigation  of 
the  physical  and  chemical  state  of  these 
elements.  The  method  described  above  is 
founded  on  the  analysis  of  the  characteris- 
tic X-ray  spectrum  of  the  investigated  ele- 
ment by  reflection  on  a  crystal  plane  of  a 
crystal  with  known  space  grating  constant, 
e.g.,  calcite,  rocksalt  or  gypsum.  But  we 
can  conversely  also  try  to  determine  the 
crystal  structure  of  our  ipreparation  with 
the  aid  of  monochromatic  X-ray  light  of 
known  wave-length.  About  this  side  of  X- 
ray  analysis  I  will  only  make  some  remarks 
which  could  be  of  interest  in  connection 
with  the  above.  Ordinary  qualitative  ana- 
lysis is  able  to  inform  us  that  a  certain 
preparation  contains,  e.g.,  calcium  and 
potassium  and  a  chloride  and  a  nitrate,  but 
this  analysis  does  not  directly  give  the  fur- 
ther information  as  to  whether  we  have  a 
mixture  of  calcium  nitrate  and  potassium 
chloride,  or  of  calcium  chloride  and  potas- 
sium nitrate.  An  examination  of  the  crys- 
tal structure,  however,  will  throw  light  upon 
this  question  also.  For  this  purpose  the 
most  adequate  method  is  the  "  pulverised 
crystal  method."®  Naturally  it  is  not  pos- 
sible to  use  a  diagram  of  a  crystal  mixture 
for  calculating  the  different  crystal  struc- 
tures which  are  present  in  the  mixture,  but 
this  is  not  necessary.  The  only  thing  we 
want  is  a  collection  of  standard  diagrams  of 
the  crystal  structures  which  may  be  sup- 
posed to  be  present  in  the  mixture.      By  a 


«  P.  Dehye  and  Scherrer,  Phys.  Zs., 
1916,  XVII.,  277;  A.  W.  Hull,  Phys.  Re- 
view, 1917,  X.,  661. 


comparison  of  the  diagram  of  the  mixture 
and  the  standard  diagrams  it  is  easy  to  see 
which  crystals  are  present  and  which  not. 
In  this  way  Dr.  A.  Hadding,  of  Lund— as 
he  kindly  told  me— has  used  X-ray  analysis 
to  determine  the  components  of  dense 
mineral  ores  and  other  mineral  aggregates. 


OKGANIG  COMPOUNDS  OF    ARSENIC. 

PART  I. 

By  R.  F.  Hunter,  F.C.S. 

The  organic  compounds  of  arsenic  are 
some  of  the  most  interesting  and  valuable 
substances,  both  from  the  point  of  view  of 
academic  interest  and  from  that  of  thera- 
peutic value,  and  hence  a  brief  survey  of 
our  knowledge  might  be  given. 

The  subject  carries  us  back  to  the  year 
1760,  when  Cadet  produced  his  "fuming 
liquid"  by  the  distillation  of  arsenious  acid 
with  sodium  acetate  in  equal  proportions 
by  weight :  Two  liquids  appeared  in  the  re- 
ceiver used  in  the  distillation,  the  more 
volatile  compound  exhibited  acid  properties 
while  the  less  volatile  oomtpound  was  a  red- 
brown  liquid  which  filled  the  receiver  with 
fumes.  Both  components  had  a  most 
sickening  odour,  resembling  to  some  degree 
the  odour  of  garlick.  The  heavier  of  the 
two  liquids,  that  is  to  say,  the  red-brown 
compound  exhibited  spontaneous  inflanuua- 
bility  when  an  attempt  was  made  to  pour  it 
from  the  receiver  at  ordinary  temperature. 
Madet  and  Durande,  who  subsequently  in- 
vestigated the  reaction,  showed  the  heavy 
liquid  to  possess  the  viler  stench  and  to  be 
the  component  possessing  spontaneous  in- 
flammability. 

The  most  sickening  foetid  odour  of  the 
compound  deterred  investigators  from  the 
subject  for  nearly  eighty  years.  This  is  not 
so  suriprising  when  we  consider  the  lack  of 
means  for  experiment  of  the  time,  coupled 
with  the  stupefying  odour  which  produced 
nausea  and  unbearable  irritation  of  the 
nasal  mucous  membrane,  which  the  com- 
pound possessed. 

In  the  years  1887-1843,  Bunsen  carried 
out  his  classical  researches  on  this  com- 
pound. The  preparation  was  repeated  on  a 
large  scale,  500  gms,  of  both  constituents 
being  distilled  together : 

Analysis  gave  the  formula  C^HjaAsjO, 
and  Bunsen  showed  the  compound  to  be 
tetra-methyldiarsine  oxide. 


AUGUST  3,  1923. 


THE  CHEMICAL  NEWS. 


71 


(CH3),  As  O  As  (CH3),, 
and    the      reaction      to      be      our      usual 
test  for    an  acetate    in  minute    quantities, 
viz. :  — 
AsjO,  +  4CH,C00Na  = 

(AsMeJjO  +  2Na2  CO,  +  2C0,. 

The  free  radical  cacodyl  or  dimethylar- 
sene  was  subsequently  isolated  by  the  action 
of  zinc  cli)i)ping8  on  the  chloride  of  cacodyl, 
the  reaction  carried  out  in  an  atmosphere  of 
CO..  This  is  only  a  brief  historical  survey, 
and  the  complete  accounts  can  be  found  in 
the  references  at  the  end  of  the  article. 

Aliphatic  arsenicals,  such  as  methylar- 
sines,  etc.,  have  been  prepared  by  the  usual 
methods  given  in  text  books  of  organic 
chemistry,  viz.,  such  reactions  as  the  actirm 
of  zinc  alkyls  on  arsenious  chl(Mnde.  alkyl 
halides  on  sodium  arsenide,  etc. 

Examples :  — 
2  As  CI3  +  3ZnMe,  =  2A8Me,  +  SZnCl,. 

As  Na,  +  SCHjI  =  AsMe.  +  SNal. 

The  compounds  o|, several  series  of  this 
type  have  been  studied,  for  instance. 
Ethylarsines,  Propyl,  Allyl,  and  Butyl,  and 
amyl  arsincs  and  their  derivativ)^  have  beon 
d'^scribed  by  various  workers. 

The  aromatio  compounds  are  of  more  in- 
terest to  us,  however,  from  the  point  of 
view  of  their  closer  relationshiip  to  the  im- 
portant medicinal  compounds  of  arsonic 
such  as  snlvarsan,  etc.,  which  are  of  groat 
importance  in  the  treatment  of  protozoni 
diseases. 

As  far  back  as  1868  Bechamp  found  that 
arsenic  could  react    with    aniline    without 
oxidation    of  the    base,    hv    obtained    apart 
from  his  other    products,    such  as    dyes    of 
magenta  type.     A  compound, 
C  H,NHAs(OH),. 
It   is    reniHrkable     that    only    within     th« 
last   ten  y«'ar»   or   so   have    we  come  U*  re- 
gard the    acid  as    having    the    constitution 
which  was  assigned  to  it  by  its  discoverer. 

The  sodium  salt  was  introduced  into 
medicine  under  the  name  of  "  atoxyl." 
which  was  much  used  at  one  time  as  a  cure 
for  sleeping  sickness.  The  compound  was 
used  in  the  form  of  intravenous  injections. 
It  was  a  compound  remarkably  fatal  to  tho 
trypanoflones  of  sleeping  sickness,  but  suf- 
fered from  the  dsiadvantage  that  the  patient 
very  often  exhibited  symptoms  of  arsenical 
poisoning  after  such  an  injection,  the 
poisonous  oflFocts  being  cumulative  such 
that  they  could  finally  give  rise  to  complete 
blindness  and  kidney  complications. 

Hosts  of  researchers  in  the  field  of  aro- 
matic   arsenicals    have    produced    a    large 


number  of  compounds    of  varying    Lm|>ort- 
ance. 

The  classes  of  compounds  produced  might 
have  been  divided  as  follows:  — 

(1)  Benzene  derivation  with  one  aromatic 
nucleis  attached  to  one  arsenic  atom. 

Exargples :  Phenylarsenious  chloride, 
C,H,  -  AsClj,  compounds,  such  as  the 
methyl  ethyl  phenyl  esters  of  phenylarseni- 
ous acid : 

Phenylareenic  acid,  C,HjAsO(OH)„  its 
salts,  esters  and  halogen  derivatives,  but 

Arsenobenzene,  CgHjAs  As  C,Hj,  is  the 
most  interesting  compound  of  this  class 
owing  to  its  relatiMi  to  salvarsan. 

(2)  Benzene  derivatives  with  two  aroma- 
tic nuclei  attached  to  one  arsenic  atom,  ex- 
amples of  which  are  diphenylarsenious  chlor- 
ide, phenylcacodyl,  (C,HJj,  As  As  (C.Hj),, 
diphenyiarsine  and  its  derivatives. 

(3)  Benzene  derivatives  with  three  aroma- 
tio nuclei  attached  to  one  arsenic  atom.  Tri- 
phenylarsine,  Ph,As,  is  simplest  example. 

(4)  Toluene  derivatives  with  one  aromatic 
nucleus  attached  to  one  arsenic  atom. 

Examples  of  this  are  o-Tolyarsenious 
chloride,  o-Tolylarsenious  oxide,  o-tolylar- 
senious  aoid,  and  the  corresponding  m  and 
p  compounds. 

We  navo  also  mixed  tertiary  arsenic  with 
a  tolyl  radical,  an  example  of  which  is  p- 
tolydimethyl  arsino. 

(5)  Toluene  derivatives  with  two  or  three 
aromatic  nuclei  attached  to  one  arsenic 
atom. 

These  we  further  sub-divide  into  triaryl 
and  diaryl  series,  examples  being  tri-p- 
tolyarsine  and  Di-p-toly arsenious  chloride. 

(6)  Benzvl  derivatives,  of  which  triben- 
zylaraine,  .\s(CH2C,H5).,  is  an  example. 

(7)  Aromatic  arsenicals  containing  higher 
aryl  groups :  Compounds  such  as  m-xylyl- 
arseDious  chloride;  oxide,  sulphate,  etc.,  are 
examples. 

(8)  Arsenical  derivatives  of  naphthalene, 
these  are  of  peculiar  interest,  and  examples 
are :  a-Naphthylarsenious  Chloride,  C,oH^- 
AsC,; 

Arsenic  a-mvphthalene,  C,oH,A8  As 
^loH. ; 

a-Naphthylarsenic  acid,  CjoH^As  O 
(OH)  ; 

/S-Naphthylarsenic  acid,  C,„H^A8  0  (OH),. 

(9)  Benzarsenic  acids  and  derivatives 
which  are  further  sub-divided  into: 

(a)  Toluene  series. 
(h)  Xylene  series, 
(c)  Pseudo  cumene  series. 
p-Benzarsenic  acid. 


72 


THE  CHEMICAL  NEWS. 


AUGUST  3.  1923. 


CO^HCeH.AS  0  (OH)^, 
is  an  example  of  the  first,  and  phenyl- 
ditolylarsineoxidecarboxylic  acid,  triphenyl- 
arsineoxidetetracarboxylio  acid,  are  ex- 
amples of  the  second,  and  phenyldixylylar- 
sineoxidedicarboxylic  acid  and  phenylditolyl- 
arseneoxidetetracarboxylic  acids  are  ex- 
amples of  the  third. 

(10)  Betaines  of  Aromatic  Arsenicals. 
Phenyldiethylarseuicbetainehydrochloride, 

and  triethylarsenibenzobetaine  are  good 
examples. 

(11)  Nitro  derivatives  of  aromatic  arseni- 
cals, compounds  such  as  m-nitrophenylar- 
senio  acid,  m-nitroiphenylarsenicals,  bro- 
fide  sulphides,  sesquisulphide,  dinitro- 
diphenylarsenious  sulphide,  chloride,  etc., 
are  examples. 

Of  particular  interest  in  the  group  are  the 
reduction  products  of  3-nitro-tolyarsenic 
acid : 

3:8  dinitro  arsenic  p-toluene. 

3-nitro-4-tolyarseniou8  sulphide. 

3-amine-4-tolylthioar8inic  acid,  etc. 

We  have  now  to  consider  the  two  classes, 
comipounds  which  are  of  immense  import- 
ance in  medicine,  and  which  will  be  dealt 
with  under  the  titles  of  Atoxyl  and  its  deri- 
vatives, Salvarsan  and  its  derivatives. 


RELATIVE  DETERMINATION  OF  THE 

ATOMIC    WEIGHT    OF  CHLORINE    IN 

BAMLE  APATITE. 

By  Margot  Dorenfeldt. 
Introduction. 

This  work  was  undertaken  at  the  sugges- 
tion of  Dr.  Ellen  Gleditsch  in  connection 
with  an  investigation  carried  out  by  Gle- 
ditsch and  Samdahl,^  the  object  being  to 
determine  whether,  in  an  old  mineral  which 
has  not  been  in  contact  with  water,  the 
two  chlorine  isotopes  of  atomic  weights  35 
and  37  occur  in  the  same  proportion  as  in 
ordinary  chlorine.  The  mode  of  attack  was 
to  compare  the  specific  gravities  of  satur- 
ated solutions  of  sodium  chloride,  one  solu- 
tion being  made  from  ordinary  sodium 
chloride  and  the  other  from  Bamle  apatite, 
the  method  being  similar  to  that  described 
by  Fajans  and  Lembert.^ 

^  Oleditsch  and  SamdahJ,  Compt.  rend., 
1922,  CLXXIV.,  746.  Arch.  Math.  Natur- 
vidensk.,  1923.  XXXVIII. 

^  Fajans  and  Lemhert,  Z.  anorg.  Ghem., 
1916,  XCV.,  297. 


Apparatus  and  Materials. 

The  pycnometer  was  an  exact  copy  of  one 
described  by  Fajans  and  Lembert,^  a  modi- 
fied Sprengel-Ostwald  type.  The  tempera- 
ture variations  of  the  thermostat  cannot  be 
given  accurately,  but  a  0.1°  thermometer 
showed  no  change.  The  glass  test-tubes  in 
which  the  solutions  were  rotated  in  the 
thermostat  were  of  thick  glass,  14  cm. 
long,  and  of  22  mm.  internal  diameter.  The 
clean  tubes  and  the  rubber  stopipers  were 
soaked  in  warm  brine  solution  for  12  hours, 
after  which  treatment  they  were  carefully 
rinsed.  The  balance  was  a  Biinge  with  a 
sensitiveness  of  0.4  mg. ;  no  mirror  was 
used,  but  i  divisions  could  easily  be  read. 

The  "ordinary  sodium  chloride"  was  a 
commercial  highly  purified  preparation 
which  was  further  purified.  A  saturated 
solution  was  treated  with  chlorine,  the  ex- 
cess chlorine  removed  by  boiUng,  the  salt 
precipitated  with  hydrogen  chloride,  re- 
crystallised  several  times,  ignited,  and  then 
recrystallised  several  more  times.  All  final 
crystallisations  were  made  in  platinum  with 
twice-distilled  water,  the  second  time  from 
alkaline  permanganate. 

The  apatite  was  from  the  Odegaarden 
mines  in  Bamle,  and  was  comiparatively 
rich  in  chlorine,  but  the  presence  of  con- 
siderable fluorine  made  it  difficult  to  obtain 
a  preparation  free  from  silica.  It  was 
heated  with  70  per  cent.  c.p.  sulphuric  acid 
and  the  acid  distillate  of  hydrochloric,  hy- 
drofluoric and  sulphuric  acids  and  silicon 
tetrafluoride  was  neutralised  with  a  highly 
purified  commercial  sodium  carbonate.  The 
precipitated  silica  was  removed,  and  after  3 
crystallisations  the  salt  was  divided  into  2 
portions,  from  1  of  which  was  made  a  satur- 
ated brine  solution  and  from  the  other  was 
generated  a  stream  of  hydrogen  chloride 
which  was  brought  to  the  surface  of  the 
brine  solution.  The  precipitate,  dried  by 
suction,  was  heated  to  redness  in  platinum, 
dissolved,  filtered,  recrystallised  7  times, 
ignited  again,  dissolved  and  filtered,  and 
then  recrystallised  5  times. 

Specific-Gravity  Determinations  of  the 
Saturated  Solutions. 

The  two  salt  solutions,  one  from  ordinary 
sodium  chloride,  the  other  from  apatite, 
were  evaporated  until  crystallisation  began. 
The  warm  solutions  were  transferred  to  the 
tubes,  and  when  cool,  the  tubes  were  tightly 
closed  with  rubber  stoppers. 

After  3  days'  rotation  the  first  weighings 
of  the  filled  pycnometer  were  made,  No.  1 
in  the  table  below.       The  "apatite  sodium 


AUGUST  3,  1923. 


THE  CHEMICAL  NEWS 


73 


chloride"  solution  was  slightly  cloudy,  the 
numerous  recurring  opalescence  must  have 
been  due  to  traces  of  fluoride.  Bar}ta 
water  was  added,  whereupon  a  distinct  tur- 
bidity appeared,  and  the  solution  was  fil- 
tered. The  excess  of  barium  hydroxide  was 
precipitated  by  carbon  dioxide  gas,  the  ex- 
cess of  carbon  dioxide  driven  out  by  boiling, 
and  the  solution  filtered.  The  filtrate  was 
neutralised  with  a  few  drops  of  "  apatite 
hydrochloric  acid,"  evaporated  to  satura- 
tion and  precipitated  with  alcohol.  The 
ignited  powder  was  reprecipitated  with  al- 
cohol and  then  crystallised  several  tinas. 
The  "  ordinary  sodium  chlc»ide  "  was 
evuiporuted  to  dryness,  heated  to  redness, 
dissolved,  filtered,  and  recrystallised  several 
times. 

After  3  days'  rotation  another  weighing 
was  made,  No.  2  in  the  table.  The  specific 
gravity  of  the  "ordinary  sodium  chloride" 
being  unchanged    shows  the  preparation  to 

Table  I. 
Specific  Gravities  of  Saturated 
Solutions. H 

"Ordinary  "Apatil' 

Sodium  SodiuiM 

Expt.               Chloride"  Chloridi" 
Temp.,  18° 

1  1.202791  1  ,  ,,^^,^,,,  1.203(598 

2  1.202790  f  l.-i0^7'l  1.204691 

3     1.203,j'j7 

4  1.202791 

5     1.202857 

6  1.202867  1.202852 

H  Vacuum  corrections  wt  re  applied  lo  all 
weighings,  taking  8.4  as  the  specific  gravity 
of  the  brass  weights  by  the  usual  formulcr. 

be  pure,  but  the  "apatite  sodium  chloride" 
was  again  treated  as  above,  giving  value  No. 
3.  This  solution  was  then  evaporated  to 
dryness,  ignited,  and  recrystallised  thrice. 
Weighing  gave  value  No.  4,  1.202791,  which 
agrees  with  that  found  for  "ordinary  so- 
dium chloride,"  1.202791  and  1.202790. 

After  the  work  had  been  abandoned  for  a 
time  the  "apatite  sodium  chloride"  solu- 
tion was  evaporated,  iffliited,  recrystallised 
two  or  three  times,  and  the  specific  gravity 
again  determined  (No.  6).  Another  evapor- 
ation, ignition  and  recrystallsation  gave 
value  No,  6,  the  specific  gravity  of  "ordi- 
nary sodium  chloride"  being  determined  at 
the  same  time. 

The  slight  difference  between  the  first 
and  the  last  determinations  for  "ordinary 
sodium  chloride"  may  be  accounted  for  by 


a  new  setting  of  the  thermostat  regulator. 
The  measurements  taken  at  the  same  time 
under  identical  conditions  are  in  good  agree- 
ment. Thus  the  average  for  "ordinary  so- 
dium chloride"  under  the  earlier  conditions 
agrees  precisely  with  the  value  for  the 
purest  "apatite  sodium  chloridse"  (No.  4), 
while  the  later  value,  1.202867,  for  "ordi- 
nary sodium  chloride"  agrees  closely  with 
the  average,  1.202855,  of  the  later  values 
for  the  still  further  purified  "  apatite 
sodium  chloride." 

A  sample  was  then  taken  from  each  of 
the  two  soluticxis  by  means  of  the  pycno- 
meter  and  ignited  to  constant  weight  in 
platinum,  all  precautions  being  observed. 
When  corrected  to  vacuum  the  "ordinary 
sodium  chloride"  weighed  3.31262,  while 
the  "apatite  sodium  chloride"  weighed 
3.31267,  or  0.05  mg.  more,  a  difference  less 
than  the  errors  of  weighing  (0.1  mg.).  It 
follows  that  the  atomic  weignt  of  tne  apa- 
tite chlorine  does  not  differ  from  that  of  or- 
dinary chl(Hnne  by  an  appreciable  amount. 
Even  if  the  solubilities  found  (26.357  per 
cent  at  18*  or  35.790  g.  per  100  g.  of  water) 
were  not  absolutely  correct,  the  atomic 
weight  85.46  calculated  from  the  relative 
values  would  still  hold  good. 

Incidentally,  we  have  compared  the  solu- 
bilities we  found  with  thoee  calculated  from 
the  formula  of  Andreae'  which  are  in  good 
agreement  with  many  recent  determina- 
tions.^ The  calculated  value  is  26.363  per 
cent.,  while  we  found  26.357  per  cent., 
which  is  in  excellent  agreement. 

Summary. 

The  chloriiie  isotopes  in  Bamie  apatite 
occur  in  the  same  proportion  as  in  ordinary 
sfxHum  chloride. 

Christiania,  Norway. 

(From  the    "  Journal    of    the    American 
Chemical  Society,"  July,  1923,  1577-1579). 
[Contribution  from  the  Chemeal  Laboratory 
of  the  University  of  Wisconsin.] 


'  Andreae,  J.  prakt.  Chem.,  1884,  XXIX., 
467. 

*  Taylor,  J.  Phys.  Chem.,  1896-1897,  I., 
718.  Berkeley,  Phil.  Trans.,  1904,  CCIII., 
189.  Fontein,  Z.  physik.  Chem.,  1910, 
LXXIIL,  212.  Cohen,  ibid.,  1912,  LXXV. 
Schreinemakers,  Aroh.  Neer.  tci.  nat.,  XV. 


74 


THE  CHEMICAL  NEWS. 


AUGUST  3,  1923. 


THE  ACTION  OF  SELENIUM 
OXYCHLORIDE    ON  PURE  RUBBER. ^ 
By  Carl  E.  Frick. 

In  the  studies  on  the  oxychloride  of  sele- 
nium which  have  been  in  progress  in  this 
Laboratory,  Lenher^  has  shown  that  pure 
imbber,  vulcanised  rubber,  and  vulcanite, 
react  chemically  with  selenium  oxychloride. 
It  seemed  advisable  to  undertake  a  quanti- 
tative study  of  this  reaction,  if  possible,  as 
any  information  would  be  interesting  in 
view  of  our  incomplete  knowledge  of  the 
nature  of  the  rubber  hydrocarbon.  The 
products  obtained  by  the  action  of  selenium 
oxychloride  on  2  wild,  and  2  plantation 
rubbers,  and  a  synthetic  rubber  preipared 
from  isoprene,  were  investigated. 

Preparation  of  Materials. 

Selenium  Oxychloride. — The  method  ff 
Lenher^  was  used. 

Pure  Rubber  Hydrocarbon. — Samples*  of 
crude,  unworked  rubber  were  washed  in 
frequent  changes  of  water  until  dirt  and 
soluble  impurities  were  rertioved,  dried,  and 
freed  from  resins  by  extraction  with  boihng 
acetone  for  24  hours.  The  residue  was  freed 
from  acetone  and  the  rubber  hydrocarbon 
dissolved  in  pure  carbon  tetrachloride.  The 
undissolved  protein  was  filtered  off  and  the 
rubber  precipitated  by  absolute  alcohol. 
The  sample  was  freed  from  alcohol,  redis- 
solved  in  c£U"bon  tetrachlorido,  reprecipi- 
tated  by  alcohol  7  times,  and  finally  redis- 
solved  and  kept  in  pure  carbon  tetrachlor- 
ide. The  following  natural  rubbers  were 
used  in  this  study :  Upriver,  fine,  hard 
Para;  first  latex  Pale  Crepe;  Upper  Caucho 
Ball ;  and  ribbed  Smoked  Sheet. 

Synthetic  "  Isoprene  Rubber."  —  This 
was  prepared  from  pure  isoprene  by  the 
well-known  method  discovered  practically 
simultaneously    by  Mathews'    in    England 


^  This  paper  is  constructed  from  a  part  of 
a  thesis  submitted  by  the  author  to  the 
Graduate  School  of  the  University  of  Wis- 
consin in  partial  fulfilment  of  the  require- 
ments for  the  degree  of  Doctor  of  Philoso- 
phy, January,  1923. 

^  Lenher,  Jour.  Amer.  Chem  .Soc,  1921, 
XLIII.,  29. 

'  Lenher,  ibid.,  1920,  XLIL,  2498. 

*  These  samples  were  kindly  furnished  by 
Dr.  W.  G.  Geer,  of  the  B.F.  Goodrich  Co., 
and  Prof.  H.  E.  Simmons,  of  the  University 
of  Akron. 

'  Mathews  and  Strange,  Brit.  pat.  24,790, 
1912. 


and  Harries*^  in  Germany,  using  metalUc 
sodium  to  effect  the  polymerisation.  The 
rubbery  mass  was  washed  with  acetone,  dis- 
solved in  carbon  tetrachloride,  reprecipi- 
tated  by  alcohol,  redissolved  and  reprecipi- 
tated  several  itmes,  and  thus  purified  in 
exactly  the  same  manner  as  the  natural 
rubbers.  The  samjple  was  finally  redissolved 
and  kept  in  pure  carbon  tetrachloride. 

Isoprene. — The  isoprene  was  prepared 
from  dMimonene  (dipentene)  by  passing 
the  vapours  over  an  electrically-heated  pla- 
tinum wire,  using  the  princiiple  of  Harries' 
isoprene  lamp.'  The  limonene  was  ob- 
tained from  washed  orange  oil,  which  was 
over  96  per  cent,  pure  limonene.  The  crude 
isoprene  was  free  dfrom  any  contained  amy- 
lene  by  allowing  it  to  stand  for  several  days 
in  contact  with  barium  dioxide,  dried  with 
fused  calcium  chloride  and  distilled,  then 
dried  with  metallic  sodium  and  redistilled, 
using  a  Vigreaux  fractionation  column.  Os- 
tromuislinskii's"  method  of  purification  by 
forming  the  tetrabromide  and  then  remov- 
ing the  bromine  by  treatment  with  zinc 
dust  at  0°  in  absolute  alcohol  solution  was 
found  to  be  impractical  when  it  was  desir- 
able to  prepare  a  litre  or  more  of  pure  iso- 
prene. The  material  was  colourless;  b.p., 
33.2-33.8°  (742  mm.). 

Solvents. — Acetone  was  freshly  distilled 
over  anhydrous  potassium  carbonate,  and 
the  fraction  boiling  at  56-57°  used.  Carbon 
tetrachloride  was  purified  by  treatment 
with  saturated  chlorine  water  for  several 
days  in  diffused  sunlight.  It  was  then 
washed  thoroughly  with  distilled  water, 
dried  over  fused  calcium  chloride  and  dis- 
tilled. 

Experimental    Part. 

When  crude  rubber,  vulcanised  rubber, 
or  even  vulcanite  is  placed  in  selenium  oxy- 
chloride, a  vigorous  reaction  sets  in,  and 
the  rubber  is  dissolved  with  evolution  of 
heat.  The  solution  becomes  reddish  brown 
in  colour  and  contains  selenium  monochlor- 
ide  and  selenium,  in  addition  to  the  decom- 
position products  of  the  rubber.  In  order 
to  study  this  reaction,  it  became  evident  at 
once  that  the  reaction  would  have  to  be 
more  carefully  controlled,  and  further  that 


«  Harries,  Ann.,  1911,  CCCLXXXIIL, 
157. 

'  Harries  and  Gottlob,  Ann.,  CCCLXXX- 
IIL, 228. 

'^OstroDiuisliiisliii,  J.  Russ.  Phys.  Chem. 
Soc,  1916,  XLVIL,  1983. 


AUGUST  3,  1923. 


THE  CHEMICAL  NEWS. 


76 


the  results  would  be  the  easier  to  interpret, 
the  purer  the  samples  of  rubber  used.  The 
reactions  of  selenium  oxychloride  on  the 
purified  rubber  hydrocarbon  in  solution  in 
carbon  tetrachloride,  were  carried  out  in  all 
cases  as  follows. 

To  a  known  quantity  of  a  5  per  cent,  solu- 
tion bv  weight  of  pure  rubber  in  dry  carbon 
tetrachloride,  cooled  to  0°,  was  added  slow- 
ly, with  vigorous  stirring,  an  excess  of  a  5 
per  cent,  solution  of  selenium  oxychloride 
in  dry  carbon  tetrachloride,  also  cooled  to 
0°.  The  selenium  oxychloride  was  added 
in  slight  excess  as  otherwise  the  solution 
could  not  be  filtered  because  the  excess  of 
rubber  clogs  the  filter.  A  yellowish-whit**, 
amorphous  substance  immediately  settled. 
The  solution  was  filtered  quickly  through  a 
IJiichner  funnel,  the  precipitated  material 
transferred  to  a  lK?aker  containing  cold  car- 
bon tetrachloride  and  agitated  in  order    to 


free  the  material  from  the  slight  excess  of 
selenium  oxychloride.  This  operation  was 
repeated  several  times,  using  fresh  portions 
of  cold,  dry  carbon  tetrachloride.  The  pre- 
cipitated materia  Iwas  finally  brought  on 
to  the  filter  paper  and  the  q^rbon  tetra- 
chloride replaced  by  ethyl  ether.  The  ether 
was  quickly  evaporated,  the  dry,  amor- 
phous powder  transferred  to  a  glass-stop- 
ptred  weighing  bottle  and  this  container 
kept  at  (f.  Due  to  its  instability  at  ordinary 
room  temperatures  and  the  consequent  evo- 
lution of  hydrogen  chloride,  the  material 
had  to  be  handled  in  this  way.  This  insta- 
bility also  prevented  further  purification  of 
the  material  by  any  of  the  usual  methods. 

Table  I.  shows  the  comparative  results 
based  on  the  averages  of  all  of  the  com- 
plete analyses  of  the  various  reaction  pro- 
ducts of  selenium  oxychloride  with  the 
natural  rubbers  and  the  synthetic    isoprene 


Tablb  I. 


AvBRAOE  Analyses' OF  TUB  PiiouucTS  UF  TUB  Ubactio.n  rktwken  Rubber  and  Selenium 

OXYCHLORIDB 


SeOCl,  reaction  C              H 

products  with  %              % 

"Isoprene  Rubber"       ....  28.72  4.67 

Pale  Crepe       28.76  4.87 

Smoked  Sheet       21.60  4.66 

Para          28.86  J. 42 

Caucho  Ball       24.40  4.87 

Discussion. 

Attention  is  called  to  several  fXMnts 
brought  out  in  this  table.  (1)  It  will  Ix- 
noted  that  the  average  con  lent  of  carbon  in 
the  various  reaction  products  of  either  syn- 
thetic rubber  from  isoprene,  or  the  natmnl 
rubbers,  varies  less  than  1  per  cent.,  ex- 
cept in  the  case  of  the  product  from  Smoktd 
Sheet,  which  is  about  2  per  cent,  lower.  (2) 
The  average  contents  of  hydrogen  in  the 
various  reaction  products  vary  less  than  0.1 
of  1  per  cent.  (3)  The  average  content  of 
selenium  in  the  synthetic  isoprene-nibhfr 
pro<luct  is  practically  the  same  as  in  th<' 
plantation  Pale  Crepe  prduct.  The  amount 
of  selenium  in  reaction  products  of  the  other 
3  natural  rubbers,    varies  only  within  1  per 

•  The  "average  analyHCs"  are  the  inrann 
of  the  rPHuUa  of  10  to  12  (hternnnaiioyin  ov 
different  samples  of  the  same  material 
haridled  under  as  nearly  the  same  conditions 
aa  possible.  The  average  analysis  for  each 
constituent  is  accurate  to  at  least  1  per  cent. 


8e 

01 

(Diff.) 

% 

% 

% 

22.67 

23.79 

26.26 

22.81 

24.28 

24.84 

27.04 

24.00 

22.01 

26.74 

26.03 

18.06 

26.09 

26.36 

19.70 

Ratio 
C:H 
10:23.3 
10:22.3 
10:26.0 
10:22.1 
10:21.1 

cent.,  but  all  are  4  to  6  per  cent,  higher  than 
in  the  case  of  the  Pale  Crepe  or  the  syn- 
thetic isoprene  rubber.  It  will  be  noted, 
however,  that  the  products  from  all  3  of  the 
natural  nibb<'rs  in  which  the  latex  was  co- 
agulated by  smoke  have  a  selenium  content 
of  26  to  27  (per  cent.  The  Smoked  Sheet 
comes  from  exactly  the  same  source  as  the 
Pale  Crepe  (cultivated  Hevea  brasiliensis), 
but  the  latex  of  Pale  Crepe  is  coagulated  by 
acetic  acid,  while  the  latex  of  Smoked  Sheet 
is  only  partially  coagulated  by  acetic  acid 
and  is  then  smoked  to  complete  the  process. 
Possibly  this  difference  in  the  selenium  con- 
tent of  the  2  reaction  products  can  be  attri- 
buted to  the  method  of  coagulation.  (4) 
The  average  content  of  chlorine  in  the  vari- 
ous reaction  products  from  either  the  syn- 
thetic or  the  natural  rubber  varies  about  2.2 
per  cent.  (5)  The  ratio  o  carbon  to  hydro- 
j?en  haH  changed  from  C,„H,„  in  the  pure 
rubber,  up  to  C,nHj,  in  the  reaction  pro- 
ducts. (6)  Parallel  with  the  chemical 
changes  in  the  various  kinds  of  rubber  upon 
treatment  with  seleniu  moxychloride,  there 


w 


76 


THE  CHEMICAL  NEWS. 


AUGUST  3,  1928. 


is  a  great  change  in  their  physical  proper- 
ties. The  products  are  all  amorphous  pow- 
ders, having  lost  their  elasticity  and  swell- 
ing power,  and  are  insoluble  in  the  ordinary 
rubber  solvents,  such  as  benzene,  carbon 
tetrachloride,  chloroform  and  ether.  (7) 
The  two  most  important  conclusions  that 
can  be  drawn  fro  mthe  comparative  data  on 
these  reaction  products  are :  (a)  the  pure 
rubber  hydrocarbon  from  natural  Hevea 
rubbers,  shows  a  slightly  different  behaviour 
in  its  reaction  with  selenium  oxychloride, 
depending  upon  the  source  of  the  rubber 
and  its  method  of  coagulation;  (b)  judging 
by  the  behaviour  towards  selenium  oxy- 
chloride, there  is  no  difference  in  empirical 
composition  between  the  pure  rubber  from 
a  typical  natural  rubber,  such  as  Pale  Crepe, 
and  a  synthetic  rubber,  made  by  the  poly- 
merisation of  isoprene  by  metallic  sodium. 
This  statement  is  in  contradiction  to  the  re- 
cent article  of  Kirchof.^"  Kirchof  has  com- 
jared  the  ultimate  analyses  that  have  been 
made  on  the  rubber  hydrocarbon  from  dif- 
ferent sources  and  also  the  analyses  of  the 
various  derivatives  that  have  been  reported. 
He  concluded  that  synthetic  rubber  is  a  true 
polymer  of  the  corresponding  hydrocarbon, 
CgHg,  but  that  the  hydrocarbon  of  Para 
rubber  has  the  empirical  cormposition 
CiqHj^,  and  cannot  be  formed  from  the  hy- 
drocarbon CgHg  through  polymerisation,  as 
Harries  supposed.  According  to  Kirchof, 
neither  the  empirical  composition  nor  the 
structure  of  synthetic  rubber  is  identical 
with  that  of  Para  rubber. 

The  present  work  tends  to  support  the 
conclusion  that  Harries  reached  after  a 
study  of  the  hydrolysis  products  of  the  ozon- 
ides  of  various  kinds  of  natural  and  synthe- 
tic rubbers,  namely,  that  there  is  no  essen- 
tial difference  in  constitution  between 
natural  rubber  and  the  polymerised  iso- 
prene. 

The  author  wishes  to  express  his  appre- 
ciation to  Professor  Victor  Lenher,  at 
whose  suggestion  and  under  whose  direction 
this  work  was  carried  out;  also  to  Professor 
Homer  Adkins  for  helpful  suggestions. 

Summary. 
1.  The  reactions  between  selenium    oxy- 
chloride and    the  natural,    Hevea    rubbers, 
Pale  Crepe,  Smoked  Sheet,  Para  and  Caucho 
Ball,  have  been  studied. 


i»  Kirchof,  Kolloidchem.  Beihefte,    1922, 
XVI.,  47. 


2.  The  reaction  between  selenium  oxy- 
chloride and  a  synthetic  rubber  made  by 
polymerising  isoprene  has  been  studied. 

3.  It  has  been  found  that  when  the  vari- 
ous rubbers  are  treated  with  selenium  oxy- 
chloride their  physical  properties  are 
changed.  The  products  are  all  amorphous 
powders,  having  lost  their  elasticity  and 
swelling  power,  and  are  insoluble  in  the 
ordinary  solvents  for  rubber. 

4.  It  has  been  shown  that  the  pure  rub- 
ber hydrocarbon  from  natural,  Hevea  rub- 
bers, shows  a  slightly  different  behaviour  in 
its  reaction  with  selenium  oxychloride,  de- 
pending upon  the  source  of  the  rubber  and 
its  method  of  coagulation. 

5.  It  has  been  shown  definitely  that, 
judging  by  their  respective  behaviours  to- 
wards selenium  oxychloride,  there  is  no  dif- 
ference in  empirical  comtposition  between 
the  pure  rubber  hydrocarbon  from  the 
Hevea  tree  and  the  synthetic  rubber  made 
by  polymerising  isoprene  with  metallic 
sodium. 

Madison,  Wisconsin. 

{From  the  "  Journal  of  the  American 
Chemical  Society,"  July,  1923,  1800-1804). 


SOCIETY  OF  GLASS  TECHNOLOGY. 
In  connection  with  the  visit  of  members 
of  the  Society  of  Glass  Technology  to 
France,  during  the  first  week  of  July,  two 
meetings  with  French  glass  manufacturers 
were  held  on  Monday  July  2.  In  the  morn- 
ing, the  visiting  party  was  received  by  the 
Chambre  Syndicale  cies  Maitres  Verreries, 
and  was  welcomed  by  its  President,  Mons. 
L.  Houdaille,  who  described  to  the  visitors 
how  the  French  glass  manufacturers  were 
all  united  in  one  body— the  Chambre  Syn- 
dicale— which  was  divided  into  six  sections 
representing  various  branches  of  the  indus- 
try. The  work  of  these  sections  was  organ- 
ised in  such  a  way  as  to  prevent  ruinous 
competition  between  members,  and  at  the 
same  time  encouraged  individual  research 
and  development.  Mons.  L.  Delloye  sipoke 
of  the  need  for  co-operation  among  manu- 
facturers of  different  countries.  Prof  W 
E.  S.  Turner,  Col.  S.  C.  Halse  and  Mr.  E. 
A.  Hail  wood  replied  for  the  Society  of  Glass 
Technology. 

In  the  afternoon  (after  a  lunch  at  which 
visiting    members    were    the  guests  of    the 


AUGUST  8,  192a 


THE  CHEMICAL  NEWS. 


77 


Chambre  Syndioale  des  Maitres  Verreries), 
a  joint  meeting  of  the  Societe  des  Ing^nieurs 
Civils  and  the  Society  of  Glass  Technolc^y 
was  held.  In  the  absence  of  Mens.  Guillet, 
President  of  the  Society  des  Ing^nieurs 
Civils,  Mons.  L.  Delloye  welcomed  the 
visitors.  The  follo\^g  papers  were  com- 
municated :  — 

Prof.  H.  Le  Chatelier,  La  Methode 
Scientifique  dans  I'Industrie. 

Db.  a.  Granger,  Lea  Verres  Opaques  et 
Colores,  et  les  Glaeures  C^ramijues  de 
Metiie  Espece. 

Mons.  Lafon,  La  Dilatation  des  Verves 
et  Cristaux. 

Prof.  W.  E.  S.  Turner,  Specifications 
for  Glass  Products. 

Mr,  T.  Teisen,  Improvnncnis  in  the  De- 
sign  of  Recuperative  Glass  Pot  Furruices. 

Mr.  S.  English  and  Prof.  W.  E.  S.  Tur- 
ner, The  Physical  Properties  of  Boric  Oxide 
Glasses. 

During  the  week-end  visits  were  paid  to 
the  following  glass  works :  (a)  Etablisse- 
ments  Jjegras  at  St.  Denis,  (b)  Verrerie«  de 
Ileims  (Messrs.  Charbonneaux  &  Cie),  (c) 
New  plate  glass  works  at  Chantereine,  (d) 
Glaceries  de  St.  Gobain,  Chauny  and  Cirey. 
Members  took  the  opportunity  when  nt 
licitns  of  visiting  the  battlefields  in  that  dis- 
trict. A  visit  was  also  paid  to  the  sand 
quarries  at  Nemours,  and  to  the  Forest  and 
Castle  of  Fontainebleau. 

The  social  side  of  the  excursion  was  not 
neglected.  In  addition  to  the  reception  and 
lunch  already  mentioned,  a  complimentary 
dinner  was  given  by  members  of  the  visiting 
party  to  Mons.  L.  Delloye,  who  had  been 
responsible  for  making  all  the  arrangements 
on  the  French  side.  At  Noyon  the  party 
woA  kindly  invited  to  lunch  by  the  directors 
of  Les  Glaceries  de  St.  Gobain,  Chauny  and 
Cirey.  A  reception  was  also  given  to  visi- 
tors by  Mons.  G.  Desprct  (Administrat<>ur 
des  Verreries  de  Boussois),  Paris,  when  an 
interesting  exhibition  of  artistic  glass  was 
on  view. 

Altogether,  some  thirty  British  members 
of  the  Society  and  their  friends  took  ipart  in 
the  visit.  It  will  be  recalled  that  a  party 
of  members  of  the  Society  visited  America 
in  1P20.  Encouraged  by  the  success  of  both 
those  visits  it  is  proposed  to  arrange  other 
tours  as  opportunity  arises. 


THE  INSTITUTE  OF  CHEMISTRY  OF 

GREAT  BRITAIN  AND  IRELAND. 

July  Examinations  :  1923. — Pass  List. 

The  following  candidates  have  passed  the 
examination  fat  the  Associateship : — 

In  General  Chemistry:  Anderson,  Alex 
Carr,  B.Sc.  (Lond.),  University  College, 
Nottingham;  Baruett,  John,  East  London 
College;  Beard,  Herbert  Greensmith,  Hud- 
derstield  Technical  College;  Bennett,  Wil- 
liam iVederick,  Central  Technical  School, 
Liverpool;  Booth,  Walter,  Central  Techni- 
cal School,  Leeds;  Bott,  Thomas  Harold. 
B.Sc.  (Lond.),  College  of  Technology,  Man- 
chester; Buob,  Frederick  James,  B.Sc. 
(Lond.),  East  London  College;  Child,  Regi- 
nald, King's  College,  London;  Crombie, 
WiUiam,  Imperial  College  of  Science  and 
Teohnolocr;  Crutchlow,  Bemanl  William 
Aiired,  King's  College,  London;  Curtis, 
Ronald  Hamilton,  University  College,  Lon- 
don; Faichney,  Peter,  Heriot-Watt  College, 
Edinburgh;  Fairgrieve,  Adam  Wilson, 
iloriot-Watt  College,  Edinburgh;  Groves. 
Adam  Traill,  Heriot-Watt  College,  Edin- 
burgh; Harrow,  Andrew  Nicoll,  Heriot-Watt 
College,  Edinburgh;  Hibbert,  Sydney, 
A.M.C.T.,  College  of  Technology,  Man- 
chester; Hill,  Herbert  Eric,  University  of 
Western  Australia;  Jones,  Norman  Ella- 
thomo,  King's  College,  London;  Kimmins, 
liionol  (ioorge,  B.Sc.  (Lond.),  University 
College,  London;  Kirby,  Christoiphor  Stan- 
hope, University  College,  London;  Laing, 
William  Mossman,  Heriol-Watt  College, 
Edinburgh;  Leaper,  Percy  Joshua,  Univer- 
sity College,  Southampton;  Lindsay,  Rob- 
ert, University  College,  London;  McGrath, 
James,  Royal  Technical  College,  Glasgow; 
Mieras.  Adrian  Pieter,  Heriot-Watt  College, 
P^dinburgh ;  Moeley,  Martin  Aaron,  Univer- 
sity College,  Nottingham;  Moyes,  Robert 
Baird.  Heriot-Watt  College,  Edinburgh; 
Oliver.  James  Herbert,  B.Sc.  (Lond.); 
Paul.  David,  Heriot-Watt  College,  Edin- 
burgh; Pound,  Albert,  B.Sc.  (lyond.),  Uni- 
versity College,  Exeter;  Rosewame,  Joel 
.Mfrofl  Henry  Tetterdell,  King's  College, 
London;  Russell,  William  Lyle,  Heriot- 
Watt  College,  Edinburgh ;  Saunders,  Harold 
Nicholas,  B.Sc.  (Lond.),  University  Col- 
lege, Exeter;  Scott,  Robert,  Heriot-Watt 
College,  Edinburgh ;  Smith,  Charles  George, 
King  8  College,  London ;  Snehis,  Miss  Su- 
zanne ^^abel  Tjavinia,  College  of  Techno- 
logy. Manchester,  and  Sir  John  Cass  Tech- 
nical Institute ;  Thacker,  Gilbert  Doe  Dwyer 


78 


THE  CHEMICAL  NEWS. 


AUGUST  3,  1928. 


Way,  East  London  College ;  Thomas,  Bryn- 
mor,  M.Sc.  (Dun.).  Central  Technical 
School,  Liverpool;  Threadgold,  Herbert, 
B.Sc.  (Lond.),  University  College,  London; 
Tully,  James  Duncan,  B.Sc.  (Lond.),  Uni- 
versity College,  Southampton;  Walker, 
John,  Technical  College,  Huddersfield ; 
Wells,  William  Herbert,  University  College, 
London;  Wilkie,  Alexander  Stewart,  Heriot- 
Watt  College,  Edinburgh;  Wilson,  George 
Edward,  Heriot-Watt  College,  Edinburgh; 
Wood,  Thomas,  Central  Technical  School, 
Liverpool;  Wylie,  Andrew  Robertson. 
Heriot-Watt  College,  Edinburgh.  (28  can- 
didates failed  to  satisfy  the  examiners.) 

In  Branch  (b) :  Metallurgical  Chemistry  : 
Howard,  Thomas  George,  Sir  John  Cass 
Technical  Institute. 

In  Branch  (e) :  Chemistry,  including 
Microscopy,  of  Food  and  Drugs,  and  Water : 
Woodhead,  John  Ezra,  B.Sc.  (Lond.), 
Birkbeck  College,  and  Northern  Polytechnic 
Institute,  London. 

In  Branch  (g) :  Chemical  Technology : 
Martin,  George  Frank,  Royal  College  of 
Science,  London. 

The  following  Associates  have  passed  the 
examination  for  the  Fellowship:  — 

In    Branch     A :     Inorganic     Chemistry : 

Hackney,  Norman,  B.Sc.  (Lond.);  Wynn, 
William  Owen  Roderick. 

In  Branch  C:  Organic  Chemistry :  Cohen, 
Abraham,  B.Sc.  (Ix>nd.). 

In  Branch  D  :     Agricultural    Chemistry  : 
Ritchie,  John  Edwin,  M. A.,  B.Sc.  (Aberd.). 
By  Order  of  the  Council, 

Richard  B.  Pilcher, 

Registrar  and  Secretary. 

30,  Russell  Square,  Tjondon,  W.C.I. 
June  27,  1923. 


PRESENTATION  OF  THE  SOCIETY'S 
ALBERT  MEDAL  TO  SIR  DAVID 
BRUCE  AND  SIR  RONALD  ROSS. 

he  Council  of  the  Royal  Society  of  Arts 
attended  at  Clarence  House,  St.  James's, 
on  July  13,  when  His  Royal  Highness,  the 
Duke  of  Connaught  and  Strathearn,  K.G., 
President  of  the  Society,  presented  the  So- 
ciety's Albert  Medal  for  the  present  year 
in  duplicate  to  Major-General  Sir  David 
Bruce,  K.C.B.,    D.Sc,    LL.D.,    F.R.C.P., 


F.R.S.,  and  Colonel  Sir  Ronald  Ross, 
K.C.B.,  K.C.M.G.,  D.Sc.,  LL.D.,  M.D., 
F.R.C.S.,  F.K.S.,  "in  recognition  of  the 
eminent  services  they  have  rendered  to  the 
Economic  Development  of  the  World  by 
their  achievements  in  Biological  Research 
and  the  Study  of  Tropical  Diseases." 

The  Duke  of  Connaught  was  attended  by 
Lieut. -Colonel  Sir  Malcolm  Murrav, 
K.C.V.O.,  C.B.,  CLE. 


A  PEROXIDE  ELECTRIC  CELL. 
By  a.  E.  J.  Pettet  &  A.  W.  W^arrington. 

The  writers  apologise  if  the  cell  they  arc 
about  to  describe  is  not  new. 

The  elements  and  iwts  of  an  ordinary 
Bunsen  cell  are  used.  The  zinc  is  amalga- 
mated and  placed  in  the  outer  cell,  contain- 
ing a  solution  of  zinc  sulphate  (144  gm.  of 
the  crystallised  salt  per  litre).  The  carl>on 
is  placed  in  the  porous  iar  and  is  in  con- 
tact with  a  "  20 "  volume  solution  of 
hydrogen  peroxide,  acidified  with  sulphuric 
acid  (one  volume  of  acid  to  every  ten 
volumes  of  the  peroxide.). 

The  cell  verv  rapidly  reaches  its  full 
strength.  Its  E.M.F.  is  about  1.6  volts. 
The  internal  resistance  of  the  cell  used  by 
the  writers  was  about  1  ohm.  (The  outer 
cell  had  a  liquid  capacity  of  about  480  c.c, 
and  the  inner  cell  of  about  210  c.c.)  The 
cell  is  very  clean  to  work  with,  and  for  re- 
newal only  the  contents  of  the  inner  com- 
partment need  be  replenished.  It  may  be 
left  for  about  a  week  on  open  circuit  with- 
out appreciable  deterioration. 

The  cell  is  very  constant.  With  a  cur- 
rent of  0.06  ampere  it  will  run  for  48  hours 
unchanged,  and  for  another  24  hours  with 
only  a  slight  fall  in  current.  If  used  con- 
tinuously it  has  a  total  output  of  about 
26,500  (25,000)  coulombs.  It  runs  down 
quite  rapidly  at  the  end  of  about  three 
days,  owing  to  decomposition  of  the  per- 
oxide. It  worked  well,  however,  until  only 
about  one-twentieth  of  the  original  amount 
of  available  oxygen  was  present.  ' 

It  is  admirably  adapted  foi"  use  with  a 
copper  voltameter.     Running  for  one  hour  '; 
throus^h  a  copner  voltameter,  and  carrying  i 
a   mean    current    of    0.2082    ampere,    the  [ 
highest   reading  of  the  galvanometer,   the 
needle  of  which  was  suspended  by  a  silk 
fibre,  indicated  a  current  of  0.2185,  and  the 
lowest  of  0.2019  ampere.    Running  for  two 
hours   through    a    copper    voltameter,  and' 
carrying  a  mean  current  of  0.0990  ampere, 


AUGUST  3,  1923. 


THE  CHEMICAL  NEWS. 


79 


the  current  varied  between  0.0998  and 
0.986.  With  a  current  of  0.06  ampere  it 
will  run  continuously  for  tw  o  or  three  days, 
as  already  stated,  with  almost  inappreciable 
change  in  current  strength. 

The  writers  have  no  hesitation  in  recom- 
mending its  use  in  schools  in  place  of  the 
Daniell  cell. 


ARTIFICIAL  SILK. 

Canadian  Chemistry  and  MriaUurgy,    July, 

1923. 

Artificial  silk  is  the  rather  inappropriate 
name  given  to  a  product  of  cotton  or  wood 
fibre  which  diflFers  both  physically  and 
chemically  fjom  the  gum  of  the  silk  worm. 
So  long  as  it  is  called  "artificial"  a  certain 
prejudice  against  its  use  is  bound  to  exist, 
as  was  the  case  with  cotton  in  its  early 
days  when  it  was  looked  upon  as  a  substi- 
tute for  linen.  Cellulose  silk — a  more  fit- 
ting term — is  a  commodity  in  a  class  of  its 
own,  and  of  indisputable  value.  The 
world's  piesent  output,  though  nearly 
twice  that  of  pre-war  days,  is  far  from  suffi- 
cient to  meet  the  demand,  and  the  indus- 
try, wherever  carried  on,  is  enjoying  a 
prosperity  that  suffered  no  interruption 
even  in  the  1921  period  of  general  busincs.s 
depression.  The  great  artificial  silk  finn 
of  England,  Courtaulds,  Limited,  reported 
a  net  profit  for  1922  of  X3,018,431,  which 
compares  with  Xil  .684,593  in  1921  and 
;{;i ,804,796  in  1920. 

Of  the  four  processes  in  common  use  for 
the  making  of  cellulose  silk,  the  most  popu- 
lar is  the  viscose,  which  is  an  entirely 
British  discovery,  depending  upon  the  for- 
mation of  a  soluble  xanthate  compound. 
The  raw  material  for  this  process  is  woo<l 
pulp,  and  tile  principal  chemical  reagents 
caustic  soda  and  carbon  bisulphide.  The 
viscose  factories  in  Europe  draw  their  sup- 
plies of  sulphite  pulp  from  Scandinavia  and 
Canada,  It  is  the  labour,  however,  not  the 
raw  material,  that  constitutes  the  heaviest 
item  of  cost ;  but  this  will  not  be  so  much 
in  evidence  when  the  present  'machinery  is 
inii>roved  and  additional  mechanism  ap- 
plied. 

The  possibilities  of  cellulose  silk  appear 
to  Ix;  almost  limitless.  It  is  extensively 
used  in  the  braiding  and  millinery  indus- 
tries; and,  woven  with  real  silk,  wool,  cot- 
ton or  other  fibres,  it  is  gaining  in  import- 
ance every  day  in  the  manufacture  of  wear- 
ing apparel  and  of  beautiful  textures  of  all 
kin<ls.  Ribl)on  straw,  artificial  horsehair, 
cloth,  and  even  imitation  Sniynia  rugs  and 


Gobelin  tapestries  are  now  made  in  arti- 
ficial silk  plants.  Though  not  a  substitute 
for  natural  silk,  cellulose  silk  has  a  broad 
market  on  account  of  its  comparative 
cheapness,  and  the  world's  output  will 
soon  exceed  that  of  cocoon  silk.  The  che- 
mistry of  cellulose  offers  unlimited  scope 
for  research,  so  new  developments  can  be 
looked  forward  to  that  will  still  further  ex- 
tend the  use  of  cellulose  silk. 

In  view  of  the  Finance  Minister's  tariff 
recommendations  and  the  trading  advan- 
tages Canada  has  with  some  countries 
through  her  preferential  tariffs,  the  time 
would  appear  to  be  opportune  for  examin- 
ing fully  into  the  feasibility  of  establishing 
the  cellulose  silk  chemi£.al  industry  in 
Canada.  Sulphite  pulp  and  the  necessarj- 
chemicals  can  be  manufactured  cheaply, 
and  our  domestic  market  is  not  insignifi- 
cant, as  statistics  for  1922  reveal  that  over 
$2,000,000  was  expended  on  imports  of 
ccllulosc-silk  yarn  and  filaments,  about 
$1,000,000  on  manufactures  from  the 
United  States  and  the  United  Kingdom 
alone,  and  large  quantities — not  to  be 
identified  in  trade  fignires — of  fabrics  from 
these  and  other  countries. 

Just  as  we  go  to  press  we  learn  that  the 
l;irM:e  Briti.sh  firm  of  Courtaulds  has  de- 
cided to  establish  a  plant  near  Quebec  City 
for  the  manufacture  of  artificial  silU  yam. 
Truly  we  are  getting  on. 


NOTICES  OF  BOOKS. 
Organic  Chemistry,  by  Ira  Rbmhen, 
Revised  and  Enlarged  by  W.  R.  Orn- 
DoBFF.  Pp.  XL  +  667.  London:  Muc- 
millan  &  Co.,  Ltd.,  St.  Martin  Street, 
W.C.2.     1928.     109.  net. 

Prof.  Remnen's  textbooks  posseee  the  ed- 
mirablo  quality  from  the  teaching  stand- 
point, of  being  simple  and  containing  a 
miuiiHum  of  de.scrii)tive  matter. 

This  volume  on  Organic  Chemistry  is  not 
over- burdened  with  the  modes  of  prepara- 
tion and  the  properties  of  countless  com- 
pounds. Indeed,  in  this  edition,  revised 
I  with  the  help  of  Prof.  Omdorff,  the  practi- 
cal directions  for  preparing  even  important 
substances  has  been  omitted.  This  is  not, 
however,  a  serious  drawback,  since  it  allows 
more  attention  to  be  devoted  to  principles 
and  generalisations.  Further,  it  is  now  cus- 
tomary to  use  laboratory  manuals  in  connec- 
tion with  practical  organic  chemistry. 

The  judicious  intr<xluction  of  new  dis- 
oovenes  and  developments    has  been    ably 


80 


THE  CHEMICAL  NEWS. 


AUGUST  3,  1923. 


done,  and  very  few  errors  —  and  these  are 
trivial — have  been  noticed. 

This  new  and  enlarged  edition  is  well 
adapted  fo  rthe  use  of  students  attending  an 
introductory  course  of  Organic  Chemistry, 
and  should  commend  itself  to  lecturers  in 
the  subject. 


CHEMICAL  SOCIETY'S    LIBEAEY. 

Owing  to  the  work  of  redecorating  the 
rooms  of  the  Society,  the  Library  will  be 
closed  during  the  entire  month  of  August, 
and  in  accordance  with  the  usual  practice 
will  close  at  5  p.m.  daily  from  September 
1  to  17. 


No.  340.  Production  of  Explosives  in  the 
United  States  during  the  Calendar  Year 
1922,  by  William  W.  Adams.     Pp.  25. 


NOTES. 
Messrs.  Longmans,  Green  &  Co.  an- 
nounce that  the  new  edition  of  Sir  Edward 
Thoripe's  Dictionary  of  Applied  Chemistry 
will  extend  to  seven  volumes,  a  great  part 
of  the  last  volume  being  devoted  to  a  com- 
plete index  to  the  work. 

BOOKS  EECEIVED. 

Etude  sur  la  Tannerie  et  les  Industries 
conncxes  an  Marx,  Ch.  Ziegler  Ingenieur 
Chimiste.  Pp.  122.  1923.  La  Chaussiere 
Francaise,  141,  Boulevard  Sebastopol, 
Paris.     7fr.  50c. 

The  Ventilation  of  Public  Buildings,  by 
Egbert  Boyle.  Pp.  LI.  +  V.  1923.  Messrs. 
Eobert  Boyle  &  Son,  64,  Holborn  Viaduct, 
E.C.I.     6s.  net. 

The  Publications  Department,  Bourn- 
ville,  has  issued  two  pamphlets  by  A.  W. 
Knapp,  B.Sc,  F.I.C,  entitled  The  Appli- 
cation of  Science  to  Cacao  Production,  and 
The  Separation  and  Uses  of  Cacao  Shell,  i 
price  6d.  each.  I 

The  articles  were  originally  prepared  for  1 
the  International  Congress  of  Tropical  Agri-  i 
culture,  and  appeared  originally  in  the  j 
Journal  of  the  Society  of  Chemical  Indus-  j 
fny,  but  have  been  revised  and  brought  up-  j 
to-date. 

Both  are  interesting  and  informative,  and  ; 
are  written  in  a  way  suitable  for  those  who  ] 
are  not  specialists  in  this  particular  subject.       i 

The  U.S.  Department  of  the  Interior, 
Bureau  of  Mines,  has  issued  the  following 
bulletins: —  '< 

No.  204.  Underground  Ventilation  at  ■ 
Butte,  by  Daniel  Harrington.     Pp.    31.  j 

No.  339.  Coal-Mine  Fatalities  in  the  j 
United  States,  1922.  by  Wm.  W.  Adams.  | 
Pp.  VI.,  97, 


I.H18  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chance -y  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent  Applications. 
18008— Bloxam,  A.  G. — Manufacture     of  azo     dye- 
stuffs.    July  11. 
18087 — Bodrero,   B. — Production     and   use  of     sul- 

Bhuro-pnosphate.    July  12. 
►reyfue,  H. — Treatment    of  cellulose     deri- 
vatibes.    July  12. 
18092 — Farbwerke     vorm.     Meister,     Lucius,     and 
Bruning. — Manufacture       of      highly-active 
charcoal.    July  12. 
17764— Lilienfield,     L. — Manufacture     of     cellulose 

efliers.    July  9. 
17808— Mooller,  J.  F.  L.— Method  of    treating  car- 

lx)naoeou8  materials.    July  10. 
17837— Moeller,  J.  T.  L.— Fractional  diBtiHation  of 

hydrocarbons.    July  10. 
18107 — Trnmble,     M.     J.— Treating     hydrocarbons. 

July  12. 
18250— Vogel,  H. — Manufacture     of     colloidal     sul- 
phur.   July  14. 

Specifications  PuJ>lished  this  Week. 
1997.50— Joyner,  R.  A.,  and  Nobel's  Explosive  Co., 

Ltd. — Manufacture  of  hydrazine. 
lG6759--TTir(hl)erg,   L.   M.     Manufacture     of  aque- 
ous .solutions  of  formaldehyde. 
199^60— TIircl)l>er,  L.   M.— Production  of  formalde- 

hyde  by  catalysis. 
199766— Han n a,'  R.  W. — Process  for  the  continuous 

Eroduction  of  low  boiling-ix)int  hydroc^r- 
ons  from  petroleum  oils. 
199870 — Farbwerke  vorm.  Meister,  Lucius,  and 
Bruning. — Manufacture  of  therapeutically 
active  acridine  derivatives. 
ISS.'JS,') — Appareils  et  Evaporateurs  Kestner. — Pro- 
cess of  extracting^  sodium  bicarbonate  and 
other  salts  contained  in  natural  soda  bi- 
carbonated  mineral  waters. 

Abstract  Published  this  Week. 
197848— Tliymol.— Howard  &  Sons,  Ltd.,  Uphall 
Works,  Ilford,  and  J.  Blagden,  Apple  Tree 
House,  Grove  Road,  South  Woodford,  both 
in  Essex. 
Thymol,  thymol  sulphonic  acids,  m-cresol  sul- 
phonic  adds. — Thymol  is  prepared  by  sulphonat- 
ing  m-cresol  under  conditions  suitable  for  pro- 
ducing a  polysulphonio  acid,  such  as  the  di-  or 
even  tri-sulphonic  acid,  which  is  then  condensed 
with  isopiopyl  alcohol,  the  sulphonic  groups  split 
off  and  the  thymol  steam-distilled.  According  to 
an  example  m-cresol  is  treated  with  oleum,  con- 
taining 88  per  cent,  total  sulphur  trioxide,  first  at 
100°  and  then  at  150°  C.  A  solution  of  isopropyl 
alcohol  in  sulphuric  acid  is  run  in  and  the  mix- 
ture maintained  at  80-90°  C.  for  several  hours.  It 
is  then  heated  to  130°  C.  and  a  current  of  steam 
passed  in,  the  thymol  distilling  off.  A  small  quan- 
tity of  by-product  may  be  removed  by  solution  of 
the  thymol  in  alkali.  A  little  isomeric  thymol, 
melting  at  114°  C,  is  also  formed. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  iforward  on  post  free  for  the  price  of  Is.  fid, 
each, 


AUGUST  10,  1923. 


THE  CHEMICAL  NEWS. 


81 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.     No.  3304. 


PERCHROMIC   ACID. 
By  Geoffrey  N.  Hidlby. 

I. — FORMULiE. 

Perchromic  acid  has  been  given  two  form- 
ulae— HCrOj  and  H,CrO,.  It  therefore  de- 
viates from  the  path  followed  by  its  "  rela- 
tive," permanganic  acid,  whose  f^-mula  is 
given  as  HMnO^  or  HjMnjO,.  The  equation 
representing  the  formaticm  of  Uie  acid  by 
the  interaction  of  chromic  acid  and  hydro- 
gen peroxide  may  be  written  thus: 

2H,CrO,  +  7H,0,  =  2H,CrO,  +  6H,0. 

This  reaction  occurs  when  the  hydrogen 
peroxide  is  in  excess.  Otherwise,  acid  cor- 
responding to  the  probable  formula  HCrO. 
is  produced.  In  the  hvpothetical  oase  oi 
the  formula  for  perchromic  aoid  being 
HjCr,0,,  the  formation  of  the  oomf>ouna 
UKvy  be  expressed  thus: 

2H  CrO    +  H.O,  =  HXr.O,  +  2H,0. 

It  bus  been  suggestecf  that  chromium 
may  form  an  octovakut  compound,  per- 
chromic acid  consisting  of  a  ccnnbination  of 
Cr,Oy  with  H.Oj,  or  CrO,  with  H,0. 

II. — Chemical  Behaviour. 

The  etherial  solution  of  pcrchrtHnic  acid 
reacts  with  an  alkaline  carbonate,  such  as 
sodium  carbonate,  resulting  in  the  produc- 
ti<Mi  of  a  normal  chromate. 

(a)  4HCrOa  +  4Na,C0,  =  4Na,CrO,  + 
4C0»  +  2H,0  +  30,. 

03)  4H,CrO,  +  4Na,C0,  =  4Na,Cr0,  + 
OH,0  +  4C0,  +  70,. 

A  pcrchromate  of  sodium  does  not  appear 
to  be  formed  by  the  direct  reaction  between 
carbonate  and  acid,  but  a  sodium  pcrchro- 
mate, Na,Cr,0.,,28H,0,  may  be  prepared 
by  adding  NajO,  to  an  aqueous  paste  of 
Cr(0H)3. 

The  solution  of  perchromic  acid  has  an 
acid  reaction  towards  litmus,  and  acts  upon 
magnesium  with  npprccia5le  vigour.  The 
metal  becomes  coated  with  a  deposit  of 
magnesium  chromate,  portions  of  which  ore 
converted  into  the  diohrdtnate : 

(a)  4HCrO,  +  4Mg  =  4MgCrO,  -i-  2H,0 
+  O,. 

(/3)  4H,CrO,  +  4Mg  =  4MgCrO,  +  611,0 
+  5O3. 
Perchromic  acid  is  without  action    upon 


copper.  Chemical  activity  between  the  acid 
and  phosphorus  is  not  visible,  but  on  warm- 
ing and  allowing  the  ether  to  slowly  eva<por- 
ate,  a  greenish  substance  is  left,  which,  in 
view  of  its  chemical  behaviour,  is  thought 
to  be  a  phosphide  of  chromium. 

III. — Decomposition. 

Perchromic  acid  undergoes  decomposition 
by: 

(a)  Nascent  hydrogen. 

(b)  Aoids. 

(c)  Compounds,  viz.,  carbonates, 
(a)  Metals,  viz.,  magnesium. 

(e)  Water. 

(/)  Rise  in  temperature. 
The  reductic«    by  hydrogen   is  expressed 
thus : 

(a)  2HCrO.  +  3H,  =  2H-CrO,  +  2H,0 
to  2H,Cr0,  +  7H,  =  2H,Cr0,  +  8H,0. 

The  addition  of  strong  sulphuric  aoid  to 
perchromic  acid  brings  about  the  rapid  dis- 
solution of  the  blue  compound,  accom- 
panied by  the  evoluti<m  of  a  o<xisiderable 
quantity  of  oxygen : 

(a)  2HCrO,  +  3H,S0,  =  Cr,(SOJ,  + 
4H,0  +  80,. 

08)  2H,CrO,  +  3H,S0,  =  Cr,(SOJ,  + 
6H,0  +  60,. 

As  regards  the  decomposition  of  perchro- 
mic aoid  by  water,  the  action  is  slow  and 
only  brought  about  in  a  short  8(paoe  of  time 
by  much  shaking.  The  acid  is  gradually  re- 
moved from  the  ether  colouring  the  water  a 
pale  purple,  which  readily  changes  to  a 
brownish-red,  whence  it  is  concluded  that 
cither  dichromic  or  chromic  acid  is  in 
solution. 

If  a  small  quantity  of  acetone  is  added  to 
the  etherial  solution  of  perchromic  acid,  the 
fluid  may  be  heated  gently  to  a  temperature 
neighbouring  on  50°  C.  The  blue  colour  of 
the  liquid  gradually  changes  through  grey  to 
purple  and  to  dark  reddish-brown.  This  is, 
in  all  probabilitv,  dichromic  add,  and  its 
formation  may  be  expressed  thus : 

(a)  4HCrO,  ->  2H,CrO^,  CrO,  +  30,. 

(/8)  4H,CrO,  ->   2H,CrO„CrO,  +  4H,0 
+  70,. 

What  may  be  called  the  "conditions  of 
preservation"  of  perchromic  acid  constitute 
iiiiiportant  determining  factors  in  connec- 
tion with  the  decomposition  of  the  com- 
pound. The  conditions  of  preservation  are: 
Low  temperature  and  in  a  free  state;    ordi- 


82 


THE  CitEMiCAL  NEWS 


AUGUST  10,  1923. 


nary  temperature  and  in  solution;  ordinary 
temperature  and  free;  elevated  temperature 
and  in  solution,    the  solvent    being    ether. 

Condition  of  Preservation. 
Low  temperature. 
Free  state. 
Solid. 

Ordinary  temperature. 
In  solution. 
Ordinary  temperature. 
Free  state. 
High  temperature. 
In  solution. 


The  general  remark  is  :  that  perohromic 
acid,  when  in  solution,  owes  its  stability  to 
the  solvent;  when  free,  to  the  temperature. 

IV. — Isolation. 

The  following  remarks  with  regard  to 
the  crystallising  of  perohromic  acid  may  be 
of  interest. 

Perchromic  acid  has  been  isolated ;  briefly 
the  process  is  this : 

A  solution  of  chromium  trioxide  in 
methyl  ether  at  -30**  C.  is  treated  with  97 
per  cent,  hydrogen  peroxide  solution.  The 
blue  crystals  formed  are  said  to  be  those  of 
perchromic  acid. 


The  relation  between  these  conditions  and 
the  dissolution  of  perchromic  acid  is  shown 
in  the  table. 

Remarks  on  Docomtposition. 
Temperature.  Speed. 

-20°  C. 

to  Rapid. 

-25°  C. 
Ordinary  Very  slow. 

temp.  (Several  hours.) 

Ordinary  Immediate, 

temp. 
35°  C. 

to  Gradual. 

50°  C. 

If,  on  the  other  hand,  a  frozen  solution 
of  potassium  dichromate  at  -12°  C.  be 
treated  with  conveniently  cooled  and  acidu- 
lated hydrogen  peroxide,  the  superincum- 
bent ether  assumes  a  deep  blue  colour.  The 
temperature  being  low,  all  remams  soiid, 
allowing  the  blue  etherial  solution  to  be 
poured  off.  At  a  temperature  between  -20° 
and  -25°  C.  this  liquid  deposits  blue  crys- 
tals, which  melt  very  rapidly  when  removed 
from  the  freezing  bath. 

This  exiperimeut  was  carried  out  by  the 
writer  previous  to  receiving  information 
concerning  the  method  by  which  per- 
chromic acid  was  isolated  in  1914. 


ORGANIC  COMPOUNDS  OF   ARSENIC. 

PART  II. 

By  R.  F.  Hunter,  F.C.S. 

In  Part  I.  some  account  was  given  of 
atoxyl  in  general  terms,  and  it  is  now  pro- 
posed to  treat  the  matter  more  thoroughly. 

Atoxyl. 
Owing  to  theoretical  considerations  cur- 
rent among  the  French  school  of  chemists 
of  Bechamp's  time,  B^champ  was  pre- 
vented from  arriving  at  the  correct  conclu- 
sion for  his  reaction,  and  further,  the 
chemists  of  his  day  refused  to  regard  his 
compound  obtained  from  arsenic  acid  and 
aniline  as  a  true  organic  arsenic  compound, 
and,  as  stated  in  Part  I.,  not  until  the  work 
of  Ehrlich,  to  whom  we  owe  the  discovery  of 
our  present  most  efficient  cure  for  sypbillus, 
aippeared  in  the  year  1907,  was  the  true 
nature  of  Bechamp's  compound  demon- 
strated. Ehrlich  and  his  co-worker  Ber- 
theim  showed  atoxyl  to  be 

p.  NH^  C^H^  As  0  (OH)a, 


and  further,  the  commercial    sodium  com- 
pound to  be 

NHjCeH.AsO  (OH)  O  Na  n  H^O, 
where  n  varies  between  2  and  6. 

Researchers  in  this  field  following  Ehr- 
lich, applied  the  B^champ  reaction  to  other 
aromatic  amines  with  a  free  para,  position, 
this  led  to  the  discovery  of  2-aminotolyl-5- 
arsenic  acid  from  o-toluidine. 

As  stated  before,  the  main  trouble  in- 
volved in  the  use  of  atoxyl  for  injections  is 
its  toxic  nature;  acetylation  in  the  case  of 
such  compounds  as  aniline  had  yielded  the 
less  toxic  acetanilide.  Consequently  atoxyl 
was  acetylated,  and  a  drug  of  constitution, 
CH3C  O  N  H  C^H,  As  O  (OH)  O  Na  n  H^O, 
was  introduced. 

It  is  necessa^  to  examine  systematically 
the  derivatives  of  atoxyl,  and  I  prqpose  to 
again  use  Gibson's  method  of  classification. 

Gibson,  in  his  recent  work  :  Organic  com- 
pounds of  arsenic  and  antimony,  has 
divided  the  atoxyl  derivative  as  follows:  — 

(1)  p-Arsanilic  acid  and  its  N-Acyl  and 
Alkyl  derivatives.  p-Arsanilic  acid,  Bd- 
champ's  compound,  is  usually  prepared  by 


^i 


AUGUST  10,  1923. 


THE  CHEMICAL  NEWS. 


83 


heating  corresponding    quantities  of  aniline 
and  arsenic  acid  at  180°  for  some  two  hours. 

CeH.NH,  +  H,As  O,  = 

NH^C.H^  As  O  (OH),  +  HjO, 
the  sodium  salt  is,  of  course,  atoxyl. 

Mercuric  di  rivative  of  p  Ar^anilic  acid. 

Sometimes  known    as    "  Asyphil,"    iias 
sometimes  been  used  for    injection  in    the 
case  of  syphillis,  it  has  a  structure 
[NH,  CgH.AsO  (CH)  0]^  Hg. 

The  important  acyl  derivatice  of  atoxyl  is 
the  acetylone  "Arsacelin"  which  is  sodium 
Acelyl  p-arsenilate  and  has  received  con- 
siderable application. 

Some  other  acyl  derivatives  are : 

Forrnyl,  chloracetyl,  butyryl,  malonyl, 
benzoyl,  allylthio  carbamino,  theo  carbami- 
no,  methyl  carbamino,  phenyl  carbamino, 
p-arsanilic  acids. 

p-Sulphomethyl   aminophenylarsinic  acjd. 

SO3  H  CH,NH  C.H,  AsO  (OH),  is 
worthy  of  note,  and  is  prepared  by  treating 
atoxyl  with  formaldehyde  and  sodium  bisul- 
phite in  aqueous  solution. 

Three  other  series  of  compounds  belong- 
ing to  the  group  are  :  — 

.Vldehyde  condensation  products  of  atoxyl 
phenylylycine  arsenic  acid  and  homo- 
logues  and  phenylmethyl  glycine  parsene 
acid  and  its  c.  esters. 

(2)  Isomerides  of  p-Arsanilic  acid,  viz.,  m- 
Aminophenylarsenic  acid  and  its  deriva- 
tives. 

(8)  Homologucs  and  suhstituticm  pro- 
ducts of  p-Arsenilic  acid  homologues,  such 
as  Aminotolvarsenic  acids,  the  2-aminotolyl- 
5-arsenic  acid  is  important,  and  the  sodium 
derivative  NH,  C.H,(CH,)  AsO  (OH)  O  Na 
has  found  aipplication  under  the  title  of 
"  Kharsin." 

o-Anisidine-4-ar8enic  acid  is  the  most 
common  derivative.  2  :  Acetyl  1 :5  benzar- 
senic  acid  is  an  interesting  example  of  an 
aminobtnzarsenic  acid. 

The  halogen  derivatives  are  not  impor- 
tant, the  thio  derivatives  are  classified 
under 

(a)  Bisulphides, 

(b)  Sesquisulphides, 

(c)  Monosulphi.des. 

(4)  Homologues  and  derivatives  of  o- 
Arsanilic  acid  4-aminotolyl-3-ar8enic  acid  is 
worthy  of  mention  prepared  from  p-tolui- 
dine  and  H,AsO^. 

(5)  Nitroso,  azo,  diazo  and  triazo  phenyl 
arsenic  acids  and  derivatives'. 

Th.'  azo  coinpoi'ids    aro  of  use  in  medi- 
cine since  they    have  a  fatal    effect  on    the 
protozoa  of    certain  diseases,    for  instance, 


trypan  red  had  been  used  in  sleeping 
ness,  and  has  a  structure, 


^o^flo. 


si.: 


and  is  prepared  by  diazotisation  of  both 
amino  groups  in  benzidine  or  the  sulphonic 
acid  and  coupling  with  2-naphthylamine-3 : 
(5-disulphonic  acid. 

(6)  Orgauo  mercurial    compounds  of    p- 
Arsenilic  acid  and  derivatives. 

From  the  beneficial  results  of  the  use  of 
mercury  compounds  in  the  treatment  of 
venereal  disease,  we  should  expect  a  com- 
pound of  the  nature  of  p-arsenilic  acid  and 
mercury  to  be  quite  a  good  cure.  Conse- 
quently it  was  attempted  to  combine  the 
therapeutic  properties  of  mercury  with 
those  of  atoxyl,  and  the  results  were  benefi- 
cial. Condensation  of  mercury  acetate  with 
atoxyl  being  main  reaction,  from  which 
were  obtained  on  successive  concentration 
sodium  3 :5-dehydroxymercuri-4-aminophe- 
nylarsinate. 

A  new  compound    tested    clinically    with 


poor  reiults  is 
composition. 


Hydryl,"    which  has    the 


HO  M, 


HO  Ml 


0 


HjOH 
Ma  OM 


H, 


o 


(7)  4:4'  Diaminodiaryl  arsenic  acids. 
These  were  discovered  as  a  result  of  apply- 
ing the  Bechamp  condensation  to  aniline 
and  o-toluidine. 

4:4'  Diaminodiphenylareenic  acid. 
(NH,  C.HJ.  As  O  OH  is  the  best  example. 

(8)  Mixea  aromatic  aliphatic  p-amino 
arsenic  acids. 

(9)  Nitro  derivatives  of  arsenilic  acids. 
Some  of  these  are  important: 
r)-nitro-2-aminophenylarsenic  acid. 
6-Nitro-m-arsenilic  acid. 
2-nitro-4-aminophenylarsenic  acid. 
2.nitro-3-aininophenylar8enic  acid. 
8.nitro-4aminophenylar8enic  acid  are  wor- 
thy of  note. 

(10  )I)iaminophenylarsenic  acids: 

Kxnmples  of  these  are: 

2-3  diaininophenylarsenic  acid, 

:nh:),  c.h,  As  ojt,. 


84 


THE  CHEMICAL  NEWS. 


AUGUST  10,  1923. 


3 : 4  Diaminoiphenylarsenic  acid  are  ex- 
amples. 

(11)  TJie  Hjdronyphenylarsenic  acids. 
Phenol-p-arsenic  and  liomologues. 

These  are  of  interest  and  represent  the 
extension  of  the  Bechamp  condensation  of 
phenols. 

Phenol-p-arsenic  acid, 

P  HO  CeH^  AsO  (OH)^, 
is  prepared  by  heating    phenol  and    arsenic 
acid  in  proiportions  required  by  theory. 

o-Cresol-4-arsenic  acid, 

HOCH3  C0H3  As  O  (0H)2, 
in  same  manner  from  o-Cresol  and    corres- 
ponding m-compound. 

Naphthol-4-arsenic  acid,  HO  CioHgAsO- 
(0H)2,  is  obtained  by  adding  iced  NaNOa 
solution  to  l-aminonathphyl-4-arsenic  acid 
in  15  per  cent.  HgSO^. 

2-Hydroxy-l  :5-Benzarsenic  acid, 
HO  (CO2H)  GJi,  As  0  (0H)2, 
prepared  from  2-acetylaminotolyl-5-arsenio 
acid  by  oxidation  with  KMnO^  followed  by 
NaOH  hydrolysis.  Its  sodium  salt  is  less 
toxic  and  is  used  sometimes  in  cases  of 
syphillis. 

2:4  Dehydroxyphenylarsenic  acid. 
2-Methoxy-4-hydroxyphenylarsenic   acid. 

2  :4-dimethoxyiphenylarsenic  acid. 

3  :4-dehydroxyphenylar8enic  acid  and  4:- 
4-dehydroxydiphenylarsenic  acid  have  also 
been  prepared. 

(12)  Nitro  derivatives  of  hydroxyphenyl- 
arsenic  acids. 

3-nitro-4-hydroxyphenylarsenic       acid     is 
produced  by  nitration  of  sodium.     p-Phenol 
arsenate  with    a    mixture    of     HNO3     and 
H2SO4  at  0°  C,  and  has  a  structure, 
HO  (NO2)  C.Hj  As  O  (OH)^. 

4-nitro-2-hydroxyphenylarsenic  acid  is 
prepared  from  diazotisation  of  4-nitro-2- 
aminqphenol,  followed  by  warming  to  de- 
compose diazo  salt. 

5-nitro-2-hydroxyphenylarsenic  acid,  3:5- 
dinitro-2-hydroxyphenylarsenic  acid,  and  5- 
nitro-2  :4-dehydroxyphenylarsenio  acid  have 
been  prepared,  and  are  worthy  of  mention. 

(13)  Arsenic  acids  of  amino  phenols.  3- 
amino-4-hydroxyphenylarsenic  acid, 

HO  (NHJ  CgHg  As  0  (OH)^, 
is  typical  and  is  prepared    by  reduction    of 
corresiponding  nitro  compound. 

3-amino-2-hydroxytolyl-5-arsenie  acid,  4- 
amino-3-hydroxyphenylarsenic  acid,  carbe- 
thoxy,  3-aminophejiol-6-arsenic  acid.  4-di- 
methyl  amino-2-hydroxyphenylarsenic  acid, 
and  3 :5-diamino-4-hydroxyphenylarsenic 
acid  have  been  described  and  deserve  men- 
tion. 


PAN  FORMATION  IN  SOILS  IN  THE 

LIGHT  OF  THE  LIESEGANG 

PHENOMENON. 

By  N.  G.  Chatterji,  D.Sc,  A.I.C. 

The  formation  of  pans  in  soils  has  been 
the  subject  of  much  investigation,  and  it 
may  now  be  taken  for  granted  that  the 
whole  process  is  intimately  connected  with 
the  colloidal  properties  of  soils.  The  latest 
work  on  the  subject  has  been  ably  summar- 
ised by  Morison  {Trans.  Farad.  Soc,  1922, 
XVII.,  2,  321-323),  in  which  the  author 
comes  to  the  conclusion  that  the  whole 
process  is  a  transformation  of  soil  colloids 
from  the  "sol"  to  the  "gel"  form  with  sub- 
sequent dehydration  and  deposition. 

Whilst  substantially  agreeing  with  the 
above  conclusion,  an  attempt  has  been 
made  in  the  present  paper  to  bring  forward 
evidence  showing  the  similarity  between 
pan  fornuition  and  that  general  type  of 
I)eriodic  precipitation  known  as  Liesegang 
phenomenon,  after  the  name  of  the  dis- 
coverer. This  phenomenon  was  first  ob- 
served by  the  discoverer  when  doing  the  fol- 
lowing experiment:  — 

A  glass  plate  was  coated  with  5  per  cent, 
gelatin  solution  containing  a  small  amount 
of  potassium  chromate.  A  drqp  of  strong 
silver  nitrate  solution  was  then  placed  on 
the  gel,  and  it  inunediately  began  to  diffuse 
into  the  latter.  The  silver  nitrate,  of 
course,  reacted  with  the  chromate  in  the 
gel,  forming  the  insoluble  red  silver  chro- 
mate. But  although  there  was  a  continuous 
supply  of  both  the  components,  the  in- 
soluble silver  salt  was,  however,  not  de- 
posited in  a  continuous  zone  round  the  peri- 
phery of  the  original  drop,  but  in  a  series  of 
concentric  rings,  separated  by  apparently 
clear  zones. 

The  general  conditions  observed  with  the 
soils  ir  which  pans  are  formed  are  here 
given  briefly,  taken  mainly  from  a  paper  on 
the  subject  by  Morison  and  Sothers  {Journ. 
A(jri.  Scien.,  1914,  VI.,  84).  The  pan  layer 
in  a  soil  consists  more  or  less  of  a  weil- 
defined  band  of  material  where  the  gradual 
transition  from  the  surface  to  the  under- 
ground soil  is  broken.  The  characteristics 
of  this  layer  are  a  large  diminution  of  pcre 
space  of  the'  soil  cutting  off  the  air  and  water 
movement  and  preventing  the  penetration 
of  plant  roots.  The  concentration  of  the 
soil' into  such  a  layer  may  be  of  two  kinds  : 
it  may  be  caused  by  the  continued  passage 
of  heavy  instruments  of  tillage  to  a  given 
depth,  or  by  the  removal  of  material  either 


AUGUST  10.  1923. 


THE  CHEMICAL  NEWS. 


85 


in  the  form  of  colloid  sols  or  in  the  state  of 
solution  and  its  deposition  at  lower  depths 
in  the  soil  where  it  acts  as  the  cementing 
material  to  the  normal  soil  particles. 

The  present  paper  is  concerned  with  the 
latter  kind  of  pan. 

Pan  formation  of  this  nature  is  almost 
always  confined  to  soils  composed  i<x  the 
most  part  of  quartz  sand,  and  as  the  normal 
drainaj^e  in  such  soils  is  rapid,  the  exist- 
ence of  the  imipervious  layer  is  very 
marked.     The  pan  layer,  which  occurs  at  a 


Bleached 
sand. 

Fe^O,        0.253 

AljOj        0.180 

CaO        trace 

MgO       O.Oir) 

The  main  facts,  therefore,  in  oonnection 
with  the  presence  of  pans  in  soik  are  tin- 
following: 

(1)  The  f<«*mation  of  pans  <,'encrally  in 
sandy  smls  of  open  texture. 

(2)  A  considerable  accumulation  of  or- 
ganic matter  in  the  surface  soil. 

(3)  Concentration  of  iron  and  aluminium 
hydroxides  in  the  pan  layer  and  other  lower 
layers. 

(4)  Thf  almost  complete  absence  of  cnl- 
cium  carbonate  in  the  surface  soil. 

Various  theories  have  from  time  tci  tiiiu" 
been  advanced  to  explain  this  phenomenon 
from  the  chemical  point  of  view,  such  as 
the  alternate  reducticrti  and  oxidation  of 
iron  humates,  but  an  exhaustive  examinn- 
tion  of  these  (Morison  and  Sothers,  loc.  cU., 
Stremme,  Kolloid  ZcHsch.,  1917,  XX.,  161) 
shows  that  the  most  probable  explanation 
of  the  phenomenon  lies  in  the  coll^dal  pro- 
perties of  soils. 

We  have  already  mentioned  the  curious 
phenomenon  of  banded  structure  of  the  pre- 
cipitate of  silver  chromate  formed  by  the 
internction  of  silver  nitrate  solution  with 
potassium  chromate  in  gelatin  gel.  It  lias 
been  found  that  various  other  media,  such 
as  agar-agar  and  silicic  acid  gels  also  be- 
have in  the  .same  way  as  gelatin.  But  the 
action  of  gels  in  bringing  about  periodic  pre- 
cipitation is  sipecific.  For  example,  silver 
chromate  forms  rings  in  gelatin,  but  not  in 
agar-agar,  while  lead  iodide  gives  these  in 
the  latter  but  not  in  the  former.  We  have 
observed  that  ferric  hydroxid(>  gets  precipi- 
tated in  rings  when  a  soluble  ferric  salt  is 
present  in  silicic  acid  gel,  and    gets  slowly 


depth  of  5-60  cms.,  varies  in  colour  from  a 
dark  brown  to  a  recITlijih  yellow.  The  sub- 
soil appears  to  be  the  ordinai'y  and  typical 
sand  of  the  lociility,  unaltered  in  any  way. 
The  zone  immediately  above  the  pan  is  re- 
markable in  the  fact  that  it  is  almost  free  of 
ir<Mi  and  aluminium,  and  hence  has  a 
bleached  appearance.  The  surface  soil  is 
usually  rich  in  acid  humus,  and  is  almost 
completely  free  from  calcium  carbonate. 
The  analytical  figures  for  two  typical  sam- 
ples of  pan-benrin*;  soils  are  given  below: 


stadt, 

Swarzwald. 

Swarzwald. 

Pan 

Bleached 

Pan 

layer. 

^iibstMl. 

sand. 

layer. 

Subsoil. 

1.857 

0.906 

0.193 

0.767 

0.552 

4.946 

1.268 

0.455 

2.133 

0.975 

0.019 

0.210 

0.031 

0.036 

0.029 

0.118 

0.088 

(1.011 

0.025 

0.031 

acted  upon  by  an  alkali  from  above.  Re- 
cently. Bhatnagar  and  Mathur  {Kolloid 
ZcH.,  1922.  XXX.,  3(>8-71)  have  been  suc- 
cessful in  |)reparing  a  number  of  different 
kinds  of  periodic  precipitates  in  this  gel. 

No  satisfactory  explanation  has  yet  been 
forthcoming  for  this  interesting  phenome- 
non, but  as  shown  by  Chatterji  and  Dhar 
(Kolloid  Zeitsch.,  1922  XXXI.),  peptisation 
plays  an  important  part  in  the  fonnation  of 
banded  precipitates.  In  almost  all  cases 
where  banded  precipitates  are  formed,  the 
phenomenon  of  peptisation  has  also  been 
noticed.  The  facts  observed  in  connection 
with  the  formation  of  these  banded  precipi- 
tatcA  may  be  summarised  as  follows : 

(1)  The  phenomenal  takes  place  in  a  gel 
in  which  one  of  the  reacting  substances  is 
dispersed. 

(2)  The  spaces  above  and  between  the 
rings  are  almost  entirely  free  from  the  re- 
acting substances. 

(8)  Complex  organic  matters  of  a  col- 
loidal nature  help  the  taking  place  of  the 
phenomenon. 

If  we  compare  the  above  facts  with  those 
that  have  been  set  forth  before  in  the  case 
of  pan  formation,  the  similarity  becomes  at 
once  obvious.  The  formation  of  pans  in 
soils  is  in  all  probability  another  example 
of  periodic  precipitation  on  a  large  scale  in 
nature.  At  first  the  soluble  salts  of  iron 
and  aluminium  are  present  in  a  state  of 
solution  throughout  the  mass  of  a  medium 
of  silicic  acid  gel.  The  gel  is,  of  course, 
formed  from  the  silicic  acid  sol  resulting 
from  the  gradual  disintegration  of  rocks  by 


THE  CHEMICAL  NEWS. 


AUGUST  10,  1923. 


rain  water  and  their  colloidal  dispersion. 
The  alkali,  naturally  present  in  the  soil,  or 
ammonia  formed  from  the  organic  matter, 
begins  to  react  with  the  salts  of  iron  and 
aluminium  producing  the  insoluble  hydrox- 
ides, which  get  precipitated  in  rings  or  nar- 
row bands  in  the  silicic  acid  medium.  In 
course  of  time  the  silicic  acid  gel  dries  up 
and  gives  rise  to  the  typical  open  texture 
sandy  soil,  consisting  of  quartz  grains,  the 
zones  of  ferric  and  aluminic  hydroxide  pre- 
cipitates forming  hard,  compact  masses, 
commonly  known  as  "  pan." 

If  this  view  about  the  formation  of  pans 
in  soils  is  more  or  less  correct,  we  can 
easily  assign  reasons  for  a  number  of  facts 
which  have  been  observed  in  connection 
with  this  phenomenon,  and  which  have  pre- 
viously been  overlooked.  Thus  if  we  scru- 
tinise the  analytical  figures  given  above  for 
the  pan-bearing  soil,  it  would  be  found  that 
the  iron  and  aluminium  contents  of  the  soil 
below  the  pan  are  much  higher  than  those 
above,  so  that  there  seems  as  if  there  is  not 
one  layer  of  pan,  but  several  layers  of  it 
close  to  one  another.  This  is  what  is  ex- 
pected from  the  point  of  view  of  periodic 
precipitation.  Again,  pan-bearing  soils  are 
rich  in  organic  matter,  and  as  has  been  said 
before,  the  presence  of  this  considerably 
enhances  the  ipeptising  power  of  the  medium 
and  helps  in  the  subsequent  formation  of 
banded  precipitates.  The  almost  entire 
absence  of  calcium  carbonate  from  the  soil 
cannot  at  present  be  more  satisfactorily  ac- 
counted for,  beyond  the  fact  that  the 
periodic  precipitation  of  substances  are 
specific  in  nature  and  that  calcium  hy- 
droxide or  carbonate  does  not  bring  about 
the  preliminary  peptisation  of  iron  or  alu- 
minium hydroxides  in  silicic  acid  gel. 

Technological  Institute, 
Caivnpore  (India). 


FARMING  METHODS  IN  NORTHERN 

MANCHURIA. 

(Journal  of  the  Royal  Society  of  Arts,  July 

20,    1923.) 

Northern  Manchuria  is  pre-eminently  a 
country  of  small  landowners.  The  land- 
owner himself  works  his  fields  in  the 
majority  of  cases,  but  the  larger  landowners 
often  turn  their  farms  over  to  tenants. 

The  division  of  the  land  into  small  par- 
cels and  the  low  purchasing  power  of  the 
individual  fanner  have  been  serious  draw- 


backs to  the  introduction  of  modern  farm- 
ing machinery,  and  Chinese  conservatism 
and  loyalty  to  traditions  have  also  been  op- 
posed to  new  methods  of  farming.  In  a 
district  covering  an  area  pf  approximately 
250,000  square  miles  there  are,  according 
to  information  furnished  by  one  of  the  large 
dealers  in  agricultural  machinery,  only 
about  300  ploughs  of  the  American  type 
and  some  500  German  Sack  ploughs. 
There  are  only  300  disc  harrows,  and  very 
few  mowers,  reapers,  and  self-binders. 
Even  these  are  not  Chinese  Of.ned,  but 
belong  to  Russian  farmers  who  have  settled 
in  the  zone  of  the  Chinese  Eastern  Rail- 
way. 

In  Northern  Manchuria,  according  to  a 
report  prepared  in  the  American  Consulate 
at  Harbin,  the  land  is  very  carefully 
worked,  great  attention  being  paid  to  ferti- 
lisation. The  land  is  ploughed  in  para'.iel 
ridges  and  furrows.  The  soil  is  worked 
twice,  which  enables  the  roots  to  draw 
moisture  from  the  night  air,  even  in  time 
of  drought. 

The  plough  used  is  very  primitive.  Into 
a  wooden  frame  is  set  a  spade-shaped 
ploughshare,  which  is  clamped  to  the  bent 
wooden  lever  or  l>cam.  The  other  end  of 
ithis  leyer  serves  as  a  handle,  and  at  the 
middle  of  it  is  fastened  a  grader.  The 
ploughshare  is  held  in  almost  a  perpendicu- 
lar position  to  the  surface  of  the  land  and 
tears  it  effectively.  This  plough  is  usually 
drawn  by  two  animals  (horses,  mules,  or 
oxen),  and  is  attended  by  two  lalpourers, 
one  of  whom  guides  the  plough  and  the 
other  the  animals.  It  is  transix>rted  to  and 
from  the  field  on  a  special  wooden  drag. 

There  are  two  methods  of  ploughing  the 
soil.  Either  the  ploughshare  follows  the 
ridge,  and  where  last  vear  there  was  a 
ridge  there  will  be  a  furrow  this  year,  or 
the  ploughshare  follows  the  furrow,  and 
where  last  year  there  was  a  furrow  there 
will  also  be  a  furrow  this  year. 

Sowing  or  seeding  is  seldom  performed 
by  hand,  the  use  of  a  "  chan  hu  lu  "  being 
more  popular.  This  is  a  dried  pumpkin, 
which  has  an  opening  made  in  the  narrow 
end.  The  pumpkin  is  filled  with  seeds  and 
the  opening  is  then  closed  with  a  cork,  into 
which  is  fitted  either  a  reed  or  some  kind 
of  piping  in  such  manner  that  the  seeds 
will  scatter  if  the  instrument  is  slightly 
tipped  and  lightly  tapped  with  the  hand. 
One  workman,  carrying  the  "  chan  hu  lu," 
walks  along  the  furrow,  and  tapping  the 
pumpkin  with  his  right  hand,  he  scatters 


AUGUST  10,  1923. 


THE  CHEMICAL  NEWS 


87 


the  seed  so  that  they  fall  on  the  ridges. 
Another  man,  walking  along  the  ridge, 
stamps  the  seeds  down  with  his  feet.  Be- 
hind them  follows  a  third  man,  with  a 
horse  which  pulls  a  small  stone  roller.  This 
roller  follows  the  two  ridges.  On  the  new 
ridge  it  levels  out  the  crest,  and  on  the 
other  it  smooths  out  the  tracks  of  the 
second  labourer's  feet  and  covers  the  seeds 
with  earth. 

When  weeds  begin  to  appear  the  Chinese 
farmer  once  more  follows  along  the  furrows 
with  his  plough,  deepening  them  by  half  a 
foot  so  as  to  surround  the  sprouts  with 
'fresh  earth.  When  the  sprouts  have 
reached  considerable  height  the  plough  is 
again  used  for  bringing  the  deeper  roots 
closer  to  the  surface,  thus  enabling  them 
to  absorb  more  moisture  from  the  air.  By 
this  process  weeds  are  also  destroyed  be- 
tween the  ridges.  On  the  ridges  them- 
selves weeding  is  done  bv  means  of  hoes. 

For  the  harvest  of  cereals  the  Chinese 
farmer  uses  a  special  scythe,  which  is  simi- 
lar to  the  American  scythe  but  of  .smaller 
dimensions.  Very  few  Chinese  farmers  in 
Northern  Manchuria  are  familiar  with 
flails.  In  threshing,  the  plants  are  placed 
in  a  circle,  with  heads  toward  the  centre, 
and  over  these  is  drawn  bv  animals  a  heavy 
stone  roller.  Before  the  kaoliang  is 
threshed,  however,  the  heads  are  cut  off 
from  the  stalks  to  prevent  these  being 
six>iled  bv  the  roller,  for  the  kaoliang  stalk 
plays  an  important  rfile  on  the  farm,  ina» 
much  as  it  is  used  for  roofing,  fencing, 
fuel,  and  many  other  purposes.  The  roller 
process  is  continued  until  all  the  grains 
have  been  removc<l.  Winnowing  is  done 
with  shovels  and  old-fashioned  hand  sifters. 
The  threshed  and  cleaned  grain  i§  stored 
either  in  pits  or  in  specially  constructed 
cylindrical  silos,  covered  with  a  conical 
roof.  These  silos  vary  in  size  according  to 
the  requirements  of  the  individual  fann. 
They  are  built  of  poles,  which  are  plaited 
with  dry  twigs,  the  whole  structure  being 
plastered  inside  and  outside  with  a  com- 
I)osition  of  clay  and  straw  cuttings.  It  is 
divided  into  two  or  three  compartments  for 
the  different  kinds  of  cereal.  Besides  these 
silos  the  Chinese  employ  so-called 
"chantzc."  These  resemble  wells  and  are 
made  of  boards. 

The  threshed  grain  is  ready  for  the  mar- 
ket and  for  the  feeding  of  cattle.     For  pre- 
paring human   food,  however,  it  is  neces- 
sary that  the  hulls  be  removed.      This  is 
done   bv   the   "  chantze  "—a    round,    sta- 


tionary, horizontal  millstone,  upon  which 
rotates  a  stone  cylinder  with  a  rough  sur- 
face. This  cylinder  is  usually  moved  by 
small  donkeys. 

The  Chinese  plough  is  particularly  un- 
suitable for  breaking  new  ground,  and  this 
is  one  reason  why  the  Chinese  farmer  is 
reluctant  to  take  up  virgin  land.  Some 
years  ago  the  Government  conceived  the 
idea  of  ploughing  up  large  tracts  of  land  in 
order  to  sell  them  to  immigrants  from  the 
south.  It  is  believed  the  plan  fell  through 
because  of  some  unfortunate  financial 
manipulation  in  connection  with  the  pur- 
chase of  machinery.  It  seems,  neverthe- 
less, that  this  idea  may  be  revived  by  some 
enterprising  manufacturer,  with  a  view  of 
introducing  modern  farming  machinery  on 
a  large  scale  through  the  agents  of  the 
Government.  There  apr>ears  to  be  a  ten- 
dency at  the  present  time  to  encourage  im- 
migration into  the  Nonni  Valley  and  other 
parts  of  Heilungchiang  Province. 

The  Chinese  Kastem  Railway,  which 
maintains  two  agricultural  experiment  sta- 
tions in  the  district — one  of  300  acres  at 
Station  Anda,  and  one  of  250  acres  at  Old 
Harbin,  together  with  an  experimental 
farm  of  700  acres  at  Station  Echo — appro- 
priated 60,000  gold  roubles  for  farming  ex- 
periments during  the  year.  The  represen- 
tative of  a  large  American  firm  has  been 
conducting  tractor  trials  on  these  grounds, 
and  they  are  generally  reported  to  be  ex- 
ceptionally satisfactor\'.  Two  tractors  are 
being  experimented  with — one  pulling  two- 
bottom  ploughs  and  the  other  pulling  four- 
bottom  ploughs.  This  representative  is  of 
the  opinion  that  the  future  of  these  tractors 
in  Northern  Manchuria  is  most  encour- 
aging. 

The  market  in  Northern  Manchuria  ap- 
pears to  \)c  worthy  of  study  on  the  part  of 
manufacturers  of  agricultural  implements, 
especiallv  the  smaller  tvTxi  of  implements, 
such  as  ploughs,  cultivators,  seeders, 
threshers,  and  fanjiing  mills. 


THE  PREPARATION  OF  STIBINE 
FROM  ATJ.OYS. 

By  Edward  J.  Weeks,  M.Sc,  F.C.S. 

Variotis  workers  have  given  the  percent- 
age composition  of  alloys  of  zinc  and  anti- 
mony best  suited  for  the  pro,pnration  of  sti- 
bine,    but  if  these  results  are    summarised 


88 


THE  CHEMICAL  NEWS. 


AUGUST  10.  1923. 


no  agreement  is  found  among  them.     Thus 
we  find  the  following  alloys  given : 

Parts  of     Parts  of 
Zinc.  Antimony. 
L.  Thompson,     Phil.    Mag., 

1837,  (3),  10,  353  1  1 

K.       Olsgewski,       Monatah. 

Chem.,  1886,  7,  371  1.5         1 

Berthelot  &  P.  Petit,  Compt 

Rendus,  1889,  108,  546  ...     2  1 

A.  Stock  &  W.  Doht,  Ber., 

1901,  34,  2339      4  1 

A.  Stock  &  W.  Boht,  Ber., 

1902,  35,  2270      4  1 

2.5  1 
In  1889  Berthelot  and  P.  Petit  (loc.  cit.) 
stated  that  no  stibine  is  obtained  unless  5 
atoms  of  zinc  are  present  to  one  atom  of 
antimony.  This  gives  1  part  by  weight  of 
antimony  to  2.8  parts  of  zinc. 

It  is  noticed  from  the  above  that  A. 
Stock  and  W.  Doht  give  as  the  best  alloy 
2.5  parts  of  zinc  to  1  part  of  antimony,  or 
1.35  atoms  of  zinc  to  1  atom  of  antimony. 
This  does  not  agree  with  the  statement  by 
Berthelot  and  P.  Petit,  and  indeed  these 
workers  themselves  state  that  stibine  may 
be  prepared  from  an  alloy  of  2  parts  of  zinc 
to  1  of  antimony,  or  1.09  atoms  of  zinc  to  1 
atom  of  antimony,  an  exiperiment  which 
does  not  agree  with  their  own  statement. 

We  must,  therefore,  conclude  that  there 
is  no  actual  best  composition  of  the  zinc, 
antimony  alloy  for  the  preparation  of  sti- 
bine, but  that  the  same  amount  of  stihine 
may  be  obtained  from  any  alloy  of  compo- 
sition varying  from  1  part  of  zinc  to  4  parts 
of  zinc  to  1  of  antimony. 

Sir  John  Cass  Institute, 
Jewry  Street. 

2/8/23. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  INSTITUTE  OF  METALS. 

Autumn  Meeting,  Manchester, 
Septrmber  10  TO  13,  1923. 
A  very  full  programme  has  been  ar- 
ranged, including  visits  to  important  works. 
On  the  evening  of  the  first  day,  a  lecture 
will  be  given  by  Lieut. -Colonel  Sir  Henry 
Fowler,  K.B.E.,  on  The  Use  of  N on-Ferrous 
Metals  in  Engineering,  and  during  the 
meeting  the  following  communications  are 
expected  to  be  submitted  : 


E.  A.  Bolton,  M.Sc,  Birmingham,  The 
Cause  of  Red  Stains  on  Sheet  Brass. 

H.  W.  Brownsdon,  M.Sc,  Ph.D., 
F.I.C.  (Member  of  Council),  Note  on  Brmell 
Hardness  Numbers. 

H.  I.  CoE,  M.Sc,  Swansea,  The  Be- 
haviour of  Metals  under  Compressive 
Stresses. 

HiKOZO  Endo  (Sendai,  Japan),  On  the 
Measurement  of  the  Change  of  Volume  in 
Metals  during  Solidification. 

Ulick  R.  Evans,  M.A.,  Cambridge,  The 
Electrochemical  Character  of  Corrosion. 

Marie  L.  V.  Gayler,  M.Sc,  Teddington, 
The  Constitution  and  Age-Hardening  of  the 
Quart emary  Alloys  of  Aluminium,  Copper, 
Slagncsiutn,  and  Magnesium  Silidde. 

D.  Hanson,  D.Sc,  C.  Maryatt,  B.Sc, 
and  (trace  W.  Ford,  B.Sc,  Teddington, 
Investigation  of  the  Effects  of  Impurities  on 
Copper.  Part  I. — The  Effect  of  Oxygen  on 
Copper. 

Douglas  H.  Ingall,  M.Sc,  Wednes- 
bury,  Experiments  with  some  Copper  Wire  : 
Cohesion  a  Function  of  both  Temperature 
and  Cold-work. 

A.  H.  Mundey  and  C.  C.  Bissett,  B.A., 
B.Sc,  B.Met.,  London,  Note  on  The  Ef- 
fect of  Small  Quantities  of  Nickel  upon 
High-Grade  Bearing  Metal. 

A.  H.  Mundey  and  John  Cartland, 
M.C.,  M.Sc,  London,  Stereotyping. 

Hugh  O'Neill,  M.Met.,  Manchester, 
Hardness  Tests  on  Crystals  of  Aluminium. 

Albert  M.  Portevin,  Paris,  and  Pierre 
Chevenard,  Imphy,  A  Dilatometric  Study 
of  the  Transformations  and  Thermal  Treat- 
ment of  Light  Alloys  of  Aluminiiim. 

R.  C.  Reader,  Ph.D.,  M.Sc,  Birming- 
ham, Note  on  Effects  of  Rate  of  Cooling  on 
the  Density  and  Composition  of  Metals  and 
Alloys. 

E.  L.  Rhead,  M.Sc.Tech.,  and  J.  D. 
Hannah,  Manchester,  Crystallisation  Ef- 
fect on  Galvanised  Iron  Sheets, 


AUGUST  10.  1923. 


THE  CHEMICAL  NEWS 


89 


Professok  p.  Soldau,  Petn^ad,  Russia, 
Equilibrium  in  the  System  Gold-Zinc 
(baaed  on  Investigations  of  Electrical  Con- 
ductivity at  High  Temperatures). 

Full  particulars  can  be  obtained  from  the 
Secretary,  G.  Shaw  Scott,  M.Sc,  36,  Vic- 
toria Street,  London,  S.VV.l. 


THE  BRITISH  CHEMICAL  AND  DYE- 
STUFFS  TRADERS  'ASSOCIATION. 

The  Committee  of  the  above  Association 
have  forwarded  a  memorandum  from  H.M. 
Treasury,  containing  proposals  that  it  is 
suggested  may  lead  to  increased  shipments 
of  chemicals  from  this  country — as  the  mat- 
ter seems  to  us  to  be  of  special  importance, 
we  reproduce  it  in  full  below  :  — 

[Copy.] 

Memorandum  from  The  British  Chemical 
and  Dyestufjs  Traders'  Association  on  the 
method  of  payment  of  duties  under  The 
Safeguarding  of  Industries  Act,  1921 — 
Part  I. 

Importers  of  goods  schedul.d  uivU-r  i'art 
I.  of  The  Safeguarding  of  Industrios  Act, 
1921,  have  to  pay  the  duty  of  33|  per  cont. 
at  the  time  the  goods  are  landed  aiid 
cleared  at  H.M.  Customs. 

This  procedure,  it  is  understood,  is  gov- 
ornwl  by  Section  39  of  the  Customs  Con- 
solidation Act,  1876,  whoroby  H.M.  Trcu«- 
ury  are  given  ipower  to  decide  whether  goods 
liable  to  import  duties  shall  be  allowed  to 
be  bonded  or  not. 

The  Treasury  Order  in  respect  of  The 
Safeguarding  of  Industries  Act,  1921 , 
stipulated  that  the  duties  should  be  paid  at 
the  time  of  landing  and  clearance  of  the 
goods  at  H.M.  Customs. 

During  the  period  this  Act  has  been  in 
orce  it  has  been  found  that  tJbe  present 
method  of  payment  of  duties  as  outlined 
above  is.  in  many  ways,  having  a  detrimen- 
tal effect  on  the  commerce  of  this  country. 
The  following  points  are  submitted  in  sup- 
port of  this  view : 

1. — Prior  to  the  introduction  of  The  Safe- 
guarding of  Industries  Act  and  the  import 
duties  it  entails,  merchant  iirnporters  were 
in  the  habit  of  holding  as  stocks  bulk  sup- 
plies of  goods,  and  were  thus  enabled  to 
meet  both  home  and  overseas  demands 
without  delay.      The  re-exportation  aspect 


was  then  of  very  considerable  importance, 
it  being  estimated  that  quite  half  the  vol- 
ume of  imports  njw  liable  to  Key  Industry 
duty  were,  when  previously  allowed  free 
import,  disposed  of  by  way  of  re-expwt 
sales.  Careful  and  exhaustive  enquiry  has 
been  made  as  to  what  effect  the  payment  of 
im{>ort  duties  under  the  Act  has  had  on  this 
important  branch  of  the  chemical  trade, 
and  it  has  been  found  that : 

(o)  The  difficulties  and  uncertainty  of 
obtaining  "drawbacks"  of  duties  paid  at 
the  time  of  importation  make  it  impracti- 
cable for  merchants  to  compete  in  overseas 
markets.  For  instance,  unless  a  merchant 
holding  stocks  of  goods  on  which  duty  under 
this  Act  has  been  paid  can  ascertain  defi- 
nitely and  quickly  whether  he  can  recover 
such  duty  upon  re-exportation,  he  is  unable 
to  arrive  at  nis  selling  price,  and  is  thus 
prevented  from  competing  for  overseas 
business.  It  is  certain  that  if  he  does  not 
allow  for  a  "drawback"  his  price  to  the 
foreigner  would  not  be  competitive. 

(b)  That  on  account  of  this  position  the 
volume  of  re-exports  of  goods  liable  to  Key 
Industry  duty  has  fallen  away  in  a  very  de- 
plorable manner,  and  merchants  are  con- 
tinually complaining^  that  they  have,  and 
still  are,  losing  sucli  business,  and  state 
that  it  is  largely  due  to  the  disadvantages 
arising  out  of  the  present  methotl  of  collec- 
tion uf  duties  levied  under  the  Safeguarding 
of  Industries  Act,  1921,  Part  I. 

(c)  Some  firms,  in  an  endeavour  to  over- 
come this  barrier  to  re-export  trade,  are 
now  holding  stocks  at  Continental  ports  and 
meeting  demands  in  that  way.  This  must 
entail  loss  of  freif^hts  to  the  shipping  in- 
terests of  this  country;  loss  of  employment 
at  the  docks,  in  warehouses,  and  in  various 
other  directions.  It  has  been  found  that  in 
this  way  only  is  it  possible  and  practicable 
for  merc'hants  in  this  country  to  hope  to 
compete  successfully  in  overseas  markets. 

(d)  Claims  for  drawbacks  usually  take  a 
considerable  time  to  settle,  and  in  many  in- 
stances where  the  goods  in  question  have, 
since  their  importation,  changed  hands  one 
or  more  times,  it  has  been  found  almost  im- 
possible to  satisfy  H.M.  Customs  as  to 
their  identity.  While  the  merchant  is  at- 
tempting to  overcome  these  difficulties  the 
overseas  business  is  lost. 

2. — As  regards  sales  of  dutiable  goods  in 
this  country,  merchants,  in  order  to  carry 
on  their  business  as  economically  as  pos- 
sible and  to  fulfil  their  function  as  distribu- 
tors, arc  in  the  habit  of  importing    in  bulk 


90 


THE  CHEMICAL  NEWS. 


AUGUST  10,  1923. 


quantities.  Such  goods  are  gradually 
liquidated,  and  in  many  instances  the  duty 
paid  at  the  time  of  importation  may  not  be 
recovered  in  full  for  twelve  months,  or  even 
longer.  For  instance,  the  importer  of  duti- 
able goods  to  the  value  of  i£3,000  has  to 
pay  £1,000  as  duty  at  the  time  of  innporta- 
tion,  and  it  is  not  exceptional  for  the  period 
mentioned  to  elapse  before  the  whole  of  the 
importation  is  sold  and  the  duty  thus  re- 
covered. In  this  way  considerable  amounts 
of  capital  are  locked  up.  to  the  detriment 
of  the  merchant  and  trade  in  general. 

It  is  submitted  that,  in  the  case  of  re- 
exports, if  merchants  were  given  the  oppor- 
tunity of  putting  goods  liable  to  Key  Indus- 
try duty  into  bonded  warehouses  at  the 
time  of  imjportation  and  thus  be  relieved  of 
the  immediate  payment  of  duty  and  the  un- 
certainty of  obtaining  drawbacks,  the  trade 
of  this  country  in  re-exports  of  chemicals 
would  be  materially  facilitated,  and  would 
undoubtedly  increase  in  volume. 

In  the  case  of  sales  to  buyers  in  this  coun- 
try, duty  would  only  be  paid  at  the  time 
they  were  taken  out  of  bond  for  actual  de- 
livery. Under  this  arrangement  compara- 
tively large  amounts  of  capital  would  be  at 
the  importers'  disposal,  instead  of  being 
locked  up,  as  is  the  case  under  the  present 
conditions. 

Consideration  has  been  given,  and  en- 
quiry made,  as  to  whether  there  would  be 
objection  on  the  part  of  warehouse  interests 
to  accepting  goods  scheduled  under  Part  I. 
of  the  Safeguarding  of  Industries  Act,  on 
account  of  their  dangerous  character  in 
themselves  or  when  stored  with  other  goods. 
It  aippears  that  as  these  materials  are 
packed  in  such  a  manner  as  to  satisfy  ship- 
ping lines,  who  accept  them  at  ordinary 
rates,  and,  for  the  same  reason,  insurance 
of  such  goods  is  effected  at  low  rates,  it  is 
believed  that  warehouse  interests  would 
approve  of  the  suggested  system  of  bond- 
ing. 

It  is  therefore  suggested  that,  as  the  pre- 
sent system  of  collection  of  duties  under 
the  Safeguarding  of  Industries  Act,  1921, 
Part  I.,  is  doing  great  harm  to  the  com- 
merce of  this  country,  especially  in  the 
matter  of  re-exports,  the  Order  made  by 
H.M.  Treasury  at  present  in  force  should 
be  suitably  amended  so  as  to  allow  duti- 
able goods  to  be  put  into  bond. 

Fonvarded  to  H.M.  Treasury,  and  copy 
to  H.M.  Cnatoms. 

B.  C.  and  D.  T.  A.,  London,  4th  August, 
1923. 


THE  BEITISH  CAST  IKON  RESEARCH 
ASSOCIATION. 


Monthly  Circular. 


•JuxE,  1923. 


No.  19. 


RESEARCH    DEPARTMENT. 

Progress  of  Research  in  Hand. 

Shrinkage  Defects  Research.  —  Experi- 
mental castings  are  continually  being  made 
in  various  foundries.  These  ai-e  being  tested 
under  conditions  to  obtain  definite  data  in 
respect  of  chemical  and  physical  properties. 
IiTiportant  results  bearing  upon  draws  and 
shrinkages  are  being  obtained. 

Foundry  Sand  Research. — Important  ar- 
rangements are  being  made  for  carrying  out 
a  thorough  investigation  upon  foundry 
sands.  The  work  will  probably  be  done  at 
the  Birmingham  University,  and  in  one  of 
the  large  foundries.  The  bureau  are  issu- 
ing a  complete  bibliography  of  sand  litera- 
ture. 

Cast  Iron  to  Resist  Sea  Water. — A  Joint 
Research  with  the  Electrical  Research  As- 
sociation is  being  arranged  to  carry  out  this 
important  work.  It  is  estimated  that  the 
experimental  work  will  occupy  about  two 
years,  and  will  be  carried  out  at  the  coast 
and  in  tidal  rivers.  The  results  of  such 
work  will  be  very  beneficial  to  the  electrical 
industry  and  our  own  members. 

Internal  Covibustion  Engine  Castings. — ■ 
This  research,  carried  out  jointly  by  this 
Association,  the  Motor  Research  Associa- 
tion, and  the  Motor  Cylinder  Research  As- 
sociation, is  reaching  a  stage  when  some 
beneficial  results  should  accrue.  Engine 
cylinders  made  in  this  country'  and  abroad 
have  been  examined  and  reported  upon. 
Test  castings  to  variable  specifications  have 
been  made,  and  are  now  being  subjected  to 
test. 

Cast  Iron  Moulds  for  Bottle  Mahing. — 
This  joint  research  with  the  Glass  Research 
Association  is  progressing,  and  test  moulds 
are  now  being  experimented  upon  and  tried 
in  special  bottle  making  machines. 

Malleable  Cast  Iron  Research. — It  should 
not  be  necessary  to  report  every  month  that 
the  progress  of  this  very  important  work  is 
hampered  by  the  lack  of  support  given  by 
the    malleable    industry.       Malleable    irou- 


AUGUST  10.  1923. 


THE  CHENnCAL  NEWS. 


91 


founders  should  call  a  conference  and  dis- 
cuss the  position  of  their  industry.  The 
Bureau  Bulletin  gives  a  complete  biblio- 
graphy of  the  literature  upou  malleable  iron 
as  published  since  1722,  which  is  very  in- 
teresting reading. 

Standard  Specification  for  Grey  Iron 
Castings. — The  Association  considers  that 
the  time  has  arrived  when  a  standard  etpeci- 
fication  few  grey  iron  castings  should  be 
drawn  up,  and  steps  have  been  taken  to 
have  this  carried  out  in  conjunction  with 
the  B.E.S.A. 

Problems  Sent  in  bv  Members. 

Members,  during  the  past  month,  havo 
sent  in  problems  for  the  Dinetor's  advice 
upon  the  following:  Pwosity  in  cylinder 
castings;  defects  in  pump  castings;  defec- 
tive pig  iron;  annealing  niidleable  iron; 
liners  for  semi-Dicsel  engint -^ ;  C.I.  bevel 
wheels;  Cupola  design;  pumps  for  sea 
water;  pin-holes  in  malleal)l<>  C.I.;  shrink- 
age in  castings;  malleable  annealing  ovens; 
C.I.  valve  guards;  glass  bottle  moulds;  de- 
fects in  heavy  castings;  stripping  plate  pat- 
terns; porosity  in  malleable  castings. 

The  Bureau  and  Library. 

Further  books  and  papers  .  n  pre- 

sented to  the  library  during  i  li    The 

library,  which  has  been  closed  foe  the  cata- 
loguing work,  is  now  reojM'ned  for  issm*  of 
books. 

The  following  new  foundry  hook  has  bi-en 
sent  for  review  in  the  next  bulletin: 

Pattern  Making,  bv  MeCracken  and 
Sampson.  Published  l»y  Scott  Oreenwo<^  • 
ft  Son. 

All  new  books  are  reviewcfl  in  the  Bune 
tin,  and  members  should  consult  same. 

Membership. 

The  gradual  increase  in  the  membership 
is  very  gratifying.  The  increase  during  the 
past  month  has  been  exceptionallj-  good, 
and  places  the  success  ot  the  Association's 
futuH'  work  l)evond  doubt.  With  trade  im- 
proving, iron^ounders  are  recognising  the 
necessity  of  membership,  and  it  only  needs 
the  present  number  to  be  very  materiailv 
increased  to  enable  the  larger  research 
works  to  be  commenced. 

SUOOESTIONR     F'OR      RkSBARCH. 

Members  havo  assisted  the  Research 
Committee  by  making  suggestions    for    re- 


search to  be  carried  out.  These  have  been 
of  very  great  value.  The  field  for  foundry 
research  is  so  great,  there  are  so  many  prob- 
lems to  attack,  that  members  should  advise 
the  Association  as  to  the  problems  they  con- 
sider are  of  the  most  urgent  importance  to 
the  industry.  Veiy  effective  co-operation 
can  thus  take  place. 

Take,  for  instance,  Cupola  practice :  ttie 
.\ssociation  has  assisted  a  large  number  of 
members  in  their  Cuipola  melting  methods, 
yet  it  is  very  remnrkable  to  find  the  very 
variable  conditions  under  which  this  is  car- 
ried out ;  there  is  no  standardised  practice. 
Here  is  a  wide  field  for  work  by  the  Associa- 
tion and  of  vital  interest  to  every  grey  iron 
founder  in  the  country,  and  yet,  due  either 
to  apat.iy  or  to  the  peculiar  foundry  conser- 
vation., he  holds  out  in  joining  the  Associa- 
tion and  obtaining  its  advice. 

Internal  Combustion    Engine  Cylinder 
Kkskarch. 

"'The  continued  examples  of  failure  of 
metal,  not  necessarily  confined  to  the 
marine  Diesel  engine  industry,  seem  to  in- 
dicate that  metallurgical  science  either  has 
not  reached  the  high  standard  which  wo 
have  lately  been  accustomed  to  believe,  or 
the  results  of  investigation  in  working  prac- 
tice and  in  experimental  research  are  not 
coiunumicated  in  a  sulticiently  ext<>nsive 
manner  to  those  concerns  immediately  or 
indiitctly  interest^'d.  In  the  case  of  Diesel 
engine  construction  it  appears  particularly 
advisable  that  no  efforts  should  be  spared  in 
the  direction  of  further  research,  and,  what 
is  of  vital  importance,  the  j)ublication8  of 
specifications  of  alloys,  records  of  experi- 
■  .....,«.  with  n'latirm  to  the  behaviour  of 
in  high  temperatures,  and  data  re- 
;.  iiiiig  to  wear  of  parts. 

"We  believe  that  much  time  and  labour 
could  b.'  saved  if  there  were  more  co-opera- 
tion between  marine  Diesel  en^ne  builders, 
particularly  with  regard  to  their  experimen- 
tal sections.  Undoubtedly,  with  such  in- 
volved subjects  demanding  investigation, 
collabf  ration  would  benefit  the  largest  con- 
cerns equally  with  the  smallest.  Definite 
standards  could  l>e  set  up,  guess-work  and 
rule  of  thumb  practices  abolished,  and  data 
of  exceptional  value  afforded.  With  refer- 
ence to  sipecifications  of  metal,  doubt  as  to 
the  capabilities  of  certain  types  of  cast-iron 
has  led  to  a  plethora  of  costly  expedients, 
by  which  the  designer,  bringing  to  his  aid 
constructional  complications,  aims  at  a  re- 
sult   which    should    be     attained    by    more 


92 


THE  CHEMICAL  NEWS. 


AUGUST  10,  1923. 


direct  and  simple  means.  The  present 
work  of  the  British  Cast  Iron  Kesearoh  As- 
sociation should  be  valuable  in  this  direc- 
tion."— (Motor  Ship,  June,  1923.) 

Central  House,  New  St.,  Birmingham. 
Thos.  Vickers,  Secretary. 


KOYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

Weekly  Evening  Meeting,  Friday,  May 
4,    1923. 

Sir  James  Crichton-Browne,  M.D.,  LL.D., 

F.R.S.,  Treasurer  and  Vice-President, 

in  the  Chair. 

THE  ORIGINS  OF  THE  CONCEPTION 
OF  ISOTOPES. 

A  Lecture  delivered  by  Frederick  Soddy 
M.A.,  F.R.S. 

One  of  the  most  important  consequences 
of  the  study  of  the  chemistry  of  the  pro- 
ducts of  radioactive  change  has  been  the 
discovery  of  isotopes  and  the  interpretation 
in  consequence  of  the  Periodic  Law  in  terms 
of  modem  views  of  atomic  structure.  It  is 
one  of  the  few  fields  in  the  vast  borderland 
between  physics  and  chemistry,  overrun  of 
recent  years  by  an  advancing  swarm  of 
mathematicians  and  physicists,  armed  with 
all  sorts  of  new-fangled  weapons,  in  which 
the  invaders  have  found  the  chemist  already 
in  possession.  The  broad  highways  they 
have  hewn  thereto  are  already  dusty  with 
the  tread  of  pilgrims,  and  are  being  watered 
by  the  tears  of  candidates  for  "  Plonours." 
But  the  somewhat  intricate  bye- ways 
through  which  the  chemist  first  found  his 
way  into  this  virgin  territory,  and  the  views 
on  the  road  before  it  was  in  sight,  may  still 
preserve  something  of  their  pristine  interest. 

The  word  isotope  signifies  "  the  same 
place,"  m  allusion  to  isotopes  occupying 
the  same  place  in  the  Periodic  Table.  Be- 
fore this  word  of  theoretical  meaning  was 
coined,  isotopes  were  experimentally  well 
known  as  elements  non-separable  by  chemi- 
cal methods  and  completely  identical  in 
their  whole  chemical  character.  The  ana- 
lysis of  the  constituents  of  matter,  to  which 
we  were  born  and  brought  up  to  regard  r.s 
the  most  searching  and  fundamental,  is  an 


analysis  by  means  of  its  chemical  proper- 
ties. Although,  later,  a  new  and  even  more 
powerful  method,  spectroscopic  analysis, 
was  developed,  it  merely  dotted  the  t's  and 
crossed  the  t's  of  chemical  analysis,  filled  in 
a  few  vacant  places  in  the  Periodic  Law, 
and  handed  over  the  newcomers  to  the 
chemist  to  classify  along  with  the  rest  of 
the  eighty  or  so  "foundation  stones"  of 
which  he  supposed  the  material  universe  to 
be  built  up.  Then,  with  the  close  of  last 
century,  another  new  method,  radioactive 
analysis,  was  developed,  which  is  aipplicable 
of  course  only  to  the  radio-elements — that 
is,  to  the  elements  uranium  and  thorium 
and  the  thirty-four,  as  we  now  know,  suc- 
cessive unstable  products  of  their  spontane- 
ous disintegration.  Each  of  these  possesses 
a  definite  radioactive  character;  it  is  pro- 
duced from  one  and  changes  into  another 
element,  and,  in  both  changes,  rays  charac- 
teristic of  the  two  substances  are  expelled, 
which  are  as  fine  a  hall-mark  of  their  iden- 
tity as  any  of  the  "tests"  of  chemical  analy- 
sis. But  radioactive  character,  unlike  spec- 
troscopic character,  is  completely  indepen- 
dent of  chemical  character.  The  latter 
might  be  called  "  existence  proiperties," 
whereas  the  radioactive  character  is  that 
attending  the  explosion  of  the  atom  which 
terminates  the  existence  of  the  element  as 
such.  It  provided  the  necessary  indepen- 
dent method  of  analysis  capable  for  the 
first  time  of  distinguishing  between  ele- 
ments identical  chemically  and  occupying 
the  same  place  in  the  Periodic  Table — i.e., 
between  isotopes. 

The  Earlier  Chapter  of  Radio-Chemistry. 

Not  a  hint  of  this,  however,  was  afforded 
by  the  earlier  chapter  of  radio-chemistry. 
On  the  contrary,  no  development  could  ap- 
tpear  more  normal.  Just  as  rubidium,  thal- 
lium, etc.,  were  detected  by  the  spectro- 
scope before  anything  of  their  chemistry 
was  .known,  so  radium  was  detected  in 
pitchblende  by  its  radioactivity  in  concen- 
tration thousands  of  times  less  than  is 
necessary  to  show  a  single  line  of  its  spec- 
trum. But  with  more  concentrated  pre- 
parations a  new  spectrum  was  discovered, 
and  then  a  new  element,  which  was  found 
to  possess  a  chemical  character  entirely 
new  and  sufficing  for  its  separation  in  the 
pure  state  from  all  other  elements.  As  in 
the  case  of  the  elements  discovered  by  the 
spectroscope,  radium  was  found  to  occupy 
a  place,  hitherto  vacant,  in  the  Periodic 
Table.  But  as  it  happened  radium  is  ex- 
ceptional in  this.       Its  chemical    character 


AUGUST  10,  1923. 


THE  CHEMICAL  NEWS. 


9d 


was  quite  normal,  and  indeed  could  have 
been  largely  predicted  beforehand  for  the 
missing  element  occupying  this  place.  The 
development  of  the  subject  showed  it  to  be 
but  one  of  some  thirty-four  radio-elements 
formed  from  uranium  and  thorium.  But 
there  are  not  thirty-four  vacant  places  in 
the  Periodic  Table  to  accommodate  them. 

Met.\-Elements. 
So  far  as  I  am  aware,  there  is  no  antici- 
pation, prior  to  the  systematic  study  of  the 
chemistry  of  the  radio-elements,  of  the 
idea  that  there  may  exist  different  elements 
with  absolutely  identical  chemical  charac- 
ter. Sir  William  Crookes,  it  is  true,  once 
thought,  though  the  idea  has  not  survived 
mwe  extended  examination,  that  the  pro- 
perties of  the  elements,  as  we  know  them, 
rnight  be  a  mean  value,  and  that  the  indi- 
vidual atoms  composing  the  element  might 
differ  in  weight  and  chemical  character  con- 
tinuously Ml  either  side  of  this  mean.  If 
80,  more  refined  methods  might  serve  to 
resolve  the  element  into  a  collection  of 
what  he  termed  "Meta-Elements,"  possess- 
ing the  main  character  of  the  original,  but 
differing  from  one  another  to  a  slight  ex- 
tent. Misled  by  the  phosphorescence  spec- 
tra, which  are  now  known  to  be  characteris- 
tic of  mixtures  rather  than  chemically  ho- 
mogeneous substances,  he  thought  at  one 
time  that  he  had  been  successful  in  resolv- 
ing yttrium.  But  the  present  idea  that  ele- 
ments may  exist,  absolutely  the  sanje  in 
chemical  nature  and  yet  absolutely  different 
in  other  properties,  such  as  radioactivitv 
and  atomic  weight,  is  totally  distinct  froiii 
this. 

The  Experimental  Method  that  First 
Revealed  Isotopes. 

I  venture  to  think  that  no  more  elegant 
extension  of  our  method»s  of  gaining  new 
knowledge  has  ever  been  obtained  than  that 
which,  in  due  course,  was  to  reveal  the 
existence  of  isotopes.  The  original  observa- 
tions, upon  which  the  theorv  of  atomic  dis- 
integration was  first  founded,  were  that 
thorium  is  continuouslv  producing  a  new 
radioactive  substance,  tKorium  X,  separable 
from  it  by  precipitation  with  ammonia,  but 
not  with  other  precipitants,  and,  aft^er 
separation,  continuously  re-forming  again. 
The  thorium  X  was  short-lived,  and  changed 
again  into  a  gas,  the  thorium  emanation,  for 
wnich  the  name  thereon  has  recently  been 
proposed,  which  was  even  shorter-lived  and 
changed  again  to  a  solid,  the  "  excited  activ- 


ity," now  known  as  the  active  deposit, 
which  again  went  through  further  changes. 
The  rays  resulted  from  these  'successive 
changes,  a-rays  in  the  first,  and  a-,  fi-  and 
y-rays  in  the  last  changes.  Below  is  the 
first  part  of  the  thorium  disintegration 
series  as  it  appeared  to  Sir  Ernest  Ruther- 
ford and  myself  in  1903 :  — 

a  a  a 

Thorium —^Thorium  X— ;^Thoron-^  etc. 
In  1905,  Sir  William  Ramsay  and  0. 
Hahn  were  engaged  in  extracting  radium 
from  thorianite,  a  new  Ceylon  mineral  con- 
taining both  uranium  ana  thorium  in  im- 
portant quantities.  The  radium  was 
separated  with  the  barium,  and  the  chlor 
ides  fractionated  in  the  usual  way.  They 
found  a  new  radio-element  to  be  present, 
and  to  be  separated  from  the  radium  with 
the  barium.  It  proved  to  be  the  direct 
parent  of  thorium  X,  and  intermediate  in 
the  series  between  the  latter  and  thorium, 
and  they  called  it  radiothorium.  In  spite 
of  this  easy  and  apparently  straightforwiid 
setparation,  the  experience  of  a  number  of 
chemists  showed  that  something  remained 
to  be  explained,  for  it  was  found  to  be  difli- 
cult  to  the  verge  of  impossibility  to  separate 
radiothorium  from  thorium.  Ramsay  and 
Hahn  had  in  fact  "separated"  isotopes  in 
1905,  for  radiothorium  and  thorium  are  iso- 
topes. Yet  further  work  has  shown  the 
two  to  be  so  alike  that  no  separation  by 
ohemical  means  is  possible ! 

Then  in  1907,  along  with  the  radium 
which  had  been  separated  from  thorianite, 
Hahn  discovered  another  new  radio-ele- 
ment, mesothorium,  the  direct  parent  of 
radiothcM-ium  and  intermediate  between  it 
and  thorium.  In  the  next  year  he  showed 
that  mesothorium  consists  of  two  successive 
products — the  first,  the  direct  product  of 
thorium,  mesothorium  1,  being  practically 
rayless  and  generating  a  short-lived  product, 
mesothorium  2,  giving  powerful  ft-  and  -y- 
rays. 

This  resolved  the  mystexy,  and  one  can- 
not do  better  than  to  quote  the  words  of 
McCoy  and  Ross  (J.  Amer.  Chem.  Soc, 
1907,  XXIX,  1709) : 

"  Our  experiments  strongly  indicate  that 
radiothorium  is  entirely  inseparable  from 
thorium  by  chemical  processes.  .  .  . 
The  isolation  of  radiothorium  from  thorian- 
ite and  from  pure  thorium  nitrate  . 
may  have  been  accomplished  by  the  separa- 
tion of  mesothorium,  which  in  time  changed 
spontaneously  into  radiothorium." 
Thus    the    radiothorium    seiparated    from 


04 


Tli^l  CHEMICAL  NEWS. 


AUGUST  10,  102B. 


the  mineral  thorianite  by  Ramsay  and 
Hahn  was  not  the  radiothorium  in  the 
mineral,  but  that  subsequently  produced 
from  the  easily  separated  mesothorium, 
after  it  had  been  removed  from  the  thoriurn. 
If  they  had  fractionated  the  radium-me^^o- 
thorium-barium  mixture  at  once  they  would 
not  have  discovered  radiothorium.  Tiie 
lapse  of  time  after  the  separation  of  the 
mesothorium  is  essential.  Nowadays  many 
non-separable  radio-elements  are,  like  radio- 
thorium, "grown"  from  their  separable 
parents.  Thus  radium  D,  an  isotope  of 
lead,  is  grown  from  the  radium  emanation 
(radon),  although  it  cannot  be  separated 
from  the  mineral,  which  always  contains 
lead  in  quantity. 

The  first  part  of  the  thorium  series  now 
runs* :  — 

a 

Thorium ^Mesothorium  1 — —^ 

2.10'''  years  9.67  years 

0 

Mesothorium  2 ^ 

8.9  hours 

a  a 

Radiothorium ^Thorium   X ^ 

2.91  years  5.25  days 

a 

Emanation ^etc. 

7S  seconds 

In  this  series  thorium  and  rndiothoriuni 
and  mesothorium  and  thorium  X  are  two 
pairs  of  isotopes  If  we  represent  the  suc- 
cessive products  by  balls  of  different  colours 
to  indicate  their  chemical  character,  iso- 
topes being  of  the  same  colour,  chemical 
analysis  will  sort  the  balls  into  their  differ- 
ent colours,  and  the  lapse  of  time  will  cause 
some  of  the  colours  to  change.  The  ball 
representing  mesothorium  will  in  time  turn 
into  that  representing  radiothorium,  so  that 
the  latter,  before  indistinguishable  from 
thorium,  becomes  known  as  a  separate  in- 
dividual. 

The  Isotopes  of  Uranium. 
It  will  be  noted  that  the  niethod  of 
separating  isotopes  depends  upon  th^ir 
being  alternate  rather  than  successive  in 
the  series.  If  radiothorium  had  been  the 
direct  product  of  thorium,    the  two    would 


*  The  periods  shown  in  the  second  line 
are  the  periods  of  average  life  of  the  succes- 
sive products.  These  are  1.443  times  the 
period  required  for  one-half  of  the  elem,ent 
to  change. 


never  have  been  separated  to  this  day.  The 
changes  of  chemical  character  are,  as  we 
shall  later  see,  intimately  connected  with 
the  electric  charges  on  the  a-  and  y8-particies 
expelled.  For  successive  products  to  have 
the  same  character  no  rays,  or  at  least  no 
charged  particles,  must  be  expelled.  It  is 
always  as  well — and  no  subject  illustrates 
the  point  better  than  that  of  isotopes — to 
r(?flect  not  only  upon  what  our  methods  are 
able  to  reveal,  but  also  upon  what  they 
cannot  reveal. 

At  first  it  seemed  as  if  uranium  itself  was 
a  case  of  successive  isotopes.  Boltwood,  in 
1908,  proved  from  his  study  of  the  relative 
activities  of  the  successive  products  giving 
a-rays  in  minerals,  that  whereas  all  of  them, 
except  uranium,  gave  off  only  one  a-particie 
per  atom  disintegrating,  uranium  gave  off 
two.  By  direct  observation  with  the  scin- 
tillation method  it  was  proved  that  the  two 
a-particles  from  uranium  are  not  smiul- 
taneously  expelled,  and  later  it  was  shown 
that  they  possess  different  velocities.  If 
the  slower  comes  from  uranium  itself  (ura- 
nium I),  the  period  of  which  is  known  to  be 
6.10*  years,  the  swifter  must  come  from 
the  isotope  (uranium  II),  and  its  period 
must  be  some  three  million  years.  This  is 
an  example  of  isotopes  being  revealed  by 
difference  of  radioactive  nature  simply, 
though  no  other  evidence  of  their  separate 
existences  is  available.  Owing  to  the  long 
periods  of  the  a-ray  giving  members  of  the 
earl  ypart  of  the  uranium  series,  it  has  been 
much  more  difficult  to  unravel  than  the 
thorium  series.  As  a  result  of  researches 
too  numerous  to  detail,  it  has  been  con- 
cluded that  the  main  series  is  almost  en- 
tirely analogous  to  the  thorium  series,  and 
runs : — 

a  _  /3 

Uranium  I — .—^Uranium  X^ ^ 

6.10«  years  35.5  days 

i8 
Uranium  Xj — •— ^ 
1.65  minutes 
a  a  a 

Uranium   II ^Ionium ^Radium ^ 

8.10*  years  10^  years      2440  years 

a 

Radon ^  etc. 

5.55  days 

Though  two  short-lived  products  probably 
intervene  between  the  two  uraniums,  ana- 
logous to  the  two  mesothoriums  between 
thorium  and  radiothorium,  the  relation  of 
their  period  to  that  of  their  product,  ura- 
nium II,  is  so  hopelessly  unfavourable  that 


AUGUST  10,  1923. 


THE  CHEMICAL  NEWS. 


there  is  no  hope  of  ever  being  able  to  put 
the  separate  existence  of  uranium  II  into 
evidence  in  the  same  way  as  was  done  for 
radiotorium.  For  all  practical  purposes  the 
two  uraniums  are  as  non-separable  by  this 
method  as  if  they  were  actually  successive 
products.  I  spent  many  years,  before  this 
part  of  the  series  was  at  all  well  known, 
looking  for  the  product  of  uranium  X,  and 
separated  this  constituent  from  50  kilo- 
grams of  uranium  nitrate  repeatedly  in  the 
attempt.  I  was  looking  for  a  growth  of  u- 
rays  concomitantly  with  the  decay  of  the 
/S-rays  of  the  uranium  X.  If  the  product 
had    been    ionium,     as    at    first    thought 

a  a  pa 

(U  I—  U  II—  UX—  lo^  ),  it 
should  have  been  just  possible  to  detect  it. 
But  since  it  is  the  thirty  times  longer-lived 
uranium  II,  the  attempt  is  hopeless,  especi- 
ally as  uranium  X  and  ionium  are  isotopes, 
and  therefore  the  uranium  X  seiparatcd 
must  always  possess  a  certain  initial  a- 
activity  due  to  ionium. 

The  Absolute  Chemical  Identity  of 
Isotopes  and  its  Implications. 

The  years  1908-1910  were  productive  of 
many  prolonged  and  serious  efforts  to 
separate  isotopes  by  chemical  means.  In 
1908  Boltwood  discovered  icmium,  and 
showed  that  it  resembled  thorium.  Keet- 
man,  who  with  Marckwald  discovered 
ionium  independently,  tried  twelve  good 
methods,  all  known  to  be  cffectivi',  in  the 
purification  of  thorium  in  the  attempt  to 
separate  the  ionium  from  thorium,  com- 
pletely without  success.  Auer  von  Wels- 
bach,  on  a  technical  scale,  separated  the 
ionium  and  thorium  from  30  tons  of  ipitch- 
blende,  and  tried  fresh  methods  in  the  hope 
of  separating  them,  but  failed.  It  was  with 
this  preparation  that  Exner  and  Haschek 
tried  without  success  to  find  the  ionium 
spectrum,  and  Russell  and  Rossi  confirmed 
their  result,  that  the  spectrum  was  that  of 
pure  thorium.  When  later  I  had  deter- 
mined beyond  doubt,  from  measurements 
of  the  rate  of  growth  of  radium  from  ura- 
nium, that  the  period  of  ionium  was  100,000 
ycEirs,  and  that  Welsbach's  preparatinn 
must  have  been  approximately  30  per  cent, 
ionium  and  70  per  cent,  thorium  by  weight, 
it  followed  that  the  spectra  of  isotopes 
must,  like  their  chemical  character,  also  he 
identical.  The  difference,  if  any  exists,  is 
almost  beyond  the  limit  of  detection  by  the 
most  powerful  methods. 

{To  be  Continued.) 


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BOOKS  RECEIVED. 

Landolt  Bomatein,  Phyaikaliaeh-Cheni- 
iscUe  Tabcllen,  by  Db.  Walther  A.  Roth 
und  Dr.  Karl  Scheel.  2  Vols.  Pp.  XV.  + 
1695.  1st  Ed.,  1923.  Verlag  von  Julius 
Springer,  Linkstrasse  23-24,  Berlin,  W.9. 

The  Discovery  of  the  Nature  of  the  Air 
and  of  its  Changes  during  Breathing,  by 
Clara  M.  Taylor,  M.A.  Pp.  IX.  +  84.  1st 
Edition,  1923.  Messrs.  G.  Bell  &  Sons, 
Ltd.,  York  House,  Portugal  St.,  London, 
W.C.2.    Is.  Od.  net. 

Materie  Elektrizitat  Energie,  by  Dr. 
Walther  Gerlach.  Pp.  195.  1923.  Ver- 
la  gvon  Theodor  Steinkopfif,  Dresden  und 
Leipzig. 

BULLETINS     PUBLISHED     BY     THE 

U.S.    DEPARTMENT    OF    THE 

INTERIOR. 

Cadmium  in  1922,  by  C.  E.  Siebentual 
and  A.  Stoll. 

Petroleum  in  1919-1921,    by  G.  B.  Ricb- 

ARDSON. 

Natural  Gas  in  1919-1921,  by  R.  S.  Mc- 
Bride  and  E.  G.  Sievbrs. 


96 


THE  CHEMICAL  NEWS. 


AUGUST  10,  1923. 


732 :  Geology  and  Ore  Deposits  of  Sho- 
shone County,  Idaho,  by  Joseph  B.  Umple- 
BY  and  E.  L.  Jones,  Jun.     Pp.  V.  +  156. 

740 :  Mica  Deposits  of  the  United  States, 
by  Douglas  B.  Sterrett.    Pp.  XI,  +  342. 

741 :  The  Jarbidge  Mining  District,  Ne- 
vada, with  a  Note  on  the  Charleston  Dis- 
trict, by  Frank  G.  Schrader.  Pp.  V.  +  86. 

743 :  Geology  of  the  Oatman  Gold  Dis- 
trict, Arizona;  a  Preliminary  Report,  by  F. 
L.  Eansome.     Pp.  IV.  +  58. 

Water- Supply  Papers. 
488 :  The  Floods  in  Central  Texas  in  Sep- 
tember, 1921,  by  C.  E.  Ellsworth.       Pp. 
IV.  +  56. 

493 :  Hydroelectric  Power  Systems  of 
California,  and  their  extensions  into  Oregon 
and  Nevada,  by  Frederick  Hall  Fowler. 
Pp.  XLIX.  +  1276. 


NOTICES  OF  BOOKS. 

La  Tannerie  au  Maroc,    par  Ch.  Zeig- 

LER.     Pp.  122.      Paris:     Edite  par    "  La 

Chaussure  FranQaise,"  Boulevard  Sebas- 

topol.     1923.     Price  7fr.  50. 

The  native  leather  trade  in  Morocco  ha- 
always  been  prosperous,  cattle  rearing  being 
a  simple  matter,  and  various  vegetable 
bodies  suitable  for  tanning  are  to  be  found 
near  to  hand.  The  processes  are  still  con- 
ducted in  a  primitive  manner,  almost  iden- 
tical with  those  employed  in  England  dur- 
ing the  seventeenth  and  the  beginning  of 
the  eighteenth  centuries.  The  French  have, 
however,  recently  introduced  certain  im- 
provements. 

Three  kinds  of  tanning  bodies  are  used, 
viz.,  crudely  crushed  oak  bark,  Tizra  (Rhus 
pentaphylla),  and  Takaout  (the  gall  of 
Tam,arix  Articulata). 

The  Tizra  is  a  tree  which  seldom  attains 
more  than  eight  feet,  but  the  bark  of  the 
trunk  contains  about  13  per  cent,  of  tan- 
nins. The  bark  of  the  roots  and  branches  is 
also  used. 

Several  varieties  of  tamarix  gall  are 
known,  and  usually  contain  40  per  cent,  of 
tanning  matter.  It  is  used  especially  for 
-sheep  and  goat-skins. 

The  bark  of  three  sipecies  of  oak,  Quercus 
suber,  2.  ilex,  and  2  coccifera,  are  also  em- 
ployed. Certain  other  native  plants  are 
quoted  as  having  slight  application. 


For  making  leather,  the  skins  are  fiist 
depilated  by  immersion  in  several  baths  of 
milk  of  lime  of  increasing  strength.  They 
are  then  thoroughly  washed  and  scraped, 
and  it  is  customary  to  steep  the  skins  for  a 
week  in  water,  to  which  dried  figs  have  been 
added.  The  sugar  present  in  this  bath  is 
supposed  to  give  a  suppleness  to  the  leather. 
The  actual  tanning  is  then  conducted  in  a 
bath  of  one  or  other  of  the  bodies  men- 
tioned, and  lasts  about  three  or  four  days. 

The  processes  throughout  are  most  un- 
hygienic, and  are  usually  carelessly  con- 
ducted. Further,  although  the  leather  so 
produced  can  be  of  a  high  quality,  its  value 
is  often  diminished  by  faults  in  the  skin, 
due  to  careless  killing  of  the  beasts,  and 
sometimes  to  the  presence  of  parasites. 

The  author  has  described  the  preparation 
of  the  skins  and  their  sale  in  the  markets, 
and  gives  other  details  of  general  interest, 
together  with  numerous  photographs  and 
some  coloured  illustrations  of  native  shoes. 

J.G.F.D. 


i'his  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent  Applications. 

18573 — Ostro-Products  Corporation  of  America,. — 
Manufacture  of  medical  preparations  con- 
taining arsenic.    July  16. 

18574 — Ostro-Products  Corporation  of  America.— 
Manufacture  of  paraoxymetanitrophenyl- 
arsenious  acid.    July  18. 

18362 — Carbide  &  Carbon  Chemicals  Corporation. 
— Purifying  chlorine,  &c.    July  16. 

18439 — Naugatuck  Chemical  Co. — Process  for  halo- 
genatiiig  latex,  &c.    July  17. 

18552 — Shimadzu,  G. — Manufacture  of  powder  of 
lead  suboxide  intermingled  with  powder  of 
metallic  lead.    July  18. 

Abstract  Published  this  Week. 
198576— Metaldehvde.    J.  Y.  Johnson,  47,  Lincoln's 
Inn  Fields,  London. 

Metaldehyde  is  produced  by  the  action  of  the 
following  catalysts  on  aoetaldehyde  at  tempera- 
tures below  10°  C,  (1)  titanium  chloride,  (2)  a 
bromide  of  an  alkali  or  alkaline-earth  metal,  such 
as  lithium  or  calcium  bromide,  (3)  a  halide  of  an 
alkali  metal,  alkaline-earth  metal,  aluminium, 
zirconium,  thorium,  cerium,  lanthanum,  yttrium, 
ytterbium  or  titanium,  in  conjunction  with  an 
aoid,  such  as  hydrochloric  or  hydrobromic  acid, 
an  acid  salt,  or  a  comi>ound  having  acid  proper- 
ties, such  as  ferric  chloride,  aluminium  chloride, 
or  sulphur  and  antimony  haloids. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  le.  6d. 
each. 


AUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


97 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3305. 


SIR  WILLIAM  CROOKES'  ANTI-GLARE 
GLASSES. 

By  J.  H.  Gardiner,  F.Inst.P. 

I  suppose  that  I  have  the  privilege  of 
knowing  as  much  as  anyone  about  this  sub- 
ject, having  been  intimately  associated  with 
the  late  Sir  William  Crookes  for  more  years 
than  I  care  to  count,  working  under  him  in 
all  the  researches  connected  with  the 
glasses  that  bear  his  name.  Sir  William 
was  deeply  interested  in  the  subject,  and 
was  engaged  upon  the  work  at  the  time  of 
his  death. 

A  few  words  briefly  giving  the  history  of 
the  research  may  not  be  out  of  place.  The 
work  on  the  radiation  transmission  of  trans- 
parent substances  began  with  an  enquirj'  in- 
to the  cause  of  glass-maker's  cataract,  and 
several  years  of  hard  work  were  devoted  to 
it;  in  1914  a  paper  was  read  before  the 
Royal  Society  in  which  formulae  were  given 
for  many  glasses  having  special  optical  pro- 
perties, and  manufacturers  were  encouraged 
to  produce  them  for  general  use.  As  a  re- 
sult, Sir  William  was  inundated  with  en- 
quiries from  private  people  needing  aseist- 
ance  for  eyesight  trouble,  and  from  glass 
manufacturers  who  wished  to  use  his  name 
for  glasses  that  they  had  succeeded  in  mak- 
ing from  his  published  formulae. 

It  soon  became  evident  that  further  work 
was  necessary  to  produce  a  glass  that  would 
absorb  as  much  ultra-violet  radiation  as 
possible,  and  at  the  same  time  transmit  the 
bulk  of  the  visible  rays;  the  glass  also  had 
to  be  pleasing  in  appearance.  It  was  evi- 
dent that  it  would  be  necessary  to  make  a 
variety  of  tints  to  suit  different  climatic 
conditions. 

The  work  was  carried  out  with  the  assist- 
ance of  Mr.  Harry  Powell,  of  Whitefriars 
Glass  Works,  whose  death  unhappily 
occurred  a  few  days  ago.  Agreements  were 
made  between  Sir  Wiliam  and  Mr.  Nelson 
Wingate,  of  Wigmore  Street,  W.,  for  the 
glasses  to  be  placed  uipon  the  market  as 
soon  as  conditions  made  their  production 
possible.  Some  of  these  glasses  are  on  ex- 
hibition here  to-night.  Many  causes,  that  I 
need  not  enter  upon  now,  have  prevented 
very  large  production,  but  it  is  hoped  that 
the  output    will  be    increased  shortly;    the 


glass  is  of  a  very  special  character,  and  pre- 
sents unexpected  technical  difficulties. 

On  the  death  of  Sir  William  the  whole  of 
the  data  for  the  preparation  of  the  glasses, 
and  the  apparatus  that  had  been  devised  for 
obtaining  measurements  of  the  radiation 
transmitted  and  absorbed  by  them,  were 
given  into  my  charge;  the  apparatus  will 
shortly  be  erected  at  the  Laboratories  of  the 
new  Whitefriars  Glass  Works  at  Weald- 
stone,  where  we  hope  to  be  able  to  produce 
the  material  in  larger  quantities  than  has 
been  possible  at  the  old  works  in  London. 

Discussion. 

Dr.  L.  C.  Martin:  I  would  like  to  draw 
attention  to  the  work  of  Verhoeff  and  Bell 
on  the  "Pathological  Effects  of  Radiant 
Energy  on  the  Eye"  {Proc.  Amer.  Acad. 
AHs  and  Sciences,  July,  1916,  LI.,  No.  13). 
A  systematic  review  of  the  literature  is 
given  by  Dr.  C.  B.  Walker  in  the  same 
issue.  The  authors  show  that  the  radiations 
possessing  "abiotic"  power  (or  power  of 
destructive  action  on  living  tissue)  are  con- 
fined to  wave  lengths  shorter  than  0.305  /<. 
It  is  under  exceptional  conditions  that  such 
harmful  action  can  be  caused  by  sunlight 
which  possesses  very  little  energy  at  0.305  fi 
and  contains  no  wave  lengths  snorter  than 
0.295  fi  at  the  earth's  surface  owing  to  at- 
mospheric absorption.  Similarly  the  possi- 
bility of  abiotic  action  with  the  light  from 
ordinary  enclosed  sources  of  artificial  light 
is  very  remote,  although  with  naked  arcs, 
etc.,  special  protection  must  be  given. 

In  ordinary  life  the  causes  of  eye  strain 
and  inflammatory  conditions  must  be 
sought  in  conditions  other  than  the  abiotic 
action  of  light,  and  attention  would  be  bet- 
ter directed  to  the  regulation  of  the  inten- 
sity of  the  visually  apparent  radiations,  to 
general  health,  and  to  the  provision  of  pro- 
per refractive  correction.  The  conclusions 
set  out  in  my  patper  on  "Light  Filters  for 
Eye  Protection"  (Trans.  Opt.  Soc,  April, 
1917,  XVIII.)  agree  with  those  of  Verhoeff 
and  Bell,  and  I  would  like  again  to  draw 
attention  to  that  paper  in  the  present  con- 
nection. 

Mr.  H.  H.  Emsley :  I  associate  myself 
with  Dr.  Martin  to  the  extent  of  expressins 
some  confusion  of  mind  as  to  what  exactly 
Crookes'  glass  is  intended  to  do.  My  recol- 
lection of  Crookes'  work  on  the  subject  is 
that  it  was  found  that  cataract  in  glass- 
workers'  eyes  was  caused  by  the  infra-red 
radiation  and  not  by  the  ultra-violet.  Now- 
adays one  hears  no  word  about  the  infra-red 
absorbing  properties  of  the  glass.    It  is  true 


98 


THE  CHEMICAL  NEWS 


AUGUST  17,  1923. 


that  Crookes  extended  his  investigation  as 
he  proceeded  and  encountered  many  difficul- 
ties, but  I  am  not  clear  as  to  why  the  ultra- 
violet is  continually  referred  to  and  practi- 
cally nothing  is  stated  about  the  infra-red. 

(From  "Transactions  of  the    Optical  So- 
ciety," Vol.  XXIV.,  No.  2,  1922-1923.) 


SOME  PROPERTIES  OF  THE  META- 
PHOSPHATES  OF  SILVER. 

By  John  Missenden,  B.Sc,  and  F.  E. 

LlECHTL 

The  di-salt,  which  is  mainly  produced  by 
the  action  of  the  nitrate  upon  an  alkaline 
metaphosphate,  is  of  a  curiously  hard  crys- 
talline structure,  insoluble  in  water;  nor 
is  any  water  released  from  the  substance  oy 
heating  to  dull  redness.  It  is  quite  possible, 
however,  to  prepare  a  monohydrated  •'/- 
salt  (i.e.,  the  monohydrated  silver  dimeta- 
phosphate,  Ag2P20eH20)  in  the  following 
reaction :  Add  to  a  solution  of  silver  nitrate 
about  one-half  by  weight  of  lithium  di- 
sodium  metaphospnate,  and  gently  apply 
heat  until  evaporation  has  dispelled  30  per 
cent,  of  the  water.  The  crystals  will  seipar- 
ate  upon  cooling. 

In  a  similar  way,  the  monohydrated  silver 
trimetaphosphate ,  AgjP^OgH^O,  may  be 
obtained  from  the  action  of  the  nitrate  upon 
a  concentrated  solution  of  sodium  trimeta- 
phosphate. Some  doubt  was  expressed  as 
to  the  correct  proportions  of  the  constitu- 
ents. A.  Weislerj  used  three  times  as 
much  of  the  nitrate  as  the  trimetaphos- 
phate, but  C.  G.  Lindbom^  was  successful 
with  an  excess  of  the  latter.  The  writers 
have  found,  however,  that  equal  propor- 
tions give  the  best  results ;  but  a  most  inter- 
esting point  is  that  far  larger  crystals  can 
be  obtained  if  the  metaphosphate  is  In  ex- 
cess, although  sodium  comprises  part  of 
their  content  up  to  (and,  in  rare  cases,  over) 
0.45  per  cent.  The  monohydrated  silver  tri- 
metaphosphate has  been  found  to  yield  64.2 
per  cent,  of  its  water  at  100°  C,  but  re- 
absorbs the  greater  part  from  the  atmos- 
phere, and  will  not  make  a  further  yield 
when  reheated  to  a  similar  temperature,  al- 
though the  whole  of  the  water  is  lost  upon 
liquefaction. 


^  Zeit.  anorg.  Chem.,  1901,  XXVIII.,  177. 
»  Acta  Lund.,  1844,  X.,  7. 


The  hcxametaphosphate,  obtained  in 
gelatinous  white  flakes,  takes  the  formula, 
AggPftOjg,  and  is  quite  insoluble  in  water. 
It  can  be  prepared,  however,  in  a  decided 
crystalline  form,  and  may  be  divided  into 
silver  tetraphosphate,  AgeP^O^a,  and  an 
acid  solution.  Treatment  with  sodium  sul- 
phide produces  sodium  hcxametaphosphate. 

By  the  action  of  silver  nitrate  upon  the 
sUghtly  soluble  sodium  dimetaphosphate,  a 
new  compound,  silver  decametaphosphate, 
-^gio^iu^ao^HjO,  is  formed,  which  lost  the 
greater  portion  of  its  water  upon  heating  to 
135°  C.  The  most  stable  form  of  this  com- 
pound is  the  tetrahydrated  salt.  The  action 
of  silver  nitrate  upon  sodium  hcxameta- 
phosphate gives  two  more  compounds, 
sodium  pentasilver  hexametaphosphate, 
Na  Agj  (POj)^,  and  disodium  tetrasilver 
hexatnetaphosphate ,  Naj  Ag^  (P03)g.  By 
using  a  potassium  hexametaphostphate, 
K2  Ag^  (POs)^  has  been  produced,  but  we 
do  not  believe  that  the  potassium  pentasil- 
ver salt  exists. 

W.  Henneberg's  theory  that  the  interior 
of  the  grey  viscid  mass  produced  by  the 
action  of  hot  water  upon  silver  hexameta- 
phosphate is  composed  of  silver  pyrometa- 
phosphate,  Ag^PfijAg^P^O^,  is  well 
founded,  but  the  mass  only  contains  about 
40  per  cent,  of  this  compound,  the  re- 
mainder     being      silver      tetraphosphate, 

A.  V.  Kroll^  has  discussed  a  series  of  the 
order  Ag^O :  PjO^  :  :  1  :  2  (and  as  1  :  3). 
He  has  termed  them  the  ultraphosphates. 
Little  is  known  of  this  series. 


FISH  MEAL  AND  GUANO. 

J.    O'SULLIVAN. 

Endeavours  hitherto  made  for  the  manu- 
facture of  fish  meal  and  guano  have,  in 
some  cases  only,  when  favoured  by  circum- 
stances, given  good  results.  The  chief 
causes  why  manufacture  has  not  been 
more  widely  adopted  are :  unsuccessful 
local  attemipts;  high  cost  of  plant;  the  low 
prices  of  the  products  and,  especially, 
doubts  as  to  which  wej-e  the  best  methods. 
The  question  now  presents  itself  in  quite  a 
different  light.  In  the  first  place,  the  laws 
regarding  destruction  of  refuse  are  very 
strict,  and  it  is  more  expensive  for  those  re- 


'    Ueber    Ultraphosphate.       Zeit.    anorg. 
Chem.,  1912,  LXXVI.,  406. 


AUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


99 


sponsible,  and  then  the  products,  at  the 
present  time,  realise  relatively  good  prices. 
Moreover,  it  has  been  ma'de  possible  to 
transfonri  fish  oil  into  solid  fat  by  hydro- 
genation  and  sell  it  for  various  industrial 
purposes.  The  protein,  after  suitable  treat- 
ment, can  be  utilised  as  food  for  animals 
(especially  pigs),  so  that  prices  are  quite 
likely  to  be  higher  than  those  for  the 
guano.  Finally,  a  number  of  engineering 
firms  have  undertaken  a  scientific  study  of 
this  question,  hitherto  neglected. 

From  the  technical  point  of  view,  the 
problem  can  be  epitomised  in  one  condition, 
viz.,  complete  separation  of  the  three  com- 
ponent parts,  water,  fat,  and  dry  matter. 
The  simplest  mechanical  methods  consist 
in  treatment  of  the  raw  materials  in  a  hy- 
draulic (press  or  under  heated  rollers.  Re- 
sults have  not  been  satisfactory.  In  the 
first  case  the  water  and  fat  are  not  com- 
pletely extracted,  and  the  meal  has  to  be 
subsequently  dessicated.  The  followinff  is 
an  analysis  of  meal  made  with  hot  rollers 
which  have  the  same  inconvenience  as 
presses :  — 

Whole  Meal. — Crude  protein,  58.29  per 
cent. ;  fat,  28.79  per  cent. 

Herring  Meal. — Water,  8.32  per  cent. ; 
crude  protein,  68.91  per  cent. ;  fat,  14.02 
per  cent. 

The  percentage  of  fat  is  much  too  great, 
and  this  can  only  be  employed  as  a  fertili- 
ser and  not  as  food,  which  would  give  flesh 
and  milk  an  oily  flavour.  Tho  chemical 
methods  arc  very  numerous.  Treatment 
with  suliphurio  acid,  sulphuric  saponifica- 
tion, is  often  adopted,  and  gives  better 
separation  of  the  fat  than  by  boiling  the 
materials  in  presence  of  sulphuric  acid. 
After  pouring  off  the  fat  the  solid  residue  is 
neutralised,  dried  and  crushed  or  treated 
with  nitro-sulphate  of  calcium.  Another 
method  is  boiling  the  fish  waste  under 
pressure,  mixed  with  caustic  soda.  The 
cells  are  broken  up  and  the  fat  saponified. 
The  soap  is  obtained  by  preciipitation,  and 
the  resiaue  dried  and  crushed. 

Finally,  the  materials  are  transformed 
into  a  fertiliser  by  aid  of  a  potassium  salt, 
to  be  then  dried.  The  chemical  processes 
have  been  but  little  studied  from  the  con- 
structive point  of  view,  and  the  plant  is 
generally  very  rudimentary.  The  chief  de- 
fect is  tnat  the  products  are  only  fit  for  fer- 
tilisers and  results  of  manufacture  conse- 
ouently  less  favourable.  The  process  by 
aisplacement  (solvents  like  benzine,  car- 
bon tetrachloride;  and  all  derivatives  of 
chlorine,  methane  and  ethane)  removes    fat 


sufl&ciently,  and  gives  a  residue  in  form  of  a 
fertiliser,  after  drying  and  crushing.  Con- 
sequently this  method  has  acquired  greater 
importance  and  been  more  carefully 
studied.  Analysis  of  a  meal  made  from 
haddock  with  benzine  gave :  water,  14.3 
per  cent. ;  protein,  58.55  per  cent. ;  crude 
fat,  1.76  per  cent.;  dry  residue,  15.67  per 
cent.  Solvents,  however,  cause  certain 
difficulties.  The  crude  material  is  made  im- 
permeable by  benzine,  and  must  be  treated 
on  a  surface.  Then,  as  the  percentage  of 
water  in  the  fish  is  great,  the  consumption 
of  solvents  is  also  great.  The  thermo- 
ohemical  method  gives  the  best  results,  the 
materials  being  treated    with  steam  under 

Sressure  which  separates  the  fat  and  the 
ry  residue  can  then  easily  be  treated.  The 
toxins  in  the  fish  are  destroyed  by  the 
steam,  and  the  meal  obtained  can  be  used 
as  a  feeding  stuff  for  animals.  After  hav- 
ing made  a  study  of  this  new  problem,  a 
firm  of  Zurich  (Messrs.  Escher,  Wyss  A 
Co.)  have  solved  it  by  aid  of  a  very  simple 
and  inexpensive  plant  which  gives  all  the 
advantages  of  the  thermo-chemical  method 
for  treating  large  quantities  of  fish,  4  to  6 
metric  tons,  in  10  to  12  hours.  This  in- 
stallation comprises:  (1)  A  horizontal  auto- 
clave (extraotw)  with  a  double  heating 
jacket  and  perforated  rotary  drum  inside. 
The  mouth  of  the  autoclave  is  at  one  end. 
The  drum  is  w<wked  by  pulleys  and  an  end- 
lesB  screw;  (2)  a  vertical  vessel,  to  which 
the  autoclave  is  connected,  communicating 
by  pipes  with  (8)  a  continuous  press  above 
the  autoclave  and  resting  on  a  gallery;  (4) 
a  fat  pan  fed  by  the  press ;  (6)  an  air  pump 
for  tho  autoclave;  (6)  a  steam  boiler;  h)  an 
electric  motor  drivmg  the  autoclave  drum, 
pump  and  prese.     Working  is  as  follows:  — 

The  fish  waste  is  put  into  the  perforated 
drum,  the  autoclave  being  then  shut  her- 
metically. Hot  steam  is  ^hen  admitted, 
the  drum  rotating  continually.  A  mixture 
of  oil,  solid  and  liquid  substances,  run 
through  t^e  openings  in  the  drum  into  the 
vertical  vessel,  where  they  separate  by 
gravitation.  When  everything  in  the  auto- 
clave has  been  run  off,  the  rat  which  col- 
lects on  the  top  is  drawn  off,  leaving  the 
liquid  and  solid  matter  in  the  vessel  to  pass 
through  the  pipes  into  the  press,  which 
separates  much  of  the  water  and  fat  from 
the  solids. 

The  oily  liquid  runs  into  the  pan  fed  by 
the  press,  and  the  solid  parts  fall  through 
an  opening  into  the  autoclave.  Then  the 
latter  is  shut,  and  again  heated,  the  drum, 
which  is  furnished    ^^^th  agilators    on    the 


100 


THE  CHEMICAL  NEWS. 


AUGUST  17,  1028. 


circumference,  being  set  in  moton.  The 
air  pump  produces  a  vacuum  in  the  auto- 
clave, which  makes  dessication  easy.  This 
pump  is  also  used  to  draw  off  the  fumes 
which  are  then  got  rid  of  by  condensation. 
The  crude,  dry  materials  are  automatically 
discharged  from  the  extractor,  simply  by 
making  the  drum  rotate  in  the  opposite  di- 
rection. A  little  boiler  supplies  steam,  and 
a  9  h.p.  electric  motor  power.  Thus  this 
plant  is  very  simple  and  highly  efl&cient. 
Consumption  of  steam  is  reduced  to  a 
minimum  in  drying  the  meal,  as  much  of 
the  water  in  the  fish  is  previously  extracted 
and  that  of  coal  is  also  very  small,  scarcely 
15  per  cent,  of  the  weight  of  the  fish. 

The  meal  produced  is  thus  much  freer 
from  fat  than  in  the  ordinary  thermo- 
chemical  method,  as  the  following  analysis 
demonstrates :  water,  12  to  15  per  cent. ; 
fat,  6  to  8  per  cent. ;  residues,  13  to  28  iper 


cent.  These  r'^sidues  themselves  pontaiu 
phosphate,  5  to  7  per  cent. ;  crude  protein, 
46  to  52  per  cent  ;  non-nitrogenov>us  iiiat- 
ter,  6  to  14  per  cent.  The  great  value  of 
the  method,  however,  is  lue  to  the  fact 
that  the  meal  can  be  used  as  a  feeding 
stuff,  and  results  nave  been  so  encouraging 
that  it  is  not  rash  to  assert  that  this  method 
will  grow  more  and  more  important,  all 
technical  difficulties  having  been  overcome 
and  good  plant  available.  The  feeding 
value  of  fish  meal  bas  been  illustrated  ex- 
perimentally with  the  following  results:  — 

Dry 

Meal.  Matter.       Protein.     Fat.     Residues. 

I.       87  p.o.  48.9  2.1  25.6 

II.         81ip.c.  51.5         4.8  13.5 

Two  groups  of    pigs  were    fed  with    one 

quality  of  meal,  the  daily  rations  being  as 

follows  in  kilogrammes:  — 


Groups 

Boiled 

Waste 

Potato 

Meal. 

of  pigs. 

potatoes. 

flesh. 

Flakes. 

Maize 

1.                    11. 

a 

4 

0.5 

0.172 

0.263 

0.568 

b 

4 

0.5 

0.172 

0.263 

0.668 

c 

1 

0.5 

0.172 

0.263 

—                 0.648 

d 

4 

0.5 

0.127 

0.263 

~                 0.648 

Calculations  made  after  killing  the  pigs 
demonstrate  that  the  amount  of  meal  (in 
kilogrs.)  to  obtain  a  nett  increase,  in  weigh; 
of  the  pigs,  of  100  kilogrammes,  is:  — 


Weight  of 
meal 

equivalent 
to  the 

Assimilable 

assimilable 

Groups, 
a 

Weight.     Protein 
....     399         54.12 

iprotein. 
123 

b 

...     386        52.32 

.    118 

c 

...     388        52.46 

114 

d 

...     366        49.54 

108 

The  flesh  of  the  pigs  was  of  the  finest 
quality  and  without  any  odour  of  fish.  The 
commercial  yield  will,  of  course,  depend 
upon  quantity  and  quality  of  the  raw 
materials.  However,  the  following  may  be 
taken  as  example :  2  to  10  per  cent,  fat  and 
15  to  35  per  cent.  meal.  The  profits  real- 
ised by  treating  4  to  6  metric  tons  of  fish 
per  day,  to  obtain  3  per  cent,  fat  and  20  per 
cent,  meal,  were  56,400  francs  for  the  year, 
which  is  regarded  as  very  satisfactory.  The 
method  described  reduces  Ihe  bad  odours  to 
a  strict  minimum,  and  they  cause  no  incon- 
veniences. —  (Revue  General  du  Froid, 
June-July,  1922.) 


DESCLOIZITE  FROM  SOUTH-WEST 
AFBICA. 

By  Percy  A.  Wagner,  Ing.D.,  B.Sc, 
F.G.S.,  M.A.I.M.M.E. 

(Communhated  by  permission  of  the 

Honourable  the  Minister  for  Mines  and 

Industries.) 

Superficial  deposits  of  vanadium  ore  are 
worked  at  a  number  of  localities  in  the 
Grootfontein  district  of  the  South-West  Pro- 
tectorate and  form  the  basis  of  quite  an  im- 


portant industry.  The  ores  occur  for  the 
most  part  in  sand  or  rubble-filled  solution 
cavities  and  karrenf elder  in  the  surface  of 
the  Otavi  dolomite,  most  rarely  in  open 
solution  fissures  and  in  surface  breccias,  and 
finally  as  actual  retplacements  of  the  dolo- 
mite, these  being,  however,  always  con- 
nected with  one  or  another  of  the  previously 
mentioned  types  of  deposit. 

Some  of  the  occurrences  have  descloizite 
as  the  predominant  ore  mineral,  others  mot- 
tramite,    and  yet  others    (Berg    Aukas)  ap- 


JiUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


lol 


parentlv  vanadinite.*  Excellent  descrip- 
tions of  some  of  the  earlier  discovered  occur- 
rences have  been  published  by  H.  Schneider- 
hohn,^  but  no  comprehensive  study  of  the 
deposits  has  as  yet  been  made.  It  is  evi- 
dent, however,  from  what  is  known,  that 
these  are  all  of  the  nature  of  residual  accu- 
mulations formed  by  the  concentration,  at 
favourable  loci,  by  descending  meteoric 
waters  of  small  amounts  of  vanadium  dis- 
seminated through  originally  overlying  de- 
posits of  copper-lead-zinc  ore  in  ihe  Otavi 
dolomite  or  the  ore-bearing  aplite  intrusive 
in  that  formation.'  As  the  vanadium  com- 
pounds are  the  last  to  survive  the  degrada- 
tional  processes,  tiiey  are  evidently  pecu- 
Uarly  resistant  to  chemical  erosiwi,  which 
is  all  powerful  in  a  karst  region  su(^  as  that 
under  review. 

The  object  of  the  present  note  is  to  de- 
scribe some  exceptionally  handsome  speci- 
mens of  descloizite  ore  recently  sent  to  the 
writer  by  Mr.  C.  G.  C.  Clarke,  of  the  South- 
West  Africa  Company,  Limited.  They  are 
rom  two  localities,  namely,  the  farm  Oli- 
fant«fontein  West,  situated  12  miles  north- 
west of  Grootfontein  North,  and  the  farm 
Abcnab,  situated  20  miles  north  of  Groot- 
fontein. 

At  the  former,  according  to  the  descrip- 
tion acconjip^nying  the  specimens,  the  de- 
posit takes  the  form  of  a  well-defined  verti- 
cal cleft  in  the  dolomite,  the  walls  of  which 
are  lined  with  dark  lustrous  crystals  and 
crystal  aggregates  of  descloizite  forming 
continuous  crusts,  several  superimposed 
crusts  being  in  places  present. 

In  the  material  sent  to  the  writer,  the 
crystals  range  in  length  from  a  millimetre 
and  less  to  1.7  cm.  Actually  the  largest  had 
a  length,  measured  along  the  c  axis,  of  1.72 
cm.,  and  a  breadth  measured  along  the  b 
axis  of  0.8  cm.  They  are  made  up  of  the 
unit  pyramid  and  the  unit  prism,  ihe  faces 
of  the  latter  being  generally  horizontally  fur- 
rowed owing  to  an  oscillatory  combination 
of  the  two  forms.  More  rarely  the  pyrami- 
dal faces  are  terraced  owing  to  the  same 
cause.  The  habit  of  the  crystals  is  some- 
times prismatic,    the  grooving  of  the  prism 

'  According  to  a  valuahle  unpublished 
Memorandum  by  Mr.  O.  E.  B.  Frood,  In- 
npector  of  Mines    South-West  Protectorate. 

'  cf.  "Die  Erzlagerstdtten    dcs    Oiaviber- 
glandes,     Deutsch-Siidwcstafrilxa,"    Metail 
und  Erz.,    XVII.,  13.  16,  10,  24,  A  XVI.  •. 
IDA  n. 

■•  Schneiderhohn,  loc.  cit.,  p.  38. 


faces  being  then  especially  pronounced. 
More  usually  the  pyramid  and  prism  faces 
are  about  equally  developed.  Among  the 
smaller  individuals,  however,  crystals  of 
pyramidal  habit  are  fairly  common.  Single 
crystals,  as  a  matter  of  fact,  are  rare.  Even 
what  appear  at  first  sight  to  be  simple 
forms  are  generally  found  to  be  made  uip  of 
sub-parallel  intergrowths  of  severe  crystals, 
and  complex  spear-headed  and  branching 
groups  made  up  of  a  number  of  such  crys- 
tals sometime*  symmetrically  arranged 
about  a  central  dominant  stem  crystal  are 
very  common.  The  OTystal  faces  give  verj' 
poor  signals  and  do  not  lend  themselves  to 
accurate  measurement,  this  applying  parti- 
cularly to  those  of  the  unit  prism.  The 
only  angles  which  could  be  determined  by 
means  of  a  Fuess  reflecting  goniometer  witn 
even  a  fair  degree  of  accuracy  were  as  fol- 
low:— 

00/     =  (111)  :  (111)  =  89*  24' 
00"  =  (111)  :  (111)  =  52"  30' 
the  corresponding    values    given  by    Dana* 
being  89**  6'  and  53'  4'. 

The  crj'stals  are  of  a  very  dark  oUve  green 
colour  and  their  lustre  is  brilliant.  On  frac- 
tured surfaces  the  colour  is  orange  brown, 
the  fracture  being  uneven.  The  streak  is 
pale  canary -yellow.  In  the  process  of 
grinding  down  the  crystals  to  prepare  thin 
sections  an  imperfect  cleavage  parallel  to 
(100)  is  brought  out. 

Under  the  microscope  the  crystals  are 
seen  to  have  a  well-defined  zonal  structure, 
being  built  up  of  alternations  of  thick  green- 
ish and  thinner  brown  or  yellow  layers  ar- 
ranged parallel  with  the  faces.  These  layers 
are  markedly  pleochroic,  the  greenish  show- 
ing:— 

Z  =  a=:ipale  yellowish-green, 

Y  =  b  =  pale  apple-green, 

X  =  c  =  very*  pale  yellowish-green, 
and  the  brown  or  yellow : 
Z  =  a = reddish- brown , 

Y  =  b=greenish  yellow, 
X=o=pale  yellow. 

The  brownish  layers  have  a  much  stronger 
absorption  than  the  greenish.  It  should  be 
statea  that  the  colours  ^iven  refer  to  a  fairly 
thick  section.  In  addition  to  the  brown  and 
greenish  zones,  a  practically  colourless  zone 
18  generally  present  in  the  peripheral  por- 
tion of  the  crystals.  In  one  of  the  sections 
examined  this  showed: 

Z  =  pale  yellow, 

Y= colourless. 


*  "  A  System  of  Mineralogy,"  p.  787. 


102 


THE  CHEMICAL  NEWS. 


AUGUST  17,  1923. 


The  precise  significance  of  the  zoning  is  not 
clear.  It  may  be  taken  for  granted,  how- 
ever, that  the  differently  coloured  shells  also 
differ  in  chemical  composition,  so  that  in- 
stead of  dealing  with  a  homogeneous 
mineral  we  have  to  do  with  at  least  three 
isomorphous  substances. 

A  chemical  analysis  by  Dr.  J.  McCrae,  of 
some  selected  crystals  is  given  under  I.  in 
the  following  table  :  — 

I.  la.  II.         III. 

PbO       55.45      0.25       55.93       54.03 

ZnO      15.50       0.19       15.94       12.62 

CuO      3.80      0.05         1.15         8.13 

FeO      —  —  0.70  — 

Fe^Og       ....       0.30        —  —  —  ^ 

V^Og      22.00      0.12       20.80       22.47| 

As^Og     Nil.  —  0.32         0.28 

PA      —  —  0.27         0.17 

SiO^      Nil.  —  0.18  — 

H^O      2.50      0.14         4.37        2.70 

H^O    (110°)      0.05        —  —  — 

Total     ...     99.60  99.82       99.74 

Sp.  Gr 6.20 


Under  la.  are  given  the  molecular  propor- 
tions corresponding  with  the  analysis.  It 
will  be  seen  that  the  figures  agree  fairly 
closely  with  the  theoretical  composition  of 
the  mineral,  corresponding  with  the  form- 
ula 2  PbO.  2(ZnCu)  0.  V^-  2  H,0,  accord- 
ing to  which  lead  oxide  and  zinc  plus  copper 
oxide  are  present  in  equimolecular  propor- 
tions, and  the  ratio  of  (Pb  Zn  Cu)  O :  V^Os 
:  :  4  :  1.  The  analyses  under  II.  and  III. 
are  adduced  for  comparison.  II.  is  an  ana- 
lysis by  W.  F.  Hillebrand  of  descloizite  from 
Beaverbrook,  Montana,  0.03  per  cent,  of 
CaO  and  0.06  per  cent,  of  MgO  being  pre- 
sent in  addition  to  the  constituents  named. 
III.  is  an  analysis  of  cuprodescloizite  from 
an  unnamed  locality  quoted  from  Dana.'^ 
As  the  term  cuprodescloizite  appears  to  be 
reserved  for  varieties  containing  a  minimum 
of  6  per  cent,  of  copper  oxide,  the  Olifants- 
fontein  mineral,  which,  as'  we  have  seen,  is 
iprobably  a  complex  isomorphous  mixture 
of  at  least  three  distinct  substances,  is  best 
described  as  cupriferous  descloizite. 

The  associated  minerals  are  peilucid 
bluish- white  quartz  and  calcite.  The  latter 
occurs  in  mammillary  crusts  up  to  1  centi- 
metre in  thickness.  In  these  the  calcite  is 
is  eviently  paramorphic  after  aragonite — a 
phenomenon  also  noted  at  other  localities  in 
the  Otavi  Eange.*       The  original  aragonite 

-'  "  A  System  of  Mineralogy,"  p.  789. 
^  cf.  Schneiderhohn,  loc.  cit.,  p.  41. 


was  clearly  of  later  formation  than  the  des- 
cloizite, having  been  deposited  on  the  crys- 
tals of  that  mineral  which  project  into  the 
crusts.  The  quartz,  on  the  other  hand, 
appears  to  be  of  earlier  formation  than  ^he 
descloizite. 

Ahenah. — The  Abenab  ore  is  a  breccia  of 
strikingly  handsome  appearance  made  up  of 
angular  fragments  of  pink  surface  limestone 
and  reddish  dolomite  encased  by  crusts  of 
dark  green  or  brown  descloizite  crystals,  the 
cementing  medium  being  coarsely  crystal- 
lised white  calcite.  The  latter  forms  a  net- 
work of  irregular  veins  up  to  2  centimetres, 
across  which  are  interspersed  with  vughs 
lined  with  crystals  of  descloizite  and  colour- 
less calcite.  At  least  four  varieties  of  des- 
cloizite are  present,  namely:  — 

(1)  A  blackish  green  variety  occurring 
in  well-formed  pyramidal  crystals  some- 
what elongated  in  the  direction  of  the 
macrodiagonal.  The  prism  faces  are 
only  very  poorly  developed,  and  the  habit 
of  the  crystals  is  not  unUke  that  of  the 
descloizite  from  Lake  Valley,  New  Mexi- 
co, shown  in  Fig.  3,  j).  788,  of  Dana's 
Mineralogy.  With  the  aid  of  a  contact 
goniometer  the  following  forms  were 
found  to  be  present :  — 

0  =  111 

w  =  110 
t;  =  021 

(d).?  =  012 
On  some  crystals  the  faces  of  the  unit 
prism  are  bevelled  by  those  of  another 
prism,  probably  /  =  (130),  On  others  the 
edge  (111)  :  (111)  is  terraced  owing  to  an 
oscillatory  combination  of  the  two  clino- 
domal  faces. 

(2)  A  bottle-green  variety  occurring  in 
smaller  crystals  of  practically  the  same 
habit,  the  prism  being,  however,  even 
more  poorly  developed.  One  peculiar 
feature  of  these  crystals  is  that  the  clino- 
domal  faces  often  have  a  peculiar  green- 
ish-yellow coating.  Whether  or  not  this 
is  due  to  the  alteration  of  the  descloizite 
is  not  clear. 

(3)  A  dull  greenish- brown  variety  in 
which  the  habit  of  the  crystals  is  tabular 
owing  apparently  to  the  abnormal  de- 
velopment of  the  macropinacoid,  the 
other  forms  present  being  the  unit  pyra- 
mid and  the  unit  prism. 

(4)  A  lustrous  chrome -brown  variety 
occurring  mostly  in  peculiar  parallel- 
growth  aggregates,  up  to  1.5  centimetres 
in  length,  imbedded  in  white  calcite.  The 
aggregates  are  due  to  the  regular  con- 
junction   of  small  crystals   of    pyramidal 


AUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


103 


habit  and  are  terminated  by  the  unit 
pyramid.  '  Some  of  them  are  doubly  ter- 
minated. 

Chemically  the  several  varieties  enumer- 
ated appear  to  differ  mainly  as  regards  their 
copper  content.      The  bright  chrome-brown 
variety  is  practically    free    from  that    ele- 
ment, whereas  the  very    dark  variety    con- 
tains fair  quantities  of  it.       No  analysis  of 
any    particular  variety    is  available,    but    a 
sample  of  the  concentrate    obtained  by  jig- 
ging the  crushed  ore,  in  which  all  of  item 
are  iprobably  represented,  showed: — 
PbO  =  51.81  per  cent. 
ZnO  =  18.06 
CuO=   1.10 
V  A  =  20.60 
PA=   0.06        „ 
The  writer's  thanks  are  due  to  Dr.  F.  E. 
Wright  and  Professor  Charles    Pa]a<^e    for 
assistance  in  his  investigations. 

(From  "  The  South    African   Journal    of 
Science,"  Vol.  XIX.,  142-145.) 


T?OYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

Wbkkly  Evening  Meeting,  Fbiday,  May 
4,  1923. 

Sib  James  Crichton-Browne,  M.D.,  LL.D., 

F.R.8.,  Treasurer  and  Vicb-Prksident, 

IN  THE  Chair. 

THE  ORIGINS  OF  THE  CONCEPTION 
OF  ISOTOPES. 

A  Lecture  delivered  by  Frederick  Soddv. 
M.A.,  F.U.S. 

(Continued  from  Page  96.) 

Similarly,  the  chemical  identity  of 
radium  D  and  lead  was  established  as  a  con- 
sequence of  very  profongrd  and  refined 
chemical  examination.  Panoth  and  Hevesv 
established  upon  this  their  well-known 
method  of  using  radioactive  isotopes  as  in- 
dicators for  elements  in  too  small  quantity 
to  be  dealt  with  except  by  such  methods. 
On  the  principle  that  wherever  the  radio- 
active element  is  there  will  its  inactive  iso- 
tope be  also,  provided  that  they  have  once 
been  properly  mixed,  many  difficult  or  un- 
certain chemical  analyses  may  be  converted 
into  simple  radioactive  ones. 

In  1909  Stromholm  and    Svedberg  made 


what  was  probably  the  first  attempt  to  fit  a 
part  of  the  disintegration  series  into  the 
Periodic  Table,  and  although  the  effort  in 
itself  was  in  an  important  respect  errone 
ous,  in  their  paper  is  to  be  found  the  first 
£inticipation  that  the  chemical  non-seipara- 
bility  found  for  certain  pairs  and  groups  of 
radio-elements  may  also  apply  to  the  non- 
radioactive elements.  Remarking  on  the 
fsict  that  there  are  three  parallel  and  inde- 
pendent radioactive  series,  they  suppose 
this  to  proceed  down  through  the  Periodic 
Table,  "  but  that  always  the  three  elements 
of  the  different  genetic  series,  which  thus 
together  occupy  one  place  in  the  periodic 
system,  are  so  alike  that  they  always  occur 
together,  and  also  have  not  been  able  to  be 
appreciably  separated  in  the  laboratory." 
They  point  out  also  this  idea  would  explain 
the  exceptions  to  the  periodic  system  "  if 
the  elements  of  the  scheme  were  mixtures 
of  several  homogeneous  elements  of  similar 
but  not  completely  identical  atomic 
weight." 

In  the  next  year  I  arrived  independently, 
and  without  in  the  least  postulating  any 
continuance  of  the  genetic  series  beyond  the 
radio-elements,  at  a  similar  view.  Marck- 
wald  and  I  found  independently  that  meso- 
thorium  I  was  chemically  similar  to  radium, 
a  fact  undoubtedly  known  to  Hahn  and 
thoee  engaged  in  the  technical  extraction  of 
mesothorium,  but  kept  secret.  It  was 
known  from  some  work  of  Boltwood  that 
precipitating  barium  sulphate  in  a  solution 
containing  mesothorium  removes  it,  but  it 
was  thought  that  the  action  of  the  barium 
sulphate  was  similar  to  that  in  removing 
uranium  X,  for  which  it  had  long  been  used 
— namely,  a  simple  adsorption.  I  was  sur- 
prised to  find  it  absolutely  different.  The 
removal  of  the  barium  from  the  mesothor- 
ium, as  from  radium,  could  only  be  accom- 
plished by  the  fractional  crystallisation  of 
the  chlorides.  In  this  fractionation  the 
radium  and  mesothorium  remained  together 
and  behaved  as  a  single  element.  Within 
the  limit  of  erroi  of  tne  most  careful  radio- 
active measurements,  there  was  no  change 
in  the  relative  proportiMi  of  the  two  ele- 
ments at  the  end  of  the  process,  from  that 
in  which  they  exist  in  the  original  mineral. 
Chemistry  has  many  cases  of  elements 
similar  in  chemical  character,  but  nothing 
approaching  this.  For  we  know,  before- 
hand, that  wc  are  dealing  with  a  mixture  of 
two  substances,  and  can  estimate  accur- 
ately the  proportion  of  each  individual.  Yet 
to  all  chemical  operaticms  they  behave  as  a 


104 


THE  CHEMICAL  T^EWS. 


AUGUST  17,  1923. 


single  substance.  The  differences  of  atomic 
weight  are  considerable,  two  units  in  the 
cases  of  mesothorium  and  radium,  and  of 
ionium  and  thorium,  and  four  units  in  that 
of  radiothorium  and  thorium.  It  was  cer- 
tain that  if  isotopes  existed  in  the  case  of 
the  ordinary  chemical  elements,  the  ab- 
sence of  a  second  radioactive  natm-e  inde- 
pendent of  the  chemical  nature  would  make 
it  impossible  for  them  to  have  been  recog- 
nised. Hence  the  implication  followed 
that  any  supposed  element  may  be  a  mix- 
ture of  several  chemical  identities  of  differ- 
ent atomic  weight,  and  any  atomic  weight 
might  be  merely  a  mean  number  (Ann.  Re- 
ports, Chem.  Soc.,  1910,  286).  There  is  an 
element  of  tragedy  in  this.  The  life-time 
labours  of  the  chemists  who,  since  the  time 
of  Stas,  have  devoted  themselves  to  the 
exact  determination  of  atomic  weight,  ap- 
pear to  have  as  little  theoretical  interest 
now,  as  if  you  sought  to  determine  the 
average  weight  of  a  collection  of  beer 
bottles,  all  exactly  alike,  but  not  all  quite 
full. 

The  Radio-Elements  and  the  Periodic 
Law. 

The  years  from  1911-1913  were  crowded 
with  imiportant  advances,  and  to  do  the 
exact  history  justice  would  take  an  undue 
share  of  the  available  time.  In  1911  the 
chemistry  of  most  of  the  a-ray  giving  mem- 
bers were  sufficiently  known  for  it  to  be 
seen  that  the  expulsion  of  the  a-particle 
caused  the  element  expelling  it  to  move 
from  the  place  it  occupied  in  the  Periodic 
Table  to  the  next  place  but  one  to  it  in  the 
direction  of  diminishing  mass. 

At  this  time  the  chemistry  of  the  post- 
emanation  members  had  scarcely  been 
studied,  though  von  Leroh,  from  electro- 
chemical researches,  had  put  forward  the 
rule  that  the  successive  products  are  each 
electrochemically  "nobler"  than  the  last,  a 
rule  which  describes  well  enough  the  elec- 
trochemical behaviour  of  the  first  three — 
the  A  to  C  members,  as  they  are  called. 
Then  as  a  result  of  the  experiments  of 
Schrader  and  Russell,  it  was  found  that 
their  volatility  was  much  affected  by 
chemical  treatment  and  by  the  atmosphere 
in  which  they  were  volatilised.  Thus,  in 
hydrogen,  radium  C  volatilises  at  as  low  a 
temiperature  as  360°  C,  though,  in  air,  a 
temperature  of  1200°  C.  is  necessary.  This 
clearly  indicated  the  possibility  that  even 
these  excessively  ephemeral  elements  have 
a  definite  chemical  character.  Hevesy 
showed,    by  electrochemical  methods,    that 


the  three  B-members  are  identical  in  pro- 
perties among  themselves,  and  also  the 
three  C-members. 

But  the  work,  which,  more  than  any- 
thing else,  served  to  reveal  as  in  a  flash 
the  simple  and  sweeping  generalisation 
which  covers  the  evolution  of  the  radio- 
active elements  was  that  of  A.  Fleck  in  my 
laboratory  in  Glasgow.  He  studied  the 
chemistry  of  the  various  members,  still  un- 
characterised,  from  the  definite  point  of 
view  of  aficertaining  to  which  element  each 
most  closely  approximated  in  chemical 
character,  and  then  whether  it  was  separ- 
able from  that  element  or  not.  In  addition 
to  confirming  more  rigorously  many  con- 
clusions already  reached,  he  proved  that 
mesothorium  2  was  non-separable  from 
actinium,  the  three  B-members  from  lead, 
like  radium  D,  and  the  three  C-members 
and  radium  E  from  bismuth. 

Hevesy  and  Russell — the  first  with  re- 
gard to  the  valency  of  the  radio- elements 
and  the  second  with  regard  to  the  positions 
they  occupy  in  the  Periodic  Table — pub- 
lished early  in  1913  statements  of  the  full 
law  underlying  radioactive  evolution,  but 
only  in  part  correct.  Within  a  month,  K. 
Fajans  in  Carlsruhe  published  the  scheme 
correct  and  complete,  including  the  com- 
plicated branchings  that  occur  at  the  C- 
members.  In  a  pajper,  amplifying  and 
amending  Russell's  scheme,  I  arrived  inde- 
pendently at  the  same  place  as  Fajans 
Each  a-ray  expelled  causes  a  shift  of  two 
places  in  the  Periodic  Table  in  the  direc- 
tion of  diminishing  mass,  and  each  ^-ray  a 
shift  of  one  place  in  the  opposite  direction. 
In  its  present  form  the  scheme  is  shown  in 
the  figure.  The  chief  uncertainty  remain- 
ing is  whether  the  actinium  branch  starts 
from  uranium  II,  as  shown  in  the  figure  for 
convenience,  or  from  uranium  I,  or  even 
from  a  third  independent  isotope  of 
uranium.  So  that  the  atomic  weights 
shown  for  the  actinium  series  are  purely 
provisional. 

By  the  consistent  application  of  the  two 
rules  mentioned  the  members  found  to  be 
non-separable  from  one  another  fall  in  the 
same  place  in  the  Periodic  Table.  The 
chemical  character  has  nothing  to  do  with 
the  radioactivity,  nor  with  the  series  to 
which  the  element  belongs,  nor  with  its 
atomic  weight.  It  depends  upon  a  num- 
ber, now  called  the  atomic  number,  shown 
at  the  top  of  the  place  in  the  figure. 

Before  passing  on  to  this,  the  chief 
practical  consequences  of  the  generalisation 


AUGUST  17.  1923. 


THE  CHEMICAL  NEWS 


105 


may  be  briefly  enumerated. 

(1)  Of  the  members  still  uncharacterised, 
the  A  and  C  members  must  be  the  iso- 
toipes  of  polonium  (radium  F),  and  radium 
C2  (now  called  C"),  actinium  D  and  thor- 
ium D  must  be  isotopes  of  thallium.  Fleck 
at  once  verified  theee  predictions  as  regards 
radium  A,  actinium  D  and  thorium  D. 


RADIO-ELEMENTS 

AND  THE 

PERIODIC  LAW. 

AU  £l£M£0rS  IN  THt 
SAMi  V£ftTKAl  COIUMM 
AK   ISOTOP£S 


(2)  Uranium  X.  like  niesothorium,  must 
consist  of  two  successive  /8-rny  giving  pro- 
ducts, intermediate  between  the  two 
uraniums.  Fajans  and  Gohring  at  once 
succeeded  in  separating  from  "uranium  X" 
ft  very  short-lived  product,  uranium  X,,  giv- 
ing the  more  penetrating  of  the  two  types 
of  ^-ray  expelled,  the  uranium  Xj  giving 
the  loss  penetrating  )3-rays. 

(3  The  parent  of  actinium  in  the  Ilird 
family  must  be  an  isotope  of  radium,  if 
actinium  is  formed  in  a  /3-ray  change — a 
conclusion  I  at  once  exiperimentally  dis- 
proved— or  it  must  be  an  isotope  of  uranium 
-X,  in  the  Vth  family,  if  actinium  is  fornu'd 
m  an  a-ray  change.  This  was  proved  by 
Cranston  and  myself,  and  the  name  "ekn 
tantalum"    given  to  the  new  element,    and 


by  Hahn  and  Meitner,  who  named  it  proto- 
actinium.  It  is  linked  to  uranium  through 
uranium  Y,  a  branch  member  discovered  by 
Antonoff  in  1911,  and  suspected  to  be  in 
the  actinium  series. 

Protoactinium,  to  give  it  Hahn  and  Meit- 
ner's  name,  has  been  shown  by  them  to 
give  a-rays,  and  to  be  chemically  so  like 
tantalum  that  hitherto  it  has  not  been 
separated  from  it.  Its  period  is  about 
17,000  years,  and  from  this  it  may  be  cal- 
culated that  there  is  about  one-fifth  as 
much  of  it  by  weight  in  minerals  as  there 
is  of  radium.  This  may  be  sufficient  to 
enable  it  to  be  isolated  and  for  its  spectrum, 
atomic  weight  and  chemical  character  to 
be  ascertained.     The  branch  series  rune:  — 

U VUY-->Pa   ->-Ac >-RaAc — > 

VI  IV  V  III  IV 

a  a 

AcX ^  An ^  tc. 

II  0 

in  which  the  figures  in  the  second  line  refer 
to  the  family  in  the  Periodic  Table  to 
which  the  element  belongs. 

(4)  All  the  ultimate  products  in  all 
branches  are  isotopes  of  lead.  The  atomic 
weight  of  the  two  products  of  thorium  are 
both  206,  and  of  the  major  branch  of  ura- 
nium 206.  As  is  well  known  this  had  only 
to  be  tested  to  be  (proved  correct.  The 
atomic  weight  of  the  lead  from  the  purest 
thorium  minerals  is  as  high  as  207.9,  and 
of  that  from  the  purest  uranium  minerals 
206.  The  spectra  of  these  isotopes,  but 
for  the  possible  infinitesimal  difference  al- 
ready alluded  to,  are  identical.  But  the 
densities  are  proportional  to  their  atomic 
weights.  This  was  a  very  simple  predic- 
tion I  made,  before  testing  it,  from  the 
theoretical  views  about  to  be  dealt  with. 

The  Thkoretical  Interpretation  of 
Isotopes. 

Tlu  result.-,  wii  the  theoretical  side  were 
no  less  definite  and  important,  and  isotopes 
found  ft  ready  exiplanation  on  the  nuclear 
theory  of  atomic  structure  put  forward  in  a 
tentative  form  by  Rutherford  in  1911.  j-ius 
theory  accounted  for  the  large  angles 
through  which  occasional  a-particles  were 
deflected  in  their  passage  through  atoms, 
by  the  existence  of  a  very  minute  highly 
charged  nuelous  at  the  centre  of  the  atom, 
the  rest  of  the  atom  being  occupied  by 
separate  charges  of  opposite  sign  equal  in 
nunjber  to  the  nuclear  charge.  For  such  an 
atom  scattering  should  be  proportional  to 
the  square   of  the  nuclear  chcu-ge.      Expert- 


l06 


THE  CHEMICAL  NEWS. 


AUGUST  17,  1923. 


ment  showed  that  scattering  was  apiproxi- 
mately  proportional  to  the  square  of  the 
atomic  weight.  So  that  it  looked  as  if,  as 
in  the  a-particle .  itself,  there  existed  one 
unit  of  nuclear  charge  to  each  two  units  of 
atomic  weight.  This  would  make  the  nu- 
clear charge  of  uranium,  of  atomic  weight 
about  240,  120  +. 

Since  the  a-particle  carries  two  positive 
charges  and  the  ^-particle  one  negative,  the 
obvious  inference  from  the  figure  is  that  the 
successive  places  in  the  Periodic  Table  cor- 
respond with  unit  difference  in  the  intra- 
atomic  charge.  This  view,  and  also  that 
each  unit  of  charge  corresponded  to  two 
units  of  mass,  had  been  suggested  indepen- 
dently by  van  der  Broek  in  1911.  At  first 
he  tried  to  stretch  the  Periodic  Table  to 
make  it  accommodate  120  places.  But,  in 
1913,  he  pointed  out  that  the  experimental 
results  for  scattering  were  completely  in  ac- 
cord with  his  own  view  (that  the  number  of 
the  place  is  the  same  as  the  intra-atomis 
charge),  on  the  existing  Periodic  Table, 
which  accommodates  only  some  90  ele- 
ments. It  would  not  be  inconsistent  with 
his  other  view  (that  the  nuclei  of  the 
heavy  elements  are  made  up  of  helium  nu- 
clei) if  there  were  electrons  in  the  nucleus 
as  well  as  in  the  outside  shell.  Thus 
uranium  in  the  90t.h  place  would  have  to 
have,  in  addition  to  the  60  helium  nuclei  in 
its  nucleus  to  account  for  its  weight,  30 
electrons,  to  account  for  its  charge  of  90+. 

The  existence  of  electrons  as  well  as 
positive  charges  in  the  atomic  nucleus  was 
also  postulated  by  Bohr  to  explain  the 
emission  of  j8-rays,  for  on  his  theory  the 
electrons  in  the  external  shell  form  a  stable 
configuration  and  could  only  be  dislodged 
by  the  expenditure  of  work. 

The  Periodic  Law  generaHsation  practi- 
cally settled  this  question.  jS-ray  changes 
are  no  less  transmutational  than  a-ray 
changes,  and  are  shaiiply  to  be  distinguished 
from  the  numerous  processes,  such  as  fric- 
tion, chemical  change,  action  of  ultra-violet 
light  and  incandescence,  during  which  elec- 
trons are  detached  from  atoms.  The  effect 
on  the  chemical  character  produced  by  the 
expulsion  of  one  a-particle  is  exactly  undone 
by  the  expulsion  of  two  jS-particles,  and  the 
product  becomes  isotopic  with  the  original 
parent.  This  means  that  both  a-  and  ^- 
particles  must  be  expelled  from  the  nucleus, 
and  that  isotqpes  are  elements  the  atoms  of 
which  have  the  same  neti  nuclear  charge — 
i.e.,  the  same  excess  number  of  positive  over 
negative  charges  in  the  nucleus,  but  differ- 
ent numbers  of  positives  and  negatives 
reckoned  separately.    For  such  systems  the 


electronic  shell  would  be  identical,  and  so 
the  identity  of  the  chemical  and  spectro- 
scopic character  is  explained.  Also  the 
atomic  volume  is  the  same  —  that  is,  the 
density  must  be  proportional  to  the  atomic 
weight. 

We  were  able  to  get  an  interesting  confir- 
mation of  this  view.  In  the  change  of 
uranium  X^  to  uranium  II  two  electrons  are 
lost  as  ^-rays.  In  the  oxidation  of  a  ura- 
nous  salt  to  a  uranic  or  uranyl  salt  two  elec- 
trons are  also  lost. 

U  +  +  +  =  U  +  +    +  +  +  +  2  E. 

If  these  come  from  the  same  region  of  the 
atom  as  the  ^-particles,  then  uranous  salts, 
so  long  as  their  valency  does  not  change, 
should  be  like  uranium  X^,  chemically  non- 
separable  from  thorium.  Fleck,  trying  this, 
found  great  similarity  in  chemical  proper- 
ties between  uranous  salts  and  thorium, 
but  not  identity.  He  was  able  to  separate 
thein  by  chemical  methods  without  chang- 
ing the  valency  of  the  uranous  salt. 

The  great  merit  of  the  nuclear  atom  from 
the  chemist's  point  of  view  was  that  it  af- 
forded for  the  first  time  a  clear  picture  of 
the  difference  between  a  chemical  and  a 
transmutational  (or  radioactive)  change. 
The  latter  occur  in  the  nucleus  and  are  ir- 
reversible. The  external  shell  accomraio- 
dates  itself  instantly  to  the  change  of  the 
nucleus.  But  any  change  suffered  by  the 
external  shell  (chemical  change)  has  no  ef- 
fect on  the  nucleus,  which  always  acts  so  as 
to  make  the  external  shell  conform  to  one 
most  stable  configuration. 

The  atom  is  an  imperium  in  imperio,  and 
like  most  such  systems  is  very  conservative 
and  resistant  to  change.  The  electrons  in 
the  shell,  that  govern  almost  all  the  atomic 
properties,  except  mass  and  radioactivity, 
are  in  turn  but  the  bureaucratic  instruments 
of  the  real  government,  which  is  the  in- 
tensely charged  central  nucleus.  The  trans- 
mutation of  atoms,  as  of  social  systems,  is 
alike  impossible  because  the  apparent  gov- 
ernment is  not  the  real  government. 
Kutherford's  exiperiments,  on  the  bombard- 
ment of  atoms  by  a-particles,  show  that 
only  about  one  out  of  a  hundred  thousand  of 
the  latter  in  passing  through  hydrogen  ever 
hit  a  hydrogen  nucleus,  and  the  proportion 
of  hits  to  misses  is  something  like  one  in  one 
thousand  millions.  In  politics,  contrasting 
the  number  of  missiles  hurled  with  the  i*e- 
sults  achieved,  the  shooting  seems  even 
worse.  It  is  only  when  the  atomic  or  social 
systems  break  up  or  break  down  that  we 
learn  even  of  the  existence  of  their  real  in- 
ternal constitution,  F.S. 


AUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


i07 


GENERAL    NOTES 


THE  BRITISH  INDUSTRIES  FAIR, 
1924. 

Considerations  Governing  the  Change 
OF  Date. 

After  oonsidering  all  sides  of  the  question 
and  canvassing  interested  trade  opinion, 
the  Department  of  Overseas  Trade  and  the 
Birmingham  Committee,-  the  respective 
organising  authorities  for  the  London  and 
Birmingham  sections  of  the  British  Indus* 
tries  Fair,  have  decided  that  next  vear's 
Fair,  instead  of  taking  place  at  the  end  of 
February,  as  would  normally  be  the  caee, 
shall  be  postponed  for  two  months. 

This  means  that  the  British  Industries 
Fair  will  open  in  London  on  April  28,  con- 
tinuing until  May  9,  while  the  Birmingham 
section  will  open  on  the  Monday  following 
the  close  of  the  Fair  in  London. 

Visitors  from  the  Dominions. 

In  selecting  these  dates  the  organising 
authorities  appreciated  that  the  holding  of 
the  big  British  Emipire  Exhibition  from 
April  to  October  of  1924  must  materially 
affect  the  attendance  of  overseas  buvers.  It 
is  certain  that  few  buyers  from  tlie  Do- 
minions will  make  two  visits  to  the  United 
Kingdom  in  the  course  of  a  single  year,  as 
would  be  necessary  if  the  Fair  were  to  be 
held  two  months  before  the  opening  of  the 
Empire  Exhibition.  On  the  other  hand,  it 
is  probable  that  many  of  these  vi8it<;rs  will 
make  a  point  of  arriving  in  this  country  in 
time  for  the  opening  at  Wembley,  a  prob- 
ability which  becomes  almost  a  certainty  if 
they  can,  in  the  course  of  the  trip,  inspect 
both  the  Exhibiton  and  the  British  Indus- 
tries Fair. 

The  later  date  is  also  likely  to  benefit  the 
Fair  owing  to  the  probable  large  increase  in 
the  number  of  Dominions  business  men  who 
will  make  every  possible  effort  to  come  to 
the  United  Kingdom  next  year.  Nor  need 
it  be  considered  that  this  increase  of  visitors 
will  be  limited  to  the  Dominions  and  Colo- 
nies; so  large  an  exhibition  as  that  of  th<' 
British  Emipire  promises  to  he,  is  a  mnj;not 
to  both  the  business  man  and  the  holiday- 
maker.  With  the  Fair  running  concur- 
rently with  the  Exhibition,  many  Contineti- 
tal  buyers  will  assuredly  seize  the  opportun 
ity  of  combining  business  with  pleasure  by 
visiting  this  country  in  May  next. 

Exhibition  and  Fair  Complemfntarv.  , 
While  the  British  Industries  Fair  and  the 


British  Empire  Exhibiton  have  a  common 
object  in  the  promotion  of  Empire  trade, 
theur  activities  are  complementary  rather 
than  competitive.  Participation  in  the 
Fair  will,  as  always,  be  confined  to  British 
manufacturers,  and  admission  will  be  re- 
stricted to  trade  buyers.  The  exhibition,  on 
the  other  hand,  is  for  the  public,  arid  wel- 
comes participation  by  any  British  firm, 
whether  manufacturers,  merchants  or  re- 
tailers. 

Mutual  benefit  to  both  the  Exhibition 
and  the  Fair  will  also  be  possible  from  a 
combined  publicity  campaign. 

Trades  to  be  Exhibited. 

The  schedules  of  trades  for  the  Londoa 
and  Birmingham  sections  of  the  Fair  will 
be  similar  to  those  of  last  year,  London 
covering  mainly  the  lighter  lines  of  "^-vxls 
such  as  pottery,  jewellery,  leather  anJ 
fancy  goods,  sports  goods,  musical  instru- 
ments, stationery  and  chemicals,  while  ex- 
hibits at  Birmingham  will  consist  of  hard- 
ware, engineering,  metals,  power,  building, 
mining  and  agricultural  implements. 

Application  forms  for  space  will  be  issued 
to  eligible  United  Kingdom  firms  at  the 
beginning  of  October. 

Since  this  general  statement  was  writoru 
many  re<)lie8  have  been  received  hy  the  De- 
partment of  Overseas  Trade  to  their  circular 
regarding  the  change  of  date.  It  is  satis- 
fact<rt7  to  record  that  the  vast  majority  of 
these  express  not  only  the  intention  of  the 
various  firms  to  exhibit,  but  also  universal 
approval  to  the  dccisiMi  to  alter  the  dates  in 
the  ^>ecial  circumstances  ruling  next  year. 


NEW    POWER    SCHEME    FOR 
JOHANNESBURG. 

H.M.  Senior  Trade  Commissioner  in 
South  Africa  reports  that  the  Johannesburg 
Town  Council  has  now  voted  in  favour  of 
the  proposed  new  power  station  and  advises 
its  erection  on  the  vacant  site  between  the 
present  power  station  and  Jappe  Street.  ^  It 
also  recommended  that,  in  the  period  which 
must  elapse  before  the  new  power  station  is 
completed,  a  10,000  kilowatt  generator, 
adaptable  to  the  new  conditions,  should  be 
installed  in  the  old  power  station  on  tem- 
porary foundations,  to  be  afterwards  re- 
moved to  its  permanent  position  in  the  ne»v 
station,  and  that  the  matter  should  be 
treated  as  urgent  in  order  to  have  the  set 
running  before  the  winter  of  1925. 

The  total  cost  of  the  new  station    will  be 


108 


THE  CHEMICAL  NEWS. 


AtGUST  17.  1923. 


about  £500,000;  it  will  be  equipped  with 
two  10,000  k.w.  generators,  together  with 
two  generators  from  the  old  station,  so  as  to 
give  a  capacity  of  39,000  k.w. 

The  Finance  Committee  has  also  recom- 
mended the  erection  of  this  power  station, 
provided  that  authority  is  obtained  from 
the  Administrator  to  borrow  an  amount  of 
£525,000. 

Copies  of  press  cuttings  in  connection 
with  this  matter  may  be  inspected  by 
United  Kingdom  firms  interested  on  appli- 
cation to  the  Department  of  Overseas 
Trade  (Koom  52),  35,  Old  Queen  Street, 
London,  S.W.I.  (Reference  No.  llbVU/ 
E.D./E.P.) 


IN  PARLIAMENT. 

In  the  House  of  Commons,  Mr.  Shin  well 
asted  the  President  of  the  Board  of  Trade 
whether  he  was  aware  that  sulphate  of  am- 
monia for  export  from  the  Clyde  was  not 
being  weighed  and  checked,  and  that  sealed 
samples  were  no  longer  taken ;  and  whether, 
since  this  was  contrary  to  custom,  he  pro- 
posed to  take  action  in  the  matter. 

Viscount  Wolmer,  Under-Secretary  to  the 
Board  of  Trade,  said  :  The  official  control  of 
the  export  of  sulphate  of  ammonia,  which 
was  instituted  during  the  war,  i^;  now  at  an 
end.  The  export  is,  accordingly,  subject 
only  to  the  ordinary  Customs  regulations, 
and  I  have  no  reason  to  think  that  these  re- 
gulations are  not  being  observed.  The  hon. 
member  appears  to  be  referring  to  certain 
trade  arrangements,  over  which  the  Board 
of  Trade  have  no  control. 

Mr.  Herbert  Spencer  asked  the  President 
of  the  Board  of  Trade  whether  his  atten- 
tion had  been  called  to  the  statement  of  the 
President  of  the  Colour  Users'  Association 
to  the  Manchester  Chamber  of  Commerce  of 
23rd  February,  1923,  in  which  he  asked  the 
Government  to  redeem  its  pledge  that  the 
Act  should  not  jeopardise  the  using  indus- 
tries ;  and  whether  the  Government  did  pro- 
pose to  do  so ;  further,  whether  his  attention 
had  been  called  to  the  statement  of  the  Pre- 
sident of  the  Colour  Users'  Association  that 
prices  both  of  home-produced  and  repara- 
tion dyestuffs  were  at  an  artificially  high 
level,  300  to  400  per  cent,  above  pre-war ; 
and  what  steips  he  proposed  to  take  to 
remedy  this. 

Sir  Philip  Lloyd-Greame  replied :  I  am  in 
constant  communication  with  the  represen- 
tatives of  the  dye-making  and  dye-using  in- 


dustries, and  every  effort  is  being  made  to 
secure  that  the  Dyestuffs  (Import  Regula- 
tion) Act  is  administered  in  such  a  manner 
as  to  promote  the  best  interests  of  both 
parties. 


In  a  lecture  recently  given  by  Evan 
James  McGillivray,  at  the  Institute  of 
Chemistry,  some  interesting  points  are 
raised  as  to  the  right  to  use  the  title 
"  Chemist." 

Mr.  McGillivray  made  some  extracts 
from  Dr.  Spratt's  "  History  of  the  Royal 
Society,"  written  in  the  17th  century,  where 
it  is  suggested  that  the  chemist  "  must  be 
rather  innocent  and  virtuous  than  knowing" 
— qualifications  that  are  well  worth  bearing 
in  mind. 

According  to  Dr.  Spratt,  chemists  of  his 
day  might  be  divided  into  three  ranks — 

"  Such  as  look  after  the  knowledge  of 
Nature  in  general." 

"  Such  as  seek  out  and  prepare  medi- 
cines." 

"  Such  as  seek  after  riches  by  transmuta- 
tions and  the  great  Elixir." 

The  lecturer  suggested  that  those  who 
comiposed  the  Chemical  Society  at  the  time 
of  its  foundation  were  the  successors  of  the 
men  to  whom  Dr.  Spratt  refers  as  those 
"who  look  after  the  knowledge  of  Nature  in 
general,"  and  that  they  were  very  little 
known  to  the  general  public. 

Of  the  other  two  ranks,  the  pharmaceuti- 
cal chemist  is  still  known  to  the  public  as  a 
chemist,  while  those  who  sought  after 
riches  by  transmutations  and  the  great 
Elixir  have  disappeared — killed  by  ridicule 
and  failure. 


We  have  received  a  copy  of  the  Index  to 
Vol.  I.  of  the  Bureau  of  Bio-Technology, 
and  are  asked  to  make  it  known  that  it  may 
be  obtained  on  application  to  Messrs. 
Murphy  &  Son,  Ltd.,  Cedars  Laboratories, 
Sheen  L.ane,  Mortlake,  London,  S.W.14. 


DEPARTMENT  OF  OVERSEAS  TRADE. 
Report  on  His  Majesty's    Trade  Commis- 
sioner AT  Toronto  in  regard  to  an  Ofp'icjal 
Tour  of  Western  Ontario;  June,  1923. 

An  official  tour  was  made  by  His 
I^ajesty's  Trade  Commissioner  at  Toronto 
(Mr.  F.  W,  Field)  to  cities  and  towns  in 
Western  Ontario  during    the  early  part    of 


AUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


109 


May  and  the  latter  end  of  June.  Among 
the  places  visited  were  Hamilton,  St. 
Catherines,  Niagara  Falls,  Thorold,  Brant- 
ford,  London,  Chatham,  Stratford,  Wind- 
sor, Walkerville,  Ford,  Amberstburg,  and 
Ojibway. 

A  large  number  of  calls  were  made  upon 
manufacturers,  who  are  importers  of 
various  oommidities,  merchants,  and  others 
likely  to  be  interested  in  sources  of  supply 
in  the  United  Kingdom. 

These  ofl&cial  tours,  which  are  a  part  of 
the  duties  of  all  of  His  Majesty's  Trade 
Commissioners,  are  believed  to  be  of  con- 
siderable value  in  relation  to  the  expansion 
of  British  trade.  In  the  case  under  review, 
contact  was  established  or  maintained  with 
Chambers  of  Commerce,  Industrial  Com- 
missioners, Purchasing  Agents,  and  others 
interested.  The  Trade  Commissicjper  re- 
ports that  business  men  in  Ontario  generally 
appreciate  the  work  of 'the  Department  of 
Overseas  Trade  in  assisting  to  develop  Brit- 
ish trade  here  in  face  of  keen  foreign  com- 
petition. He  adds  that  he  is  always  given  a 
friendly  reception  and  evenr  poeeible  as- 
sistance. Considerable  publicity  in  the  in- 
terests of  British  trade  was  also  secured 
through  press  interviews  at  the  various 
points  visited. 

Enquiries  were  received  by  the  Trade 
Commissioner  during  his  tour  fw  prices  of 
United  Kingdom  manufacturers  of  yams, 
dyeing  machinery,  alloy  steels,  wire  draw- 
ing machinery,  paper  tubes,  vegetable 
parchment  paper,  nuospar,  duck  filter  cloth, 
soda  ash,  etc.  These  were  brought  to  the 
notice  of  United  Kingdom  firms.  A  recent 
enquiry  of  this  character  has  led  to  an  im- 
portant new  connection  or  United  Kingdom 
chemical  manufacturers. 

Silk  Dyeing. 
A  visit  was  made  to  the  silk  dyeing  works 
which  were  recently  established  in  St. 
Catherines,  Ontario,  where  it  was  learned 
that  a  considerable  volume  of  silk  goods  in 
the  grey  are  being  imported  from  foreign 
countries  and  dyed  locally.  A  special  re- 
port on  this  matter  is  available  to  firms  in- 
terested upon  application  to  the  Depart- 
ment of  Overseas  Trade. 

American  Branch  Works. 
American  companies  continue  to  erect 
branch  works  in  Western  Ontario.  Two  of 
the  most  recent  additions  are  the  United 
States  Light  and  Heat  Company  and  the 
Dominion  Insulator  and  Manufacturing  Co. 
The  latter  firm  are  one  of  two  insulator 
manufacturers  in    Ontario  which    specialise 


in  high  voltage  work.  Clay  is  imported 
from  the  parent  company  prepared  ready 
for  use  in  the  Canadian  works. 

The  establishment  in  Canada  of  so  many 
branch  works  of  United  States  firms  natur- 
ally tends  to  divert  trade  to  the  United 
States.  Many  of  the  Canadian  branches 
purchase  a  substantial  portion  of  their  re- 
quirements through  their  head  ofl&ce  in  the 
United  States  which  in  some  cases  entirely 
controls  the  purchasing  policy  of  the  Cana- 
dian branch.  Production  costs  in  Ontario 
are  frequently  reported  as  being  higher  than 
in  the  parent  works  in  the  United  States. 
American  Capital  in  Canada. 
It  was  recently  estimated  by  a  reliable 
authority  that  mcwe  than  two  hundred 
branch  fact<»ies  were  opened  in  Canada  by 
Americans  in  1919,  and  a  great  number  in 
1020  and  1921,  and  that  late  in  1922  there 
must  have  been  over  seven  hundred  such 
estftbUshments,  with  a  further  number 
seeking  suitable  locations.  One  of  the  in- 
centives for  this  development  is  that  the 
American  manufacturers  can  thus  supply 
the  Canadian  market  and  at  the  same  time 
escape  the  Canadian  tariff.  Another  is  that 
by  manufacturing  in  Canada  they  are  able 
to  enjoy  the  preferential  treatment  accorded 
to  Canadian  goods  by  many  countries  with- 
in the  British  Empire,  while,  under  the 
t^rms  of  an  agreement  with  France  existing 
since  1907,  Canada's  products  enter  that 
country  under  especially  favourable  ccai- 
ditions. 

British  Branch  Works. 
A  number  of  United  Kingdom  manufac- 
turers are  believed  to  be  considering  the 
matter  of  branch  works  in  Canada,  particu- 
larly in  Ontario  and  Quebec  Provinces. 
These  include  makers  of  artificial  silk  yarn 
and  engineering  lines.  An  English  firm  of 
tobaooo  merchants  recently  established  pro- 
cessing works  in  Ontario. 

Chemical  Industries. 
The  Norton  Company  proposes  to  enlarge 
its  electric  furnace  plant  at  Chippewa,  near 
Niagara  Falls,  by  adding  a  furnace  building 
to  be  used  exclusively  for  the  manufacture 
of  a  carbide  of  silicon  abrasive  known  as 
Cry  stolon.  The  develoipment  will  cost 
about  $165,000,  and  ensure  a  25  per  cent, 
increase  in  production  of  this  line. 

There  are  two  cities  bearing  the  name  ol 
Niagara  Falls.  One  is  in  Ontario  and  one  in 
New  York  State.  They  face  each  other,  the 
river  dividing  them.  Both  are  the  sitee  of 
important  industries.  The  Falls  themselves 
are  just  as  much  a  Canadian  institution  as 


110 


THB  CHEMICAL  NEWS. 


AUGUST  17.  1923. 


they  are  American,  and  the  famous  "Horse- 
shoe Falls"  of  Niagara  are  in  Canada. 
Power  is  developed  at  Niagara  Falls,  On- 
tario, by  the  Hydro-Electric  Power  Com- 
mission of  Ontario  for  long  distance  trans- 
mission to  all  parts  of  Ontario  and  to  seve- 
ral parts  of  new  York  State. 

The  American  Cynamid  Company  have 
works  at  Niagara  Falls,  where  the  com- 
pany's output  is  equally  divided  betwctn 
cynamid,  one  of  the  raw  materials  of  ferti- 
liser, and  cyanide,  used  in  mining.  The 
mining  industry  has  shown  marked  improve- 
ment, with  the  result  that  sales  of  cyanide 
have  been  made  to  the  gold  mines  in  the 
South  African  Eand  as  well  as  in  Canada, 
the  United  States  and  Mexico. 
Business  Conditioks. 

Business  conditions  in  Western  Ontario 
still  leave  something  to  be  desired,  but  they 
are  gradually  improving.  The  iron  and  steel 
industries  have  recently  been  more  active, 
largely  as  a  result  of  orders  placed  by  the 
railway  organisations  and  by  those  respon- 
sible for  bridge  and  office  building  construc- 
tion. I^nitted  goods,  sports  clothing,  and 
ladies'  clothing  manufacturers  have  also 
been  busy,  but  men's  wear  factories  have 
been  less  active.  The  demand  for  machine 
tools  is  only  fair,  but  shows  improvement. 
Cotton  mills  are  well  occupied.  Woollen 
mills  have  some  idle  machinery  and  com- 
plain of  active  British  competition.  Chemi- 
cal makers  are  experiencing  an  active  de- 
mand.    Motor  car  makers  are  busy. 

Wholesale  houses  report  a  good  demand 
for  staple  lines  and  retail  shops  are  doing  a 
satisfactory  seasonable  trade. 

Collections  continue  to  be  reported  as 
difficult. 

British  manufacturers  have  made  some 
headway  recently  in  securing  a  share  of  On- 
tario's import  trade.  This  is  true  of  the 
woollen,  hosiery,  and  chinaware  trades  par- 
ticularly. British  trade  has  also  been 
fairly  good  in  fancy  leather  goods,  sporting 
goods  and  cloths,  chemicals  and,  to  a  lesser 
extent,  in  metals  and  machinery. 

The  competition  to  be  met  in  Ontario  is 
very  keen  in  the  majority  of  lines,  both 
from  Canadian  and  United  States  manufac- 
turers, France,  Belgium,  Sweden,  and 
Japan  are  also  active  in  certain  trades. 
Machinery. 

Much  machinery  of  United  States  manu- 
facture is  in  use  in  Ontario  factories,  and 
orders  continue  to  be  placed  there  by  local 
buyers.  Many  factories  assist  the  sales  of 
machinery  competing  with  that  of  United 
Kingdom  manufacturers.     For  example,  the 


majority  of  Canadian  machinists  are  accus- 
tomed to  work  on  American  machines,  and 
some  difficulty  and  trouble  are  experienced 
in  training  them  to  use  machines  to  which 
they  are  not  accustomed.  Operators  some 
times  state  that  they  prefer  the  light-weight 
machines  of  our  competitors  rather  than 
heavier  build  of  British  machines,  although 
there  is  no  doubt,  as  a  rule,  as  to  the  better 
finish  and  durability  of  British  machines. 
The  difficulty  in  having  repairs  made  with- 
out delay  and  in  securing  the  rapid  delivery 
of  spare  parts  are  other  reasons  operating 
against  larger  sales  of  British  machines. 
The  Trade  Commissioner  expressed  the  be- 
lief that  there  appears  to  be  an  opportunity 
for  increased  sales  of  machinery  of  various 
makes  in  this  market,  including  air  com- 
pressors, hoisting  machinery,  mining  equip- 
ment, textile  machinery,  and  various  other 
lines  in  which  United  Kingdom  firms  liave 
proved  specialists.  Three  of  the  factors 
operating  against  greater  business  are  the 
lack  of  sufficient  local  representation  and 
active  salesmanship,  the  failure  of  United 
Kingdom  manufacturers  to  keep  in  constant 
touch  with  those  who  have  purchased  their 
machines,  and  the  inability  to  effect  re- 
pairs and  supply  spare  parts  at  short  notice. 
While  the  business  in  any  one  line  may  not 
be  large  enough  to  justify  the  establish- 
ment of  a  proper  local  organisation,  which 
should  remove  the  difficulties  noted,  it 
might  prove  feasible  for  several  manufac- 
turers of  non-competing  machinery  to  have 
joint  representation  here,  with  a  technical 
man  to  look  after  repairs;  a  good  sales  or- 
ganisation, which  would  adqpt  the  Ameri- 
can "follow  up"  system,  as  it  is  termed; 
and  a  stock  of  the  spare  parts  which  are 
most  likely  to  be  needed.  Unless  some  such 
system  is  adopted,  it  is  to  be  feared  that 
the  imports  of  United  Kingdom  machinery 
to  this  market  will  become  continually 
smaller. 

Visits    to    Canada. 

The  Trade  Commissioner  has  again 
strongly  recommended  a  personal  visit  of 
United  Kingdom  manufacturers  to  the  On- 
tario market  in  order  to  appreciate  fully  the 
difficulties  which  United  Kingdom  manu- 
facturers have  to  solve  in  order  to  secure  a 
profitable  amount  of  the  business  offering. 
Indeed,  he  states  that  unless  the  United 
Kingdom  manufacturer  is  fully  conversant 
with  what  is  termed  the  "selling  atmos- 
phere" of  the  market,  little  success  is  likely 
to  result  from  efforts  to  establish  or  extend 
trade  in  that  particular  market. 

The  Canadian  mana:ger    of  branch  works 


AUGUST  17,  1923. 


THE  CHEMICAL  NEWS. 


Ill 


of  a  United  Kingdom  manufacturer  of  en- 
gineering equi4)ment  has  suggested  that 
Unite  dKingdom  firais  establishing  wwks 
in  Canada  should  consult  the  Trade  Com- 
missioners in  regard  to  other  branch  houses 


there,  in  order  that  equipment  and  supplies 
may  be  purchased  as  far  as  possible  from 
other  United  Kingdom  firms  in  Canada, 
rather  than  from  foreign  suppliers. 


DOMINION    BUREAU  OF  STATISTICS, 
CANADA. 

R.  H.  Coats,  B.A.,  F.S.S.,  F.R.C.S., 
Dominion  Statistician;    S.  J.  Cook,  B.A., 
A. I.e.,  Chief  of  the  Mining  Metallurgi- 
cal and  Chemical  Bkanch. 

REVISED  STATISTICS  ON  THE 

MINERAL  PRODUCTION. OF 

CANADA,  1922. 

No.    1. — Cobalt. 

Date  of  Is8ue,  July  16,  1923. 

The  Dominion  Bureau  of  Statistics  issues 

the  following  finally  revised  statistics  <»i  the 

ppoductdon    of    cobalt    in    Canada    during 

1022. 

The  major  portion  of  the  world's  supply 
of  cobalt  for  almost  two  decades  has  been 
derived  from  the  silver-oobalt-nickel  ar- 
senides ol  the  Cobalt  district. 

.Summary  of  Cobalt  P 
Cobalt  ores  and  residues  treated  or  in 
Metallic  cobalt  conUnt  of  the  above 

Output  of 


Total 
lb. 

Metallic  cobalt  106.274 

Cobalt  oxide     860,496 

Mixed  oxide      86,780 

Residues  exported  A 

Total      Quantity 

Com  putted 
value 


During  1922,  three  smelters  in  Ontario 
treating  ores  and  residues  from  this  district 
marketed  cobalt  oxide,  metallic  oobalt,  co- 
balt sulphate,  cobalt  carbonate,  cobalt  hy- 
droxide, unseparated  oxide  and  stellite  (an 
alloy  of  cobalt  used  for  high  speed  tool 
metal).  The  cobalt  residues  from  the  cy- 
anide process  were  mainly  treated  in  Can- 
ada during  1922,  although  some  of  these,  as 
well  as  smelter  residues  amounting  in  all  to 
518  tons,  otmtaining  173,211  lbs.  of  cobalt, 
were  shipped  abroad  for  treatment. 

The  oobalt  production  of  Canada  in  1922 
was  569,900  lbs.,  which,  at  $3.25  per  pound, 
would  be  worth  $1,852,370.  These  figures 
were  obtained  as  the  total  of  the  meta!  co- 
balt contained  in  smelter  products  made  in 
1922  and  oobalt  in  residues  exported  (at 
treatment,  valued  at  $3.25,  which  was  the 
average  New  York  quotation  for  cobalt 
during  the  year. 

boduction  Statistics,  1922. 
prooeas,  8,719  tons, 
(by  aaeay).  586,400  lbs. 
Sm(  * 


Smelters. 

Cobalt 

Cont'aine<l 

lb. 

106.274 

252.317 

39,02.} 

172,311 

569,960 

1,862,370 


Quantity 

lb. 

109,067 

398,697 

123,605 

l,036.fJ00 


Marketed. 

Value  as 
reported  by 
Smelters. 

$ 
282,602 
798,271 
99,687 
166,402B 


1,336,962 


A  —  Not  given ;  B  —  Estimated . 


NOTICES  OF  BOOKS. 

The  Discovery  of  the  Nature  of  the  Air 
and  of  its  Changes  during  Breathing,  by 
Clara  M.  Taylor,  M.A.  Geo.  Bell  k 
Sons,  Ltd.,  London.  1923.  Price  Is. ,6(1. 
net. 

This  work  forms  part  of  a  series  of  classics 
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ledge. 
The  volume  in    question    contains    eight 


112 


THE  CHEMICAL  NE^S. 


AUGUST  17.  1923. 


chapters  referring  to  researches  from  those 
of  Robert  Boyle  in  1627-1691  to  those  of 
Lavoisier  in  1743-1794.  A  great  many  illus- 
trations and  portraits  are  given  of  the  men 
whose  works  are  described,  and  many  de- 
tails are  recorded  of  the  work  of  these  early 
investigators  that  it  would  be  diflScult  for 
the  ordinary  student  to  obtain.  The  book 
is  written  in  a  style  that  it  is  very  easy  to 
follow.  At  the  end  of  each  chapter  there 
is  a  short  summary  giving  the  dates  of  the 
investigations  and  the  evidence  they  ob- 
tained. 

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are  quoted  in  full,  particularly  that  of 
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through  the  lungs. 

The  book  ends  with  a  summary  of  the 
progress  in  knowledge  of  respiration,  com- 
mencing with  Harvey's  discovery  of  th3  cir- 
culation of  the  blood  in  1678  to  the  work  of 
Lavoisier  in  1743. 


BOOKS  RECEIVED. 

The  Paper-Makers'  Directory  of  All 
Nations.  Pp.  XLIX.  +  971.  Thirty-Second 
Edition,  1923.  Messrs.  Dean  &  Son,  Ltd., 
Debrett  House,  29,  King  Street,  Covent 
Garden,  W.C.2.     Price  2l8. 


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18944 — Pratt,     J.     T. — Desulphurising  iron,     steel, 
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Specifications  Published   this    Week. 

17528 — Posseyer  Abwaseer-und-Wasserreini-Gungs 
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178824 — Metz,  H.  A. — Complex  arseno-stibino  com- 
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200151— Howards  &  Sons,  Ltd.,  and  Blagden,  J.  W. 
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Chemical  Industry  in  Basle,  Switzerland. 

l-(2-Methyl-S-8ulpho-5-i9opropy)  phenyl-3-methyl- 
5-pyrazolone  is  prepared  by  condensing  the  liy- 
drazine  from  2-aminooymene-6-sulphonic  acid  with 
ethyl  acetoacetate.  An  example  is  given  in  which 
diazotized  aminocymene  sulphonio  acid  is  re- 
duced with  sulphite  and  the  hydrazine  then  con- 
densed with  etnyl  acetoacetate. 

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similar  to  those  of  tartrazine  but  faster  to  light 
are  obtained  by  coupling  the  above  described  pyra- 
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benzene  or  naphthalene  series;  in  an  example 
diazo-benzene  is  used. 

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w 


THE  CHEMICAL  NEWS. 


118 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3306. 


ORGANIC  COMPOUNDS  OF  ARSENIC. 

PART  IIlA. 

By  R.  F.  Hunter,  F.C.S. 
Salvarsan. 

The  high  physiological  activity  of  the 
cacodyl  compounds  is  traced  to  the  pre- 
sence of  tervalent  arsenic.  This  led  Erlick 
to  study  the  tervalent  arsenic  compounds 
which  are  generally  obtained  by  reducing 
the  corresponding  atoxyls. 

A  drug  of  high  trypan    ocidal  power    is 
"  Spirarsyl,"  and  has  a  constitution 
CO,  Na  CH,  N  H  C.H^  As  = 

As  C.H,  N  H  C  H.CO,  Na. 
and  is  much  less  toxic  than  atozyl. 

The  work  that  has  been  done  on  this  sub- 
ject (I  refer  to  salvarsan)  at  first  sight, 
appears  overwhelming,  and  no  attemjpt  can 
be  made  to  give  anything  liki  a  complete 
survey  of  the  work.  The  suggeaticm  is, 
then,  to  follow  Morgan's  classification,  and 
to  oon,sider  a  few  of  the  more  important 
compounds.  The  preparation  of  salvarsan 
following  KoUeman  can  be  represented : 
C.H.(OH)  P  (OH)C,H,  AhO(OH), 

As  0(0H)3  C.H,  (N0),0H 
As  0(0H),  C,H,  (NH,)0H 

AsO  C^H,  (NH,)  oh 
HO  (NH,)  C,H,  As:  As  C.H,  (NH  )  Oil 
I. — Reduction     products    of     p-hydroxy- 
phenyl  arsenic  acid  and  derivatives: 
These  we  can  enunciate  briefly  as 
ip-hydroxy  phenyl  arsenious  oxide ; 
p-arsenophenol ; 
S'etra  chlorarsenophenol ; 
and  arsenobenzene  is  H  oxymethylene  car- 
boxvlic  acid 

COjH  CHjO  O.H^As  As  C,H,0  CH,CO,H, 
which  found  great  use  in  case  of  animals 
infected  with  trypanosomes. 

2, — Amino  aryl  derivatives  which  con- 
tain tervalent  arsenic : 

p-Amino  phenyl  arsenious  oxide,  NH,C,- 
IT^.\s  2H3O,  is  prepared  by  n ducing  atoxvl 
with  SO2  and  HI. 

Derivatives  worthy  of  note  are : 
2-Aminotolyl-5-arseniou8    oxide     2-acetyl 
amino  1  :5-henzar8enious  comle. 
3. — Salvarsan : 

3 :   3'  Diamine    4 :  4'  dehydroxy    arseno- 
benzene 


NHv 


H  o/~~~~^*i^  As/ 


OH 


Commercially  the  compound  is  generally 
used  as  its  hydrochloride. 

Commercial  samples  contain  impurities, 
and  in  some  recent  investigations  King  iso- 
lated a  number  of  sulphur  compounds  from 
the  commercial  salt  {J.C.S.,  1921). 

The  solution  of  salvarsan  in  water  is 
acid,  and  it  is  necessary  to  neutralise  this 
acidity  previous  to  injection,  one  of  the 
disadvantages  of  salvarsan.  As  a  deriva- 
tive of  arsenobenzene,  salvarsan  is  exceed- 
ingly readily  oxidised  by  air.  This  is  im- 
p(^ant  because  the  product  of  oxidation  is 
3-amine-4-hydroxyphenyl  arsenious  oxide, 
which  is  very  much  more  toxic  than  salvar- 
san. 

Sodium  salvarsan  has  been  muoh  used  in 
venereal  work. 

Copper  salvarsan  in  sleeping  sickness : 
Methylation  of  salvarsan  decreases  its  heal- 
ing powers. 

4. — Isomerides  of  salvarsan  : 

The  medieinal  value  of  the  isomerides  is 
in  all  cases  less  than  that  of  salvarsan.  Thi 
fol Towing  isomerides  have  been  prepared : 

4 :  4'  diamino. 

8 :  8'  dehydroxv  arsenobenzene 

2:  2'  .*. 2:  2'  

2:  2'  5:   5'  

and  4:  4'  , 2:  2'  

5. — Derivatives  and  homologues  of  sal- 
varsan : 

Some  of  these  are  worthy  of  mention. 

3-Methylamino-4-hydroxy  phenyl  arsenic 
acid.  Sym.  3:3'  dimethylamino  4:4'  de<^ 
hydroxy  arsenobenzene. 

*  3-I^imethylamino-4-hydroxy  phenylar- 
senic  acid  are  examples  of  N.  methyl  deri- 
vatives, while 

3  3'  diamino  2  2'  dehydroxy  5  5'  arseno- 
toluene  4  4'  diamino  5  5'  dehydroxy  2  2'  ar- 
senotoluene  are  examples  of  C  methyl  deri- 
vatives. 

5  5'  dichloro  4  :  4'  diamino  3  3'  dehydroxy 
arsenobenzene  4  4'  diamino  a-arsenonaph- 
thalene  and  3 :  3'  diamino  4  4'  dehydroxy  a- 
arsenonaphthalene  have  been  prepared. 

Stilbene  analogues  such  as 

5  :  5'  diamino  2  :  2'  stilbene  1 :  1'  diarsen- 
ic  acid  5 :  5'  diamino  4 :  4'  dehydroxy  1 :  1' 
arsenic  2:  2'  stilbene,  are  known. 

Also  the  mixed  aromatic-aliphatic  cacoc- 
lyl  analogue  of  salvarsan,  viz.,  3:  3'  di- 
amino 4 :  4'  dehydroxy  diphenyl  dimethyl 
disu^ine  has  been  prepared. 


114 


THE  CHEMICAL  NEWS 


AUGUST  24,  1923. 


6. — Tetraminoarsenobenzenes : 

Among  the  reduction  products  of  2 :  4  di- 
nitro  iphenylarsenic  acid  we  might  mention 

2 :  4  Dinitro  phenyl arsenious  oxide,  and 
2  :  4,  2' :  4'  Tetranitro  arsenobenzene. 

7.-5 :  5'  Diamino  2:4  :  2'  4'  tetra  hy- 
droxy arseno  benzene  and  derivatives: 

Among  the  preparations  which  have  been 
carried  out  are  those  of 

2 :  4  Dihydroxy  phenyl  arsenic  acid  and 
5  :  5'  Diamino  2  :  2'  dimefchoxy  4  :  4'  dehy- 
droxy  arsenobenzene. 

8. — Hexamino  arsenobenzene  and  deriva- 
tives : 

4:  4'  Tetramethyl  3:4  :  5  :  3'  :  4'  : 
5'  hexaminoarseno  benzene  is  said  to  be  a 
promising  tervalent  arsenic  compound. 

PAKT  IIlB. 

Neo    Salyarsan  : 

Sodium  3  :  3'  Diamino  4 :  4'  dehydrox y 
arsenobenzene.     N.   Methylene  sulphinatte 


HO 


<  )^'< 


Neo  salvarsan  is  prepared  from  salvarsan 
hydrochloride  by  treatment  with  sodium 
formaldehyde  sulphoxylate  in  aqueous  solu- 
tion, followed  by  10  per  cent.  Naj  C03  when 
3 :  3'  diamino  4 :  4'  dehydroxy  arsenoben- 
zene N.  methylene  sulphonic  acid  precipi- 
tates from  which  the  sodium  salt,  neo  sal- 
varsan, can  be  obtained, 

Neo  salvarsan  is  neutral  in  solution;  its 
curative  effect  is  much  the  same  as  salvar- 
san, but  greater  doses  must  be  applied. 

2. — Galyl  4  :  4'  dehydroxy  arsenobenzene 
3:  3'  phosphamic  acid  is  an  arsenical  drug 
which  is  acidic  and  dissolves  in  aqueous 
NajCOg  to  a  neutral  solution  and  is  very 
suitable  for  intravenous  injection  in  treat- 
ment of  syphillis. 

Ludyl  or  benzene  m  3' :  3'  disulphamino 
bis  3  amino  4 :  4'  dehydroxy  arsenobenzene 
is  also  used  in  syphillis,  and  has  a  structure 


5. — Arsenoary]  glycines,     an     example    of 
which  is  arseno  phenyl  p  glycine, 
CO,  H  CH,  NH  CeH.  As : 

As  C.H,  NH  CH,  CO,  H 


the  sodium  salt    of    which    is    "  spii*asyl." 
Arsenohiippuric  acid  has    ivceutly  been  pre- 
pared and  has  a  constitution 
CO2  H  CH2  N  H  C  0  GJL^  As : 

As  CgH^  CO  N  H  C  H,  CO,  H. 

In  conclusion,  we  have  surveyed  in  an 
infinitesimally  small  way  the  work  which 
has  been  done  on  arsenic  organic  com- 
pounds. 

That  the  ultimate  cure  for  syphillis,  the 
worst  of  the  two  venereal  diseases,  will  be 
an  arsenic  aromatic  or  hetero  cyclic,  there 
can  be  little  doubt;  when  we  consider  that 
in  1918  the  figures  given  for  British  troops 
suffering  from  venereal  disease  amounted  to 
200,000,  we  get  a  vague  conception  of  the 
magnitude  of  the  vital  problem  of  arsenic 
organic  derivatives.  From  the  brilliant  work 
done  by  our  scientific  men  in  this  field  of 
research,  we  are  sanguine  enough  to  hope 
that  in  a  few  years'  time  we  shall  see  the 
advent  of  a  cure,  better  by  far  than  either 
neo  salvarsan  or  its  derivatives,  if  not  the 
absolute  cure  for  that  filthy  and  contagious 
disease,  once  unknown  in  this  country,  now 
having  spread  and  spreading  to  a  ghastly 
degree,  which  we  call  "syphillis"  by  name. 


NOTES  ON  THE  QUANTITY  AND 

PEOPEETIES  OF  CHAECOAL 

OBTAINED  FEOM  VAEIOUS  KINDS 

OP  SIAMESE  WOODS. 

By  Dr.  G.  Bossoni,  Eoyal  Naval  Ordnance 

Department,  Bang  Na  (Siam). 

March,  ivZB. 

It  is  well  known  how  great  is  the  imiport- 
ance  of  charcoal  in  the  manufacture  of 
black  powder,  and  how  the  quality  and  pro- 
perties of  charcoal  are  intimately  connected 
with  the  quality  and  properties  of  Ijlack 
powder. 

In  fact,  the  combustion  of  black  powder 
depends  in  great  part  on  the  facility  and 
rapidity  of  the  combustion  of  charcoal, 
therefore  before  proceeding  to  the  manufac- 
ture of  black  powder,  it  is  necessary  to  study 
the  properties  of  the  charcoal  which  enters 
into  the  composition  of  the  powder.  For 
this  purpose.  Section  IV.  of  the  E.  Siamese 
Naval  Ordnance  Dcpt.  has  undertaken  some 
experiments  on  the  quality  and  quantity  of 
charcoal  yielded  by  several  kinds  of  com- 
mon Siamese  woods,  and  as  the  yield  of 
charcoal  depends  not  only  upon  the  kind  of 
wood,  but  also  upon  the  manner  of  charring 
employed,    so  the  experiments  were    rigor 


4 


AUGUST  24,  1923. 


THE  CHEMICAL  NEWS. 


115 


ously  performed  under  the  same  conditions 
and  at  the  same  temperature  (350°  C.)  for 
all  the  woods. 

The  wood  was  cut  from  trees  approxi- 
mately three  years  old  during  the  dry  sea- 
son, and  the  branches  not  more  than  4  cen- 
timetres thick,  about  50  centimetres  long, 
were  striippcd  of  the  bark  and  then  charred. 

Table  No.  1  shows  the  various  kinds  of 
woods  in  the  order  of  their  yield  of  charcoal, 
together  with  the  specific  gravity  of  the 
charcoal. 

Table  No.  2  shows  the  results  obtained 
from  the  analysis  of  charcoal  residue  in  the 
still,  per  cent. 

As  the  charcoal  most  suitable  for  the 
manufacture  of  gun  powder  is  the  one  which 
burns  most  quickly  and  gives  the  least  quan- 
tity of  ash,  experiments  were  undertaken  to 
determine  the  rate  of  combustion  of  the 
various  kinds  of  charcoal,  according  to  thc^ 
Proust's    method.      A    mixture    of    0.64') 


grammes  of  saltpetre  to  0.130  gramme  of 
charcoal  was  placed  in  copper  tubes  6  cen- 
timetres long  and  6  millimetres  in  diameter, 
and  ignited  by  a  little  meal  powder.  Table 
No.  3  shows  the  results  obtained. 

In  conclusion,  from  the  above  exiperi- 
ments  it  appears  that  although  the  quan- 
tity of  charcoal  obtained  from  100  parts  of 
Mai  Makham  Teth  (Pithecolobium  dulce), 
and  Mai  Kaa  (Sesbania  grandiflora)  is 
higher  than  the  quantity  yielded  by  the 
other  woods,  the  charcoals  obtained  from 
Mai  Thonglang  (Erytrina  indica)  and  Mai 
Tinpet  (Alstonia  scholaris)  is  richer  in  car- 
bonium  and  bums  more  quickly. 

I  wish  to  take  this  opportunity  of  express- 
ing my  thanks  to  Dr.  F.  G.  Kerr,  of  the 
Botanical  Section,  Dept.  of  Commerce,  and 
Mr.  W.  F.  Lloyd,  Conservator  of  Forests, 
for  informations  with  regard  to  the  botanical 
names  of  trees. 


Drying. 

Weight  of  the 
wood. 


Mai  Makham   Teth 
(Pithecolobium 
aulce)      

Mai   Kaa  (Sesbania 
gi-andi  flora) 

Mai   Pho  Tale  (Hi- 
biscus Tiliaoeus) 

Mai  Tinipct  (Alsto- 
nia scholaris)  .... 

Mai  Thonglang 

(Erytrina  Indica) 

Mai   Lampoo  (Son- 
neratia  acida)   ... 


25.00  15.97 

22.00  19.27 

18.00  16.14 

22.50  12.35 

25.00  22.80 

20.00  9.24 


Table  No.  1. 


Loss. 


0)    ** 

wo 


o 


9.03  86.12 

2.73  12.40 

1.86  10.33 

8.15  89.76 

2.20  8.80 

10.76  53.80 


Charring. 

Weight  of  the     -^ 
wood  dried         g  § 
previously 
at  100°  C 


o  5 


•4-1     CD 


bo 

<4-l     CO 


§1 


12.35 


CIS 
u 

o 

«o  o 
•S  2 


15.97        6.06      37.94       1.74 
19.27        7.09      36.79       1.318 
16.14        5.43      33.ffl       1.31 


3.49       28.25       1.47 


22.80         5.20       23.20       1.75 
9.24        2.18      23.59       1.57 


il6 


THE  CHEMICAL  MEWS. 


AUGUST  24,  1923. 


Table  No.  2. 


Analysis 

of  Charcoal  obtained  from  Carbon. 

Pithecolobium  dulce   78.10 

Sesbania  grandiflora 77.90 

Hibiscus  tiliaceus  77.02 

Alstonia  scholaris   80.13 

Erytrina  indioa 81.23 

Sonneratia  acida      76.85 


Oxygen.  Hydrogen.  Nitrogen. 


Table  No.  3. 

Mixture  of  0.645  gm.  of  Duration 
KNO3  and  0.130  gm.  of  of 

charcoal  made  from  :   Combustion. 

Pithecolobium   dulce    ...  16  sees. 

Sesbania  grandiflora   ....  15  do. 

Hibiscus   tiliaceus    18  do. 

Alstonia  scholaris   12  do. 

Erytrina  indica      11  do. 

Sonneratia  acida      20  do. 


Weight 

of  resi- 
due in 
gramme. 

0.388 

0.378 

0.395 

0.362 

0.375 

0.450 


BOARD    OF   EDUCATION. 

Arrangements  and    Conditions  for  the 

Award  of  National  Certificates  in 

Chemistry  to  Students  in  Technical 

Schools  and    Colleges  in    England 

and  W^ales. 

NOTE. — The  Institute  of  Chemistry  is 
undertaking  the  functions  assigned  to 
it  in  these  Rules  at  the  invitation  of  the 
Board  of  Education.  In  these  Rules 
the  Institute  of  Chemistry  is  referred  to 
as  the  "  Institute,"  and  the  Board  of 
Education  as  the    "  Board." 

1. — The  Institute  in  conjunction  with  the 
Board  is  prepared  to  approve  schemes,  sub- 
mitted by  technical  schools  or  colleges,  for 
the  award  of  certificates  relating  to  part- 
time  and  full-time  grouped  courses  in  chem- 
istry conducted  under  approved  conditions. 
To  avoid  possible  misunderstanding,  the 
certificates  will  bear  a  statement  indicating 
that  they  are  distinct  from  the  Associate- 
ship  and  Fellowship  Diplomas  awarded  by 
the  Institute. 

Part-Time  Courses.  • 
2. — Courses  for  the  purpose    of  a    part- 
time  course  certificate    under    these    Rules 
must  be  carried  on  for  at  least  180  hours  in 
each  year.     If    the  instruction  is  given  ex- 


16.50 
16.40 
17.00 
14.90 
14.02 
16.80 


3.67 
3.75 
3.70 
3.68 
3.50 
3.90 


Traces 
do. 
do. 
do. 
do. 
do. 


Ashes. 
1.60 
1.85 
2.25 
1.15 
1.10 
2.40 


clusively    in  evening    classes,    the    course 
should,  as  a  rule,    be  carried    on  for    three 
evenings  a  week  during  the  school  session. 
These  courses  are  classified  as  follows:  — 
(i)  Senior,  adapted  to  the  needs  of  stu- 
dents who  have  comipleted  satisfactorily  a 
junior    part-time    course     of    two    years' 
duration,    or  have  had  full-time  continu- 
ous education  up  to  the    age  of    15  or  16. 
Senior  courses  must  extend  over  at  least 
three  years;  and  should  include,  in  addi- 
tion to  Chemistry,  suitable  Physios    and 
Mathematics  as  cognate  subjects.     Certi- 
ficates relating  to  senior    courses  will    be 
termed  "  Part-time  Course  Certificates  in 
Chemistry  (Ordinary)." 

(ii)  Advanced,  adapted  to  the  needs  of 
students  who  have  completed  satisfactor- 
ily a- senior  part-time  course  or  are  other- 
wise suitably  qualified  (see  paragraph  5), 
and  aim  at  reaching,  within  the  limits  of 
the  subjects  covered  by  them,  the  stand- 
ard of  university  work.  Advanced  courses 
must  extend  over  at  least  two  years ;  and 
should  include,  in  addition  to  Chemistry, 
suitable  cognate  subjects.  They  may  in- 
clude the  study  of  the  application  to 
chemical  practice  of  scientific  principles 
with  which  the  students  have  become 
familiar.*  Certificates  relating  to  ad- 
vanced courses  will  be  termed  "  Part- 
time  Course  Certificates  in  Chemistry 
(Higher)." 

As  a  rule,  the  whole  of  a  part-time 
course  must  be  taken  by  the  student  at  one 
school,  but  subject  to  previous  approval  by 
the  Institute  and  the  Board  different  years 


*  With  the  approval  of  the  Institute  and 
the  Board  this  study  may,  in  certain  sub- 
jects, be  commenced  in  the  third  year  of  a 
senior  course. 


AUGUST  24.  1923. 


THE  CHEMICAL  N3WS. 


117 


of  the  course  may  be  assigned  to  different 
sohools  with  suitably  co-ordinated  curri- 
cula; and  the  courses  of  instruction  pre- 
viously taken  by  a  student  who  has  migrated 
from  one  area  to  another,  or  by  a  student 
who  has  received  satisfactory  instruction  in 
science  at  a  secondary  school  or  elsewhere, 
may  be  accepted  in  lieu  of  such  portion  of  a 
part-time  course,  other  than  the  final  year, 
as  may  be  approved  previously  by  the  Insti- 
tute and  the  Board  in  each  case. 

The  Part-time  Course  Certificates  (Ordi- 
nary and  Higher)  will  record  the  subjects 
constituting  the  coarse. 

FuLL-TiME  Courses. 

3. — Courses  for  the  purpose  of  a  full-time 
course  certificate  under  these  Rules  are 
classified  as  follows:  — 

(i)  Full-time  Course  in  Chemistry,  suit- 
able for  students  who  have  attende3  a 
secondary  school  up  to  the  age  of  16. 
Full-time  courses  in  Chemistry  must  ex- 
tend over  at  least  three  years,  and  should 
include,  in  addition  to  Chemistry,  suit- 
able Physics,  Mathematics,  and  one  or 
more  modem  languages,  and  may  include 
other  cognate  subjects.  Certificates  re- 
lating lo  full-time  courses  in  Chemistry 
will  lie  termed  "  Full-time  Course  Certi- 
ficates in  Chemistry." 

(ii)  Full-time  Course  in  Applied  Chem- 
istry,   restricted    to    students    who    have 
completed  satisfactorily  a  full-time  course 
in  Chemistry,  or  an  cidvanced    part-time 
course  in  Chemistry,    or  other  course  ap- 
proved by  the  Institute    and  the    IJonnl. 
Full-time  courses    in  Applied    Chemistry 
must  extend  over   at  least  one  year;    and 
should  include,  in  addition  to  Chemistry, 
suitable  cognate  subjects,    one  of    which 
involves  the  study  of  the    application  to 
chemical  practice  of  scientific    principles 
with  which    the    students    have    become 
familiar.      Certificates    relating   to    full- 
time  courses  in  Applied  Chemistry  will  be 
termed  "  Full-time  Course  Certificates  in 
Applied  Chemistry." 
As  a  rule,  the  whole  of  a  full-time  course 
must  be  taken  by  the  student  at  one  school, 
but  the    Institute  and  tiic  Board  may    ap- 
prove,  cxceiptionnlly,   arrangements  for    as- 
signing portions    ot  the  course  to    different 
schools. 

The  Full-time  Course  Certificates  in 
Chemistry  and  in  Applied  Chemistry  will 
record  the  subjects  constituting  the  course. 

Approval  of  Sciibmes. 
4. — Schemes  for  the  joint  approval  of  the 


Institute  and  the  Board  must  be  submitted 
in  accordance  with  the  instructions  of  para- 
graph 13.  Before  approving  a  scheme,  the 
Institute  and  the  Board  will  require  to  be 
satisfied,  for  the  puriposes  of  the  courses 
under  these  Rules,  as  to  the  equipment  of 
tile  school,  the  qualifications  of  the  staff, 
and  the  curriculum  .and  syllabuses  of  in- 
struction in  the  several  subjects. 

The  approval  of  a  school  in  respect  of 
equipment,  staffing,  etc.,  for  the  purposes 
of  the  courses  under  these  Rules  will  not 
necessarilv  imply  that  the  school  may  be 
recognised  under  the  Institute's  Regula- 
tions as  suitable  for  the  training  of  candi- 
dates for  the  examinations  for  the  Associate- 
^p  and  Fellowship  of  the  Institute;  nor 
will  recognition  of  a  school  for  grant  under 
the  Board's  Regulations  for  Technical 
Schools,  etc.,  necessarily  imply  that  the 
conditions  in  regard  to  equipment,  staffing, 
etc.,  are  such  as  the  Institute  and  the 
Board  can  accept  for  the  purposes  of  the 
award  of  national  certificates. 

5. — Steps  must  be  taken  to  secure  that 
students  are  not  admitted  to  the  courses  un- 
less they  are  qualified  to  profit  by  them. 
For  the^  present,  evidence  of  having  passed 
an  approved  preliminary  examination  prior 
to  adnfission  to  a  senior  part-time  course 
will  not  be  required.  For  students  in  an 
advanced  part-time  course  who  have  not 
completed  a  senior  part-time  course,  evi- 
dence satisfactory  to  the  Institute  and  the 
Board  as  to  the  attainment  of  the  standard 
of  the  Part-time  Course  Certificate  (Ordi- 
nary) must  be  produced.  Normally,  evi- 
dence of  having  passed  an  approved  ipre- 
liminary  examination  prior  to  admission  to 
a  full-time  course  will  be  required,  except 
for  students  who  have  completed  an  ad- 
vanced part-time  course, 

6. — The  conditions  of  a  scheme  with  re- 
spect to  home  work,  laboratory  work  and 
records,  and  examinations  (see  paragraph  7) 
prior  to  the  final  year  of  the  course,  must 
be  submitted  for  the  approval  of  the  Insti- 
tute and  the  Board. 

7. — Examinations,  including  practical 
tests  in  appropriate  subjects,  upon  the 
courses  of  study  detailed  in  the  syllabuses 
constituting  part  of  the  approved  scheme 
must  be  held  in  each  year  of  the  course. 
These  examinations  must  be  held  by  the 
t-eachers,  or  by  an  examining  body  duly  ap- 
proved for  the  purpose  by  the  Institute  and 
the  Board;  and  for  the  examination  in  the 
final  year  of  the  course  the  examiners  must 
be  associated  with  assessors  appointed  by 
the  Institute  (sec  paragraph  9). 


118 


THE  CHEMICAL  NEWS. 


AUGUST  24,  1923. 


When  a  common  examination  is  held  in 
connection  with  the  award  both  of  national 
certificates  and  of  school  or  college  certifi- 
cates or  diplomas,  it  will  be  a  condition  of 
approval  of  a  scheme  that  no  candidate 
shall  be  awarded  a  school  or  college  certifi- 
cate or  diploma  on  the  result  of  such  ex- 
amination in  any  year  in  which  he  has  failed 
to  obtain  a  national  certificate. 

Examinations. 
8. — A  memorandum  prepared  by  the  In- 
stitute and  the  Board  as  to  the  conduct  and 
supervision  of  the  final  examinations  under 
these  Rules  can  be  obtained  from  the 
Board,  and  arrangements  in  conformity 
therewith  must  be  made  by  the  school  or 
college  authorities.  The  examinations  will 
be  open  to  inspection  by  His  Majesty's  In- 
spectors. 

The  final  practical  examinations  should 
be  conducted,  so  far  as  possible,  under  such 
conditions  as  to  time  allowance  and  hbrary 
facilities  as  would  obtain  in  ordinary  chemi- 
cal practice. 

9. — To  satisfy  the  Institute  and  the 
Board  in  respect  both  of  the  standard  of  the 
questions  set  and  of  the  marking  of  the  ex- 
amination scripts,  the  Institute  \^^1  ap- 
point assessors  who  will  act  under  tke  joint 
control  of  the  Institute  and  the  Board. 

The  assessors  will  revise  the  examination 
papers  set  at  the  end  of  the  final  year  of  the 
course,  and  will  have  the  option  of  substi- 
tuting questions  up  to  40  per  cent,  of  the 
total  number  of  questions  set.  They  may 
make  any  questions  compulsory,  provided 
that  the  number  so  made  compulsory  shall 
not  exceed  about  40  per  cent,  of  the  number 
to  be  answered. 

The  marking  by  the  examiners  of  the 
scripts  worked  in  the  final  examination  will 
be  subject  to  revision  by  the  assessors,  and 
the  marks  as  accepted  or  revised  by  them 
will  be  taken  into  account  as  exjplained  be- 
low for  the  purpose  of  awarding  certificates, 
and,  in  respect  o  advanced  part-time  courses 
and  of  full-time  courses,  for  the  purpose  of 
awarding  distinctions  in  accordance  with 
the  conditions  of  paragraph  11.  The  asses- 
sors may  also  satisfy  themselves  with  re- 
gard to  the  amount  and  standard  of  the 
laboratory  work  done  by  each  student 
throughout  the  course,  as  recorded  in  the 
laboratory  notebooks  (see  paragraph  19). 

Conditions  of  Award  of  Certificates. 
10- — To  qualify  for  the    award  of  a  certi- 
ficate a  candidate  must  have :  — 

(i)  made  not  less  than  60  per  cent,    of 


the  ipossible  attendances    in  each  year  of 
the  course; 

(ii)  fulfilled  the  conditions  of  the  ap- 
proved scheme  with  respect  to  examina- 
tions, home  work,  and  laboratory  work 
and  records  in  each  year  of  the  course 
prior  to  the  final  year  ;* 

(iii)  obtained  not  less  than  40  per  cent. 
of  the  possible  marks  in  each  subject  in 
the  final  examination; 

(iv)  obtained  in  the  final  year  not  less 
than  40  per  cent,  of  the  possible  marks 
for  home  work  and  for  laboratory  work 
and  records  respectively  in  each  subject 
for  which  such  marks  are  to  be  awarded 
under  the  approved  scheme; 

(v)  obtained  in  the  final  year  not  less 
than  50  iper  cent,  of  the  grand  total  of  pos- 
sible marks.  The  possible  marks  in  the 
final  theoretical  examination  should  con- 
stitute 40  per  cent.,  and  in  the  final  prac- 
tical examination  30  per  cent,  of  this 
grand  total;  the  remaining  30  per  cent. 
should  be  the  possible  marks  for  home 
work  and  for  laboratory  work  and  records 
for  the  final  year. 

The  Institute  and  the  Board  may  require 
the  submission  of  the  school  or  college  re- 
cords of  attendance,  the  testimonies  of 
studies,  the  laboratory  notebooks,  and  the 
worked  papers  of  any  candidate  to  whom 
the  issue  of  a  certificate  is  desired. 

11. — Distinction  may  be  awarded  to  any 
candidate  qualified  to  receive  a  Part-time 
Course  Certificate  in  Chemistry  (Higher),  or 
a  Full-time  Course  Certificate  in  Chemistry, 
or  a  Full-time  Course  Certificate  in  Applied 
Chemistry,  who  gains  not  less  than  80  per 
cent,  of  the  possible  marks  in  the  final  ex- 
amination in  any  subject  of  the  final  year  of 
the  course.  Subject  to  the  previous  ap- 
proval of  the  Institute  and  the  Board,  a 
candidate  may  take  in  such  final  examina- 
tion any  branch  of  chemistry  or  of  applied 
chemistry  studied  in  an  earlier  year  of  the 
course,  but  not  in  the  final  year,  and  may 
be  awarded  distinction  in  any  branch  so 
taken,  provided  the  conditions  of  this  para- 
graph have  been  fulfilled.  The  certificate 
will  record  any  award  of  distinction. 

12. — For   tfte  present    the  Institute    and 
the  Board  may  decide  to  issue  certificates  in 


*  A  candidate  failing  to  obtain  the  ap- 
proved minimum  percentage  marks  for 
home  work,  or  for  laboratory  work  and  re- 
cords, or  for  examinations,  in  any  class  of  a 
year  prior  to  the  final  year  of  the  course 
must  be  required  to  attend  sueh  class  again. 


AUGUST  24,  1923. 


THE  CHEMICAL  NEWS. 


119 


respect  of  a  course  taken  by  students  who 
have  not  fulfilled  completely  the  prescribed 
conditions,  subject  to  the  fulfihnent  of  such 
conditions  in  regard  to  the  last  year  of  the 
course. 

Submission  of  Schemes. 
13. — Applications  for  the  joint  approval 
of  the  Institute  and  the  Board  of  new  and 
revised  schemes  must  be  submitted  by  the 
correspondent  of  the  school  or  college  in  the 
first  instance  to  the  Board,  from  wnom  the 
necessar}'  fonns  of  application  and  all  other 
forms  required  under  these  Rules  may  be 
obtained.  Applications  in  respect  of  part- 
time  courses  should  be  made  on  Farm 
285  T.  in  duplicate,  and  those  in  respect  of 
full-time  courses  on  Form  286  T.  in  tripli- 
cate, not  later  than  30th  September  in  the 
school  year  for  which  approval  is  desired. 
In  subsequent  vears,  unless  alterations  of 
an  {approved  scheme  are  proposed  by  the 
school  or  college,  or  are  required  by  the  In- 
stitute and  the  Board,  a  renewed  applica- 
tion for  approval  need  not  be  submitted. 

Duties  of  Examinations  Officers. 

14.— Ench  school  or  college  must  appoint 
an  examinations  officer  to  conduct  on  behalf 
of  the  school  or  college  the  necessary  corres- 
pondence with  the  Institute  or  with  the 
Board  in  connection  with  the  examinati(4is. 
The  name  and  address  of  this  officer  must 
be  notified  to  the  Institute  and  to  the 
Board. 

15. — The  examinations  officer  must  ad- 
vise the  Institute  on  Form  287  T.,  not  later 
than  31st  January  in  the  final  year  of  each 
course,  of  the  probable  number  of  candi- 
dates expected  to  take  the  final  examinati(Xi 
in  that  year. 

10. — Not  less  than  two  months  before  the 
date  of  the  commencement  of  the  examina- 
tions, the  examinations  officer  must  sub- 
mit to  the  Institute  for  transmission  to  the 
assessors,  draft  examination  papers  for  the 
examinations  in  the  final  years  of  the 
courses,  and  syllabuses  of  the  work  which 
will  be  cormpleted  during  the  year. 

17. — At  least  one  month  before  the  date 
of  the  commencement  of  the  examinations, 
the  examinations  officer  must  inform  the 
Institute  on  Form  288  T.  of  the  number  of 
eandidates  entered  for  the  examinations  to 
h(^  held  in  the  final  years  of  the  courses,  and 
must  fonvard  the  fees  to  the  Institute  (see 
paragraphs  21   and  22). 

18. — The  examinations  officer  will  be  re- 
sponsible for  the  conduct  and  supervision  of 


the  final  examinations  in  conformity  with 
these  Rules  and  with  the  memorandum 
mentioned  in  paragraph  8,  and  for  the  safe 
custody  of  the  examination  papers  as  re- 
vised by  the  assessors  and  of  the  worked 
examination  scripts. 

As  soon  as  possible  after  the  scripts  of  the 
examination  of  the  final  year  have  been 
marked  by  the  examiners,  the  examinations 
officer  must  forward  them  to  the  Institute, 
together  with  schedules  of  marks  on  Forms 
289  T.  and  290  T. 

These  schedules  of  marks  will  exhibit  the 
records  of  the    candidates    for  the    several 
years  of  their  courses  in  respect  of 
^i)  attendance; 

(li)  marks  for  home  work,  and  for  labora- 
tory work  and  records; 

(iii)  examination  marks. 
The  number  of  marks  awarded  in  connec- 
tion with  each  paper  set,  or  in  respect  of 
home  work  and  of  laboratory  work  and  re- 
cords, will  be  stated  on  the  schedules  in 
each  instance  as  a  percentage  of  the  maxi- 
mum marks  severally  obtainable.  Provi- 
sion will  be  made  on  the  schedule  forms  for 
any  recommendations  or  remarks  the  teach- 
ers may  wish  to  make. 

19. — If  required,  the  examinations  officer 
must  transmit  immediately  to  the  Institute, 
at  anv  time  witliin  three  months  from  the 
last  day  of  the  final  examination,  any  can- 
didate's laboratory  notebooks  for  each  year 
of  the  course,  such  notebooks  to  be  attested 
duly  by  the  teacher  of  each  subject.  Dur- 
ing the  same  period  he  must  be  prepared  to 
produce  for  the  information  of  His 
Nfajesty's  Inspector  any  such  laboratory 
imt^'books  not  in  the  custody  of  the  Insti- 
tute. In  due  course,  any  notebooks  requi- 
sitioned by  the  Institute  will  be  returned  to 
the  examinations  officer. 

20. — The  Institute  will  issue  to  the  ex- 
aminations officer  a  list  of  the  results  show- 
ing the  names  of  the  successful  candidate's 
and  any  awards  of  distinction;  and  as  soon 
as  possible  thereafter  the  certificates  will  be 
sent  to  the  examinations  officer.  The  school 
or  college  authorities  must  keep  a  register 
containing  the  names  of  the  students  of  the 
school  or  college  to  whom  certificates  have 
been  awarded.  The  Institute  and  the  Board 
will  keep  registers  of  all  certificates  awarded 
by  them  under  these  Rules. 

Fees  and  Corrkspondence  with  the 
Institute. 

21. — For  the  present    the  following  scale 
of  fees  has  been  adopted: — 


120 


tSe  chemical  KEWS. 


AUGUST  9.4,  192^. 


(i)  Part-time  Course  Certificate. — Fee 
to  be  paid  by  the  school  or  college  author- 
ities in  respect  of  each  group  of  candi- 
dates entered  for  a  final  examination  of  a 
senior  or  advanced  course  :  Guineas. 

Senior :  In  respect  of  the  first  group        5 

In  respect  of  eeich  additional  group        2^ 
Advanced :   In  respect    of    the    first 

group 5 

In  resipect  of  each  additional  group        2.^- 
Fee  to  be  paid  in  respect  of  each  can- 
didate   entering    for  a    final  ex- 
amination         7/6 

(ii  Full-time  Course  Certificate. — Fee 
to  be  paid  by  the  school  or  college  author- 
ities in  respect  of  each  group  of  candi- 
dates entered  for  a  final  examination  in 
Chemistry  or  Applied  Chemistry  : 

Guineas. 
Chemistry :     In  respect    of  the    first 

group          10 

In  respect  of  each  additional  group        5 
Applied    Chemistry :     In    respect    of 

the  first  group      10 

In  respect  of  each  additional  group        5 
Fee  to  be  paid  in  respect  of  each  can- 
didate   entering    for  a    final    ex- 
amination       15/- 

22. — All  cheques  or  postal  orders  should 
be  made  payable  to  The  Institute  of  Chem- 
istry and  crossed  Westminster  Bank,  Ltd. ; 
and  all  correspondence  with  the  Institute 
in  connection  with  any  matters  arising  out 
of  these  Rules  should  be  prepaid,  and 
should  be  addressed  to — 
The  Registrar, 

The  Institute  of  Chemistry, 
30,  Russell  Square, 
London,   W.C.I. 


BOARD  OF  TRADE  ANNOUNCEMENT. 
Dyestuffs  Advisory  Licensing  Committee. 
Applications  for  Licences  in  July. 
The  following  statement  relating  to  ap- 
plications for  licences  under  the  Dyestuffs 
(Import  Regulation)  Act,  1920,  made  dur- 
ing July,  has  been  furnished  to  the  Board 
of  Trade  by  the  Dyestuffs  Advisory  Licens- 
ing Committee. 

The  total  number  of  applications  re- 
ceived during  the  month  was  371,  of 
which  264  were  from  merchants  and  deal- 
ers. To  these  should  be  added  the  24 
cases  outstanding  on  the  1st  July,  making 
a  total  for  the  month  of  895.  These  were 
dealt  with  as  follows: — 


Granted — ^246  (of  which  227  were  dealt 
with  within  7  days  of  receipt). 

Referred  to  British  makers  of  similar 
products — 70  (of  which  66  were  dealt 
with  within  7  days  of  receipt). 

Referred  to  Reparation  supphes  avail- 
able— 50  (ail  dealt  with  within  2  days  of 
receipt). 

Outstanding  on  the  31st  July — 29. 
Of  the  total  of  395  applications  received, 
336,  or  85  per  cent.,  were  dealt  with  within 
4  days  of  receipt. 
Board  of  Trade, 

8th  August,  1923. 


LOWEST  TEMPERATURE  YET 
OBTAINED. 

The  lecture  by  Professor  Dr.  H.  Kamer- 
lingh  Onnes  on  the  Lowest  Temperature  yet 
Obtained,  which  is  given  in  the  Trans- 
actions of  the  Faraday  Society  for  Decem- 
ber, 1922,  deals  with  a  subject  of  very  great 
interest.  As  soon  as  the  efforts  to  liquefy 
helium  had  succeeded,  it  was  of  coui"se  in- 
vestigated whether  it  could  be  solidified 
also.  This  was  even  tried  on  the  same  day 
on  which  helium  had  for  the  first  time  been 
seen  as  a  liquid.  The  method  used  was 
that  of  evaporation  under  reduced  pressure. 
After  describing  the  apparatus  and  ipre- 
liminary  experiments.  Professor  Onnes 
gives  the  following  account  of  the  crucial 
experiment. 

"  Early  in  the  morning  the  preparation 
of  24  litres  of  liquid  hydrogen  was  com- 
menced, the  previous  day  having  been 
spent,  on  the  one  hand,  in  evacuating  the 
apparatus  and  further  putting  it  in  working 
order,  and,  on  the  other  hand,  in  preparing 
a  sufficient  quantity  (more  than  50  litres)  of 
liquid  air.  Meanwhile,  the  following  pre- 
parations were  carried  out :  the  helium  cir- 
culation was  further  put  in  order;  the 
pump,  which  had  to  remove  the  hydrogen 
from  the  helium  liquefier  at  reduced  pres- 
sure, was  started;  the  space  reserved  for 
the  liquid  air  used  in  cooling  the  hydrogen 
was  next  filled,  and  the  liquid  hydrogen 
space  filled,  after  having  been  first  cooled 
with  dry  cold  hydrogen  gas.  At  12  o'clock 
the  liquid  helium  could  be  syphoned  over 
into  the  cryostat,  after  which  we  proceeded 
to  cool  this  bath  further  by  evaporation  and 
refilling  by  means  of  the  helium  circulation. 
At  1  o'clock  the  condensation  of  the  helium 
into  the  evaiporation  apparatus  could  ba 
commenced,    and  the    bottom    part  of    the 


AUGUST  24,  1923. 


THE  CHEMICAL  NEWS 


121 


evaporation  glass  was  filled  up  to  some- 
what above  the  double-walled  cap  men- 
tioned earlier.  At  about  3  o'clock  this 
helium  had  evaporated  so  far  as  to  occupy 
only  the  lower  part  of  the  evaporation  flask, 
the  evaporation  taking  place  first  under  the 
action  of  the  auxiliary  pumtp  complex,  later 
on  under  that  of  the  combined  high- vacuum 
and  auxiliary  pumps,  which  serve  for  the 
removal  of  the  heUum  from  the  evaporadoa 
apparatus.  The  evaporation  was  further 
observed  alternately  with  the  naked  eye 
and  with  the  telescope  of  a  oathetometer, 
the  screens  around  the  evaporation  flask 
being  kept  shut  as  long  as  possible.  Neither 
by  means  of  the  stirrer  nor  with  the  naked 
eye  or  with  the  telesooipe  could  anything  be 
observed  that  pointed  to  the  solidification 
of  the  helium,  .even  at  the  lowest  vapour 
pressure  observed;  the  liquid  retained  its 
great  mobility  throughout." 

Professor  Onnes  sums  up  this  part  of  the 
research  as  follows:  "  Ketuming  to  the 
question  of  the  solidification  of  helium,  we 
come  to  the  following  conclusion:  as  there 
is  provisionally  no  doubt  that  helium  has  a 
maximum  density,  and  as  it  is  even  not  • 
solidified  at  a  temperature  below  the  half  of 
that  of  the  maximum  density,  we  cannot 
escape  the  question  whether  helium  will  not 
remain  perhaps  liquid,  even  if  it  is  couled  to 
Ihc  absolute  zero." 

The  result  of  the  experiments  recorded 
by  Professor  Onnes  was  the  attainment  of 
a  temperature  of  0.82  K.,  which  ho 
sums  up  as  follows:  "  Taking  into  account 
the  uncertainty  of  the  extrapolation,  it  will 
be  better  to  say  that  the  loircst  temperature 
yet  attained  is  some  hundredths  of  a  degree 
below  0.9°  K." 

"If  it  is  considered  that  our  knowledge  of 
atomic  structure  renders  improbable  that 
another  substance  could  l)e  discovered  or 
obtained  in  another  way,  more  volatile  than 
helium,  then  the  limit  indicated  would 
seem  an  absolute  one  set  to  us  in  the  obtain- 
ing of  yet  lower  temperatures. 

We  cannot  accept  such  a  limit  otherwise 
than  as  a  provisional  one.  There  are  even 
now  definite  problems  which  require  to  be 
treated  in  the  domain  beyond  the  seemingly 
impenetrable  barrier.  A  simple  example  is 
the  question  whether  a  metal  such  as  gold 
can  be  made  super-conductive  by  cooling  it 
more  than  wo  have  been  able  to  do.  This 
kind  of  probim  reminds  us  f>f  the  problem  of 
the  liquefying  of  the  permanent  gases. 
They  withstood  the  efforts  of  the  great  ex- 
perimenter whose  glorious  name  it  attached 


to  your  Society.  Half  a  century  later,  the 
liquefaction  of  hydrogen,  the  most  incoer- 
cible  gas  with  which  Faraday  had  operated, 
was  the  brilliant  achievement  of  the  latest 
of  his  successors  in  office  at  the  Royal  In- 
stitution :  Sir  James  Dewar.  We  may  feel 
sure  that  the  difficulty  which  has  now 
arisen  in  our  way  will  be  overcome  also, 
and  that  the  first  thing  needed  is  long  and 
patient  investigation  of  the  properties  of 
matter  at  the '  lowest  temjperature  we  can 
reach." 

"  The  Vacuum- Spark  Spectrum  of  Sili- 
con," by  R.  A.  Sawyer  and  R.  F.  Paton. — 
(Astrophysical  Journal,  June,  1923.) 

The  most  recent  work  on  the  spectrum  of 
silicon  was  done  by  Sir  William  Crookes  in 
1914.  He  succeeded  in  obtaining  some 
rather  pure  samples  of  silicon,  and  using  a 
condensed  spark  between  electrodes  of  this 
silicon,  photographed  the  spectrum  with  a 
prism  sipectrograph.  The  rapid  oxidation 
of  the  silicon  made  it  very  difficult  to  main- 
tain the  spark,  and  necessitated  long  ex- 
posures. His  work  covered  the  region  A. 
6500  to  A  2100,  and  he  published  the  wave- 
lengths of  43  lines,  including  most  of  the 
lines  previously  recorded.  This  investiga- 
tion was  the  most  thorough  work  that  had 
been  done  on  silicon  up  to  that  time.  Since 
the  work  of  Crookes,  Fowler  has  mentioned 
observing  four  lines  in  the  visible  region  of 
the  spectrum,  not  previously  observed;  and 
McJiCnnan  has  extended  the  investigation 
into  the  extreme  ultra-violet,  cataloguing 
•<ome  seventeen  additional  lines. 

A  comparison  of  the  results  of  all  the 
work  that  has  been  done  on  silicon  brings 
>ut  the  fact  that  no  two  observers  have  the 
same  list  of  lines,  and  also  shows  that,  even 
in  the  lines  that  have  been  recorded  by 
several  observers,  the  disagreement  in 
wave-length  seems  almost  unaccountably 
large.      This  disagreement    may  be    partly 

i  accounted  for,  however,  by  the  fact  that 
many  of  the  silicon  lines  are  esipecially 
broad  and  hazy  when  produced  at  atmos- 
pheric pressure. 

With  the  discovery  of  the  vacuum-spark, 
a  new  source  of  light  became  available  that 
seemed  to  have  particular  advantages  in 
this  problem.  The  use  of  the  vacuum- 
spark  in  extending  the  spectrum  into  the 
extreme  ultra-violet,  had  given  results 
which  led  to  the  expectation  that  it  might 
give  new  information  in  the  rest  of  the  spec- 
trum. With  this  in  mind,  it  was  decided  to 
photograph  the    vacuum-spark  of  silicon  in 


i 


r 


122 


THE  CHEMICAL  NEWS. 


AUGUST  24,  192B. 


the  region  covered  by  Crookes,  hoping  that 
the  results  might  give  more  accurate  mfor- 
mation  concerning  the  wave-lengths  of 
some  of  the  lines,  and  even  add  to  the  al- 
ready known  list.  In  adapting  the  vacuum- 
spark  to  silicon,  it  was  found  necessary  to 
use  high  voltage  and  extremely  good  vacua ; 
but  once  obtained,  the  spark  was  brilliant, 
of  a  reddish  yellow  colour,  and  resembled 
the  vacuum-spark  of  carbon. 

A  description  of  the  apparatus  used  and 
tables  of  the  observed  lines  are  then  given, 
of  which  the  following  is  the  author's  ab- 
stract: — 

Vacuum-spark  spectrum  of  silicon  A  6700 
—  A  2100.  Silicon  electrodes  less  than  a 
millimeter  apart  were  mounted  in  a  suit- 
ably designed  brass  box  with  a  quartz  win- 
dow, the  best  obtainable  vacuum  was  pro- 
duced, and  a  highly  condensed  spark  was 
obtained  by  the  use  of  70,000  volts.  Lines 
of  iron,  aluminum,  calcium  and  oxygen  and 
the  strongest  lines  of  hydr<:^en,  nitrogen, 
copper,  zinc  and  titanium  appeared  as  im- 
purities. The  wave-lengths  of  227  lines  at- 
tributed to  silicon  in  the  region  A  6700 — A 
2100,  together  with  the  measurements  of 
other  observers,  are  given  in  Table  1.  An 
additional  75  lines,  listed  in  Table  2,  are 
given  as  doubtful,  since  they  were  faint 
lines  appearing  on  only  one  plate.  In  the 
intervals,  A  6700— A  5500  and  A  4070— 
A  5500— A  4070  and  A  3400— A  2100  to 
A  3400,  the  wave-lengths  are  believed  to  be 
accurate  to  within  0.2A,  and  in  the  intervals 
within  0.1  A. 


X-RAY  PROTECTIVE  MATERIALS. 

By  G.  W.  C.  Kaye,    O.B.E.,  M.A.,  D.Sc, 

AND  E.  A.  Owen,  M.A.,  B.Sc,  The 

National  Physical  Laboratory. 

(From  a  Paper  read  at  a  Joint  Meeting  of 

the  Physical  Society  of  London  and 

Rontgen  Society.) 

The  steady  addition  to  the  already 
lengthy  list  of  casualties  to  hospital  and 
other  X-ray  workers  led  to  the  formation 
nearly  two  years  ago  of  an  X-ray  and 
Radium  Protection  Committee  (under  the 
chairmanship  of  Sir  Humphry  Rolleston), 
which  drew  up  a  series  of  recommendations 
for  the  better  iprotection  and  general  im- 
provement of  the  working  conditions  of  the 
X-ray    operator.       These    recommendations 


have  resulted  in  a  large  number  of  X-ray 
protective  materials  being  submitted  for 
test  to  the  National  Physical  Laboratory, 
which  from  the  outset  agreed  to  work  in 
co-operation  with  the  Committee,  and  has 
inspected  the  X-ray  departments  of  many 
hospitals  from  the  point  of  view  of  the 
Committee's  recommendations. 

It  is  well  known  that  the  absorption  of  an 
atom  is  greatest  for  those  X-rays  which 
have  wave-lengths  slightly  shorter  than  one 
or  other  of  its  characteristic  radiations,  and 
partly  with  this  in  mind  it  was  thought  that 
it  would  be  of  value  to  ascertain  the  protec- 
tive efficiencies  of  the  various  materials 
which  are  commercially  available  for  the 
purpose  of  affording  protection  to  the  radio- 
logist. Among  these  are  sheet  lead,  lead 
impregnated  rubber,  lead  glass,  and  various 
wall  compositions  such  as  barium-sulphate 
plasters,  &c.  The  choice  of  one  or  other  is 
normally  dictated  by  considerations  such  as 
dielectric  strength,  portability,  electrical 
and  thermal  conductivity,  and  not  least  by 
price. 

Protection  may  be  afforded  in  a  variety 
of  ways  in  practice.  For  example,  by 
mounting  the  tube  in  a  surrounding  tube 
box  suitably  designed  to  permit  the  free- 
dom of  movecent  desired,  or  w^here  this  is 
impracticable  the  operator  and  his  controls 
are  situated  behind  a  screen  or  wall  which 
is  constructed  to  give  the  necessary  iprotec- 
tion. Less  frequently  and  conveniently 
the  operator  is  "armoured"  and  wears  pro- 
tective aprons,  gloves,  face  mask  or  goggles. 

To  the  inexperienced  the  practice  of 
speaking  of  percentage  absorption  may  be 
misleading  and  calculated  to  give  a  wrong 
impression  of  the  value  of  a  protective 
material.  It  is  not  always  realised  how 
rapid  the  rate  of  absoription  is  with  thin 
layers,  and  how  slow  with  thicker  layers. 
For  example,  in  the  case  of  tungsten  X-rays 
generated  at  120,000  volts,  a  sheet  of  lead 
only  0.1  mm.  thick  absorbs  as  much  as  80 
per  cent,  of  the  radiation,  whereas  a  sheet 
2  mm.  thick  only  increases  this  figure  to 
99.4  per  cent. 

For  simplicity,  therefore,  the  Protection 
Committee  recommended  that  the  protec- 
tion afforded  by  a  material  should  always  be 
referred  to  in  terms  of  the  equivalent  thick- 
ness of  lead.  This  use  of  lead  as  a  stand- 
ard of  reference,  while  not  wholly  free  from 
objection,  is  very  convenient  for  the  ap- 
proximate accuracy  which  suffices  in  prac- 
tice, especially  in  deahng  with  composite  or 
laminated  materials    as  the  lead  vaiucs    of 


AUGUST  24.  1923. 


THE  CHEMICAL  NEWS. 


123 


the  several  layers  can  be  regarded  as  addi- 
tive.* The  Committee  laid  down  certain 
thicknesses  of  lead  which  it  regarded  as  the 
minima  which  should  be  employed  under 
specified  conditions;    and,    in  view  of    the 

Material, 
Lead  llubber — (60  different  samples)  .. 
Lead  Glase — (40  different  samples)  ...  . 


Metab — 
Aluminium 
Brass 
Steel 


very  unsatisfactory  conditions  which  pre- 
vail in  the  majority  of  X-ray  installations  in 
this  oountrj',  we  have  been  led  to  put  on  re- 
cord some  of  our  measurements  in  this 
connection. 


Density. 
3.7  to  6.5 
3.2  to  4.1 


2.7 
8.4 
7.8 


Lead  Equivalent. 
0.25  to  0.45 
0.12  to  0.20 


0.011 

0.25 

0.15 


Miscellaneous — 

Water  

60  per  cent,  red  lead,  50  per  cent,  litharge 
Ordinary  rubber  


1.2  to  1.7 


0.004 
0.3 
0.02  to  0.05 


Concrete — 
4    stone    chippings, 

cement  

4  clinker,  1  cement  . 
4  granite,  1  cement 
Roman  mortar 
20  chalk,  1  cement  . 

6  sand,  1  lime  

Coke  breeze       


2    washed    sand,     1 


2.1 
1.5 
2.1 
1.6 
1.6 
1.8 
1.0 


0.012 
0.010 
0.013 
0.009 
0.011 
0.009 
0.004 


Bricks — 
Fletton  brick  (rod)  .. 
Stock  brick  (yellow) 
Diatomaocous  brick 


1.6 
1.4 
0.6 


0.010 
0.006 
0.003 


Protective  Wall  Plasters- 

(1)  56  p.c.  Native  Ba  Co^,  40  ip.c.  Ga  So^  2.0 

(2)  33  p.c.  Ba  So^,  33  p.c.  sand,  38  p.c. 

cement  1.5 

(3)  33  p.c.  coarse    Ba  So^,    88  p.c.    fine 

Ba  bo^,  33  p.c.  cement*  2.8 

Woods — 

Ash         0.73 

Balsa  0.096 

Bass  0.48 

Fir         0.52 

Mahogany  0.49  to  0.68 

Oak  ; 0.65 

White  Pine        0.-17 

Pitch  Pino       0.53  to  0.56 

Spruce  0.41  to  0.43 

Teak  0.58  to  0.76 

Walnut  0.64 

*  Mixture  suggested  by  Mr.  P.  J.  Neate. 


0.001 
0.048 
0.12 


0.0013 

0.0001 

0.0005 

0.0008 
0.0006  to  0.0011 

0.0008 

0.0006 

0.0008 
0.0004  to  0.0006 
0.0006  to  0.0011 

0.0008 


124 


THE  CHEMICAL  NEWS. 


AUGUST  24,  1923. 


Incidentally,  sheet  lead  is  commercially 
described  and  sold  by  its  weight  per  super- 
ficial foot,  "21b.  lead"  referring  to  sheet 
lead  weighing  21b.  per  sq.  foot.  In  this  con- 
nection the  following  table  may  be  useful : 


Weight. 

2  lb.   lead 

3 

4 

5 

6 

7 

8 

9 
10 
11 
12 


Thickness. 

0.8     mm. 

1.25 

1.7 

2.15 

2.6 

3.05 

3.5 

3.95 

4.3 

4.75 

5.2 


There  is  some  tendency  at  the  present 
time  to  employ  baryta  and  other  plasters  in 
heu  of  lead.  We  give  the  lead  equivalents 
of  three  of  these  plasters.  It  may  be  re- 
marked, to  take  the  case  of  mixture  No.  2, 
that  60  mm.  (nearly  2^  inches)  thickness 
will  be  required  to  give  the  protection  of  3 
mm.  of  lead,  and  that  the  weight  of  the 
plaster  is  nearly  three  times  that  of  the 
lead.  These  figures  would  be  more  favour- 
able for  plaster  No.  3.  We  have  no  knoM- 
ledge  of  the  costs  of  these  plasters  as  com- 
pared with  lead,  nor  of  the  cost  of  the 
labour  involved  in  erection. 

Certain  plasters  have  been  devised  con- 
taining iron  turnings.  They  possess  no  spe- 
cial merit  as  regards  absoiiption,  and  the 
tendency  to  rust  is  a  disadvantage. 

Tube  Boxes. 

Protective  tube  boxes,  if  constructed  of 
lead,  have  to  be  of  dimensions  sufficiently 
generous  to  prevent  sparking  between  the 
bulb  and  the  box.  If,  however,  the  tube  box 
is  required  to  be  in  close  proximity  to  the 
bulb,  the  former  commonly  takes  the  form 
of  a  lead  glass  bowl,  or,  alternatively,  a 
wooden  box  with  several  layers  of  lead- 
rubber  lining  or  wrapping.  The  open  glass 
bowl  is  open  to  grave  criticism :  it  is  con- 
structed of  lead  glass,  usually  affording,  as 
our  measurements  show,  a  total  protection 
of  from  0.5  to  0.7  mm.  lead;  but  in  many 
directions,  owing  to  its  design,  it  affords  no 
protection  whatever.  In  our  experience, 
where  this  type  of  chield  is  alone  emiployed, 
it  is  often  possible  to  take  a  radiograph  of 
the  hand  in  any  part  of  a  room  where  a 
tube  is  working.     The  bowl    should  be  pro- 


vided with  some  kind  of  cover  and  the 
material  increased  in  effectiveness. 

The  type  of  double  hemispherical  shield 
supplied  for  radiator  Coolidge  tubes  is  much 
better,  in  that  it  completely  encloses  the 
tube.  The  different  shields  (whether  tinted 
blue  or  yellow)  which  we  have  tested,  have 
a  lead  equivalent  of  about  0.2,  the  total 
protection  provided  ranging  between  1.2 
and  1.5  mm.  lead.  The  Protection  Com- 
mittee recommends  not  less  than  2  mni.  for 
exciting  voltages  below  100,000.  We  refer 
again  to  the  question  of  lead  glass  in  con- 
nection with  protective  windows,  etc. 

Different  makes  of  lead  rubber  differ  in 
protective  value  by  100  per  cent.,  and  the 
importance  of  this  fact  should  be  stressed. 
Care  should  be  taken  that  the  lead  rubber 
is  not  cut  away  locally  when  the  box  is 
being  constructed. 

The  choice  of  lead  rubber  or  lead  glass  in 
preference  to  lead  sheet  is  usually  dictated 
by  the  fact  that  the  former  are  electrical  in- 
sulators, at  any  rate  to  a  limited  extent. 
The  resistivity  of  lead  rubber  is  usually  of 
the  order  of  several  thousand  megohm  cen- 
timetres. The  insulating  value  may  be 
greatly  improved  by  including  a  layer  of 
micanite,  ordinary  rubber,  or  other  suitable 
insulator  among  the  layers  of  lead  rubber. 

Measurements  of  the  dielectric  strength 
have  been  made  in  the  Electrical  Depart- 
ment of  the  Laboratory  on  a  considerable 
number  of  samples.  Two  circular  electrodes 
1^  in.  in  diameter  with  rounded  edges  were 
placed  in  contact  with  opposite  sides  of  the 
material,  an  alternating  potential  of  ap- 
proximately sine  wave  form  being  applied 
and  stea/dily  increased  from  zero  until  the 
material  punctured.  For  good  specimens  of 
lead  rubber  the  breakdown  voltage  was 
about  5,000  to  12,000  E.M.S.  volts  per  mil- 
limetre thickness.  In  other  cases  the 
values  were  a  good  deal  less,  and  on  occa- 
sion the  material  acted  as  a  conductor.  For 
lead  glass  the  values  ranged  from  about 
5,000  to  9,000  E.M.S.  volts  per  millimetre. 

One  other  point  may  be  referred  to.  In 
a  prolonged  run,  especially  with  a  Coolidge 
tube  ,a  great  deal  of  heat  has  to  be  got  rid 
of,  and  it  is  usually  advisable  to  provide  for 
ventilation  of  the  tube  box ;  in  that  event 
the  openings  should  be  properly  safeguarded 
from  a  protection  standpoint.  A  knowledge 
of  the  thermal  conductivity  of  the  several 
protective  materials  may  be  useful  in  this 
connection.  Measurements  at  the  Labora- 
tory show  that    the  values    of  the    thermal 


AUGUST  24,  1923. 


THE  CHEMICAL  NEWS. 


125 


conductivity  at  room    temperature    are    as 
follows  in  c.g.s.  Centigrade  units:  — 

Woods     (various)  About  0.0003 

Ordinary      rubber       ,,      0.0008  to  0.0011* 

Lead  rubber      0.0003  to  0.0007 

Lead  glass       ,,      0.002 

Lead  ,,      0.08 

*  Depending  on  the  mineral  content. 

If  considerations  of  weight  Eire  of  first  im- 
portance, then  lead  sheet  is  almost  always 
the  lightest  among  the  protective  materials 
commonly  employed  for  tube  boxes.  For 
example,  the  protective  values  of  lead  nib- 
ber  range  between  about  0.25  and  0.55,  and 
the  densities  between  about  3.7  and  6.5.  On 
the  average,  lead  rubber  is  about  10  per 
cent  heavier  than  sheet  lead,  affording  tho 
same;  protection,  though  it  may  be  as  much 
as  25  per  cent,  and  as  little  as  5  per  cent. 

Similarly  with  lead  glass  the  protective 
values  commonly  lie  between  0.12  and  0.20, 
and  the  densities  between  3.2  and  4.1.  On 
the  average,  lead  glass  is  about  twice  as 
heavy  as  sheet  lead,  affording  the  same 
protection,  the  figures  ranging  frcwn  about 
1.75  to  2.5. 

These  results  (as  with  those  for  the 
screen  materials)  are,  of  course,  predictable, 
iiH  it  is  known  that  a  heavy  atom  is  ordi- 
narily much  more  absorbent  than  a  light. 
For  the  same  reason,  in  the  case  of  two 
composite  materials,  each  containing  a  mix- 
ture of  atoms  and  having  tho  same  density, 
the  one  containing  a  higher  proportion  of 
heavy  atoms  will  usually  have  a  higher  ab- 
sorption factor.  With  lead  rubber  the  lack 
of  proportionality  between  density  and  lead 
value  is  sometimes  pronounced,  and  of  two 
samples  tho  one  with  the  lower  density  may 
have  the  higher  lead  equivalent. 

Diaphragms  of  the  iris  type  are  oft<>n 
fitted  to  tube  boxes.  The  leaves  are  usually 
much  too  transparent.  They  should  pro- 
vide protection  equal  to  not  less  than  3 
mm.  of  lead,  and  the  simpler  rectangular 
diaphragm  with  two  motions  is  a  mor  • 
practical  job. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


IRON  AND  STEEL  INSTITUTE. 
Milan  Meeting,  September  17  A  18,  1923. 
In  accordance    with  previous    announce- 
ments, the  Autumn  Meeting  of  the  Iron  and 


Steel  Institute  will  be  held  at  the  Chaipbor 
of  Commerce,  Milan  (via  Mercanti  2-4),  on 
Monday  and  Tuesday,  September  17  and 
18,  commencing  at  9.30  a.m.  on  each  day. 

At  the  conclusion  of  the  meeting  visits 
have  been  arranged  to  Florence,  Rome, 
Piombino,  Leghorn,  Genoa  and  Turin. 

The  following  is  the  list  of  papers  which 
it  is  expected  will  be  submitted  to  the 
meeting : 

C.  R.  Austin,  Alloys  in  the  Ternary  Sys- 
tem Iron-Chromium-Carbon. 

E.  D.  Campbell,  W.  L.  Fink,  and  J.  F. 
Ross,  The  Iron-Iron  Carbide  Equilibrium  in 
Dry  Hydrogen  at  950°  C. 

E.  D.  Campbell,  J.  F.  Ross,  and  W.  L. 
Fink,  The  relative  efficiency  of  Dry  and  of 
Moini  Hydrogen  on  the  Decarburisation  of 
Steel  at  950°  C,  and  the  effect  of  Hydrogen 
on  the  Phosphorus  Content. 

C.  A.  Edwards  and  L.  B.  Pfeil,  A  Note 
on  Coarse  Corrugation  in  Mild  Steel  Sheets 

G.  E.  Falck,  The  Iron  and  Steel  Industry 
of  Italy. 

F.  Giolliti,  The  Complex  Action  of  Man- 
ganese and  of  other  so-called  Deoxidising 
.igcnts  in  the  Manufacture  of  Steel. 

W.  T.  Griffiths,  The  Change  Points  in 
some  Nickel-Chromium  Steels. 

W.  H.  Hatfield,  The  Influence  of  Nickel 
and  Chromium  upon  the  Sohibility  of  Steel 
{in  relation  to  Corrosion). 

Cesare  Martblli  and  Tito  Sotgia,  The 
Iron  Ore  Mines  of  Nurra  (Sardinia). 

A.  PoRTEVix,  The  Morphology  of  Pro- 
I'utcctoid  Cementite. 

A.  PoRTEViN,  The  Corrosion  Cracking  hf 
Steel  under  the  Influence  of  Internal 
Stresses. 

S.  H.  Rees,  The  effect  of  Low  Tempera- 
ture Annealing  on  some  Mechanical  Proper- 
ties of  Cold  Drawn  Steels. 

H.  Styri,  Theory  and  Practice  of  Steel 
I  defining. 

C.  Vanzetti,  The  Manufacture  of  Heavy 
s'/rc/  Castings  from  Small  Converters. 

H.  C.  Wang,  Qrain  Growth  in  Iron  and 
SIccl. 

28    Victoria  Street,  London,  S.W.I. 
August  13,  1023. 


THE  CHEMICAL  SOCIETY. 
It  has  been  decided  to  separate  the 
Transactions  and  the  Abstracts,  and  from 
January,  1924,  these  will  aippear  monthly 
as  distinct  volumes.  A  new  feature  in  the 
Transaotions  will  bo  the  inclusion  from  time 


126 


THE  CHEMICAL  NEWS. 


AUGUST  24,  1923. 


to  time  of  "Notes"  dealing  with,  for  ex- 
ample, improved  methods  of  preparation, 
modification  of  standard  apparatus,  and 
other  matters  requiring  only  brief  notice. 


"  THE    CHEMIST  IN  RELATION  TO 

THE  SAFEGUARDING  OF 

INDUSTRIES." 

This,  the  last  of  my  headings,  has  refer- 
ence to  two  recent  Acts  of  Parliament, 
which  you  will  all  know  something  about, 
namely,  the  Dye-Sstufifs  Import  Regula- 
tions Act  of  1920,  and  the  Safeguarding  of 
Industries  Act  of  1921.  The  former  pro- 
hibits the  importation  into  this  country  of 
synthetic  organic  dyestuffs,  etc.,  except 
under  licence  from  the  Board  of  Trade.  Of 
course,  all  that  is  to  the  good  so  far  as  the 
protection  of  the  home  chemist  is  con- 
cerned. I  think  the  Safeguarding  of  Indus- 
tries Act  also  will  be  found,  in  the  long  run, 
to  be  for  the  benefit  of  the  chemist  rather 
than  otherwise.  That  Act  imposes  a  duty 
of  one-third  the  value  of  the  goods  upon 
certain  enumerated  articles,  among  which 
are  found  nearly  all  the  mechanical  appara- 
tus of  the  chemist,  and,  in  addition,  ipracti- 
cally  all  the  raw  material  which  the  chemist 
uses  in  his  researches.  At  first  sight  it 
might  be  thought  a  little  against  the  inter- 
est of  the  chemist  that  he  should  have  to 
pay  more  for  his  raw  materials  and  for  his 
apparatus,  by  reason  of  these  high  import 
duties,  because,  I  suppose,  there  are  many 
of  these  things  which,  even  now,  can  only 
be  obtained  from  abroad;  but  in  the  long 
run  it  must  be  to  the  benefit  of  the  chemist 
and  the  Empire  that  the  production  of  all 
these  things  at  home  should  be  promoted. 
When  the  crisis  came  in  1914  we  had  not 
got,  and  had  not  the  facilities  for  producing, 
many  essential  substances  and  apparatus. 
If  we  can  make  these  things  at  home,  then 
not  only  will  there  be  increased  employ- 
ment of  chemists,  but  when  we  come  to 
another  crisis  we  shall  be  better  provided  in 
that  respect  than  we  were  then.  I  think 
the  provisions  of  this  Act  will  help  to  bring 
that  about. — (From  the  Lecture  recently 
delivered  before  the  Institute  of  Chemistry, 
by  Evan  Jam.es  MacGillwray.) 


A  SENSITIVE  ELECTROSCOPE. 
By  Takeo  Shimizu. 
(Jap.  J.  Phys.,  I.  (1922),  107-111,  with  2 

fig.) 

The  electroscope  described  in  this  paiper 


is  a  modification  of  that  of  Mr.  C.  T.  R. 
Wilson.  It  consists  of  a  fine  silvered  glass 
fibre  suspended  freely  at  the  centre  and  four 
metallic  plates,  two  largo  and  two  small, 
placed  symmetrically  on  both  sides  of  it. 
The  larger  ones  are  about  as  long  as  the 
fibre  and  stand  vertically  facing  each  other 
on  each  side.  The  smaller  ones  stand  also 
vertically  but  below  the  locus  of  the  lower 
end  of  the  fibre  at  some  distance  from  each 
other  and  situated  between  the  fibre  and 
the  respective  larger  plates.  The  two  plates 
on  either  side  forin  a  single  electric  system 
and  the  two  systems  are  kept  at  the  same 
potential,  while  the  fibre  is  charged  to  a 
high  auxiliary  voltage.  When  the  electro- 
scope is  to  be  used,  one  of  the  systems  is 
isolated  and  connected  to  the  object.  The 
two  inner  smaller  plates  play  the  part  of  a 
stabilizer  and  a  comparatively  high  sensi- 
bility can  be  obtained  in  virtue  of  their  pre- 
sence. In  favourable  cases  a  sensibility 
of  about  5,000  scale  divisions  per  volt  was 
obtained,  although  such  a  sensibility  may 
not  be  suited  to  the  deflection  method,  ow- 
ing to  various  difficulties.  But  as  the  in- 
strument keeps  a  very  constant  zero  posi- 
tion by  its  design,  it  may  be  employed  as  a 
sensitive  zero  indicator. 


ON  THE  STRUCTURE  OF  THE 
SECOND  CYANOGEN  BAND. 

By  Junzo  Okubo. 

(Sci.  Dep.  Tohoku  Imp.  Univ.,  8er.  I., 
XI.  (1922),  55-86,  with  1  pi.) 

The  second  cyanogen  band  having  the 
first  head  at  A  4216  A  emitted  by  the  ordi- 
dinary  carbon  arc  in  air  was  examined.  The 
instrument  used  in  this  experiment  was  a 
concave  grating  of  a  radius  of  curvature  6.55 
m.  with  5,910  lines  per  cm.  and  77,273  lines 
in  all.  Acheson  regraiphited  carbon  rods 
were  used.  The  wave  lengths  of  1,555  lines 
lying  between  XX  4216  and  3900  A  were 
accurately  determined  in  the  international 
unit.  The  second  band  contains  many 
doublets,  some  of  which  have  been  de- 
scribed as  singlets  by  many  previous  inves- 
tigators. Tlu'ee  remarkable  series  were 
traced,  and  their  insensity  distributions  de- 
scribed. The  wave  lengths  of  the  heads  of 
four  bands  produced  by  cyanogen  were 
measured,  and  it  is  shown  that  there  exist 
some  simple  relations  among  the  wave 
numbers  of  consecutive  heads. 


AUGUST  24,  1923. 


THE  CHEMICAL  NEWS. 


127 


ON  THE  BAND  SPECTRUM  ASSO- 
CIATED WITH  HELIUM. 
By  Yutaka  Takahashi. 

[Froc.  Phys.-Math.  Soc.  Japan,  Ser.  III.. 
iV.  (1<.»2-J),  187-194). 

In  order  to  exiplain  the  origin  of  Fowler's 
•  ries  of  double  headed  bands  of  helium, 
the  author  assumes  that  when  a  discharge 
is  passing  through  a  helium  tube  there  are 
produced  some  short  living,  unstable  mole- 
cules, each  consisting  of  two  positive  nu- 
clei, which  are  liable  to  vibrate  along  the 
line  joining  them  and  to  rotate  as  a  whole 
about  the  middle  point  of  the  line,  and  elec- 
trons, one  of  which  is  removed  from  its 
stable  orbit  to  another  r>f  a  higher  quantum 
number.  By  applying  thi-  quantum  theory 
to  this  model,  it  is  shown  that  the  frequency 
V  of  the  radiation  is  of  the  form : 
v  =  A{m^,  n^,  m\,  n\)-A{m^,  n,,  m'„  n',), 
where  m  and  n  are  the  radial  and  aaimu- 
thal  quantum  numbers  respectively  due  to 
the  electron,  and  m'  and  n'  are  respectively 
those  due  to  the  nuclei.  Different  values 
of  n'  o<»Te6pond  to  the  individual  lines  of 
each  band,  and  different  values  of  m'  give 
rise  to  the  series  of  the  bandfi,  which  actu- 
ally appear  as  double  headed  bands  as  m'  is 
limited  to  zero  and  1  owing  to  the  instability 
of  the  molecule.  Two  different  o<mibina- 
tions  of  m  and  n  such  as 
m,  =  l+«,  nj=2,  m,  =  l.  fK  =  l,  a    0    I  _' 

and 

m,  =  «,       n,=8,  m,  =  0,  n,  =  2,  «    0,1,2... 

are  re8(>onfiible    for  the    two  series   of    the 
double  headed  bands  detected  by  Fowler. 


ON  THE  LANTHANUM  VIOLET  BANDS 
AND  THE  ASSOCIATED  LINES. 

By  Junzo  Okubo. 

(8oi.  Rep.  T6hoku  Imp.  Univ.,  Ser.  I.. 
XI.  (1922),  95-104,  with  1  fig.) 

The  structures  of  the  band  epectniiu 
emitted  from  lanthanum  nitrate  put  into  a 
carbon  arc  were  studied  with  a  large  con- 
cave grating.  The  wave  lengths  of  the 
edges  of  the  bands,  some  of  which  had  been 
missed  by  previous  investigators,  were  de- 
termined in  the  new  international  unit,  and 
the  opinion  was  oonfiniud  that  each  band 
is  of  double  structure.  In  the  light  of  the 
quantum  theory,  the  bands  may  be  ex- 
plained as  due  to  molecular  rotations  caused 
by  line  emissions. 


BRITISH    STANDARDISED  STEEL 

SAMPLES  ISSUED    JOIN'^'LY  BY  THE 

IRON  AND  STEEL  INSTITUTE  AND 

THE  N ATONAL  PHYSICAL 

LABORATORY. 

The  Standards  at  present  available  are : 

No.  1.— Sulphur  (S.  =0.027  p.c). 

No.  2.— Sulphur  (S.  =0.071  p.c). 

No.  3.— Phosphorus  (P.  =0.029  p.c). 

No.  5.— Carbon  (C.=0.65  p.c.)  Acid 
O— H  Steel. 

No.  6.— Carbon  (C.=0.10  p.c.)  Basic 
O— H  Steel. 

These  Samples  are  supplied,  post  free,  at 
2l8.  pt»r  bottle  containing  50  grammes,  to- 
gether with  certificate  of  Standardisation. 
They  can  be  obtained,  by  sending  order 
with  remittance,  direct  from:  — 

The  National  Physical  Laboratory, 
(Metallurgy  Dept.),  Teddingtoo, 
Middlesex ; 
or  by  post  or  personal  application  from :  — 

Dr.  C.  H.  Desch,  Dept.  of  Applied 
Science,  The  University,   Sheffield. 

Dr.  C.  A.  Edwards,  The  University  Col- 
lege,  Swansea. 

Col.  E.  L.  Johnson.  Cleveland  Technical 
Institute,  Middlesbrough. 

Mr.  D.  A.  MacCallum,  West  of  Scotland 
Iron  &  Steel  Institute,  93,  Hope  Street, 
Glasffow. 

Other  Samples  are  in  preparation  and 
will  be  issued  when  ready. 

These  samples  can  also  be  obtained  from 
all  Chemists  dealing  regularly  in  laboratory 
ware. 


NOTICES  OF  BOOKS. 

The  July  number  of  the  Bulletin  of  the 
Bureau  of  Bio-technology  contains  the  fol- 
lowing paf)ers:  — 

The  Oceurrencc  and  Effects  of  Wood- 
dcfttroying  Fungi  in  Coal  Mines. 

The  Examination  of  Bacteria  in  Beer  De- 
posits. 

Water  Softening  for  Spraying  Purposes. 

The  Suppression  of  Insect  Pests  and  Fun- 
goid Diseases. 

The  numbej"  also  contains  an  Index  for 
Vol.  1.  A  copy  of  this  Index  may  be  had 
on  application  to  Messrs.  Murphy  &  Son, 
Ltd.,  Cedars  Laboratories,  Sheen  Lane, 
Mortlake,  London,  S.W.14. 


The    Paper- makers'     Dirrriory    of    all 
Nations,  j)ublished  by  Dean  A  Sons,  Ltd., 


128 


THE  CHEMICAL  NEWS. 


AUGUST  24,  1923. 


27,  King  Street,    Covent    Garden,    price 
21s.,    will  be  found  of  value  to  those  in- 
terested in  paper  and  the  allied  trades. 
The  subject  matter  is  arranged  in  alpha- 
betical order  for    easy  reference,    and  con- 
tains a  large  number  of  trade  headings  and 
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tuses. 

The  work  has  been  produced  with  the 
usual  thoiroughnes&  and  care,  and  cannot 
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trade. 


Practical  Bacteriology  for  Chemical 
Students,  by  David  Ellis.  Longmans, 
Green  &  Co.,  39,  Paternoster  Kow.  Price 
4s.  6d.  net. 

This  valuable  little  book  consists  hi--'i\j 
of  exercises  which  are  followed  in  tiis 
author's  classes  in  the  University  of  Glav 
gow,  and  in  the  preface  it  is  pointed  out 
that  there  are  many  avenues  in  chemical 
research  that  are  closed  to  the  investigator 
owing  to  lack  of  knowledge  of  the  element- 
ary princiiples  of  bacteriology.  The  object 
of  the  book  is  to  give  to  the  trained  chemist 
sufficient  guidance  to  enable  him  to  master 
the  general  principles  of  the  subject.  The 
exercises  are  so  arranged  that  they  can 
easily  be  followed  by  any  who  desire  a 
grounding  in  the  general  principles  of  bac- 
teriology. 

The  book  opens  with  a  chapter  devoted 
to  descriptions  of  the  apparatus  used  in 
bacteriological  research,  and  it  is  very 
thoroughly  illustrated  with  both  drawings 
and  diagrams.  In  chapter  2  the  exercises 
commence  with  the  preparation  of  nutrient 
gelatine  and  agar-agar.  Chapters  are  givm 
on  the  staining  of  bacteria,  identification 
and  staining  of  spores,  isolation  of  bacteria 
from  soils,  examination  of  drinking  water 
and  sewage,  and  many  details  connected 
with  practical  bacteriology. 

The  work  is  written  in  simple  language, 
and  is  easy  to  follow.  It  is  quite  evident 
that  the  author  is  not  only  a  thorough  mas- 
ter of  the  subject,  but  also  possesses  the 
great  qualification  of  lucid  explanation.  The 
book  is  well  indexed,  and  contains  a  table 
of  contents.  It  will  be  found  of  very  great 
value  to  all  interested  in  the  subject  O'f 
which  it  treats. 


BOOKS  RECEIVED. 
Physilcalalische    Chemie :     I.,     Chemisch 
Heine  Stoffe ;    II.,  Losungen;    von  Dr.  Al- 
fred Benrafth,  a.  O.  Professor  der  Chemie 


an  der  Universtat  Bonn.  Pp.  VIII.  +  107. 
1923.  Verlag  von  Theodor  Steinkopff,  Dres- 
den and  Leipzig. 

Practical  Physical  Chemistry,  by  Alexan- 
der FiNDLAY,  M.A.,  D.Sc,  Professor  of 
Chemistry,  University  of  Aberdeen.  Pp. 
XVI.  +  298.  4th  Edition,  1923.  Messrs. 
Longmans,  Green  &  Co.,  39,  Paternoster 
Row,  B.C.4.    7s.  6s.  net. 

Petroleum  Technologist's  Pocket-Book, 
revised  by  Arthur  W.  Eastlake.  Pp.  546. 
1923.  Messrs.  Charles  Griffin  &  Co.,  Ltd., 
Exeter  Street,   Strand.     15s.  net. 


i-His  list  is  specially  compiled  for  The  Chemical 
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and.  Designs  can  be  obtained  gratuitously. 

Latest  Patent  Applications. 

19834— Buss  Akt-Ges.— Apparatus  for  production 
of  anhydrous  tin  chloride.     Aug.  2. 

19592— Constant,  G.— Reduction  of  metal  oxides. 
July  31. 

19600— Naugatuck  Chemical  Co.— Preparation  of 
reaction  product  of  acetaldehyde  and  ani- 
line.   July  31. 

19977— Weizmann,  C— Filtration  of  solutions,  etc. 
Aug.  3. 

Specifications   Published   this   Week. 
200851— Thomas,  J.,     and     Scottish     Dyes,     Ltd.— 
Method  of  producing  anthraquinone     eul- 

Shonic  acids. 
>u  Pont  de  Nemours  arid  Co.,  E.  I.— Pro- 
cess of  manufacturing  cyanides. 

179951— Heinemann,  A.— Process  of  manufacturing 
formic  aldehyde. 

189107— Barrett  Co.- Manufacture  of  aromatic  al- 
dehydes. 

190123— Soc.  Chimique  des  Usines  du  Rhone.— Pro- 
cess of  manufacture  of  the  calcium  salt  of 
acetyl  salicylic  acid. 

Abstract  Published  this  Week. 
199073— Chlorinated    montan       wax.— Stinnes,     H. 
(Firm  of),  Mulheim,  Germany. 

The  ohlorination  of  montan  wax,  obtained  by 
extraction  of  lignite  with  solvents,  is  effected  in 
the  presence  of  water,  organic  solvents  being  ab- 
sent. The  montan  wax  is  first  suspended  in 
water  or  an  alkaline  solution,  such  as  caustic 
soda  solution  or  milk  of  lime,  and  gaseous  chlor- 
ine passed  in;  or  a  suspension  of  montan  wax  in 
hydrochloric  acid  is  treated  with  chlorate,  for  ex- 
ample, by  the  addition  of  potassium  chlorate  in 
the  solid  form  or  in  aqueous  solution.  The  re- 
action may  be  accelerated  by  the  presence  of  cata- 
lysts, siich  as  ferric  chloride.  The  products  are 
useful  for  insulation  purposes,  as  a  substitute  for 
beeswax,  and  in  the  preparation  of  floor  polishes, 
boot  creams,  &e. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
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each. 


AUGUST  31,  1923. 


THE  CHEMICAL  NEWS. 


129 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3307. 


M.  CAREY  LEA,  CHEMIST. 
1823—1897. 

By  Edgar  F.  Smith,  University  of 
Pennsylvania. 

A  hundred  years  ago  (1823),  Matthew 
Carey  Lea  was  born.  His  contributions  to 
chemistry  brought  him  honour  and  distinc- 
tion among  his  colleagues  throughout  the 
world,  so  that  pause  may  well  be  made  to 
let  them  pass  in  brief  review.  Few  chemists 
of  his  day  knew  him  personally;  in  fact, 
students  of  chemistry  in  this  country  would 
probably  not  give  his  name  if  called  upon 
for  a  list  of  American  scientific  worthies, 
hence  a  brief  consideration  of  his  achieve- 
ments will  be  in  order.  They  will  augment 
our  pride  in  the  men  who  wrought  in  chem- 
istry before  these  very  modern  days  when, 
on  all  sides,  there  is  heard  a  demand  for  re- 
search, forgetting  that  the  past  in  chemistry, 
even  in  this  country,  can  present  many  ex- 
cellent e.xamples  of  earnest  devotion  to  the 
purely  scientific  asipects  of  chemistry. 

Carey  Lea  (as  he  was  usually  called)  was 
a  true  researcher.  His  first  study,  pub- 
lish(>d  in  1841,  related  to  the  Southern  Coal 
Field  of  Pennsylvania.  His  father  had  ex- 
pressed the  thought  that  "  the  hard  or 
highly  carbonised  anthracite  of  the  eastern 
end  of  the  Southern  coal  field  changes  to 
bituminous  in  the  western  end  by  nearly 
regular  gradations."  The  results  obtaineii 
by  Carey  Lea  showed  "  that  the  bituminous 
quiilities  of  the  coal  increase  with  consider- 
ahlc  regularity  from  Tamaqua  (the  eastern- 
most end)  to  Rattling  Run  (the  western- 
most extremity)." 

Lea  did  this  work  when  he  was  but 
eighteen  years  old,  in  the  laboratory  of 
Booth,  Garrett  and  Blair,  where  he  had 
gone  to  familiarise  himself  with  practical 
chemistry.  He  loved  scientific  pursuits. 
He  never  went  to  school  or  college.  His 
remarkable  training  was  "  through  the  best 
private  tutors  procurable."  His  intellectual 
powers  were  immense.  He  knew  literature, 
ninthematics,  languages,  and  the  natural 
and  physical  sciences. 

.\ftf'r  his  first    venture  into   experimental 
chemistry  he  gave  himself  to  the  study    of 
law,  and  was  admitted  to  the    Bar  in  1847. 
at  the  age    of  24.       But  this    profession  be 
abandoned  and  journeyed  to  Europe,  hoping 


to  regain  his  health,  which  had  become  pre- 
carious. However,  his  hopes  were  not 
realised,  and  he  returned  to  the  old  labora- 
tory on  Arch  Street  (Booth,  Garrett  and 
Blair)  with  the  view  of  perfecting  himself 
still  further  in  chemistry. 

In  his  earlier  days  in  the  Booth,  Garrett 
and  Blair  laboratory,  he  had  as  fellow  stu- 
dent in  chemistry  his  brother,  Henry 
Charles  Lea,  who  later  in  life  was  regarded 
as  the  first  and  greatest  of  modem  scientific 
historians.  He  was  the  author  of  seventeen 
volumes  on  Mediaeval  History  and  Law. 
And  this  same  younger  brother,  at  the  age 
of  twelve  years,  was  busily  engaged  in  a 
study  of  manganic  oxide ;  the  results  appear-  , 
ing  in  May,  1841,  in  the  American  Journal 
of  Science.  The  paper  is  interesting  and 
valuable.  Few  chemists,  at  the  age  of 
twelve,  have  ventured  forth  with  such  an 
excellent  production.    He  began  : 

"  The  peroxide  of  manganese  (Mn^Oj) 
has  never  been  investigated,  as  its  existence 
has,  until  lately,  been  questioned  by  some 
of  the  first  chemists  in  Europe,  and  the  ten- 
dency of  its  salts  to  convert  themselves 
into  proto-salts,  contributed  to  render  it 
problematical  whether  it  was  not  merely 
the  protoxide  disguised." 

Interrupting  this  digression,  it  may  be 
remarked  that  when  Carey  Lea  finally  left 
the  Booth,  Garrett  and  Blair  laboratory,  it 
was  to  enter  a  private  laboratory  installed 
in  his  home  at  Chestnut  Hill.  There  nearly 
all  his  later  experimental  work  was  done. 
But  the  notebooks  of  that  work  were,  upon 
his  death,  destroyed  in  accordance  with  his 
own  desire.  Among  these  was  a  list,  pre- 
served from  boyhood,  of  the  chemicals  and 
apparatus  imported  by  his  father  for  his 
use. 

Lea  showed  a  decided  penchant  for 
chemical  theory.  He  was  much  concerned 
about  the  chemical  properties  of  atoms  and 
their  numerical  relations,  undertaking  to 
show  "  that  the  number  of  44.45  plays  an 
important  part  in  the  science  of  stoichio- 
metry,  and  that  the  relations  which  depend 
upon  it  are  supported,  in  some  cases  at 
least,  in  a  remarkable  manner,  by  analogies 
of  atomic  volume."  This  relation  was 
found  to  extend  to  no  less  than  forty-eight 
of  the  elements.  The  first  germs  of  the 
periodic  law,  not,  however,  clearly  enun- 
ciated, were  in  his  thoughts.  And  in  1876 
and  1876  he  published  two  ingenious  papers 
on  the  Colour  Relations  of  Ions,  Atoms  and 
Molecules. 

As  early  as  1857  Lea  became  interested  in 
picric  acid,  giving  a  new  metho<l  for  its  pre- 
paration and  also  descriptions  of  many  new 


130 


THE  CHEMICAL  NEWS 


AUGUST  31,  1923. 


salts,  including  the  urea  and  quinine 
picrates.  He  concluded  that  picric  acid 
was  wholly  unreliable  as  a  test  for  potash, 
and,  indeed,  a  better  test  for  soda. 

Shortly  after  the  beginning  of  the  Civil 
War  he  advised  the  United  States  Govern- 
ment that  picric  acid  would  be  an  exiplosive 
of  greater  power  than  black  powder.  Its 
smokelessness  appealed  to  him  as  an  ad- 
vantage. The  Federal  Government,  how- 
ever, failed  to  appi-eoiate  the  importance  of 
using  an  explosive  outranging  anything  in 
use  at  the  time,  and  it  was  not  until  fifty 
years  after  that  high  explosives  on  a  picric 
acid  basis  were  adoipted. 

To  separate  the  ethylamines  Lea  recom- 
mended the  use  of  their  picrates :  triethyl- 
amine  picrate  being  extremely  insoluble,  di- 
ethylamine  extremely  soluble,  and  ethyl- 
amine  intermediate.  He  gave  some  con- 
sideration to  the  methyl  bases  and  the  pre- 
paration of  urea — with  good  and  definite  re- 
sults. By  the  interaction  of  naphthylamine 
and  sulphuric  acid  -le  obtained  ionaphthine 
— a  ne  wcolouring  matter.  On  dropping  a 
bit  of  gelatine  into  a  mercuric  nitrate  solu- 
tion the  latter  gradually  assumed  a  deep 
red  colouration — a  new  and  valuable  test 
for  gelatine.  Lea  did  not  regard  as  reliable 
the  determination  of  the  melting  point  of 
methyl  oxalate  as  a  means  of  ascertaining 
the  purity  of  methyl  alcohol  (containing 
ethyl  alcohol).  For  the  detection  of  prussic 
acid  he  suggested  the  addition  of  a  ferrous 
salt  containing  a  little  uranic  nitrate,  when 
a  beautiful  purple  coloured  precipitate  was 
formed.  A  great  increase  of  delicacy  in  the 
reaction  between  starch  and  iodine  was  ob- 
served by  Lea  on  adding  chromic  acid  to 
the  solution.  He  also  wrote  on  a  new 
method  of  determining  the  relative  affinities 
of  certain  acids  which  was  based  on  the 
amount  of  base  which  it  can  retain  in  the 
presence  of  a  strong  acid  selected  as  a  stand- 
ard of  comparison  for  all  acids.  Two  new 
methods  were  proposed  by  Lea  for  the  re- 
duction of  platinic  to  platinous  chloride — 
one  by  the  action  of  potassium  sulphite,  the 
other  by  that  of  alkali  hypophosphites.  He 
also  demonstrated  that  a  solution  of  iodo- 
quinine  affords  a  means  of  detecting  free 
sulphuric  acid,  even  in  traces,  in  presence 
of  combined  sulphuric  acid. 

In  a  collection  of  miscellaneous  pamph 
lets,  once  the  property  of  Carey  Lea,  are 
several  contributions  of  Carl  Claus  on 
"  Chemie  der  Platinmetalle,"  fully  anno- 
tated in  the  marginal  way,  thus  revealing 
that  Lea  had  more  than  ordinary  interest  in 


this  very  important  group.  He  studied  its 
members  with  care,  using  material  fur- 
nished by  his  former  teacher,  James  Curtis 
Booth.  Among  the  new  facts  disclosed  by 
him  is  the  use  of  oxalic  acid  for  the  first 
time  in  purifying  ammonium  iridium  chlor- 
ide, and  the  discovery  of  a  reaction  for 
ruthenium  which  proved  most  helpful.  If 
to  a  solution  of  sodium  hyposulphite  there 
be  mixed  ammonia  and  a  few  drops  of 
ruthenium  sesquichlQride,  a  magnificent 
red-purple  liquid  will  be  produced,  which, 
unless  quite  dilute,  will  be  black  by  trans- 
mitted light.  The  chief  value  of  this  test 
was  found  to  lie  in  the  fact  that  it  is  capable 
of  detecting  ruthenium  in  the  presence  of 
iridium.  Lea  thought  it  valuable  in  test- 
ing the  purity  of  iridium  for  "  if  the  sus- 
pected iridium  salt  be  boiled  with  hydro- 
chloric acid,  and  ammonia  added  until  the 
liquid  assumes  a  pale  olive  colour,  then,  on 
adding  the  hyposulphite  and  boiling,  any  in- 
crease of  colour  indicates  the  presence  of 
impurity.  If  the  liquid  acquires  a  red 
colour,  ruthenium  is  present;  if  a  wine 
colour,  platinum  is  probably  present,  and  if 
brown,  palladium  is  indicated."  Lea  ap- 
plied ruthenium  sesquichloride  to  detect 
sodium  hyposulphite. 

An  adequate  idea  of  Lea's  voluminous 
work,  as  investigator,  cannot  be  given  in  a 
narrow  compass,  such  as  this  article.  The 
student  should  turn  to  the  pages  of  the 
American  Journal  of  Science,  beginning 
with  the  year  1858,  and  read  forward  to  the 
year  1897,  then  some  deduction  may  be 
drawn  of  the  vastness  of  Lea's  labours. 
These  papers  deserve  very  careful  study. 
There  is  such  an  abundance  of  originality  in 
them.  In  the  volume  of  The  Chemical 
News  for  1862  will  also  be  found  four  addi- 
tional contributions.  A  review  of  all  this 
material  would  furnish  many  topics  for 
seminar  consideration. 

But  the  greatest  of  all  Lea's  efforts  to  ex- 
tend the  borders  of  human  knowledge  are 
those  dealing  with  the  chemistry  of  light ; 
for  in  photochemistry  he  was  a  true  pioneer. 
He  blazed  the  way.  Quite  early  in  his  life 
the  startling  invention  of  photography  from 
the  hands  of  Daguerre  drew  his  most 
thoughtful  attention.  He  saw  its  enormous 
possibilities  and  promptly  began  a  funda- 
mental study  of  its  chemistry,  also  its  phy- 
sics, and  its  practical  value.  From  this 
study  came  the  only  book  he  ever  wrote, 
entitled      "  Photography."  It      passed 

through  two  editions,    and  was  everywhere 
regarded  as  standard.       Its  perusal  reveals 


AUGUST  31,  1923. 


THE  CHEMICAL  NEWS. 


131 


the  masterful  mind  which  prepared  it.  It 
is  absolutely  scientific  in  its  discussion  of 
the  problems  of  photography.  But,  foreign 
scientists  were  first  in  recognising  the  value 
of  Lea's  efforts  in  this  new  field.  They  de- 
clared them  to  have  a  lasting,  permanent 
value,  in  scientific  photography,  and  that 
they  were  all  fundamentally  important  in 
physico-chemical  research.  Indeed,  tbese 
researches  were  genuine  classics.  For  col- 
loid chemistry  they  possessed  an  ever- 
increasing  interest  and  value.  Lea's  "col- 
loid silver"  and  "iphoto-haloids"  were  trans- 
lated and  heralded  abroad  as  epoch-making 
studies.  Perhaps  it  is  somewhat  of  a  re- 
flection upon  American  chemists  that  the 
importance  of  these  studies  was  first  empha- 
sised by  foreign  chemists.  However,  other 
American  labourers  in  the  field  of  chemistry 
had  their  remarkable  discoveries  pass  un- 
noticed, until  attention  was  drawn  to  them 
by  the  regard  in  which  they  were  held  by 
co-workers  in  other  lands,  as  for  example — 
J.  Willard  Gibbs  and  his  phase  rule,  Rob- 
ert Hare  and  his  classic  work  on  the  elec- 
tric furnace,  and  others. 

'J'o  be  the  discoverer  of  the  amorphous 
forma  of  silver  is  no  moan  distinction.  When 
these  come  under  the  eye  of  chemists  en- 
thusiasm is  immediately  kindled,  and  then- 
arises  an  inquiry  as  to  their  discoverer. 

As  remarked,  few  chemists  knew  I^a 
personally.  He  was  a  recluse  in  a  certain 
sense,  fw  he  rarely  appeared  in  the  com- 
pany of  scientists  or  other  groups  of  men. 
Quietly,  unostentatiously  he  laboured  on 
vrry  indcipendently,  until  his  contributions 
to  purely  photographic  subjects  reached  the 
number  of  300,  to  be  found  on  the  pages  of 
the  Amrrican  Journal  of  Science,  to  which 
reference  has  already  been  made. 

In  addition  to  his  numerous  chemical 
papers,  Lea  published  many  others  in  the 
domain  of  physics.  He  further  elaborated 
cerfain  pieces  of  apparatus  which  proved 
helpful  in  laboratory  work.  And  thus  the 
course  of  his  scientific  endeavour  proceeded, 
for  he  was  a  most  industrious  WM-ker  in  all 
regions  of  his  favourite  science.  He  was  a 
very  acute  observer.  He  knew  the  litera- 
ture of  chemistry,  both  past  and  present. 
He  had  an  intense  love  of  truth.  He  al- 
ways had  in  hand  the  facts  upon  which  he 
based  expressed  opinions.  His  opinion  was 
recognised  as  the  final  oniiiion  in  photo- 
graphic chemistry,  both  in  this  country  and 
in  Europe.  He  was  likewise  devoted  to 
literature,  the  classics  and  art. 

For  one  so  eminent  in  his  science  he  be- 
longed to  few  scientific  organisations — viz., 


the  Franklin  Institute  and  the  National 
Academy  of  Sciences,  to  which  he  was 
elected  in  1895. 

Ah  accident  in  his  laboratory,  in  early 
life,  so  seriously  injured  one  of  his  eyes 
that  it  eventually  was  removed.  His  de- 
voted wife  read  to  him  for  many  years,  so 
that  he  was  able  to  keep  up  his  interest  in 
the  current  work  of  scholars  at  home  and 
abroad. 

Carey  Lea  was  the  son  of  Isaac  Lea,  a. 
distinguished  naturalist,  who  served  as 
President  of  the  Academy  of  Natural 
Sciences  m  Philadelphia,  and  of  the 
American  Association  for  the  Advancement 
of  Science.  It  was  an  old  Quaker  family 
into  which  Carey  Lea  was  born,  August  18, 
1823.  He  was  married  twice,  first  to  his 
cousin,  Elizabeth  Lea  Jaudon,  and  after 
her  death  to  Eva  Lovering.  Carey  Lea 
died  March  15,  1897. 

The  various  apparatus  owned  by  Lea  was 
bequeathed  to  the  Franklin  Institute  in 
Philadelphia. 

'Hie  life  story  of  Lea  is  most  interesting. 
He  was,  indeedi,  a  bright  star  in  the  chemi- 
cal firmament  of  America ! 


THE  CHEMICAL  INDUSTRY  OF 
JUGO  SLA  VIA. 

The  chemical  industry  of  Jugo  Slavia 
cannot  be  said  to  have  reached  a  high  state 
of  perfection.  It,  nevertheless,  possesses 
possibilities  of  considerable  dimensions. 

It  may  be  pointed  out  that  Jugo  Slavia 
embraces  old  Serbia,  Montenegro,  Croatia, 
Carniola,  and  Dalmatia;  it  is  also  sometimes 
termed  the  kingdom  of  the  Serbs,  Croats 
and  Slovenes.  At  present  there  is  no  chemi- 
cal industry  outside  that  portion  of  the 
country  which  was  not  formerly  under  Aus- 
trian rule. 

In  this  region,  various  pharmaceutical 
preparations  are  made  from  the  extractions 
of  certain  plants.  This  is  a  branch  of 
chemical  industry  which  might  easily  be  ex- 
tended in  this  country,  which  is  well  suited 
for  the  cultivation  of  many  plants  used  for 
pharmaceutical  purposes.  At  present  the 
industry  is  almost  exclusively  confined  to 
the  preparation  of  perfumes. 

In  the  north,  at  Ljubljana  (Laibach),  the 
local  bauxite  is  exploited  for  mak- 
ing aluminium  sulphate  and  alums.  The 
metal  is  also  produced  in  a  limited  amount. 
The  salts  manufactured  are  partly  exported 
and  partly  consumed  locally  as  mordants 
by  the  small  dyeworks. 


132 


THE  CHEMICAL  NEWS. 


AUGUST  31,  1923. 


A  beginning  has  also  been  made  in  the 
exploitation  of  the  natural  mineral  resources 
of  this  district.  In  1908  a  kind  of  company, 
entitled  "  Wocheinit,"  was  founded  for 
mining  the  bauxite.  This  society  holds  all 
the  mineral  rights  for  the  district  between 
Bistrice  and  Jesenice. 

During  the  war  more  than  6,000  tons  of 
bauxite  were  mined.  The  output  has  since 
been  restricted  through  lack  of  wagons,  and 
also  as  a  result  of  transport  difficulties  over 
the  new  frontiers. 

This  bauxite  did  not  enjoj  a  good  reputa- 
tion, as  it  was  supposed  to  contain  a  high 
percentage  of  silica,  which  would  render  its 
use  by  either  wet  or  dry  methods  very  diffi- 
cult. The  latest  analyses  indicate  just  the 
opposite,  and  it  is  shown  that  there  are  two 
kinds  of  bauxite.  The  first  variety  of 
Bohinske  bauxite  is  said  to  be  of  the  most 
suitable  quality  for  the  aluminium  industry. 
It  occurs  in  large  masses  on  the  slopes  of 
the  Julian  Alps,  and  contains:  — 

Alumina      58-60  per  cent. 

Ferric  oxide      6-10         ,, 

Silica  3.5-  4.5      ,, 

Titania'         1-  2 

Vogar  bauxite  has  seams  which  are  ten  to 
fifteen  metres  thick. 

The  second  variety  of  bauxite  is  less 
pure,  but  is  very  suitable  for  making  fire- 
proof articles,  and  is  found  in  quite  separate 
shafts  from  the  purer  variety.     It  contains : 

Alumina      52-56  per  cent. 

Iron  oxide      10-16         ,, 

Silica  4.5-  5.5      ,, 

Titania 2-  3 


THE  BEITISH  CAST  IRON  RESEARCH 
ASSOCIATION. 

Research    Department. 

General  Research  Worh. — The  work  in 
connection  with  the  various  researches  is 
progressing  to  such  an  extent  that  the 
Director  proposes  to  issue  forthwith  reports 
upon  the  various  results  obtained.  These 
will  be  found  to  be  of  very  great  interest  to 
members. 

Foundry  Sand  Research. — The  Bureau, 
in  their  No.  2  Bulletin,  are  commencing  a 
series  of  articles  upon  Foundry  Sands, 
which  will  give  members  some  very  valvx- 
able  data.  The  object  of  this  research  is  to 
enable  standards  to  be  established  to  judge 
one  of  the  most  important  factors  in  the 
successful  production  of  castings. 


Bulletins. — The  Bureau  Bulletin  No.  1 
has  now  been  issued  to  members,  and  com- 
prises over  100  pages  of  very  valuable  infor- 
mation. The  Research  Bulletin  No.  3  is  in 
the  printers'  hands  for  early  issue,  and 
Bureau  Bulletin  No.  2  is  also  ready  for  the 
printer.  Members  will  recognise  by  the  re- 
ceipt of  these  Bulletins  that  the  Association 
has  carried  out  a  very  large  amount  of  use- 
ful work. 

Problems  Sent  in  by  Members. 

During  the  past  month  members  have 
sent  in  problems  upon  the  following :  Loco- 
motive Injectors;  Air  comipressing  engine 
Cylinder  liners;  Annealing  Malleable  Iron; 
Porosity  in  Castings;  Pan  Mill  Soller  Rings; 
Mottled  Castings;  Spongy  Trunk  Slides; 
Cupro  Nickel  Ingot  Moulds ;  Fluted  Cast 
Iron  Roll  Moulds;  Chilled  Iron  Rolls; 
Faulty  cores  in  Castings;  Cupola  design. 

The  Bureau  and  Library. 

The  Bureau  has  been  called  upon  to  sup- 
ply a  large  amount  of  data  and  information 
during  the  past  month,  and  whilst  there 
have  been  some  cases  whore  the  required 
information  was  not  in  the  Bureau,  it  was 
ultimately  obtained  from  abroad,  proving 
the  great  usefulness  of  the  "  Intelligence 
Service." 

The  Library  Catalogue  is  now  issued,  and 
members  will  be  able  to  use  the  Library  to 
better  advantage. 

New  books  are  continually  being  added. 
The  following  books  have  been  sent  for  re- 
view in  the  Bulletin:  — 

Causes  and  Prevention  of  Corrosion,  by 
A.  A.  PoUitt.  Published  by  Benn  Bros., 
Ltd.,  London. 

Refractories  for  Furnaces,  by  A.  B. 
Searle.  Published  by  Sir  Isaac  Pitman  & 
Sons,  Ltd.,  London. 

Engineering  N on-Ferrous  Metals  and  Al- 
loys, by  Dr.  L.  Aitchison  and  W.  R.  Bar- 
clay. Published  by  Henry  Frowde  and 
Hodder  &  Stoughton,  London. 

British  Acetylene  and  Welding  Handbook 
Published  by    The  Acetylene    and    Welding 
Journal. 

Membership. 
During  the  past  month  further  new  mem- 
bers have  been  elected.  These  include  seve- 
ral large  firms  who  recognise  the  value  of 
the  work  of  the  Association.  The  member- 
ship badge  is  very  generally  used  by  mem- 
+t!^^  T-  *^®^^  stationery,  and  it  is  reported 
that  this  has  been  of  great  value  to  several 
ot  the  members, 


AUGUST  31,  1923. 


THE  CHEMICAL  N3WS. 


133 


The  General  Council. 
To  fill  a  vacancy  that  has  occurred  on  the 
Council,  Mr.  F.  Fielding,  of  Messrs.  Field- 
ing &  Piatt,  Ltd.,  Gloucester,  has  been 
elected  to  represent  the  counties  of  Glouces- 
ter, Hereford,  and  Monmouth.  At  the 
next  annual  meetmg,  nine  members  of  the 
Council  retire,  eight  of  whom  are  offering 
themselves  for  re-election. 

Propaganda  Work. 
It  has  been  pointed  out  to  the  Council 
that  the  advantages  of  membership  of  the 
Association  would  be  better  understood  if 
meetings  were  held  at  which  the  officers  of 
the  Association  could  attend  and  discuss 
the  work  and  objects  oT  the  Association. 
The  Council  will  be  glad  if  Ironfounding 
Employers'  Associations  or  any  other  sec- 
ton  of  the  indutry  would  arrange  meetings, 
when  the  Director  of  Research  and  the  Sec- 
retary will  attend.  Several  meetings  have 
already  been  held  in  various  districts,  when 
good  results  have  accrued.  It  has  enabled 
the  officers  to  discuss  with  the  employers 
the  needs  of  the  industry  and  the  absoluto 
necessity  of  such  an  Association.  After  all 
it  should  be  remembered  that  the  Associa- 
tion is  thi'  Iroufounders'  Association.  It  is 
in  their  power,  and  to  their  interests,  to 
make  it  a  great  success. 

The  Malleable  Casting  Industry. 

Unlike  the  malleable  industry  in  this 
country,  everything  is  being  done  in 
America  to  increase  the  production  of  mal- 
leable castings,  and  to  obtain  their  adoption 
for  every  possible  engineering  use.  Fore- 
most of  all,  their  malleable  ircmfounders 
firmly  believe  in  research,  and  have  practi- 
cally all  joined  their  Research  Association 
and  have  standardised  their  products. 

Secondly,  they  arc  proving  to  the  en- 
gineer the  superiority  of  malleable  castings 
over  drop  forgings  or  stampings.  Some 
time  ago  a  complete  collection  of  castings 
for  railway  purposes  was  furnished  by  mem- 
bers of  the  American  Malleable  Research 
Association.  In  addition  to  this  exhibit  a 
working  demonstration  was  given  to 
acquaint  railway  engineers  with  the  proper- 
ties of  malleable  castings.  For  this  purpose 
a  suitable  punch  press  was  installed,  and 
was  operated  by  an  experienced  operator.  A 
supply  of  I  inch  cast  iron  plates  was  pro- 
vided. They  were  punched  with  a  }  inch 
hole  and  the  holes  were  drifted  until  thf 
diameter  was  increased  to  1^  inches  with- 
out injury  to  the  plate. 


A  torsion  machine  was  operated  to  show 
the  resistance  of  malleable  castings  to  re- 
peated strains.  Bars  1  x  J  inch  in  cross 
section  were  twisted  three  times  through 
1^°.  and  after  each  twist  straightened  to 
its  original  form.  A  further  test  was  given 
in  twisting  a  bar  through  800°  without  frac- 
ture. 

That  malleable  ironfounders  in  this  coun- 
try can  produce  castings  equal  to  America 
is  proved  by  some  tests  taJren  of  castings 
made  by  a  firm,  who  are  members  of  this 
Association,  when  the  tensile  was  25.3  tons 
with  elongation  14  per  cent. 

The  Association  consider  these  figures 
should  be  universal  in  the  industry,  if  the 
malleable  makers  will  join  the  Association 
and  co-operate  with  it  to  obtain  a  general 
improvement  in  the  castings  the  Association 
wlli  be  able  to  place  before  the  railway  and 
automobile  engineers  such  reliable  data  as 
will  convince  them  as  to  the  advisability  to 
use  malleable  work. 

The  Council  of  the  Association,  on  their 
side,  are  doing  all  they  can  to  bring  back 
the  malleable  trade,  but  they  must  have  the 
whole-hearted  support  of  the  firms  them- 
selves. The  present  time  is  the  most  op- 
portune time  to  become  members,  and  so 
prepare  for  the  trade  improvement  when  it 
arrives.  Alterations  in  methods  of  produc- 
tion arc  difficult  to  carry  out  when  the 
foundry  is  busy.  The  firms  who  have  already 
jmned  are  setting  their  houses  in  order  pre- 
paratory to  the  busy  times. 

Tnos.  Vickers,  Secretary. 
Central  House,  New  St.,  Birmingham. 


BOARD  OF  TRADE  ANNOUNCEMENT. 

Safeguarding  of  Industries  Act,  Part  I. 

Arbitrations  Under  Section  1  (5). : 

Rochelle  Salt. 

The  Referee  has  given  his  decision  in  the 
matter  of  a  complaint  under  the  above  Sub- 
section that  Kcxjhelle  Salt  has  been  im- 
properly included  in  the  Lists  of  Articles 
chargeable  with  duty  under  Part  I.  of  the 
Act.  The  Referee  states  that  there  is  no 
evidence  that  Rochelle  Salt  is  wrongly  in- 
cluded in  the  Lists,  and  he  awards  that  the 
complaint  fails. 

Board  of  Trade, 

'22nd  August,  1923. 


134 


THE  CHEMICAL  NEWS. 


AUGUST  31,  1923. 


PROTEIN  REACTIONS. 

(With  Special  Reference  to  Egg  Albumin). 

By  R.  F.  Hunter,  F.C.S. 

It  was  considered  that  the  study  of  the 
reactions  from  a  purely  elementary  qualita- 
tive point  of  view,  of  some  of  the  commoner 
laboratory  reagents  with  proteins  might  be 
a  subject  for  investigation. 

5g.  of  flaked  egg  albumin  were,  therefore, 
dissolved  in  200  ce.  o  f water  as  completely 
as  possible.  A  white  suspension  was  ob- 
tained. To  portions  of  this  in  test  tubes 
various  reagents  were  added  as  follows  :  — 

Acids : 

1. — Concentrated  H2SO4  :  white  semi- 
transparent  flocculent  precipitate,  coagulat- 
ing when  boiled. 

2. — Co.  HNO3 :  pale  yellow  solution,  pre- 
cipitate pale  yellow — coagulates  on  boiling. 

3. — Co  H  Ce :  Pale  white  flocculent  p  p, 
coagulation  on  boiling. 

4. — HgPO^ :  No  pp,  not  does  warming 
produce  pp. 

5.— HgAs  0^  :  as  for  H3PO,. 

6. — CH3COO  H :  No  apiparent  action,  no 
p  p  on  boiling. 

7.— C  0  0  H 

C  O  0  H     Indefinite. 

8. — Oleic  acid :  pale  brown  :  pp.  on  shak- 
ing. 

NaO  H :  white  flocculent  pp.  etc. 

NH.OH. 

Br  Water:  immediate  yellow  pp.,  coagu- 
lation on  boiling. 

FeClg :  Pale  yellow  pp. 

CusS  O4 :  Pale  blue  pp. 

CuSO^  +  NaO  H,  beautiful  pale  blue 
flakes. 

Ni  (N03)2 :  Pale  green  pp. 

Am2S :  boiling,  darkens  and  unpleasant 
odour. 

NajS :  boiling  produces  white  solid  which 
floats  on  surface. 

P  (CHgCOO)^  Pb 

K2  Cr  O4 :  yellow  coagulation  on  heating. 

K  Crj  Oj :  orange  pp. 

Nitroprussiate  of  sodium 

K  C  N  S 

K  Mn  O^. 

CaHgOH :  white  flocc,  pp.,  etc. 
CC2HH2O :  white  flocc.  pp.,  etc. 

CgHgN  ^2  •  pa^e  yellow  suspension. 

CgHjNHNHa  red  brown  pp.,  red  coagu- 
lation on  boiling. 

CJIJO-H)  (N02)3,  bright  yellow  pp.  co- 
agulation as  such  on  boiling. 

CH  A,        indefinite. 


The  precipitation  of  some  common  ele- 
ments in  the  presence  of  egg  albumin  was 
now  examined. 

Method :     Susipension     or    rather     dilute 
solution  of  salt  studied    and  albumin   made 
with  water. 
l._Pb(N03)3 

HCl  added— 
pure     white    precipitate     settles    into    two 
layers,  solution  apparently  floating  on  sus- 
pended precipitate. 

Sulphides : 

HgCl,: 

Sulphide  first  pp.,  orange,  then  separa- 
tion into  two  layers  takes  place,  when  we 
have  a  black  p.p  at  bottom,  and  transparent 
jelly-like  suspension  above  layer  of  black 
sulphide. 

CuSO, : 

Black  brown  p.p  appears  above  soluti:»ii. 
blue-dirty  green  coagulated  p.p  appears  ai 
bottom  of  tube. 

Bi(N03),: 

Sepia  precipitate  and  almost  red  brown 
solution.  Exp.  reipeated  with  dilute  solu- 
tion and  1  bubble  of  2S  allowed  to  pass,  red 
brown  precipitate  appears  on  the  top,  a 
white  coagulation  at  bottom  of  tube,  a<.d 
between  these  two  a  pale  brown  solution.    • 

CdClj  -  HjS  produces  bright  yellow  homo- 
geneous precipitate  filling  tube. 

AS2O3 :  a  ipale  yellow  suspension  from 
passage  of  HjS  and  a  jelly-like  chrome  solid 
floats  on  layer  of  liquid.  AmjS  added  which 
dissolves  p.p.  HCl  addition  produces 
peculiarly  formed  plastic  yellow  p.p.  filling 
tube  of  S  and  AsjSg. 

Sb  CI3  solution,  are  HCl  and  albumin 
solution : 

HjS,  beautiful  orange  red  p.p.  floats  on 
white-pink  solution. 

Sn  CI2,  deeip  brown  p.p.  floats  above,  al- 
most pink  solution. 

FegClg  and  AmOH,  deep  red  brown  floe- 
culence  on  top  of  pale  yellow  liquid. 

Chrome  alum  and  AiiiOH : 

Plastic  grey  green  flocculence  on  surface 
of  solution. 

AmjS  and  MnSO^ : 

Pale  pink  p.p.  above  solution. 

AmgS  and  ZnSO^,  yellow  colouration  on 
top,  below  this  olive  green  layer,  below  this 
dirty  grey  and  solution  below  this. 

Co  (N03)2  and  NH.OH : 

Blue  layer  above  pink  solution,  excess 
AmOH  produces  sea-green  p.p. 

It  was  thought  that  a  solution,  or,  to  be 
more  accurate,  a  suspension  of  egg  albumin, 
mighl  exhibit  some  colourations  with  sul- 
phuric acid  solutions  of  organic  bases    Con- 


AUGUST  31,  1923. 


THE  CHEMICAL  NEWS. 


135 


sequently  this  was  attempted,  the  method 
being  to  add  a  small  quantity  of  the  base  in 
its  sulphonic  acid  form  in  concentrated  sul- 
phuric acid  to  a  portion  of  the  albumin  solu- 
tion in  a  test  tube.  The  results  were  as 
follows:  — 

Phenol. — Indefinite  reaction  with  clearing 
of  suspension. 

a-Naphthol. — Yellow  solution    with    p.p. 
formation. 

(B-Naphthol. — Brown  and  cloudy. 

Sulphanilic  Acid. — Clear  and  almost  gol- 
den. 

Dimethylaniline. — Pinkish     solution    and 
flocculent  precipitate. 

Salicyclic  Acid. — White  flocculent  p.p. 

Resorcinol. — Yellow-green    solution      and 
ip.p. 

Quinol. — Bright  golden  and  yellow    p.p. 
floating. 

PyrogalUc    Acid.  —  Fale-grey-pink      and 
clear  solution. 

Phenolphthalein. — Clear  sherry    coloured 
solution. 

Fluoreaeein. — Bulky  olive  green    precipi- 
tate. 

Eosin. — Bed  brown  bulky  p.p. 

Alizarin. — Brilliant  orange  p.p. 

Anthrnvcnc. — Grey-ochre  p.p. 

Anthraquinune. — Light  grey  solution. 

Aurin. — Bright  chrome  ^::oIution  and  simi- 
lar precipitate. 

Malachite  Oreen  (leuoo). — Golden   yellow 
clear  soluticm. 

Benzidine. — Pale       violet       precipitation 
floating  on  similar  solution. 

a-Naphthyl  amine. — Indefinite. 

Diazoaminobemcne. — Deep    red    solution 
and  p.p. 

Thiocarbanilide. — Complete  white  p.p. 

m-Niiraniline.  —  Pale      yellow  -  pinkish 
tinged  p.p. 

Quinoline. — Cloudiness. 

Pyridine.  —  Cloudiness    and    floating    of 
p.p. 

The  investigation,  it  will  be  seen,  yielded 
nothing  much  worthy  of  note.  The  reac- 
tions, to  put  it  mildly,  are  indefinite,  which 
might  be  anticipated  when  one  considers 
the  complex  nature  of  such  a  substance  as 
egg  albumin,  particularly  in  solution,  for  in 
the  form  it  probably  contains  a  fair  num- 
ber of  products  of  hydrolysis,  such  as  com- 
plex amino  acids,  etc.  Its  effect  on  the 
precipitation  of  metals  from  their  solutions 
by  the  usual  methods  of  analyses  is  nothing 
remarkable.  The  only  general  effeot  appar- 
ently which  one  can  ascribe  to  it  is  the  U^n- 
dency  which  \t  promotes  for  separation  into 


layers,  viz.,  the  precipitation  of  zinc  as  zinc 
sulphide  from  its  sulphate  solution  by 
means  of  ammonium  polysulphide  in  the 
presence  of  albumin.  The  "effect  appears  to 
be  clearly  a  colloidal  one. 

The  effect  of  sulphonic  acids  of  aromatic 
bases  in  sulphuric  acid  solution  likewise 
does  not  appear  to  produce  much  worthy  of 
comment;  colour  reactions  were  obtained, 
as  one  would  expect,  but  nothing  startling 
Nvas  the  result. 

The  effects  most  interesting  were  those  of 
coagulation  and  precipitation  of  various  re- 
agents, the  work,  as  was  stated,  being  quali- 
tative in  nature.  This  effect  is  not  open  to 
deduction.  The  quantative  study  of  the 
effect  might,  however,  repay  an  investiga- 
tion at  a  later  date,  but  the  qualitative  side 
certainly  appears  to  be  of  the  nature  of  a 
failure  as  far  as  the  present  investigation 
goes. 


STUDIES  OF  IRIDESCENT  COLOUR, 

AND  THE  STRUCTURE  PRODUCING 

IT.— IRIDESCENT  BEETLES. 

By  Lord  Rayleioh,  F.R.S. 

In  this  paper  the  wonderful  metallic 
colouring  of  certain  iridescent  scalelesg 
beetles  will  be  considered. 

Many  previous  writers  have  discussed 
this  subject,    and  have  taken  widely  diver- 

fmt  views  as  to  the  cause  of  the  colours, 
or  a  summary,  reference  may  Be  made  to 
a  paper  by  mv  father,  the  late  I.K>rd  Ray- 
leigh.*  As  there  set  forth,  the  discussion 
turns  mainly  on  whether  the  iridescent 
colour  is  due  to  repeated  thin  plates,  as  in 
the  case  of  chlorate  crystals,  or  whether  it 
is  of  the  same  kind  as  the  surface  reflexion 
of  aniline  dyes.  The  latter  view  was  sup- 
ported by  the  authority  of  Prof.  Michelson,t 
but  I  understand  that  he  thinks  that  the 
last  word  has  not  been  said  on  the  subject. 
In  all  cases  of  undoubted  surface  colour 
there  is  a  very  deep  and  saturated  transmis- 
sion of  colour  of  complementary  tint. 
When,  however,  the  coloured  layer  of  an 
iridescent  beetle  is  detached  by  dissolving 
away  the  opaque  backing  and  examined  by 
transmission,  it  is  found  not  to  be  deeply 
coloured,  though,  of  course,  it  shows  some 


*  "  Phil.  Mag.,"  vol.  37,  p.  98  (1919) 
f  "  Phil.  Mag,"  vol.  21,  p.  554  (1911). 


136 


TfiE  CHEMICAL  t^fiWS. 


AUGUST  31,  1923. 


colour,  as  it  should  do  on  any  theory.  This 
was  the  argument  which,  I  believe,  weighed 
most  with  my  father,  against  the  theory  of 
surface  colour,  and  for  the  theory  of  inter- 
ference, or  structure  colour.  He  was  not 
able,  however,  to  bring  forward  any  abso- 
lutely crucial  observation,  or  argument, 
and  ended  by  saying:  "  It  must  be  con- 
fessed that  much  still  remains  to  be  effected 
towards  a  complete  demonstration  of  the 
origin  of  these  colours."  As  in  the  case  of 
the  chlorate  crystals,  I  inherited  the  speci- 
mens which  he  had  procured,  and  have 
obtained  evidence  which,  it  is  hoped,  will 
be  found  more  cogent  than  any  available 
hitherto.  This  evidence  is  in  favour  of 
multiple  thin  plates. 

The  only  important  publication  on  the 
subject  which  has  appeared  since  my 
father's  paper  is  one  by  H.  Onslow,  +  in 
which  the  whole  subject  is  further  reviewed, 
and  many  details  are  given  from  the  bio- 
logical standpoint  about  iridescent  colours 
of  insects  generally,  both  with  and  without 
scales.  Onslow  accepted  the  structural 
origin  of  the  colours  in  many  instances,  but 
for  the  scaleless  beetles  here  considered  he 
reverted  to  the  theory  of  surface  colour. 
The  argument  on  which  he  mainly  relied 
was  that  the  thickness  of  the  colour- 
producing  layer  was  too  small  to  allow  room 
lor  the  structure  of  many  parallel  reflecting 
planes  which  would  be  required  on  the 
theory  of  structure  colour.  His  estimates 
of  the  thickness  of  this  layer  were  made 
partly  in  section  under  the  microscope, 
partly  by  polishing  a  flat  on  the  convex 
coloured  surface,  so  as  to  remove  the 
colour  layer,  and  examining  the  way  in 
which  the  colour  fell  off  inwards  along  the 
normal  to  the  boundary  of  the  ipolished 
portion.  Although  I  have  not  attempted 
to  repeat  these  experiments,  and  cannot 
therefore  speak  from  personal  experience  of 
the  methods,  I  cannot  help  thinking,  for 
reasons  that  will  appear,  that  the  results 
must  be  misleading. 

Happening  to  examine  the  specimens  in 
the  sunlight  with  a  direct-vision  spectro- 
scope, I  noticed  that  in  some  cases  the 
bright  region  of  the  spectrum  correspond- 
ing to  the  selective  reflexion  showed  an  al- 
ternation of  dark  and  brigljt  bands.  The 
phenomenon  is  often  not  very  conspicuous, 
the  dark  bands  not  being  perfectly  dark. 
Again,  in  some  aspects  of  the  insect  the 
dark  bands  may  be  much  more  clearly  seen 

t  "  Phil.  Trans.,"  B,  vol.  211  (1920). 


than  in  other  positions.  In  order  to  see 
them  with  advantage,  it  is  necessary  to 
focus  the  surface  of  the  insect  on  the  slit  of 
the  spectroscope,  for  otherwise  the  re- 
flexions from  different  parts  of  the  surface 
are  superposed.  Owing  to  want  of  uniform- 
ity in  structure,  the  spectra  from  these  dif- 
ferent regions  are  not  exactly  the  same, 
and  a  loss  of  clearness  results.  I  have 
found  it  convenient  to  use  a  1-inch  micro- 
scopic objective  to  form  an  enlarged  image 
of  the  insect  on  the  slit.  An  ordinary  table 
spectroscope  or  spectrograph  can  be  used, 
but  the  adjustments  are  much  easier  with  a 
spectroscQpe  specially  designed  for  use 
with  the  microscope.  The  instrument  I 
have  used  is  of  a  pattern  designed  by  Sorby, 
and  made  by  Browning.  It  was  intended 
for  examining  absorption  spectra  of  small 
objects,  but  serves  equally  well  for  the  re- 
flexion spectrum.  A  pointolite  lamp  is 
foeussed  on  the  specimen  by  a  condenser  of 
3  inches  focus  provided  with  an  iris 
diaphragm.  The  incident  beam  may  be  at 
about  20°  to  the  axis  of  the  microsoqpe,  and 
the  reflected  beam  at  about  10°  from  the 
normal  to  the  surface  of  the  insect  passes 
up  into  the  microscope.  For  preliminary 
examination  the  upper  part  of  the  spectro- 
scope is  removed,  leaving  the  slit  opened 
wide.  The  field  is  examined  with  a  magni- 
fier. Any  desired  portion  of  the  surface  is 
next  brought  between  the  jaws  of  the  slit, 
which  is  then  narrowed,  and  the  sipectro- 
scope  replaced  for  examining  the  reflexion 
spectrum.  P^or  photography,  an  additional 
lens  and  plate  holder  are  added  above  the 
direct- vision  prism. 

Plate  4,  fig.  1,  shows  a  spectrum  by  re- 
flexion from  the  beetle  called  Pelidnuta 
sumptuosa.  The  angle  of  incidence  was 
about  22^°,  and  the  portion  of  the  insect  in 
the  field  was  a  strip  which  runs  along  the 
(right)  side  of  the  wing  case ;  this  coloured 
strip  lay  in  the  plane  of  incidence,  and  at 
the  angle  above  mentioned  it  gave  a  golden 
yellow  reflexion  of  great  brilliancy. 

The  position  of  the  insect  was  adjusted  so 
that  the  image  of  this  golden  band  lay  along 
the  slit  of  the  spectroscope.  For  determin- 
ing wave-lengths  the  helium  lines  and  green 
mercury  line  were  put  on  as  a  comparison 
spectrum.  It  will  be  seen  that  the  spec- 
trum of  the  beetle  consists  of  a  strong  cen- 
tral maximum  intensity  at  about  wave- 
length 6002,  bordered  on  either  side  by  sub- 
ordinate maxima.  The  photographed  ap- 
pearance is  very  similar  to  the  diffraction 
pattern    produced  by    a  rectangular    aper- 


AUGUST  31,  1923. 


THB  CHEMICAL  NEWS. 


137 


ture,  as  when  a  distant  linear  source  of  light 
is  examined  through  a  telescope  with  a  slit 
limiting  the  object  glass.  And  although 
there  are,  of  course,  important  differences, 
there  is  also,  according  to  the  view  here 
taken,  more  than  a  superficial  analog  be- 
tween the  two  cases.  In  the  case  of  the 
diffraction  pattern,  the  bright  centa*e  cor- 
responds to  the  place  in  the  focal  plane 
when  the  vibrations  from  the  various  ele- 
mentary strips  of  the  aperture  are  all  in  the 
same  phase.  If  we  move  away  laterally 
from  this  position  there  will  be  less  com- 
plete agreement,  and  a  position  is  eventu- 
ally reached  when  the  phases  range  over  a 
complete  period,  and  there  will  be  zero  in- 
tensity. This  corresponds  to  the  first  mini- 
mum. Beyond  this,  there  will  be  a  certain 
measure  of  recovery  until  a  further  posi- 
tion, when  the  phases  range  over  two  com- 
plete periods.  This  is  the  second  mini- 
mum, and  so  on.  All  this  is  repeated  on 
the  other  side  of  the  centre.  In  this  case 
the  light  may  be  regarded  as  monochro- 
matic ;  and,  so  far  as  it  may  not  be  so,  the 
phenomena  are  made  more  complex  by 
chromatic  effects. 

To  pass  now  to  the  present  case.  Sup- 
pose that  instead  of  a  change  of  optical  dis- 
tance among  the  component  vibrations  ns 
we  pass  away  from  the  centre  of  the  field, 
we  have  a  change  of  wave-length.  This 
will  equally  produce  a  discrepancy  among 
the  phases  which  were  originally  in  agree- 
ment, and  eventually  zero  intensity  will  be 
reached  at  the  place  where  the  phases  range 
over  a  complete  period.  Further  on  there 
will  be  a  second  minimum,  where  the 
iphases  range  over  two  complete  periods. 

Now  this  is  exactly  what  occurs  as  we 
pass  along  the  spectrum  from  the  position 
where  the  phases  of  the  waves  reflected 
from  all  the  parallel  planes  are  in  agree- 
ment. To  state  the  matter  quantitatively. 
Let  there  be  n  strata.  If  we  neglect  the 
effects  of  dispersion  in  the  passage  of  light 
through  the  strata,  then  the  whole  relative 
retardation  for  rays  reflected  at  a  given  in- 
cidence from  the  extreme  planes  of  the  sys- 
tem is  a  fixed  linear  quantity,  I,  indepen- 
dent of  the  wave-length.  If  we  suppose, 
further,  that  the  deflexion  is  of  the  first 
order,  we  have,  at  the  centre  of  the  system, 
Xo,  when  the  reflexion  is  a  maximum. 

I  =  nXo 
at  the  first  minimum  on  the  red  side  \^ 

I  =   (n-l)A.,, 
and  at  the  first  minimum  X,    on  the    violet 
side 

I   =   (n+l)A-,. 


Similarly  for  the  second  minima  we  have 
I  =  {n-2)X^    and    I  =  (n+2)A-2 
so  that  the  distance  in  angstroms    between 
the  first  minima  is 

1  1 

+    A„, 

n-1         n-+l 
and  between  the  second  minima 
2  2 

-—-  +  A„. 

n-2       n+2 
If    n  is  large,    these    distances    become 
2  4 

—  Aq  and  —  Aq  respectively.    Applying  this 
n  n 

to  the  actual  case,  we  find  from  the  meas- 
ured spectrum  that  the  first  minima  are  at 
wave-lengths  6215  and  5790;  difference 
425  A.  The  second  minima  are  at  6460  and 
5592;  difference  868  A;  sensibly  double  the 
distance  of  the  first  minima. 

Taking  the  central  wave-length  as  A  6002, 
we  get 

n  =  34. 
The  observed    appearances    are  therefore 
explained  in  detail,  not  only  as  regards  the 
central  maximum,  but    also  as  regards  the 
lateral    subordinate  maxima,    by  assuming 
the  existence    of  thirty-four  strata,    which 
are  situated    at  distances  apart  comparable 
with    half    wave-length    in    the    chitinous 
material.     This  particular  reflexion  shows  a 
much  narrower  band  in  the  stpectrum  than 
any-  other  1    have  met  with,    and  it    is  the 
only  case  where    the  subordinate    maxima 
can  be  well  made  out;  but  these  are  almost 
certainly  differences  of  degree.       This  case 
requires  a  much  larger  nymber  of  reflecting 
planes  than  most  others  to  explain  the  more 
nearly  monochromatic  character  of  the  re- 
flexion, and  they  are  probably  more  evenly 
spaced  than  usual.     Unevenness  of  spacing 
would,  of  course,  obliterate  the  subordinate 
maxima,    just  as    bad  figure  in    a  telescope 
ol)jective  tends  to  obliterate  the  diffraction 
rings  round  the  image  of  a  star. 

Bands  quite  similar  to  Plate  4,  fig.  1, 
may  be  observed  if  a  good  Lippmann  photo- 
graph of  the  spectrum  is  examined  by  re- 
flexion in  direct  sunlight  with  a  pocket 
spectroscope.  The  broad  central  maximum, 
with  the  lateral  maxima,  are  quite  well 
seen,  just  as  in  the  beetle. 

The  question  now  arises,  can  these  bands 
be  explained  with  any  degree  of  plausibility 
as  resulting  from  surface  reflexion?  It  is 
certainly  by  no  means  impossible  to  obtain 
a  surface  reflexion  showing  a  banded  spec- 
trum.    Crystals  of  potassium    permangan- 


138 


THE  CHiJMICAL  NEWS. 


AUGUST  31,  1923. 


ate  give  a  reflexion  showing  such  bands. 
These  bands,  however,  are  complementary 
to  the  bands  of  the  absorption  spectrum.* 
This  in  itself  suggests  that  their  position 
should  be  independent  of  the  angle  of  inci- 
dence, and,  in  fact,  I  have  not  been  able  to 
observe  that  their  position  changed  at  all 
when  the  incidence  was  varied  from  nearly 
normal  to  about  45°.  f 

The  reflexion  bands  shown  in  Plate  4,  fig. 
1,  vary  considerably  as  regards  their  posi- 
tion in  the  spectrum.  This  may  be  seen 
from  their  marked  inclination  to  the  lines 
of  the  coxnparison  spectrum.  As  we  pass 
from  one  part  of  the  insect  to  another,  the 
bands  shift.  This  may  result  partly  from 
change  of  obliquity,  but  I  believe  more 
from  change  of  structure.  Neither  of  these 
causes  would  be  expected  to  act  if  the  spec- 
trum were  kindred  to  that  shown  by  potas- 
sium permanganate,  for,  as  we  have  seen, 
the  permanganate  bands  only  shift  under 
extreme  variations  of  incidence,  and  we 
cannot  well  admit  a  progressive  variation  in 
the  chemical  nature  of  the  reflecting  sub- 
stance itself.  To  postulate  a  large  number 
of  different  chemical  substances  giving 
bands  in  different  positions  of  the  spectrum 
would  be  to  place  an  intolerable  burden  on 
the  theory  of  surface  reflexion  as  the  cause 
of  the  bands. 

Moreover,  the  broad  central  band  with 
lateral  maxima  conforms  exactly  to  the  re- 
quirements  of  the  theory    of  multiple    re- 

*  See  Stokes,  "Phil.  Mag,"  vol,  6,  p.  393 
(1853),  or  "  Mathematical  and  Physical 
Papers,"  vol.  4,  p,  47". 

f  Beyond  this  point  the  bands  are  rather 
difficult  to  make  out,  but  as  was  shown  by 
Stokes,  they  can  be  brought  into  view  by 
polarising  the  incident  light  perpendicularly 
to  the  plane  of  incidence.  Introducing  a 
nicol  to  do  this,  I  have  observed  that  at  an 
incidence  of  70°  there  is  a  slight  shift  of  the 
bands,  amounting  to  about  80  A.  or  say 
one-third  of  the  tcidth  of  a  band  as  com- 
pared with  the  position  of  the  bands  at 
small  incidence,  or  in  the  absorption  spec- 
trum of  the  solution.  This  displacement  is 
towards  the  violet,  in  the  same  direction 
therefrom  as  the  bands  due  to  interference, 
but  relatively  very  small  in  am,ount.  I  have 
only  made  a  few  casual  observations  on  the 
subject.  It  deserves  to  be  pursued,  m-ore 
closely.  The  existence  of  the  displacem,ent 
was  confirmed  by  photographing  the  spec- 
tra along  with  a  comparison  spectrum. 


flexion  from  thin  plates.  On  the  other 
hand,  so  far  as  I  know,  there  is  no  absorp- 
tion spectrum  or  surace  reflexion  spectrum 
having  these  features. 

When  it  is  permissible  to  sacrifice  the 
sipecimen,  I  have  found  it  convenient  to  cut 
a  small  piece  about  1  mm.  square,  and  to 
mount  it  on  the  microscope  stage  on  a 
special  holder,  which  allows  the  piece  to  be 
rotated  in  its  own  plane,  and  also  about  an 
axis  which  lies  in  that  plane.  The  specimen 
can  then  readily  be  brought  to  a  position 
which  shows  the  spectra  to  advantage. 

I  have  examined  in  this  way,  one  of  the 
golden  beetles,  Gallodus  parvulus,  which 
shows  a  remarkable  spectrum  of  bands 
(Plate  4,  fig.  2).  These  are  most  pronounced 
at  the  red  end  of  the  spectrum,  and  come 
out  more  distinctly  when  the  condenser  iris 
is  narrowed  to  a  few  millimetres,  so  as  to 
define  more  precisely  the  angle  at  which  the 
incident  rays  fall  upon  the  specimen. 

If  the  spectroscope  is  replaced  by  an 
ordinary  eye -piece,  it  can  be  seen  that  the 
bright  reflexion  from  a  given  small  area  on 
the  specimen  persists  when  the  specimen  is 
rotated  over  as  much  as  10°  of  arc.  In  this 
observation  the  incident  pencil  was  very 
narrow. 

The  surface  of  the  insect  appears  to  be 
divided  up  into  a  large  number  of  areas 
which  differ  somewhat  in  structure,  each 
giving  a  slightly  different  spectrum  from  its 
neighbours.  Thus,  the  spectrum  is  divided 
vertically  into  a  number  of  strips  differing 
from  one  another  as  to  the  exact  position  of 
the  dark  spectral  bands.  The  photograph 
as  reproduced  has  a  vertical  magnificaiion 
of  about  ninety  times.  It  may  be  inferred 
that  the  areas  on  the  insect  have  linear  di- 
mensions of  about  10  fx,  and  it  aippears  that 
the  wide  angular  range  of  reflexion  is  due 
to  the  small  size  of  the  optically  continuous 
reflecting  areas.  The  case  is  in  this  respect 
similar  to  that  already  encountered  in  the 
case  of  labradorite.*  It  may  be  that  the 
absence  of  a  definite  polarising  angle  is  ex- 
plicable in  the  same  way. 

The  bands  in  this  spectrum  are  to  be  ac- 
counted for  generally  in  the  same  way  as 
the  bands  seen  in  certain  chlorate  crystals 
of  complex  structure.!  It  is  necessary  to 
postulate  a  group  of  planes  giving  a  spec- 
trum band  limited    to  the  red  region,    and 

*  "  Roy.  Soc.  Proc,"  A,  vol.  103,  p.  34 
(1923), 

f  "  Roy.  Soc.  Proc,"  A,  vol.  102,  p.  668 
(1923). 


AUGUST  31,  1923. 


THE  CHEMICAL  NEWS. 


139 


another  group  situated  at  a  distance  from 
the  former  which  gives  a  reflexion  extending 
over  the  yellow  and  green.  In  the  red 
region  of  the  sipectrum  where  these  two  sys- 
tems overlap,  we  get  a  series  of  b^,nds  re- 
sulting from  comparatively  high  interfer- 
ence. The  distance  from  one  dark  band  to 
the  next  was  measured  as  151  A.,  at  wave- 
lengths in  the  neighbourhood  of  6200  A. 
and  for  an  incidenc<.^  11°  from  the  normal. 
If  these  bands  were  regarded  as  due  to  the 
interference  of  light  from  two  strata  only, 
as  in  the  case  of  the  two  surfaces  of  a  single 
thin  film,  we  should  have  a  relative  retarda- 
tion of  forty-one  waves. 

The  incidence  may  be  treated  as  practi- 
cally normal,  thus  the  thickness  would  be 
20.5  waves  in  the  chitinous  material,  or 
about  8  fjL.  In  the  actual  case  the  two  in- 
te'rfering  beams  are  regarded  as  coming  not 
from  single  surfaces  but  from  two  groups 
each  consisting  of  several  planes.  The  dis- 
tance between  these  two  groups  is  the  dis- 
tance calculated  above  as  8  /x. 

This  is  a  much  longer  distance  than  the 
estimate  found  by  Onslow  from  his  polish- 
ing experiments  on  closely  allied  beetles, 
which  gave  him  0.5  /x  only  for  the  whole 
thickness  of  the  layer  concerned  in  produc- 
ing colour.  If  his  estimate  were  acoe|)ted, 
the  theory  of  interference  for  these  bands 
in  the  spectrum  would  have  to  be  aban- 
doned. 

I  cannot  think  that  any  one  who  will  i.\- 
amine  with  a  pocket  spectroscope  the 
bunds  produced  by  reflexion  fron^  h  piece 
of  mica  1/100  mm.  thick  will  be  willinf,'  to 
admit  that  the  bands  from  CaUodus  parvu- 
lus,  hero  reprcxluced  (Plate  4,  fig.  2),  are 
essentially  different  in  origin.  I  think,  to<j, 
that  a  comparison  of  Plate  4,  fig.  1  (Pelid- 
tMta  aumptuosa),  with  the  bands  seen  when 
a  Lippmann  film  is  examined  with  a  small 
spectroscope  in  strong  sunlight  will  irre- 
sistibly lead  to  the  conclusion  that  the  ori- 
gin is  simihu*  in  each  case,  and  that  the 
beetle,  like  the  Lippman  film,  shows  re- 
flexion from  numerous  planes,  uniformly 
spaced. 

Summary. 

It  is  shown  that  some  of  the  iridescent 
beetles  which  have  striking  metallic  colours 
show  band  systems  in  the  spectrum  of  the 
reflected  liglit.  Two  such  spectra  are  re- 
produced. 

The  first,  from  Pelidnota  aumpiuosa, 
shows  a  central  maximum,  bordered  on 
either  side  by  subordinate  maxima  in 
exactly  the  wa  ythat  reflexion  from  a  quite 
uniformly  stpaccd  assemblage  of  thin  plates 


would  require.  The  number  of  planes  cal- 
culated to  be  required  in  this  case  is  no  less 
than  thirty-four.  A  Lippmann  film  shows 
a  similar  spectrum. 

The  second  spectrum  is  from  one  of  the 
golden  beetles,  Callodus  parvulus.  The 
bands  are  accounted  for  on  the  supposition 
of  two  assemblages,  each  consisting  of 
several  reflecting  planes,  the  distances  be- 
tween the  assemblages  being  about  8  p.. 
This  would  result  in  a  series  of  equally 
spaced  bands  over  a  limited  range  of  the 
spectrum,   as  observed. 

The  possibility  of  either  of  these  spectra 
being  produced  on  the  alternative  theory  of 
surface  reflexion  is  discussed,  and  is  found 
to  require  a  number  of  special  suppositions, 
which  seem  very  difficult  of  acceptance. 

[Hcprinted,  by  perniiission,  from  the 
"  Proceedinga  of  the  Royal  Society,"  A. 
Vol.  103.J 


LABOliATOKY  EXPERIMENTS  ON 
THE  EXTRACTION  OF 

MESOTHOKIUM  FROM  MONAZITE 

SAND. 

By  Herman  Sciilundt.* 

In  his  paiper  on  the  chemistry  of  meso- 
thorium,  Soddy  described  several  experi- 
ments on  the  separation  of  mesothorium 
from  monazite  sand.  In  one  experiment, 
800  grams  of  monazite  sand  were  decom- 
|X)8ed  by  heating  with  twice  its  weight  of 
concentrated  sulphuric  acid  to  which  about 
0.1  per  cent,  of  barium  carbonate  had  been 
addetl  befwe  heating.  The  product  was 
stirred  with  cold  water,  and  the  muddy 
liquor  obtained  was  decanted  from  the  un- 
attacked  ingredients  in  the  sand.  The 
sediment  obtained  from  the  muddy  solu- 
tion contained  practically  all  the  meso- 
thorium and  radium  in  the  monazite.  The 
sediment  from  800  grams  of  monazite 
weighed  14.5  grams  and  contained  practi- 
cally the  whole  of  the  material.  The  un- 
attacked  sand  retained  8  per  cent,  of  the 
material.  A  further  precipitation  of  1.6 
grams  of  barium  sulphate  formed  in  the 
clear  monazite-  solution  possessed  a  small 
initial  activity,  due  to  regenerated  thorium 
X  only,  which  decayed  almost  completely 
in  the  course  of  a  month.  Soddy  estimated 
that  less  than  5  per  cent,  of  the  meso- 
thorium was  present  in  the  solution.  The 
presence  of  thorium  X  in  the  precipitate  of 

*  From  a  paper  on  Mesothorium,  pub- 
liahed  by  the  Department  of  the  Interior, 
Bureau  of  Mines,  Washington. 


140 


THE  CHEMICAL  NEWS. 


AUGUST  31,  1923. 


barium  sulphate  and  the  absence  of  meso- 
thorium  are  regarded  as  clear  evidence  that 
practically  the  whole  of  the  mesothorium 
can  be  separated  from  monazite  by  this 
method.  Measurements  were  made  by  the 
cramma-ray  method  both  of  the  original 
material  and  of  the  sediments.  The  gamma 
activity  of  the  main  sediment  fell  to  57  per 
cent,  of  its  maximum  value  in  the  course  of 
a  month,  as  the  effect  of  the  decay  of 
thorium  X  exceeded  the  increase  due  to 
the  generation  of  radium  C. 

Soddy's  procedure  for  extracting  meso- 
thorium was  repeated  in  several  experi- 
ments with  500  grams  of  monazite  sand 
containing  6.54  per  cent,  of  thorium  oxide. 
One  gram  of  barium  chloride  was  added  to 
the  samples,  before  heating  the  sand  with 
twice  its  weight  of  concentrated  sulphuric 
acid.  Four  per  cent,  of  the  acid  boiled  off 
during  cooking.  The  resulting  paste  after 
cooling  was  stirred  up  with  8  litres  of  cold 
water,  and  the  muddy  liquor  slimed  off. 
The  unattacked  sand  was  stirred  up  with 
another  litre  of  water,  and  this  liquor  was 
decanted  off  and  combined  with  the  larger 
volume,  thus  making  a  solution  containing 
about  10  per  cent,  sulphuric  acid.  The 
sediment  from  this  solution  had  a  dry 
weight  of  6.2  grams,  the  unattacked  sand 
46.2  grams.  In  the  course  of  several  days 
the  acid  liquor  gradually  gelatinised  on  ac- 
count of  the  partial  separation  of  thorium 
as  phosphate. 

As  the  measuring  instruments  were  not 
sensitive  enough  for  accurate  measure- 
ments of  the  gamma  radiation  of  monazite 
sand,  the  recovery  of  mesothorium  and  the 
losses  were  obtained  by  making  radium 
determinations  in  the  monazite,  the  sedi- 
ment bearing  the  mesothorium  and  radium, 
the  unattacked  sand,  and  the  liquors.  The 
radium  determinations  were  made  by  the 
emanation  method.  From  the  sand,  the 
unattacked  residue,  and  the  concentrate 
bearing  the  mesothorium  and  radium,  the 
emanation  was  separated  by  boiling  suit- 
able samples  of  these  materials  with  con- 
centrated sulphuric  acid,  collecting  the 
emanation  thus  liberated  quantitatively, 
and  measuring  it  electroscopically  in  cali- 
brated air-tight  electroscopes. 

As  the  liquors  coagulate  upon  boiling 
owing  to  the  separation  of  thorium  phos- 
phate, it  was  necessary,  in  order  to  hold 
the  thorium  in  solution,  to  acidify  the 
liquors  more;  for  this  purpose  concentrated 
hydrochloric  acid  was  used.  The  emana- 
tion could  then  be  separated  quantitatively 


by  boiling,  as  in  the  quantitative  detenni- 
nation  of  radium  emanation  present  in 
natural  waters. 

The  radium  content  of  the  sample  of 
monazite  sand  used,  containing  6.54  per 
cent,  thorium  oxide,  was  found  to  be 
7.98x10-1"  grams  per  gram  when  the  de- 
terminations were  made  by  decomposing 
the  sand  with  concentrate  sulphuric  acid, 
and  8.-21xl0-'"  grains  when  the  radium 
determinations  were  made  by  fusion  of  the 
finely  ground  samples  to  which  a  little 
barium  salt  had  been  added  with  mixed  al- 
kali carbonates  follow^tl  by  estimation  of 
radium  directly  in  the  refined  barium  sul- 
phate. 

The  radium  retained  in  the  unattacked* 
sands  was  to  be  6.5  per  cent,  by  the  sul- 
phuric acid  method,  and  7.4  per  cent,  by 
the  method  involving  fusion  with  mixed 
carbonates  of  sodium  and  potassium.  These 
results  confirm  the  loss  of  about  8  per 
cent,  reported  by  Soddy. 

In  the  liquors  were  found  5.6  per  cent,  of 
the  radium,  makin?  a  total  loss  of  about  12 
per  cent.  In  the  radium-mesothorium 
bearing  concentrate,  84  per  cent,  of  the 
radium  in  the  ore  charge  was  recovered, 
leaving  4  per  cent,  unaccounted  for. 
Plant  Expkuiments  on  the  Extraction  of 
Mesothorium  from    Brazilian    Monazite. 

No  experiments  were  conducted  on  a 
plant  scale  to  ascertain  whether  corres- 
ponding recoveries  of  mesothorium  could 
be  duplicated.  As  already  stated,  in  the 
plant  ru»s  the  mesothorium-bearing  con- 
centrate was  separated  at  a  later  stage  of 
operation.  The  intermediate  stages  include 
several  treatments  where  rather  large 
volumes  of  liquor  are  decanted  off,  therefore 
it  is  not  surprising  that  the  recovery  of 
mesothorium  falls  to  65  per  cent,  as  a  re- 
sult of  mechanical  losses  of  barium  sul- 
phate in  these  operations.  The  successive 
treatments  of  crude  thorium  phosphate 
eliminate  nearly  all  of  the  phosphoric  acid, 
and  when  the  thorium  chloride  solution  is 
finally  obtained,  a  black  slimy  residue  re- 
mains which  bears  the  active  barium  sul- 
phate. 

After  the  residue  had  been  washed  twice 
with  water  by  decantation,  it  was  trans- 
ferred to  a  stoneware  suction  filter  and 
given  another  washing  or  two  with  hot 
water.  Before  analytical  work  on  it  was 
begun,  the  residue  was  dried  for  several 
days  in  steam  kettles  or  on  hot  plates.  At 
this  stage  the  residue  consisted  of  small, 
I       gTeyish  black  lumps    having  the  texture  of 


AUGUST  31,  1923. 


THE  CHEMICAL  NEWS. 


141 


rather  low-grade  graphite.  This  product 
was  then  pulverised  to  pass  through  a  20- 
mesh  sieve  by  means  of  a  disc  pulveriser, 
after  which  it  was  carefully  composited  by 
quartering.  The  product  is  termed  in  this 
paiper  the  crude  concentrate  of  meso- 
thorium.  Duplicate  samples  of  500  grams 
each  were  set  aside  for  analytical  determi- 
nations of  barium,  lead,  and  radium,  and 
for  gamma-ray  measurements.  These 
samples  also  served  in  part  for  the  labora- 
tory experiments  on  the  preparation  of  re- 
fined concentrates,  which  are  described  in  a 
later  section. 

From  the  data  summarised  in  Table  7,  it 
was  concluded  that  the  addition  of  1  pound 
of  barium  chloride  to  400  pounds  of  ore,  in- 
stead   of  1  to  200  ipounds,    does  not  reduce  , 
the  percentage  recovery  of  mesothorium  in  , 
the  crude  concentrate.        In  later  runs,   it 
was  found  that  the  addition  of  one-fifth  of  I 
per  cent,  of  barium  chloride  crystals  to  the  ; 
ore    charge  was    sufficient    to    protect    the  J 
mesothorium.     The   crude     concentrate  oh-  ] 
tained  when  the  smaller  amount  of  barium  ■ 
was    added,     generally    contained     a    little 
more  than  1  milligram  of  gamma-ray  activ- 
ity per  kilogram  of  weight.  1 

The  factor  for  the  conversion  of  pure 
barium  chloride,  BaCIj  2H,()  into  barium 
sulphate  is  0.95;").  In  the  first  plant  run. 
the  crystals  of  barium  chloride  added  gave 
91.15  per  cent,  of  their  weight  of  barium  : 
sulphate.  In  the  second  run,  the  factor 
was  0.0376.  These  factors  were  Ufied  in 
calculating  the  quantities  of  barium  sul- 
iphate  that  resulted  from  the  quantities  of 
chloride  added  in  the  respective  runs. 

A  complete  analysis  of  the  crude  concen- 
trates was  not  atti'inpted.  The  analytical 
data  obtained  clearly  show  that  the  concen- 
trates are  complex  mixtures,  and  in  com- 
parison with  the  "P'irst  sulphates"  of 
radimn-barium  separated  in  the  recovery  of 
radium  from  carnotite  ores,  they  are  of  low 
grade  in  barium  content.  By  qualitative 
tests  it  was  found  that  the  crude  concen- 
trates were  practically  free  from  silica,  but 
that  1  to  2  per  cent,  of  phosphoric  acid  was 
still  ipresent,  A  small  amount  of  thorium 
was  also  retained ;  lead  was  also  present — 
some  of  it  soluble  and  some  insoluble  in 
water.  The  source  of  the  graphite  and 
amorphous  carbon  present  Mr.  Gulbrandsen 
traced  to  the  iron  pots  in  which  the  sand 
was  cooked  with  sulphuric  acid.  In  the 
early  plant  runs  the  quantity  of  carbon  pre- 
sent in  the  cnide  concentrate  was  more 
than  was  required  to  reduce  the  barium  sul- 


phate to  sulphide.  Some  lead  chloride 
could  be  extracted  from  the  concentrate  by 
digestion  with  hot  water.  By  far  tlie  larger 
proportion  of  the  lead  was  present  as  sul- 
phate. Its  amount  varied  considerably  in 
different  concentrates.  From  the  concen- 
trate obtained  in  plant  run  No.  2,  nearly  5 
per  cent,  of  lead  chloride  was  extracted  bj" 
successive  treatments  with  hot  water. 
After  the  removal  of  the  lead  chloride  from 
this  concentrate,  a  determination  of  lead 
showed  that  an  additional  15  per  cent,  of 
lead  sulphate  remained  in  the  concentrate. 
The  percentage  of  barium  sulphate  present 
in  four  different  lots  of  concentrate  analysed 
ranged  from  52  ner  cent,  in  run  No.  1  to 
87  per  cent,  in  one  of  the  later  '^lant  runs. 

By  nuiking  radium  determinations  on 
composites  of  the  different  wash  liquors,  it 
was  found  that  the  radium  losses  in  the  acid 
solutions  amcunted  to  34.6  per  cent,  in  run 
No.  1  and  only  20.2  per  cent,  in  run  No.  2. 
No  explanation  for  this  marked  difference 
was  evident.  The  Ic^sses  in  the  alkaline 
liquors  were  relatively  low — 5.7  per  cent,  in 
No.  1  and  4.5  per  cent,  in  No.  2. 

{To  be  continued.) 


EMPIRE  CANCER  CAMPAIGN. 

Appeal  for  Voluntary  Workers — 
liEKEAVED  Father's  Suggestion. 

The  British  Red  Cross  Society,  which  is 
organising  the  appeal  for  the  British  Em- 
pire Cancer  Cannpaign  (which  aims  at  rais- 
ing £1,000,000  for  Cancer  Research^  is  ap- 
pealing for  voluntary  workers  wno  will 
assist  in  the  collection  of  funds. 

t>om  the  Headquarters  of  the  Society, 
10,  Berkeley  Street,  W.l,  pamphlets  and 
leaflets  advertising  the  aims  of  the  cam- 
paign, books  of  sixpenny  and  shilling 
stamps  to  be  sold  for  the  benefit  of  the 
campaign,  and  posters  designed  for  the  pur- 
pose of  advertising  local  fetes,  concerts, 
etc.,  held  in  the  interests  of  the  campaign 
may  now  be  obtained  on  application.  Local 
organisers  willing  to  assist  the  campaign 
may  also  obtain  literature,  stamps  and 
posters  through  the  medium  of  the  local 
branch  of  the  British  Red  Cross  Society. 

A  valuable  suggestion  has  been  made  by 
Mr.  Reuben  Wood,  of  Sheffield,  who  re- 
cently suffered  the  loss  of  his  son  through 
cancer.  Mr.  Woo<l,  reading  the  appeal 
is8ue<l  in    May    by    the    promotei's    of    the 


142 


THE  CHEMICAL  NEWS. 


AUGUST  31,  1928. 


British  Empire  Cancer  Campaign,  at  once 
wrote  to  the  headquarters  of  the  camipaign, 
expressing  his  wish  to  make  a  collection  on 
its  behalf  as  a  tribute  to  the  memory  of  his 
son.  He  was  then  put  into  touch  with  the 
local  director  of  the  British  Red  Cross 
Society,  and  with  the  help  of  the  local  or- 
ganisation was  able  to  collect  £38  9s. 
amongst  his  friends  within  three  weeks. 

Mr.  Wood,  who  is  helping  to  increase  this 
sum  to  £100,  makes  the  suggestion  that  all 
who  have  suffered  a  bereavement  through 
cancer  should  follow  his  example  and  take 
active  part  in  helping  the  work  of  the  cru- 
sade which  has  been  formed  to  fight  the 
most  terrible  of  all  diseases. 

When  it  is  realised  that  cancer  was  re- 
sponsible in  1921  for  the  loss  of  more  than 
45,000  valuable  lives,  and  that  this  most 
cruel  of  all  plagues  is  taking  a  steadily  in- 
creasing toll  of  life,  it  is  hoped  that  the  ex- 
ample set  by  Mr.  Wood  will  be  followed  in 
every  town  and  village  in  the  United  King- 
dom, until  the  sum  of  £1,000,000  is 
realised  as  the  national  contribution  to  the 
fighting  fund  which  is  to  stand  between  the 
community  and  the  advance  of  this  disease. 


NOTICES  OF  BOOKS. 
The  Structure  of  the  Atom,    by    E,  N. 

DA  C.  Andrade,  D.Sc.    (London),    Ph.D. 

(Heidelberg).     Pp.  XIV.  +  314.  London : 

Messrs.  Bell  &  Sons,  Ltd.,    York  House, 

Portugal  Street,  W.C.2.     1923.    16s.  net. 

Interest  in  scientific  matters  is  not 
diminished  by  sharp  conflicts  in  theory,  for 
well-established  ideas  when  in  fundamental 
opposition  stimulate  interest  and  specula- 
tion; and  one  is  always  keenly  interested  in 
watching  the  developments  in  such  cases. 
It  is  natural  to  expect  that  the  true  or 
more  complete  theory  will  remove  the  fea- 
tures in  conflict  and  co-ordinate  the  other- 
wise discordant  data. 

At  the  present  time,  as  is  well  known, 
two  theories  hold  the  field  in  respect  of  the 
atom;  one  being  the  dynamic  theory  so 
beautifully  developed  by  N.  Bohr,  A.  Som- 
merfeld,  and  others;  the  other  being  the 
static  theory  due  largely  to  G.  N.  Lewis, 
W.  Kossel  and  I.  Langmuir. 

Before  the  above  theories  were  developed 
it  was  known  that  some  radio-active  atoms 
emitted  /3  particles,  which  are  negative 
electrons,  at  velocities  almost  that  of  the 
propagation  of  radiation  in  free  space.  This 
fact  speaks  strongly  in  favour  of  a  dynamic 


atom,  for  how  could  these  electrons  acquire 
such  a  prodigious  velocity  if  they  were  not 
circulating  in  practically  closed  orbits  with- 
in the  domain  of  the  atom ".'  It  is  true  that 
a  particles,  helium  nuclei  (He  +  +)  are  also 
emitted  in  one  case  with  a  velocity  as  high 
as  about  12,800  miles  a  second,  and  it  has 
not  been  suggested  that  they  describe  orbits 
within  the  atom;  but  enormous  forces,  rela- 
tive to  the  masses  involved,  must  exist  in 
connection  with  the  nucleus  of  the  atom  to 
give  effect  to  such  velocities,  as  radio- 
active phenomena  indicate. 

The  energy  represented  by  the  emission 
of  fast-moving  a  particles  in  the  process  of 
radio-active  disintegration  is  greater  than 
that  of  the  fast-moving  electrons  similarly 
ejected,  for  the  mass  of  the  former  is  over 
7,000  times  greater  than  that  of  the  elec- 
tron. From  the  energy  point  of  view, 
therefore,  the  argument  supports  what 
might  be  termed  the  tension  or  strain  idea 
as  against  the  circulation  idea,  but  in  either 
case  enormous  forces  relative  to  the  size  or 
mass  of  the  bodies  ejected  must  exist. 

The  smallness  of  the  electron  in  terms  of 
mass,  however,  leads  one  to  expect  it  to 
suffer  a  great  activity,  for  we  know  from 
the  kinetic  theory  of  gases  and  the 
Brownian  movement  that  the  great  concen- 
trated energy  involved  demands  anything 
but  a  quiescent  state  of  affairs.  One  is  led 
to  believe,  therefore,  that  the  electron  has 
an  orbital  activity.  If  it  has  not  such  an 
activity,  then  there  are  conditions  obtain- 
ing in  the  atom  which  make  it  possible  to 
store  energy  by  tensions  or  strains  which 
are  exceedingly  great ;  but  the  researches  of 
Sir  E.  Rutherford  and  the  studies  of  Bohr 
point  so  conclusively  to  intra-atomic  spaces 
in  which  fast-revolving  electrons  comport 
themselves,  that  the  orbit  theory  is  the 
only  natural  one  that  seems  possible.  As  is 
well  known,  Bohr  has,  by  applying  the 
quantum  theory  to  the  dynamics  of  the 
atom  m  respect  of  its  electrons,  succeeded 
in  accounting  for  the  emission  line  spectra 
of  hydrogen  and  ionised  helium  in  a  most 
remarkable  and  convincing  way.  This 
theory  is  in  such  perfect  accord  with  the 
quantum  theory  which  has  now  a  wide  ap 
plication  in  respect  of  al'  atomic  radiations, 
including  the  so-called  resonance  radiation, 
that  there  is  here  something  which  can 
hardly  bo  due  to  any  form  of  coincidence  of 
a  chance  character. 

The  orbit  theory  receives  strong  support 
from  the  investigations  of  Sommerfeld,  for 
he  has  shown    that  the  application  of  rela- 


AUGUST  31,  1923. 


THE  CHEMICAL  NEWS. 


143 


tivity  to  the  fast-moving  electrons  describ- 
ing elliptical  orbits  accounts  for  the  fine 
lines  observed  in  the  spectra  of  hjdr(^cu 
and  ionised  helium;  and,  moreover,  that  the 
principles  developed  by  this  relativity  analy- 
sis can  be  extended  to  the  movements  of 
electrons  in  atoms  of  the  heavy  elements. 
In  this  case  the  L  doublet  observed  with  X- 
ray  spectra  is  quantitatively  accounted  for 
by  the  application  of  relativity  to  electrons 
describing  Keplerian  orbits,  as  in  the  case 
of  the  hydrogen  atom. 

In  addition  to  the  above,  the  Zeeman  ef- 
fect and  the  Stark  effect  have  been  brought 
into  line  with  the  dynamic  type  of  atom 
established  by  Bohr. 

The  evidence  seems  overwhelmingly 
in  favour  of  electrons  describing  orbits 
round  the  nuclear  parts  of  atoms,  especially 
those  which  give  rise  to  the  spectrum  lines, 
but  the  static  octet  theory  developed  by 
Lewis  and  Langmuir  accounts  for  such  n 
mass  of  chemical  and  chemico-phj-sical 
data,  valency  phenomena  in  particular,  thnt 
it  balances  in  fact  the  mass  of  data  co- 
ordinated by  the  dynamic  theory,  as  already 
stated. 

The  problem  is  to  reconcile  these  two 
most  remarkable  theories  without  destroy- 
ing the  essential  features  of  either  one. 

Those  interested  in  this  problem  will  find 
Prof.  Andrade's  book  worth  careful  study, 
as  the  subject  of  atomic  structure  is  ade- 
quately treated  therein.  In  his  concluding 
remarks  he  says:  "  Something  as  to  the 
possibility  of  a  reconciliation  between  dyna- 
mical and  statistical  models  will  be  expected 
in  such  a  book  as  this,  and  a  word  on  the 
subject  will  be  attempted.  Have  wo  here 
the  complete  contradiction  which  remains  a 
mystery  f(>r  wise  men  and  weaker  brother 
alike? 

'  Denn  cin  vollkommner  Widerspruch, 
Bleibt  gleich  geheimnisvoll  fiir  Kluge  wie 
fiir  Toren.' 

The  answer  is  that  we  have  to  consider  not 
whether  an  electron  can  be  at  rest  and  in 
motion  at  the  same  time — I  am  not  suflfi 
cient  of  a  philosopher  to  attempt  an  answ  r 
to  that  question— but  rather  whether  it  fol- 
lows that,  because  for  certain  problems 
electrons  may  be  conveniently  treated  as  if 
they  were  at  rest,  they  cannot  be  in  motion? 
In  my  opinion,  by  no  means.  In  the  very 
eccentric  orbits  of  Bohr's  theory,  for  which 
the  azimuthal  quantum  number  is  L  the 
electron  visits  the  outer  parts  of  the  atom 
periodically,  and  must  have  a  preponderat- 


ing effect  on  an  electron  of  another  atom  at 
the  same  time  when  it  is  furthest  from  its 
own  nucleus.  Thus  the  external  loop,  if  I 
may  so  call  it,  of  such  an  orbit  may  well 
correspond  closely  in  its  chemical  effect  to 
an  electron  stationary  somewhere  in  the 
region  of,  say,  the  empty  focus  of  the 
ellipse  to  which  the  loop  is  known  to  ap- 
proximate in  form.  Although  the  electron 
visits  the  nucleus  periodically  this  part  of 
the  orbit  which  is  distant  from  the  nucleus 
behaves  as  if  of  different  quantum  number 
to  the  inner  part,  and  as  if  the  nucleus  had 
an  effective  charge  different  from  the  actual 
charge,  as  has  been  pointed  out  in  Chapter 
XL  Hence  it  is  not  improbable  that  this 
part  of  the  orbit  may  act  in  a  special  way, 
much  like  the  stationary  electron  or  local- 
ised orbit  demanded  by  the  followers  of 
Lewis.  These  loops  appear  locally  in  the 
surface  of  the  atom,  and  may  be  likened — to 
commit  myself  to  a  picture  for  whoso  crude- 
ness  apologies  are  due — to  handles  on  a 
spherical  jug.  It  is  true  that  there  is  a 
slow  motion  of  the  aphelion — or  apnucleon 
— of  the  orbit,  but  this  will  have  no  essen- 
tial effect  on  the  problem  under  considera- 
ticm.  The  nature  of  the  forces  which  exist 
between  the  loops  of  different  atoms  may 
be  electrostatic  or  maghetic^-ywe  need  not 
here  offer  an  opinion.  We  are  more  justi- 
fied in  considering  the  loops  as  if  they  were 
actual  attachments  to  the  atom,  in  that 
Bohr  often  speaks  of  his  orbits  rather  as  if 
they  were  actual  pipes  or  conduits  than  as 
if  they  were  mere  paths  traced  out  by  an 
electron.  I  do  not  mean  for  a  moment  to 
suggest  that  this  is  more  than  a  method  of 
drawing  attention  to  the  supreme  import- 
ance of  the  form  of  the  orbit."  To  con- 
tinue— 

"  We  can  also,  of  course,  consider  an 
electron  to  be  shared  without  it  necessarily 
being  at  rest.  It  seems,  on  general  grounds 
— which  are  admittedly  often  deceptive — 
quite  possible  that  one  electron  may  pass 
from  the  orbit  of  one  atom  to  an  orbit  of 
another  atom,  describing  either  a  figure  of 
8  orbit,  including  a  nucleus  in  each  loop,  or 
an  approximately  elliptical  orbit  of  larger 
dimensions,  including  two  nuclei  within  it. 
A  conception  of  electron-sharing  may  be  re- 
conciled with  a  dynamical  atom." 

Referring  to  Meitner's  model  for  radio- 
active nuclei,  page  116,  we  think  that  the 
statements  in  this  connection  could  be  made 
clearer  to  advantage. 


144 


THE  CHEMICAL  NEWS. 


AUGUST  31,  1923. 


Bauxite  is  an  ore  of  great  importance  in 
certain  industries.  For  example,  when  it  is 
fused  in  a  special  electric  furnace,  crystals 
of  aluminium  oxide  are  formed  which  are 
extremely  hard,  the  diamond  being  only 
slightly  harder.  This  is  known  under  the 
registered  trade  name  as  Alundum.  Alun- 
dum,  besides  being  used  for  the  well-known 
abrasive  wheels  for  grinding  and  finishing 
materials  in  the  course  of  manufacture,  is 
used  in  another  fonn  for  stair  treads,  as  for 
examiple  on  tramway  cars,  or  in  railway 
stations.  It  is  used  also  for  danger  places 
in  factories  where  slipping  must  be  pre- 
vented. It  is  quite  acid  resisting,  and  can 
be  used  in  chemical  works'  floors.  Clay  is 
used  as  a  binder  to  form  the  alundum  tiles, 
wheels,  etc. 


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Specifications   Published   this   Week. 
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metals  from  solutions. 
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tions in  sulphuric  acid  as  sulphurous  acid  com- 
pounds by  treatment  with  ammonium  sulphite  or 
bisulphite  in  quantity  corresponding  with  the 
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nium sulphate  is  recovered  as  a  bye-product,  and 
the  escaping  sulphur  dioxide  is  absorbed  in  am- 
monia to  produce  sulphite  again.  Examples  are 
p;iven  in  which  the  reaction  product  (containing 
isatine  anilide)  of  example  TTT.  of  Specification 
1.549'7/90  is  allowed  to  react  with  solutions  of 
ammonium  sulpliite  or  bisulphite,  the  isatine 
anilide  sulphurous  acid  compound  being  precipi- 
tated. 

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SEPTEMBER  7,  1023. 


THE  CHEMICAL  NEWS. 


145 


I 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.     No.  3308. 


THE    QUANTUM    THEORY. 

By  R.  F.  Hunter,  F.C.S. 

In  a  recent  lecture  delivered  before  the 
Chemical  Society  of  the  Royal  College  of 
Science,  entitled:  "  Some  Aspects  of  the 
Quantum  Theory,"  Dr.  C.  K.  Ingold,  D.Sc, 
F.LC,  rei narked  that  the  quantum  theory 
is  less  an  attempt  to  explain  than  a  focus- 
sing of  all  difficulties  into  one.  This  is 
very  true,  and  it  might  be  of  some  interest 
to  us  as  chemists  to  consider,  firstly,  the 
nature  of  the  quantum  theory,  and, 
secondly,  its  application  in  Chemistry;  for 
the  theory,  though  now  regarded  as  a  des- 
tined branch  of  Physical  Chemistry,  or 
rather  Chemical  Physics,  is  one  of  consider- 
able iniiportanoe  to  us  as  chemists,  mainly 
becausi,'  of  its  elose  connection,  or  rather 
interdependence  with  the  Bohr  thewy  of 
the  atom,  and  we  fear  has  been  too  long  re- 
garded in  the  light  of  a  piece  of  mathemati- 
cal physics,  and  its  application  in  chemistry 
as  being  almost  of  the  nature  of  trespassing 
of  chemists  in  a  field  which  is  one  of  the 
most  sacred  domains  of  mathematical 
physics,  almost  as  sacred  as  that  of  the 
theory  of  relativity.  There  would  appear, 
therefore,  no  necessity  to  apologise  for  a 
brief  elementary,  and,  as  far  as  can  be  non- 
mathematical  review  such  as  this,  in  a 
chemical  journal.  It  will  of  course  first  be 
neci'ssary  to  run  over  brielly  in  a  rough  way, 
some  of  the  considerations  of  mathematical 
physics,  such  as  the  (|nestion  of  statistical 
ineeluinics. 

EnTUoPY    .1-    TllKRMODYNAMIC    PROBABILITY, 

Etc. 
If  we  have  Xa  molecules  of  hydrogen  in  a 
given  sipace  v  and  Np  of  oxygen  in  a  space  v 
Then  it  can  be  shown  that  if  we  require  2 
molecules  of  hydrogen  to  combine  with  one 
of  oxygen,  the  chance  of  this  occurrence  is 
given  bv  the  expression  : 

Na     N^*  Np 


Na  +  Np 
will  obvionslv 


be 


l,Na  +  Npj 
and  the  rate  of  collision 
given  bv  an  expression  : 

R  =  Rate  of  Collision  =  K.  C,*  Cp, 
where  R  is  a  constant    and  Ca  and  Cp    the 
concentrations. 

The  above  is  a  simple  application  of  the 


laws    of    mathematical    probability    to    the 
kinetic  theory  of  gases. 

We  next  consider  the  question  of  entroipy 
and    thermodynamic    probability,    and    the 
relation  can  be  shown  to  be  of  form 
Entropy  a  loge  (Probabilitv) 
or  S  =  k.  loge  W. 

to  be  more  general 

S  =  k  loge  W  +  constant. 
By  means  of  Boltzmann's  expression, 
S  =        k  N  log.  u  +  k  N  log.  V  +  k. 
where  U  is  internal  energy  of  our  system. 
R  being  defined  as  above; 
N  =  Number    of    molecules    in    system 
being  a  constant. 
We  can  arrive  at 
8S  8U     8S       3  SV 

—  =  X  —      —  =  — .  kN.    L.- 
ST       T    8T    8T       2  U  sT 
3 
hence    U  =  —  k  N.T. 
2 

But  we  know  that  the  total  kinetic  energy 
of  molecules  of  a  gm  molecule  to  be 
8 

—  R  T  in  case  of  monoatomic  gas 
2 
8 
then   U  =  —  R.T. 

2 
and  we  arrive  at         N.K.  =  R. 
where  R  is  gas  constant  per  molecule,    and 

3 
for  a  perfect  gas  —  R  =  Cv,    Cv  being  gn 

molecular  heat  at  constant  volume,  and 
hence  our  equation  for  monoatomic  gas  be- 
comes 

S  =  Cv.  log  T  +  R  log  V  +  K 
S  =  entropy  of  a  gm  molecule. 

We  now  come  to  the  question  of  equipar- 
tition  of  energy  : 

We  consider  a  molecule  of  gas.  to  have, 
firsti}',  energy  of  translation;  secondly, 
energy  of  vibrations;  and  thirdly,  energy  of 
rotation.  The  molecular  rotations  being 
ascribed  to  collisions  with  other  molecules, 
anrl  quite  distinguished  from  atomic  vibra- 
tions. Instead  of  molecular  rotation  we 
might  have  precessional  vibrations.  Now, 
in  the  case  of  diatomic  molecules,  we  have 
three  degrees  of  freedom  due  to  translation, 
one  in  respect  to  linear,  and  two  in  respect 
to  molecular  rotation:  six  in  all. 

Regarding  rotation  as  impossible  and 
substituting  precessional  vibrations  corres- 
iponding  to  degrees  of  freedom,  again  we 
have  six  in  all-     Now 


146 


THE  CHEMICAL  NEWS 


SEPTEMBER  7,  11^23. 


1  1 

—  Mu=^  =  R  T  =  —  N.  mu=^ 
3  3 

3 
KE  of  gn.  mol.  =  —  R  T. 
2 
Hence,  since  gas  molecule  has  three  de- 
grees of  freedom    in  virtue    of    translation, 
applying  equipartition  principle,  we  obtain 
each       degree       of       freedom         possesses 

1 
KE  =  —  RT. 
2 

It  can  be  shown  by  application  of  ele- 
mentary mechanics  that  the  potential 
energy  of  a  particle  in  circular  vibration  is 
equal  to  the  KE  of  vibration. 

Hence  we  arrive  at  the  conclusion  that 
for  a  diatomic  molecule,  provided  the  law 
of  equitpartition  holds,  and  provided  that  all 
degrees  of  freedom  are  equally  effective  : 

7 
The  total  energy  =  —  RT. 

2 
Also  R  =  2  cals  ap. 
Therefore  Energy  =  7  cals. 
But  the    molecular  heat   of  diatomic  gas 
varies    with    temperature  in    a  way    unac- 
counted for  by  equipartition  principle 

Cp 
Where  —  =  Y        Then  of  n  =  No.  of  de- 
Cv  grees  of  freedom  of  the 

Gas  molecule 

2 

Y  =  1  +  — 

n 
and  in  a  diatomic  gas        Y  =  1.4  ..  n  =  5 

Y  =  1.3  .-.  n  =  7 
and  further  Y  is  not  constant  and  varies 
with  temperature. 

The  atomic    heat  of    solids    theoretically 

d 

can  be  shown  to  be  given  by  Cv  =  —  (3  RT) 

dT 

=  3  R  on  the  equipartition  principle. 

This  means  that  the  atomic  heat  of  a 
monoatomic  solid  should  be  constant  and 
independent  of  tem^perature ;  but  we  know 
that  atomiq  heat  of  elements  in  a  solid 
state  is  a  function  of  temperature,  and  fur- 
ther that  this,  the  atomic  heat,  is  a  con- 
tinuous function  of  temperature.  Clearly 
then,  we  are  faced  with  a  wide  discrepancy 
between  what  is  theoretical  and  what  we 
know  from  our  experimental  laboratory 
work. 

We  now  turn  from  this  subject  to  that  of 
Radiation. 


Jeans,  assuming  the  number  of  degrees 
of  freedoin  possessed  by  the  ether  to  be  in- 
finite, applying  the  principle  of  equiparti- 
tion, showed  the  energy  distributed  itself  in 
the  normal  S(pectrum  in  such  a  manner  that 
the  intensity  corresponding  to  a  region  lies 

e 

between,  say,  A  &  A  +  dA     a     — 

A* 
meaning  that  we  should  expect  the  energy 
in  the  spectrum  to  confine  itself  nearly  en- 
tirely to  the  ultra-violet  region,  and  this  is 
far  from  being  the  case,  as  shown  by  phy- 
sical measurement. 

Previously  it  had  been  shown  by  physi- 
cists that  the  intensity  of  radiant  energy 
from  a  black  body  in  equilibrium  with  the 
body  shows  a  maximum  value  for  infra-red 
waves. 

Raleigh's  experimental  work,  in  which 
we  have 

4ffkTA-^dA 
yields  a  curve  with  no  maximum,  but  rises 
rapidly  as  A  decreases. 

The  integration  of  the  Raleigh-Jean  equa- 
tion between  the  limits  Aq  and  A  oo 

4       RT 
gives  us  —      — 

4       A,^ 

This  would  lead  us  to  consider  that  |  of 
the  total  energy  will  be  for  wave  length 
>^A  o  and  |  between  Lts.  of  2Ao  &  A. .  Hence 
we  should  conclude  that  the  number  of  de- 
grees of  freedom  of  ether  is  not  by  any 
means  infinite,  and  is  insufficient  to  yield 
an  expression  which  would  involve  concep- 
tion of  equipartition  princiiple,  which  would 
agree  with  experimental  results. 

To  clear  matters  at  this  point.  Plank  put 
forward  his  quantum  hypothesis  of  quanta, 
disregarding  entirely  the  equipartition  prin- 
ciple. He  assumed  that  changes  of  energy 
between  matter  and  ether  cannot  be  con- 
tinuous, but  must  take  place  in  definite 
steps  which  are  multiples  of  some  small 
energy  unit,  the  energy  considered  being  a 
finite  function  of  the  vibration  frequency 
concerned. 

It  is  of  interest  to  note  at  this  point  that 
Sir  J.  J.  Thomson  considered  radiant 
energy  units  or  "quantum"  as  a  region  of 
periodic  disturbance  travelling  along  a 
Faraday  tube. 

Plank  laid  stress  on  mode  of  absorption 
and  of  emission  of  radiant  energy  by  mat- 
ter. The  energy  radiated  by  one  element 
of  a  black  body,  for  instance,  is  partially 
absorbed  by  the  elements.  Each  of  these 
vibrators    or    resonators    which    constitute 


SEPTEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


147 


material  elements  in  question  can  only  emit 
or  absorb  energy  in  certain  fractions. 

Plank's  resonators  in  the  infra  red,  we 
regard  as  charged  atoms;  those  in  the  ultra 
violet  as  electrons.  For  the  purpose  of 
theoretical  considerations  Plank  regards  his 
resonator  as  linear,  and  considers  only 
energy  vibration  in  one  direction,  entailintj 
one  degree  of  freedom.  The  important 
point  of  Plank's  hypothesis  fs  that  it  does 
away  with  the  use  of  the  princiiples  of  equi- 
partition  of  energy,  and  wo  can  state  his 
hypothesis  as  follows.  It  is  necessary  for 
the  energy  to  attain  a  finite  value  e  in  order 
that  the  resonators  composing  the  material 
system  may  be  able  to  absorb  or  emit  it. 

Essentially,  "quantum"  is  not  a  fixed 
and  constant  quantity  of  energy,  it  is,  ac- 
cording to  Plank,  a  function  of  vibration 
frequency,  and  we  can  express  his  view  as 
the  magnitude  of  quantum  =  hv,  where  v 
is  vibrational  frequencv  and  h  is  Plank's 
universal  constant;  nnh  further,  if  one  con- 
siders a  material  system  made  up  of  mole- 
cules, atoms  and  electrons,  such  a  system 
must  possess  resonators  of  different  dimen- 
sions, and  hence  o  difference  frequency. 

If  we  consider  a  system  of  vibrators  and 
resonators  N,  and  if  M  possess  zero  energy, 
it  can  be  shown  that  we  have  a  relation  : 

M 

N    =      

(1  -  e    .(1^) 

If  2U  is  total  energy  of  N  resonators,  we 

Ne  Nhv 

2U  =  = 

e    ^/*»  -  1  e    »"/^  -  1 

.ind  \\  radiation  density  is  u^ : 
c'      u^ 

tr   =    (a) 

8ffv» 
8;rkv»  1 

and :  Uy  dv  = . .  dv. 

o»       e     "V"  -1 
This  is  a  form  of  Plank's  radiation  form- 
ula. 

If  space  density  of  energy  be  E,  and 
AE 

—  =  EA 
AA 
it  can  bo  shown  that 

8Tch  1 

EA  = . 


m 


«*/x" 


-1 


which  i^  the  usual  form  of  Plank's  formula 
for  distribution  of  energy  in  spectrum. 

The  moaning  of  the  cf>iistant  k  is  shown 
by  consideration  of  high  temperature  vibra- 
iioa,  where  one  has  the  relation  ., 


EA  =  8;rkTA-*. 

The  above  is  the  account  of  quantrum 
theory  as  it  was  first  conceived  by  Plank. 
Plank  modified  it  later  as  follows : 

While  emission  of  radiant  energy  is  dis- 
continuous, viz.,  taking  place  in  quanta, 
absorption  can  take  place  continuouslj', 
this  consideration  giving  rise  to  a  new  ex- 
pression of  the  form 


Tf  = 


hv 


./k 


+1 


This  brings  us  to  Einstein's  work  on  the 
calculation  of  specific  heats  of  crystalline 
solids,  and  which  is  mainly  an  extension  of 
the  quantum  theory. 

Defining  specific  heat  at  constant  volume 
dU 
Cv     =     — 
dT 
when  U  and  T  have  usual  meanings. 

Consider  metals,  the  vibrational  energy 
of  atoms  about  their  C.G.S.  (three  dimen- 
sions) is  to  be  regarded  as  representing  the 
whole  internal  energy  of  the  atom,  and  we 
arrive  at  relation : 

3  R     =6  Cal., 
which  is  approximate,  and  which  on  equi- 
partition  principle  should  be  constant,  but 
which  we  know  to  vary  with  temperature. 
Using  the  expression 

hv 

fT  =   

e  "^Z"       '1 
and  denoting  the  average  vibrational  energy 
per  cm  molecule  as  U,  one  arrives  at 
'       ^  3Nhv 


U     = 


hv.kt 


-1 


Put  —  =  ,5o 
k 

R 
Then  k  =  — 


hv 


N 
R 
=  —  iSov 

N 


U  =  3R. 


iSov 


'/'  -1 


&  Cv= 


/du' 


IdxJ 


=  3R£^oTl   T 


1^0^]  2 


J 


}y  (  e  i8oVT-l)  2 

The  correction  giving  us  Cv  as  a  function  of 
temperature. 

(To  be  concluded  next  week.) 


148 


THE  CHEMICAL  NEWS. 


SEPTEMBEB  7.  1923. 


A  THEORY  OF  CHEMICAL  REACTION 
AND  REACTIVITY. 

By  E.  C.  C.  Baly,  C.B.E.,  F.R.S. 

All  theories  of  the  absorption  of  energy 
by  molecules,  more  partioularly  the  modern 
radiation  theories  of  chemical  reaction,  are 
based  on  the  assumption  that  molecules  are 
characterised  by  dehnite  free  periods  oi 
vibration.  Furtlier,  the  energy  quantum 
theory  has  as  its  basis  the  additional 
assumption  that  the  absorption  and  radia- 
tion of  energy  at  the  molecular  frequencies 
are  not  continuous  but  discontinuous.  It 
is  a  necessary  sequitur  that  any  radiation 
theory  of  chemical  reaction  developed  from 
these  two  initial  assumptions  must  be  one 
of  monochromabic  radiation.  It  was  first 
shown  by  Henri  and  Wurmser,  and  more 
conclusively  by  Langmuir,  that  all  these 
theories  entirely  fail  to  explam  the  facts, 
the  number  of  molecules  that  react  bemg 
enormously  greater  than  that  calculated 
from  the  known  amount  of  energy  absorbed, 
and  the  resulting  criticism  of  these  mono- 
chromatic radiation  theories  becomes  sm- 
gularly  cogent. 

It    is    well    known    that    any    substance 
(other  ^  than    black    bodies)    possesses    the 
power  of  selectively  radiating   and  absorb- 
ing radiant  energy  of  definite  frequencies  m 
the  infra-red,  ultra-violet,  and  sometimes  in 
the  visible,  regions  of  the  spectrum.     More- 
over, the  frequencies  exhibited  by  any  sub- 
stance in  the  visible  and  ultra-violet  are  al- 
ways exact    integral  multiples    of  a  funda- 
mental frequencv    exhibited    by    that    sub- 
stance in  the  short  wave  infra-red.     Again, 
the  fundamental  short    wave  infra-red  fre- 
quency is  always  an  exact  integral  multiple 
of  the    frequencies    exhibited    by  the    sub- 
stance in  the  long  wave  infra-red.     This  in- 
tegral   relationship    has  a  mo«t    important 
bearing  on  the  radiation  of  the  ener^v  that 
has  been  absorbed.     It  is  obvious  if  a  sub- 
stance   absorbs  energy    without  uiidergomg 
any  photo-chemical    change  that  the  whole 
of  the  energy  is  radiated  at  longer  frequen- 
cies.    Let    is  be    supposed    that  a    single 
molecule  absorbs  one  quantum  of  energy  at 
one  of  its  characteristic  frequencies,  say  in 
the    ultra-violet,    without    undergoing    anv 
photochemical    change.       This    amount    of 
energv  is  radiated  at  the  infra-red  frequen- 
cies   and  indeed    as    an    exact    number    of 
quanta  at  those  frequencies.      This  is  only 
rendered    possible  by  the  integral    relation- 
ship between    the  frequencies  exhibited  by 
the  molecule.      The  monochromatic    radia- 


tion theories  of  chemical  reaction  take  no 
account  of  the  radiation  of  the  energy  dur- 
ing the  reaction. 

it  is  possible  to  formulate  a  theory  of 
absoiiption  of  energy  which  is  based  on  as- 
siuuptions  that  are  different  from  those 
which  are  usually  made.  It  may  be  as- 
sumed first  that  an  elementary  atom  is 
characterised  not  by  a  free  period  of  vibra- 
tion but  by  a  definite  amount  of  energy 
associated  with  a  specific  physical  change 
in  the  atom,  such,  for  instance,  as  the  shift 
of  an  electron  from  one  orbit  to  another.  On 
this  assumption  an  atom  can  only  gain  or 
lose  energy  in  terms  of  this  unit  or  element- 
ary atomic  quantum  of  energy.  A  second 
assumption  may  be  made  that  the  physical 
change  in  the  atom  occupies  a  definite 
period  of  time  which  is  the  same  for  all 
atoms.  The  atom  then  becomes  capable  of 
absorbing  or  radiating  energy  of  a  definite 
frequency.  It  may  in  the  third  place  be 
assumed  that  the  elementary  quanta  of  all 
the  known  atoms  are  integral  multiples  of  a 
fundamental  unit  which  very  possibly  is  the 
elementary  quantum  of  the  hydrogen  atom. 
On  the  basis  of  these  three  assumptions 
it  is  possible  to  formulate  a  theory  of 
chemical  reaction  which  has  very  material 
advantages  over  the  better  known  mono- 
chromatic theories.  In  the  first  place  the 
theory  is  not  monochromatic  and  is  able  to 
explain  the  serious  discrepancies  noted  by 
Henri  and  Wurmser  and  by  Langmuir.  In 
the  second  place  it  appears  catpable  of  ex- 
plaining the  phenomena  of  absorption  spec- 
tra, together  with  Jihe  integral  relationships 
referred  to  above.  I^astly  it  seems  to  pre- 
sent an  interpretation  of  the  mechanism  of 
a  reaction  including  the  phenomenon  of 
catalysis. 

When  two  elementary  atoms  combine*  to- 
gether energy  is  evolved  and  the  simplest 
possible  condition  may  be  assumed,  namely, 
that  each  of  the  two  atoms  contributes  an 
equal  share  of  the  total  energy  lost.  On  the 
first  assumption  made  above  each  atom  can 
only  lose  energy  in  terms  of  its  elementary 
quantum,       and     therefore      the     smallest 

^  amount  of  energy  that  each  of  the  two 
atoms  can  lose  is  the  least  common  integral 
multiple  of  the  elementary  quanta  of  the 
two.  Thus,  if  3.7  and  7.1  represent  the 
elementary  quanta  of  the  two  atoms,  the 
smallest  equal  amounts  of  energy  that  can 
be  evolved  by  the  two  atoms  will  be  71 
quanta  of  .the  size  3.7  in  the  one  case,  and 
37  quanta  of  the  size  7.1  in  the  other.     The 

I      total  energy    lost  therefore    will  be    2   x    71 


I 


SEPTEMBER  7,  1923. 


THE  CHEMICAL  N15WS. 


149 


X  3.7  =  525.4.  It  must  be  noted  tHat  this 
is  only  possible  on  the  third  assumption  of 
the  integral  relationship  between  all  ele- 
mentary atomic  quanta. 

Furtner,  the  gain  or  loss  of  energy  by  the 
resulting  molecule  as  a  whole  must  be  a 
process  in  which  its  atoms  bear  an  equal 
share,  and  thus  the  smallest  possible 
amount  of  energy  that  the  above  molecule 
can  lose  as  a  whole  will  be  reipresented  by 
the  number  525.4.  We  arrive,  therefore,  at 
the  conception  of  a  molecular  quantum, 
which  is  a  multiple  of  the  least  common  in- 
tegral multiple  of  the  elementary  quanta  of 
its  component  atoms.  Just  as  an  atom  is 
characterised  by  a  frequency  which  is 
established  by  its  elementary  quantum,  so 
also  will  a  compound  molecule  be  charac- 
terised by  a  freijuency  established  by  its 
molecular  (juantum.  It  must  be  noted  that 
a  molecular  quantum  is  not.  strictly  speak- 
ing, a  physical  entity,  but  only  a  summa- 
tion of  an  integral  number  of  atomic  quan- 
ta. Anv  criticism  that  might  be  uttered 
against  tne  conception  of  a  molecular  quan- 
tum as  the  sunnnation  of  an  integral  num- 
ber of  atomic  quanta,  must  give  way  be- 
fore llie  necessity  on  the  Planck  theory  of 
the  radiiti-'U  of  a  single  quantum,  ab- 
sorbed by  a  molecule,  as  an  integral  num- 
ber of  smaller  quanta. 

Chemical  reaction  between  atoms,  there- 
fore, consists  in  the  joint  loss  of  an  equal 
amount  of  energy  by  the  atoms  whereby  a 
stable  molecule  is  pr(xluced.  A  very  essen- 
tial feature  of  this  theory  is  that  the  atoms 
on  combining  together  do  not  lose  their  in- 
dividuality as  absorbers  or  radiators  of 
energy.  The  molecule  will  be  able  to  ab- 
sorb its  molecular  quantum  and  also  quanta 
characteristic  of  each  of  its  component 
atoms,  and  it  is  iniiportant  to  note  that  if 
the  molecule  specified  above  be  exposed  to 
radiation  equal  to  that  of  one  of  its  atoms, 
for  example  the  atom  with  quantum  of  size 
3.7,  this  atom  will  absorb  its  quanta,  and 
when  142  of  these  have  been  absorbed  the 
whole  molecule  will  have  gained  an  amount 
of  energy  equal  to  one  molecular  quantum. 

For  the  sake  of  simplicity  the  case  was 
considiTcd  of  two  atoms  combining  to  form 
a  binary  molecule.  The  same  argument 
applies  to  more  complex  molecules,  but  in 
such  cases  the  results  are  not  necessarily  so 
simple.  Although  the  molecular  quantum 
is  always  a  multiple  of  the  least  common 
integral  multiple  of  all  the  atomic  quanta, 
and  although  the  molecule  will  on  examina- 
tion exhibit  its    molecular  and  atomic    fre- 


quencies, the  possibility  now  arises  of  defi- 
nite groups  of  atoms  within  the  molecule 
playing  their  part.  In  this  case,  in  addi- 
tion to  the  molecular  and  atomic  quanta 
and  frequencies,  there  will  be  intra-mole- 
cular  quanta  and  frequencies  characteristic 
of  the  atomic  groups.  Absorption  spectra 
observations  have  established  the  existence 
of  all  three  types  of  frequencies,  molecular, 
intra-n'olecular,  and  atomic,  and  moreover 
the  combinations  of  these  frequencies  due 
to  the  simultaneous  absorption  of  two  or 
more  quanta  have  been  recognised.  It  is  to 
these  combined  frequencies  that  the 
breadth  of  the  so-called  absorption  bands 
is  due. 

The  molecular  frequency  is  usually  situ- 
ated in  the  short-wave  infra-red,  namely, 
that  region  lying  between  the  wave-lengths 
10/11  and  3/x.  The  atomic  frequencies  lie  in 
the  verv  extreme  infra-red,  and  are  of  the 
order  of  1.5  x  10^',  which  corresponds  to  a 
wave-length  of  2000/>i,  whilst  the  intra- 
molecular frequencies  lie  in  the  region  be- 
tween the  two.  In  view  of  the  derivation 
of  the  molecular  frequency  it  is  not  neces- 
sary to  exiplain  the  fact  that  this  is  always 
an  exact  multiple  of  the  smaller  frequencies 
exhibited  by  the  same  molecule. 

Up  to  the  present  nothing  has  been  said 
of  the  origin  of  chemical  combination,  that 
is  to  say  tne  force  or  affinity  which  attracts 
the  atoms  together  in  the  first  place.  There 
is  little  doubt  that  the  explanation  of  this  is 
to  be  found  in  the  electromagnetic  force 
fields  of  the  atom.  Estch  atom  forms  the 
centre  of  an  electromagnetic  fwce  field  and 
possesses  two  faces  which  may  be  called 
positive  and  negative.  When  two  atoms 
approach  one  another  in  such  a  way  that 
their  like  faces  come  together,  they  will  re- 
pel one  another,  but  if  their  unlike  faces 
come  together  they  will  attract  one  another. 
When  two  atoms  attract  one  another  in  this 
way  they  are  able  to  lose  energy  in  common 
as  already  described,  and  we  call  the  pro- 
cess chemical  combination. 

It  nmst  be  remembered,  however,  that 
one  face  only  of  each  atom  is  concerned  in 
the  chemical  combination,  and  there  re- 
mains to  be  considered  its  second  or  what 
may  now  be  called  its  external  face.  Since 
the  ext<.>mal  faces  of  the  atoms  in  a  mole- 
cule must  be  of  different  type,  it  is  not  pos- 
sible to  assume  that  they  have  no  influence 
on  one  another.  The  lines  of  force  must 
condense  together  to  form  a  molecular 
force  field  with  the  escape  of  energy.  This 
process  obviously  is  one  in  which  the  mole- 


150 


THE  CHEMICAL  NEWS. 


SEPTEMBER  1,  1923. 


oule  as  a  whole  takes  part,  and  therefore  the 
energy  lost  must  be  in  terms  of  the  mole- 
cular quantum.  The  force  field  condensa- 
tion therefore  will  take  place  in  stages,  each 
stage  corresponding  to  the  loss  of  one  mole- 
cular quantum.  A  freshly  synthesised 
molecular  is  unstable,  and  must  lose  one  or 
more  quanta  by  the  condensation  of  its 
atomic  force  fields,  and  so  must  pass  into 
one  of  a  number  of  possible  phases,  each 
consecutive  phase  differing  in  energy  con- 
tent by  one  molecular  quantum.  It  is 
readily  shown  that  when  the  freshly  synthe- 
sised molecule  loses  one  molecular  quan- 
tum it  becomes  endowed  with  a  quantum 
which  is  twice  the  molecular  quantum,  and 
hence  with  a  frequency  which  is  twice  the 
molecular  frequency.  In  general  the  phase 
quantum  and  phase  frequency  are  x+1  times 
the  molecular  quantum  and  frequency  re- 
spectively, where  x  is  the  number  of  mole- 
cular quanta  lost  in  the  force  field  conden- 
sation. 

In  addition,  therefore,  to  its  molecular 
frequency  and  smaller  frequencies  due  to 
the  atoms  and  groups  of  atoms,  a  molecule 
will  exhibit  a  phase  frequency  which  always 
lies  in  the  visible  or  ultra-violet.  Since  this 
phase  frequency  is  an  integral  multiple  of 
the  molecular  frequency  the  whole  of  the 
arithmetic  relations  that  have  been  proved 
to  exist  between  the  frequencies  of  a  mole- 
cule are  explained.  Emphasis  may  again 
be  laid  on  these  relations.  The  phase  quan- 
tum and  molecular  quantum  are  not  real 
entities,  but  only  summations  of  an  inte- 
gral number  of  atomic  quanta.  If  a  mole- 
cule absorbs  one  phase  quantum  this  may 
be  radiated  either  as  one  quantum  of  a  less 
condensed  phase  together  with  an  integral 
number  of  molecular  or  atomic  quanta, 
which  is  the  origin  of  fluorescence  or  phos- 
phorescence, or  entirely  as  an  integral  num- 
ber of  molecular  or  atomic  quanta.  Con- 
versely a  molecule  may  gain  one  or  more 
molecular  quanta  on  exposure  to  radiation 
of  a  frequency  equal  to  one  of  its  atomic  or 
intra-molecular  frequencies. 

The  molecular  phases  may  now  be  con- 
sidered in  greater  detail.  The  particular 
phase  into  which  a  freshly  synthesised  mole- 
cule will  pass  depends  on  two  factors.  In 
the  first  place  it  will  depend  on  the  relation 
between  the  external  fields  of  its  atoms,  and 
in  the  second  place  it  will  depend  on  the 
conditions  under  which  the  molecule  exists. 
It  is  evident  that  if  the  positive  and  nega- 
tive affinities  of  the  external  atomic  fields 
are  equal  and  opposite,  the  molecular  force 


field  condensation  will  proceed  far  with  the 
escape  of  many  moleeuiar  quanta.  In  sUch 
a  case  the  phase  formed  will  be  character- 
ised by  a  highly  condensed  field  with  its 
frequency  situated  in  the  extreme  ultra- 
violet. On  the  other  hand  if  the  atomic 
fields  are  unequally  balanced,  ■  the  conden- 
sation will  not  proceed  very  fai',  and  a  bal- 
ance of  one  type  of  affinity  will  remain  un- 
coinipensated. 

When  large  numbers  o'f  molecules  are 
considered  it  must  not  be  expected  that 
they  will  all  exist  in  one  particular  phase. 
Indeed  observation  shows  that  the  most 
usual  condition  is  an  equilibrium  between 
two  or  more  phases. 

Then  again,  it  follows  that  it  is  possible 
to  change  the  phase  in  which  a  molecule 
exists  by  supplying  to  it  or  taking  from  it 
one  or  more  molecular  quanta.  One  of  the 
methods  of  doing  this  is  by  the  use  of  a  suit- 
able solvent.  The  change  in  frequency  ex- 
hibited by  a  molecule  in  the  visible  or  ultra- 
violet by  the  use  ot  different  solvents  has 
been  observed  in  a  great  number  of  in- 
stances. Similar  phase  changes  have  been 
observed  in  many  cases  with  change  of 
temperature. 

Since  the  chemical  reactivity  of  atoms  is 
a  function  of  their  force  fields,  so  also  does 
the  reactivity  qi  a  molecule  deipend  on  its 
force  field.  Ftom  what  has  already  been 
said  of  the  formation  of  molecular  phases  it 
follows  that  the  reactivities  of  the  different 
phases  of  a  given  molecule  will  be  different. 
The  difference  in  the  reactivity  of  the 
phases  can  very  easily  be  proved. 

In  order,  therefore,  that  a  molecule  can 
enter  into  a  particular  reaction  it  is  neces- 
sary to  bring  it  into  the  proper  phase,  and 
it  may  be  said  that  in  general  this  means  a 
less  condensed  phase  than  that  in  which  the 
molecule  normally  exists.  The  import- 
ance of  this  deduction  from  the  present 
theory  is  manifest.  It  at  once  gives  an 
explanation  of  the  fact  that  so  many  re- 
actions will  not  take  place  without  energy 
being  supplied  to  the  molecules,  and  more- 
over, it  enables  us  to  calculate  the  exact  in- 
crement of  energy  required  by  each  mole- 
cule. This  increment  of  energy  amounts 
to  one  or  more  molecular  quanta,  depend- 
ing on  the  initial  and  reactive  phases.  There 
is  no  method  at  nresent  known  of  directly 
measuring  the  size  of  the  molecular  quan- 
tum, but  it  may  be  obtained  by  multiplyinfj 
the  molecular  frequency,  which  can  readily 
be  observed,  into  the  time  factor,  and  for 
this  we  may  use  the  Planck  constant    6.57 


SEPTEMBEK  7,  1923. 


THE  CHEMICAL  NEWS. 


161 


X  10-^'.  If  the  initial  and  reactive  phases 
are  known,  the  necessary  increment  of 
energy  for  one  molecule  may  be  found. 

There  are  two  methods  of  supplying  the 
increment  of  energy  required  for  the  phase 
change.  In  the  first  place  the  molecule  may 
be  exposed  directly  to  a  source    of  radiant 
energy  in  the  form  of  heat  or  light,    and  in 
the  second    place    the  energy  may    be  sup- 
plied by  a  material  catalyst.       Whilst  the 
first  method    may    be  readily    understood, 
the  actitMi  of  a  catalyst  requires    some  ex- 
planation.    It  was  pointed  out  above  that 
in  those  cases    where  the  external    atomic 
fields  are  unequally  balanced  the  molecular 
force    field  condensation    will    not    proceed 
very  far  owing  to  the    unconiipensated  bal- 
ance of  affinity  of  one  type.    If  such  a  mole- 
cule forms    an  addition  complex  with    an- 
other molecule  by  virtue  of  this  uncompen- 
s^ated  balance,  there  will  now  be  nothing  to 
prevent  the  force    field  condensation    from 
proceeding  further  with  the  evolution  of  one 
or  more  molecular  quanta.       If  the  second 
molecule  in  the  complex  has  the  same  infra- 
red frequency  as    the  first,  the  one  or  more 
quanta  given  up  by  the    first  molecule  mav 
bo  nl>8orbed  by  the  second  molecule,    with 
the  result  that  the  latter  is  converted  into  a 
less  condensed  or  more  reactive  phase.  This 
explanation    of  the    change    of  phase    pro- 
duced by  a  solvent  can  readily  be  put  to  thr 
test  of  experiment.     In  the  first  place  the 
infra-red  frequencies  of  the  two,  solute  and 
solvent,  must  be  similar,  and  in  the  second 
place  if    the  solute    molecule  is    converted 
into    a  less   condensed    phase    the    solvent 
molecule  must  pass  into  a  more  condensed 
phase.      It  has  been  found  that  when    two 
molecules  form  an    addition  complex,    this 
complex  does  not  exhibit  the  molecular  fro- 
([uencies  of  its  two  components,  but  a  mole- 
cular frequency  of  its  own.  The  mechanism 
for  the  transference    of  one  or  more    mole- 
cular   quanta    from  one    molecule    to    the 
other  is  therefore  perfect.     Again,  some  re- 
cent investigations  appear  to  show  that  in 
such    a    complex,    when     one    component 
passes    into  a  less    condensed    phase,    the 
other  component  passes    into  a  more  con- 
densed phase.      The  explanation  of  the  ef- 
fect of  a  solvent  in  changing  the  phase  of  a 
molecule     is  thus  experimentally    verified. 
It  may  be  stated  that  although  this  expla- 
nation has  been    given    for  the    particular 
case  of  a  solvent  and  solute,  it  undotibt<>dly 
applies  to  all  cases    of  catalysis.       A  cata- 
lyst may  be  defined  as  a  substance  which  by 
virtue  of  its  power    of  forming    an  addition 


complex  with  the  catalyte  converts  the 
latter  into  a  less  condensed  and  more  re- 
active phase,  itself  passing  into  a  more  con- 
densed phase. 

It  will  be  evident  that  the  deductions 
made  from  the  three  original  assumptions 
as  to  the  existence  of  elementary  atomic 
quanta  lead  to  a  radiation  theory  of  chemi- 
cal reaction,  a  theory  which  differs  from 
the  better  known  theories  in  the  essential 
fact  that  it  does  not  rest  on  a  basis  of  mono- 
chromatic radiation.  The  deductions  made 
from  this  theory  may  be  briefly  recapitu- 
lated. The  existence  is  established  of 
simple  integral  relationships  between  the 
various  frequencies  exhibited  by  a  molecule 
and  of  the  combination  of  these  frequencies 
to  form  subsidiary  frequencies  within  the 
absorption  bands.  These  relationships  have 
all  been  observed. 

A  molecule  must  exist  in  one  of  a  number 
of  possible  phases,  any  two  consecutive 
phases  differing  in  energy  content  by  one 
molecular  quantum  of  energy.  Each  phase 
is  characterised  by  its  own  phase  quantum 
and  phase  frequency,  and  each  phase  is  en- 
dowed with  its  own  specific  reactivity.  A 
molecule  must  be  brought  into  the  appro- 
priate phase  before  it  can  take  part  in  a  re- 
action. Since  a  molecule  in  the  free  state 
exists  in  a  more  condensed  phase  than  the 
one  desired,  it  is  necessary  to  supply  energy 
to  the  molecule  to  produce  the  phase 
change.  This  increment  of  energy  is  exactly 
equal  in  amount  to  one    or  more  molecular 

3uanta,  the  number  depending  upon  the 
iflference  between  the  initial  and  reactive 
phases.  Ihe  energy  can  be  gained  by  the 
molecule  on  exposure  to  radiation  of  fre- 
quency equal  to  its  atomic,  intra-molecular, 
or  phase  frequency.  Changes  of  phase  pro- 
duced by  heat  and  by  light  have  frequently 
been  observed.  The  effect  of  temperature 
is  due  to  the  summation  within  the  mole- 
cule of  an  integral  number  of  atomic  or 
intra-molecular  quanta  to  give  the  one  or 
more  molecular  quanta  required.  When 
the  phase  change  is  produced  by  the  ab- 
sorption of  a  phase  quantum,  the  balance  of 
energy  over  that  required  is  radiated  as 
fluorescence  or  phosphorescence.  The  in- 
crement of  energy  may  be  supplied  by  a 
material  catalyst  which  forms  an  addition 
complex  with  the  molecule  in  question. 
Within  this  complex  one  or  more  molecular 
quanta  are  given  to  the  reactant  molecule 
hy  the  catalyst  molecule,  the  former  pass- 
ing into  a  less  condensed,  the  latter  into  a 
more  condensed  phase. 


152 


THE  CHEMICAL  WEWS. 


SEPTEMBEli  1,  1923. 


Mention  m&y  be  made  of  the  experimen- 
tal evidence  in  support  pf  this  theory.  The 
integral  relationships  between  the  frequen- 
cies exhibited  by  a  molecule  and  the  change 
of  phase  exhibited  by  a  catalyst  have  al- 
ready been  dealt  with.  The  most  important 
confirmation  of  the  theory  is  to  be  found  in 
the  explanation  which  it  gives  of  the  dis- 
crepancy observed  between  the  actual  and 
calculated  number  of  reacting  molecules. 
The  better  known  theories  make  the  very 
simple,  not  to  say  obvious,  assumption  that 
a  minimum  of  one  energy  quantum  is  neces- 
sary to  activate  a  single  molecule.  From  a 
knowledge  of  the  energy  absorbed  in  any 
given  reaction  and  the  frequency  character- 
istic of  the  reacting  molecules  it  is  easy  to 
calculate  the  number  of  molecules  which 
should  have  reacted.  In  general  the  actual 
number  is  many  million  times  larger  than 
the  calculated  number,  the  divergence  of 
the  observed  from  the  calculated  number 
being  different  in  different  cases. 

These  monochromatic  theories,  however, 
take  no  cognisance  of  the  destination  of  the 
energy  that  has  been  absorbed.  The  appli- 
cation of  the  present  theory  will  be  under- 
stood more  easily  from  a  particular  case 
which  has  been  quantitatively  studied, 
namely,  the  photochemical  union  of  hydro- 
gen and  chlorine.  As  is  will  known,  this  re- 
action proceeds  when  the  mixture  of  gases 
is  exposed  to  radiation  of  frequency  equal  to 
that  characteristic  of  chlorine.  The  equa- 
tion for  single  molecules  will  be 

H^  +  CI,  +  E  =  2HC1  +  E  +  K, 
where  E  is  the  amount  of  energy  absorbed 
by  the  chlorine  molecule,  i.e.,  one  phase 
quantum,  and  K  is  the  observed  heat  of  re- 
action for  the  formation  of  two  molecules 
of  HCl.  For  the  present  purpose  it  is  of  no 
consequence  whether  the  amount  E  is  or  is 
not  the  minimum  amount  necessary  to  acti- 
vate a  chlorine  molecule.  The  sole  point  of 
importance  is  that  E  is  exactly  one  phase 
quantum  characteristic  of  the  free  chlorine 
molecule.  During  a  reaction  two  molecules 
of  HCl  are  formed  and  the  energy  E  +  K  is 
radiated.  This  energy  is  radiated  by  the 
HCl  at  infra-red  frequencies  characteristic 
of  the  HCl  molecule.  The  quantity  E  can- 
not be  radiated  by  the  chlorine,  for  if  it  were 
so  radiated  the  chlorine  would  lose  its  re- 
activity. Now  the  HCl  molecule  has  at 
any  rate  some  infra-red  frequencies  identi- 
cal with  those  of  chlorine,  and  consequently 
the  energy  E  +  K  can  be  re-absorbed  by  the 
surrounding  Clg  molecules  with  the  result 
that  these  become  partially  or  wholly  acti- 


vated. Since  in  this  reaction  K  is  positive, 
the  reaction  being  exothermic,  the  number 
of  molecules  of  chlorine  that  react  will  very 
greatly  exceed  that  calculated  on  the  basis 
of  one  for  every  phase  quantum  absorbed, 
the  excess  depending  upon  the  proportion 
of  the  energy  E  +  K  that  is  re-absorbed. 
The  only  condition  under  which  observation 
and  calculation  can  agree  is  when  K  is 
numerically  equal  to  E  and  is  negative,  so 
that  E  +  K  =  0. 

The  proportion  of  the  radiated  energy 
that  is  re-absorbed  will  obviously  depend 
on  two  factors,  the  density  of  the  chlorine 
and  the  density  of  the  radiation.  Accord- 
ing to  the  present  theory,  therefore,  the 
divergence  from  Einstein's  law  of  one 
molecule  reacting  her  phase  quantum  ab- 
sorbed will  increase,  both  when  the  density 
of  the  chlorine  is  increased  and  when  the 
density  of  the  radiation  is  increased,  or  what 
comes  to  the  same  thing,  when  the  inten- 
sity of  the  incident  light  is  increased.  It 
has  already  been  proved  that  with  constant 
intensity  of  illumination  the  velocity  of  the 
reaction  is  proportional  to  the  square  of  the 
concentration  of  the  chlorine.  Several 
other  instances  of  the  increase  of  the  diver- 
gence from  Einstein's  law  with  increase  in 
concentration  under  constant  illumination 
have  been  noted.  It  has  recently  been 
shown  also  that  the  divergence  from  Ein- 
stein's law  increases  very  rapidly  with  in- 
creasing intensity  of  the  illumination. 
Three  observations  of  some  interest  were 
made  in  these  latter  experiments.  During 
the  first  instant  of  illumination  the  reaction 
must  obey  Einstein's  law,  but  the  re- 
absorption  of  the  radiated  energy  will  at 
once  commence  with  the  result  that  the 
rate  of  the  reaction  with  moderate  intensi- 
ties of  light  will  rapidly  increase  up  to  a 
constant  maximum  depending  upon  the 
proportion  that  is  re-absorbed.  This  phe- 
nomenon was  observed  in  every  case. 

Since  the  proportion  re-absorbed  increases 
with  intensity  of  illumination,  a  condition 
will  be  reached  with  increasing  illumination 
when  the  proportion  re-absorbed  will  be  suf- 
ficient completely  to  activate  the  surround- 
ing chlorine  molecules.  Under  this  condi- 
tion the  reaction  once  started  by  the  ab- 
sorption of  a  single  phase  quantum  will 
pass  as  an  exjplosion  wave  through  the 
whole  mixture.  The  existence  of  a  lower 
limit  to  the  intensity  of  the  illumination 
necessary  to  cause  the  explosive  combina- 
tion of  hydrogen  and  chlorine  has  long  been 
recognised. 


SEPTEMBER  7,  1923. 


THE  CHEMICAL  NfiWS 


153 


The  third  phenomenon  observed  is  one  of 
verj  great  interest.  If  the  activating 
source  of  light  be  cut  off  when  the  maxi- 
mum rate  of  reaction  has  been  reached,  the 
reaction  ceases  at  once,  but  it  is  very  sur- 
prising how  long  an  interval  of  time  must 
elapse  before  the  chlorine  reaches  its  nor- 
mal condition,  since  at  least  thirty  minutes 
are  required.  If  the  light  be  allowed  to  faK 
on  the  mixture  before  this  minimum  period 
of  rest  has  expired  the  initial  rate  of  re- 
action is  greater  than  the  normal  initial 
rate.  The  obvious  explanation  is  the  pre- 
sence of  partially  activated  chlorine  mole- 
cules, that  is  to  say  molecules  containiuy 
more  than  their  normal  number  of  atwnic 
quanta,  which,  however,  do  not  in  the  cnsi' 
of  any  one  molecule  amount  in  their  sum 
to  the  increment  of  energy  necessary  fo.- 
comiplete  activation.  This  condition  is 
readily  understood  from  the  present  theory, 
and  raises  the  possibility  of  two  samples  of 
the  same  gas  apparently  in  thermal  equili- 
brium with  one  another  but  having  differcn: 
energy  contents.  It  is  hardly  necessary  to 
point  out  that  all  the  phenomena  ob8erve<l 
in  the  photochemical  union  of  hydrogen 
and  chlorine,  originally  foretold  from  the 
present  theory  and  recently  proved  ex4)eri- 
mentally,  cannot  be  explained  by  any 
monochromatic  theory  of  reaction. 

An  extensicai  of  the  principle  of  the  re- 
absorption  of  the  radiated  energy  may  be 
mentioned,  namely  the  photocatalysis  of  ;• 
reaction  wherebv  a  molecule  is  activated, 
when  screened  from  rays  of  its  characteris- 
tis  frequency,  by  other  molecules  which  in 
absorbing  their  own  molecular  quanta  emit 
infra-red  rays,  these  being  absorbed  by  thf 
first  molecule.  Evidently  this  will  be  pos- 
sible if  the  two  molecules  have  the  same 
atoms  in  common.  It  is  o&ly  neoesearv 
here  to  record  the  fact  that  several  reactions 
have  been  successfully  photocatalysed ,  and 
of  these  not  the  least  interesting  is  the  for- 
mation of  formaldehyde  from  carbon  di- 
oxide and  water  in  visible  light  in  the  pre- 
sence of  certain  coloured  bases  such  a*^ 
malachite  green.  As  is  well  known  the 
characteristic  frequency  of  carbon  dioxide 
lies  in  the  verv  extreme  ultra-violet  and  in 
the  absence  of  the  photocatalyst  the  syn- 
thesis of  formaldehyde  requires  radiation  of 
that  frequency. 

Finally  a  brief  reference  may  bo  made  to 
some  further  observations  which  h.-ive  not 
yet  been  published.  The  possibility  of  the 
existence  of  two  samples  of  the  sanie  gas  in 
apparent  thermal  equilibrium  with  one  an- 


other but  in  different  molecular  phases  has 
ahready  been  mentioned.  This  phenomenon 
is  somewhat  strikingly  exemplified  by  am- 
monia and  its  decomposition  by  an  electric- 
ally heated  platinum  wire.  With  a  con- 
stant current  the  amount  of  ammonia  de- 
composed in  a  given  time  depends  on  the 
condition  of  the  gas.  When  the  ammonia 
is  prepared  by  the  very  slow  evaporation  of 
the  liquefied  gas  or  by  w^arming  its  concen- 
trated aqueous  solution,  the  amount  de- 
composed is  many  times  larger  than  when 
the  gas  is  obtained  by  the  rapid  evapora- 
tion of  the  liquid,  the  temperature  of  the 
two  samples  and  the  amount  of  energy  sup- 
plied to  them  being  exactly  the  same.  On 
standing  for  many  hours  the  "inactive"  am- 
monia tends  to  reach  the  normal  condition. 

Many  substances  are  known  which  exist 
in  different  molecular  phases  in  the  gaseous 
and  liquid  states,  and  in  all  probability  am- 
monia is  analogous  in  this  respect.  The 
very  rapid  evaporation  of  the  liquid  will 
give  a  gas  containing  a  greater  proportion 
of  its  molecules  in  the  more  condensed 
phase  than  is  normal.  The  result  will  be 
that  a  given  amount  of  energy  will  decom- 
pose fewer  molecules  than  in  the  case  of 
ncMmal  ammonia. 

Instances  might  be  multiplied  of  the  ap- 
iplication  of  this  theory  to  chemical  reaction 
but  sufficient  has  been  said  to  justify  the 
original  clsum  that  it  is  possible  from  the 
assumption  of  elementary  atomic  quanta 
to  formulate  a  theory  which  accords  better 
with  the  observed  facts  than  the  theories  of 
monochromatic  radiation. 

{From  "  Transaitxona  of  the  Faraday 
Society,"  Vol.  XVII.,  Part  3.) 


LABORATORY  EXPERIMENTS  ON 

THE  EXTRACTION  OF 

MESOTHORIUM  FROM    MONAZITE 

SAND. 

By  Hbrm.an  Schlundt.* 

(Continued  from  Page  141.) 

Fully  two-thirds  of  the  combined  losses  in 
the  liquors  was  confined  to  one  of  the  acid 
/Iquors.  Though  the  investigators  were  at 
first  inclined  to  attribute   the  major  portion 

*  From  a  paper  on  Mesothoriuw ,  pub- 
lished by  the  Department  of  the  Interior, 
Bureau  of  Mines,  Washington. 


154 


THE  CHEMICAL  NEWS. 


SEPTEMBEK  7,  1923. 


of  this  loss  to  chemical  action,  later,  after 
examination  of  the  sediment  in  this  liquor, 
it  was  concluded  that  the  loss  was  almost 
entirelj'-  mechanical,  barium  sulphate  hav- 
ing been  carried  over  in  the  wash  liquors 
when  they  were  siphoned  o£E.  The  loss  of 
values  in  the  unattacked  sands  appears  to 
correspond  to  the  weight.  In  the  first  run 
the  tailings  constituted  9.4  per  cent,  of  the 
monazite  sand  treated,  and  the  radium 
found  was  8.3  per  cent.  In  the  second  run 
the  unattacked  sands  constituted  6.1  per 
cent,  of  the  weight  of  the  ore,  and  the  per- 
centage of  radium  found  was  5.85  per  cent. 

In  conducting  the  analytical  work,  deter- 
minations were  generally  made  in  duplicate 
or  triplicate  by  at  least  two  methods.  In 
the  estimation  of  radium,  for  example,  in 
monazite,  and  the  concentrates,  the  two 
methods  have  already  been  outlined.  By 
following  this  plan  throughout  the  investi- 
gation it  was  learned  that  several  of  the 
methods  of  analysis  required  modification. 

The  radium  determinations  in  monazite 
sand  gave  values  5  Der  cent,  higher  when 
the  ore  was  decomposed  by  fusion  with 
mixed  carbonates  instead  of  sulphuric  acid, 
therefore  it  was  concluded  that  the  residue 
that  was  unattacked  by  sulphuric  acid  held 
materials  containing  radium.  This  con- 
clusion found  confirmation  in  the  radium 
determinations  made  on  the  unattacked 
sands  by  b;>th  methods.  When  the  oma*na- 
tion  wes  sej)arated  directly  by  boiling  with 
concentrate  s.ilphuric  acid,  the  values  were 
scarcely  a  third  as  high  as  those  obtained  by 
first  decomposing  the  tailings  by  fusion  with 
mixed  alkali  carbonates. 

Determinatione  of  Lead  and  Barium  in 

THE  Concentrate. 
In  the  first  method  of  analysis  the  lead 
and  barium  were  extracted  with  concen- 
trated sulphuric  acid,  and  the  recovered 
sulphates  were  then  refined  by  fusion  with 
mixed  alkah  carbonate,  and  finally  after 
separation  were  precipitated  as  sulphates. 
As  the  percentages  of  lead  and  barium 
found  in  this  method  stand  in  close  agree- 
ment with  the  results  obtained  by  direct 
fusion  of  the  concentrate  with  mixed  alkali 
carbonates,  confidence  was  gained  in  the 
method  of  determining  radium  in  the  con- 
centrate, when  the  emanation  is  separated 
by  boiling  samples  with  concentrated  sul- 
phuric acid.  The  fact  that  lead  and  barium 
can  be  extracted  quantitatively  from  the 
crude  concentrate  with  concentrated  sul- 
phuric acid  also  suggests  a  possible  method 


of  refining  this  product  on  a  commercial 
scale. 

In  the  analytical  determinations  5-gram 
samples  of  the  concentrate  were  boiled  for 
10  minutes  with  120  cc.  of  chemically  pure 
sulphuric  acid.  After  cooling  somewhat, 
the  insoluble  residue  was  filtered  off  on  a 
Gooch  crucible  with  asbestos  mat,  and 
washed  twice  with  hot  concentrate  acid. 
From  the  filtrate,  lead  and  barium  were  pre- 
cipitated by  dilution  with  two  to  three  litres 
of  water.  The  recovered  sulphates  were 
then  refined  by  fusion  with  mixed  carbon- 
ates and  the  washed  carbonates  were  con- 
verted into  chlorides.  To  separate  the  lead 
the  filtrate  was  made  barely  alkaline  with 
ammonia,  and  then  saturated  with  hydro- 
gen sulphide.  In  the  filtrate  barium  was 
precipitated  as  sulphate ;  lead  was  also  esti- 
mated as  sulphate  in  the  solution  obtained 
by  dissolving  the  preciipitate  of  lead  sul- 
phide in  dilute  nitric  acid. 

In  the  other  method,  5-gram  samples  of 
the  crude  concentrate  were  used  directly 
with  mixed  carbonates  in  nickel  crucibles. 
An  insoluble  residue  of  nearly  10  per  cent, 
generally  remained  when  the  washed  car- 
bonates were  treated  with  dilute  hydro- 
chloric acid.  A  second  and  third  fusion, 
however,  did  not  yield  additional  barium  or 
lead.  In  the  concentrate  from  run  No.  2 
the  writer  found  46.56  per  cent,  of  barium 
sulphate  by  extraction  with  sulphuric  acid 
and  47.26  per  cent,  by  direct  fusion  with 
mixed  carbonates.  In  run  No.  2  the  lead 
content  of  concentrate  was  estimated  as  at 
least  21  per  cent,  sulphate.  This  high  per- 
centage of  lead  sulphate  in  concentrate  No. 
2  explains  an  observation  made  subse- 
quently in  connection  with  experiments  on 
refining  the  crude  concentrate.  When 
heated,  much  sulphur  dioxide  is  liberated  at 
about  600°  C,  probably  as  the  result  of  the 
Interaction  of  lead  sulphide  formed  by  the 
reduction  of  some  of  the  lead  sulphate  by 
carbon,  with  unreduced  lead  sulphate. 

Eefining  of  Mesothorium  in  THE  Crude 
Concentrate. 

The  method  finally  employed  for  extract- 
ing the  barium  in  the  two  batches  of  crude 
concentrate  that  was  obtained  in  experimen- 
tal runs  1  and  2,  and  for  obtaining  it  in 
soluble  form,  followed  closely  the  process 
used  in  refining  the  "first  sulphates,"  pro- 
duced in  the  extraction  of  radium  from  car- 
notite  ores.  The  barium  sulphate  carrying 
the  radium  at  a  concentration  of  about  1 
mg.  kilo  was    intimately  mixed  with    char- 


SEPTEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


155 


coal,  and  was  then  reduced  to  sulphide  at 
about  1000°  C.  The  reduced  product  when 
leached  with  hydrochloric  acid  gave  a  solu- 
tion of  barium  chloride,  ready  for  further 
concentration  of  mesothorium  by  fractional 
crystallisation. 

Before  adopting  the  direct  reduction 
method,  a  number  of  laboratory  experi- 
ments were  conducted  with  o,  10,  50,  and 
100-gram  samples  of  the  crude  concentrates 
of  mesothorium-barium,  wiili  a  view  to 
securing  data  on  other  methods  of  ()oesible 
practical  value. 

In  outlining  the  methods  ui  analysis  at- 
tention was  directed  to  the  quantitative  ex- 
traction of  barium  from  the  coucentrate  by 
digesting  it  with  a  large  excess  of  concen- 
trate sulphuric  acid.  In  order  to  insure  tlie 
barium  being  completely  dissolved  in  the 
concentrate  it  nmst  be  boiled  with  at  least 
six  times  its  weight  of  acid.  Abput  40  per 
cent,  of  the  matt^-rial  remains  unattacked. 
When  the  black  residue  is  filtered  off  on  n 
suction  filter  fitted  with  asbestos  mat  and 
washed  with  two  portions  of  hot  concen- 
trate sulphuric  acid,  fully  95  per  cent,  of 
the  barium  may  be  recovered  upon  diluting 
the  acid  liquw  with  10  to  15  times  its 
volume  of  water.  The  partly  refined  sul- 
phate thus  obtained  may  be  converted  al- 
most quantitatively  into  soluble  fonn  by 
one  of  three  methods :  (1)  Reduction  to  sul- 
[)hide  at  high  t'Cmtperatures  by  carbon ;  (2) 
conversion  into  carbonates  by  fusion  in  iron 
kettles  with  a  mixture  of  sodium  hydroxid»  . 
1  part,  to  soda  ash,  2  to  3  parts,  leaching  of 
the  fused  niiiss.  washing  free  from  sul- 
phates, and  conversion  of  the  insoluble  car- 
honates  into  chlorides — recoveries  running 
as  high  as  97  per  cent,  were  obtained  by 
this  method ;  (3)  proloni^'ed  boiling  of  the  re- 
fined sulphates  with  a  concentrated  solution 
of  sodium  carbonate  about  four  times  in 
excess  of  the  sulphates  present.  With  con- 
stant stirring  by  means  of  a  mechanical 
stirrer  during  the  digestion  iperiod,  conver- 
sions as  high  as  92  per  cent,  were  obtained. 
Methods  2  and  3  can  he  npplied  directly  to 
the  crude  concentrate  with  equally  goo(J  re- 
sults. More  than  20  preliminary  experi- 
iTients  of  this  character  were  conducted 
with  .')0-grani  samples  of  concentrate'  before 
the  decision  was  reached  to  treat  the  main 
bulk  of  the  concentrate  by  direct  reduction 
with  carbon  ns  the  first  step  in  refining. 

In  the  early  reduction  experiments.  500- 
gram  charges  were  carricnl  through  and  the 
amount  of  soluble  barium  determined.  .\t 
first    enough    powdered    charcoal  or    lamp- 


black was  mixed  with  the  crude  concentrate 
to  reduce  all  of  the  barium  and  lead  sul- 
phates. In  the  course  of  the  exiperiments, 
it  was  soon  noted  that  the  residue  remaining 
after  the  reduced  product  had  been  leached 
with  hydrochloric  acid  was  nearly  as  bulky 
as  the  original  charge.  Furthermore,  some 
experiments  to  determine  the  loss  on  igni- 
tion revealed  the  reduction  of  a  large  frac- 
liun  of  the  sulphates.  In  short,  it  soon  be- 
came evident  that  the  admixture  of  graphite 
and  amorphous  carbon  present  in  the  crude 
concentrate  was  more  than  enough  to  re- 
duce the  sulphates  completely.  The  con- 
centrates from  the  two  experimental  runs 
were  reduced  in  the  technological  labora- 
tory- of  the  United  States  Bureau  of  Mines 
at  Golden,  Colo.,  and  later,  after  it  was 
found  that  the  concentration  of  mesothor- 
ium by  fractional  crystalhsation  of  the 
chlorides  and  bromides  proceeded  normally, 
t  wo  other  batches  of  concentrates  weighing, 
respectively,  349  and  745  pounds,*  were 
given  this  treatment  in  the  plant  of  the 
Welsbach  Co.  The  reductions  were  canned 
out  in  graphite  crucibles  with  30-pound 
charges  heated  4  to  5  hours  at  1100°  C.  and 
sometimes  even  higher.  The  recovery  of 
values  and  the  losses  in  the  various  pro- 
ducts were  investigated  throughout  the  ex- 
periments by  two  distinct  methods  of  analy- 
sis :  The  chemical  method  involving  deter- 
minations of  barium,  and  the  radioactive 
method,  embracing  comparisons  of  gamma- 
ray  activities  and  determination  of  radium 
by  the  emanation  method. 


THE  PULP  AND  PAPER  INDUSTRY 
OF  CANADA. 

One  of  the  outstanding  features  of  Can- 
jida's  manufacture  and  commerce  in  the 
last  two  decades  has  been  the  rapid  growth 
of  the  pulp  and  paper  industry.  This 
growth  resulted  primarily  from  the  juxta- 
position of  large  supplies  of  suitable  pulp- 
wood  timber  and  cheap  electrical  energy. 
Large  areas  of  coniferous  forest  traversed 
by  rushing  streams  and  rivers,  providing 
water  power,  form  the  basis  upon  which 
the  industry  has  been  built  up. 

Forty  years  ago  there  were  only  5  mills 
in  operation  in  Canada;    to-day  there    are 


*  Expcrimcnfal  data  arc  given  for  a  part 
of  this  concentrate,  179.3  kg,,  in  Table  8. 


156 


THE  CHEMICAL  NEWS. 


SEPTEMBER  1,  1023. 


more  than  120,  consuming  over  two  million 
cords  of  pulpwood  per  annum  and  using 
hydro-power  to  the  extent  of  637,000  h.p. 
In  1921  the  capital  invested  exceeded  380 
million  dollars,  while  the  value  of  products 
was  over  two  hundred  million  dollars. 

Export  Trade. 
From  the  point  of  view  of  the  Dominion's 
export  trade,  the  pulp  and  paper  industry 
holds  a  position  that  is  second  only  to  that 
of  agriculture.  The  figures  given  below 
give  a  comparison  of  the  exports  of  the  pro- 
ducts (animal  and  vegetable)  of  Canada's 
farms  with  pulp  and  paper  exports,  for  the 
years  indicated:  — 

Farm  Pulp  and 

Year  Produce  Paper 

(Millions  of  dollars) 

1914     245.9  19.1 

1923     467.1  122.6 

The  rapid  progress  of  the  pulp  and  paper 
industry  as  a  contributor  to  Canada's  trade 
is  shown  in  the  following  table  of  the  ex- 
ports of  pulp  and  paper  for  the  past  twelve 
years:  — 

Paper        Wood- 
Year  prod.  pulp  Total 
(Millions  of  dollars) 

1912       3.9  5.1  9.0 

1913       6.3  5.5  11.8 

1914  12.7  6.1  19.1 

1915  15.5  9.3  24.8 

1916  20.0  10.4  30.4 

1917  26.1  20.4  46.5 

1918  37.7  25.6  63.3 

1919  47.9  34.7  82.6 

1920  63.2  41.4  104.6 

1921  92.1  71.6  163.7 

1922  69.5  35.9  105.4 

1923  79.6  43.0  122.6 

The  great  fluctuations  in  price  in  the 
years  1920-22  affected  to  some  extent  the 
generally  steady  increase  in  production. 
Since  that  period,  however,  it  will  be  noted 
that  the  increase  has  been  resumed. 

Figures  of  the  total  production  of  wood- 
pulp  are  available  for  a  number  of  years 
back  Those  for  newsprint  paper  (which 
forms  from  80  to  85  per  cent,  of  the  total) 
are  available  for  certain  jjears,  and  these  tell 
the  same  story  of  progress  as  the  exports. 
Wood-  News- 

Year  pulp  print 

(tons)  (tons) 

1917       1,464,308         689,847 

1919      1,716,089         794,567 

1921       1,549,082        805,114 


Subsidiary    Industkies. 

Although  large  supplies  of  pulpwood  and 
lime  are  readily  available  in  Canada,  the 
pulp  and  paper  mills  are  at  present  im- 
porters of  many  of  the  raw  materials  enter- 
ing into  the  manufacture  of  chemical  pulps 
and  paper.  In  the  fiscal  year  ending  ]\larch 
31,  1923,  sulphur  valued  at  $1,673,662  was 
imported  chiefly  from  the  extensive  Lou- 
isiana sulphur  deposits;  of  this  amount, 
about  thiee-fifths  was  used  in  the  pulp  and 
paper  industry.  Sulphur  can  be  produced 
from  the  domestic  deposits  of  pyrites,  but 
under  present  conditions  cannot  compete 
with  the  imported  brimstone.  Imports  of 
alum  and  salt  cakes  amounted  to  over 
$1,000,000,  of  whicli  seven-tenths  was  used 
in  the  manufacture  of  kraft  pulp.  Canada's 
dependence  upon  outside  sources  for  this 
chemical  will  probably  diminish  as  the 
sodium  sulphate  deposits  of  the  Prairie  Pro- 
vinces are  gradually  developed.  Again, 
though  kaolin  or  China  clay  is  produced  in 
small  quantities  in  the  province  of  Quebec 
the  value  of  imported  clay  used  in  the  pulp 
and  paper  industry  amounts  to  about 
$200,000  yearly.  Other  products  which  are 
imported  include  resin,  alum,  pulp-stones, 
acid  proof  refractories,  and  soapstone  lin- 
ings. Some  of  these  are  being  produced  in 
Canada  and  a&  the  pulp  and  paper  industry 
grows,  a  large  enough  market  will  become 
available  to  warrant  the  develqpment  of 
Canada's  resources  for  these  comniodities. 
These  facts  are  another  reminder  of  the 
importance  of  Canada's  forests  and  of  the 
need  for  the  adoption  of  all  possible 
measures  for  their  conservation. 


GENERAL    NOTES. 


AIRCRAFT    APPRENTICES    FOR    THE 
ROYAL  AIR  FORCE. 

The  Air  Ministry  announces :  — 

The  decision  of  the  Government  to  in- 
crease the  strength  of  the  Royal  Air  Force 
for  Home  Defence  purposes  necessitates 
the  engagement  of  aircraft  apprentices,  who 
will  be  trained  as  skilled  craftsmen,  in 
largely  increased  numbers. 

For  the  entry  in  January  next,  approxi- 
mately 950  boys  of  a  good  class  will  be  re- 
quired. The  selection  to  fill  these  vacancies 
will  be  made  on  the  results  of  two  competi- 
tive examinations,  which  are  conducted  re- 


.-EPTEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


357 


spectively  by  thp  Civil  Serrice  Commis- 
sioners and  by  the  Air  Ministry  in  cMijunc- 
tion  with  the  local  Educational  Authorities 
throughout  the  country. 

Candidates  must  be  physically  fit  and  be 
between  15  and  16i  at  the  time  of  entry, 
although  in  the  case  of  the  Air  Ministry  ex- 
amination the  upper  age  limit  is,  under  cer- 
tain conditions,  extended  to  17  years. 

The  syllabus,  which  is  the  same  in  both 
examinations,  consists  of  mathematics,  ex- 
perimental science,  English,  and  a  general 
paper,  and  has  been  designed  to  be  suitable 
for  boys  still  at  school  and  following  a  nor- 
mal course  of  instruction. 

The  closing  date  for  entries  for  the  Civil 
Service  examination  is  August  80.  This 
examinatifMi  will  be  conducted  by  the 
Commissioners  at  the  following  centres:  — 
London,  Binuinghani,  Belfast,  Chatham, 
Edinburgh,  Plymouth,  and  Portsmouth. 
Apii)lications  to  sit  at  this  examination 
should  be  made  at  once  to  the  Secretary. 
Civil  Service  Comnnssicm,  Burlington  Gar- 
dens, lyondon,  \V,1.     The  entry  fee  is  58. 

The  Air  Ministry  examinatitm  is  confined 
to  boys  nominated  by  the  local  Educatimi 
Authorities  of  the  country  and  by  the  gov- 
erning bo<lies  of  certain  approved  schools 
and  associations.  The  closing  date  for  entry 
is  October  2.  Tor  this  examination  there  is 
no  entry  fee. 

lioys  who  arc  still  at  school,  who  wish  to 
compete  in  the  Air  Ministry  exafnination. 
should  make  application  to  their  head- 
masters with  a  view  to  securing  a  nomina- 
tion from  the  Education  Authorities  re- 
sponsible for  the  school.  In  the  case  of 
l>oys  who  have  left  school,  applicatitm  may 
be  made  lo  the  Advisory  Committee  for 
Juvenile  Employment  in  the  area,  while 
lK>y  scouts  can  apply  to  the  authorities  of 
the  Boy  Scout  Association,  and  Territorial 
Cadets  to  the  officer  commanding  their  unit. 

When  appointed  as  aircraft  apprentices, 
boys  are  given  three  years'  training  in  a 
skilled  trade  and  general  education  by 
civilian  schoolmasters  during  this  period  up 
to  the  standard  of  a  good  technical  school. 
The  principal  trades  open  to  boys,  who  are 
invited  in  advance  to  indicate  their  prefer- 
ence, are  canpent<^r-rigger,  fitter,  copper- 
smith, wireless  operator  mechanic,  electri- 
cian, instrument  maker  and  draughtsman. 
In  assi^^Miing  boys  to  the  various  trades, 
every  endeavour  is  made  to  ijive  effect  to 
each  l>oy's  individual  preference,  the  wishes 
of  the  boys  in  this  respect  being  considered 


in  the  order  of  their  position  on  the  exami- 
nation list. 

During  the  period  of  training  there  is 
careful  supervision  of  health  and  general 
welfare,  medical  attendance,  religious  in- 
struction from  the  chaplains  of  several  de- 
nominaticxis,  and  recreation  facilities.  Six 
weeks'  annual  leave  is  granted. 

Pay  is  given,  under  existing  regulations, 
at  Is.  6d.  a  day  until  the  age  of  18,  and  then 
at  3s.  a  day  until  the  course  is  completed. 

At  the  end  of  the  coui-se  the  aircraft  ap- 
prentice must  sit  a  ipassing-out  examina- 
tion for  promotion  to  the  rank  of  ie.iding 
aircraftsman  with  pay  varying  from  5s.  2d. 
to  5s.  6d.  per  day.  The  above  rates  may  be 
subject  to  R'vision  in  the  immediate  future. 
Those  boys  who  do  not  qualify  for  the  high- 
est grade  will  be  Jippointed  as  aircraftsmen 
with  slightly  lower  commencing  rates  of 
I)  ly. 

A  certain  number  of  the  leading  appren- 
tices are  sent  on  completion  of  their  course 
to  tlie  Royal  Air  Force  Cadet  College,  for 
training  as  commissioned  officers.  Others 
are  given  an  advanced  course,  and  are 
eventually  ji^pointed  as  N.C.O.s  with  the 
rank  of  corporal.  There  is  also  a  reason- 
able chance  of  selection  for  a  further  num- 
ber to  qualify  later  in  Hying  to  become  air- 
men pilots,  and  generally  there  is  an  oppor- 
tunity for  promotion  to  the  senior  N.C.O. 
and  warrant  officer  ranks,  and  later  to 
oommissir>ned  rank. 

Headmasters  and  others  interested  in  the 
scheme  can  obtain  copies  of  the  regulations 
for  entry  (A. P.  134),  on  application  to  the 
Secretary,  Air  Ministry,  Kingsway.  W.C.2. 


INSULIN  AND  DIABETES. 

The  subject  of  diabetes  and  its  cure  was 
discussed  at  the  British  Medical  Associa- 
tion on  July  25th,  at  Portsmouth. 

Sir  Thomas  Horder  presided  over  the 
"Medicine"  Section,  and  in  opening  a  dis- 
cussion on  diabetes  said  that  the  fact  which 
led  them  to  choose  diabetes  for  their  first 
debate  was,  of  course,  the  introduction  of 
insulin  as  a  remedy  for  the  disease.  If  they 
did  not  discuss  insulin  at  that  meeting  of 
the  association  their  patients  would  be 
much  surprised,  and  with  good  reason.  They 
would  probably  assume,  again  with  reason, 
that  in  insulin  the  profession  had  a  "cure" 
for  diabetes,  and  that  nothing  more  need  be 
said  on  the  matter.  Sir  Thomas  Horder 
continued  :  — 


158 


THE  CHEMICAL  NEWS. 


SEPTEMBER  7,  1923. 


"  I  am  afraid  a  good  many  persons  have 
already  assumed  this,  and  perhaps  such  an 
assumption  is  not  surprising  in  view  of 
certain  generalisations  that  have  got  abroad, 
and  which,  if  they  do  not  carry  the  hall- 
mark of  authority,  at  least  have  not  been 
authoritatively  contradicted."  It  might 
be,  the  speaker  added,  "  that  the  success- 
ful preparation  of  this  internal  secretion 
(insulin)  of  the  pancreas  would  prove  to  be 
as  great  an  asset  to  medical  science  by  as- 
sisting the  interpretation  of  phenomena 
hitherto  obscure  as  in  the  provision  of  a 
therapeutic  agent  in  diabetes.  Only  a 
superficial  hearer  would  read  into  that  re- 
mark a  detraction  from  the  great  value  of 
Dr.  Banting's  discovery,  in  reality  such  re- 
marks enhanced  its  value.  Had  not  the 
essence  of  the  problem  of  diabetes  hitherto 
been  the  almost  certain  fact  that  under  that 
name  we  had  been  dealing  not  with  one  bio- 
chemical disturbance  only,  but  with  seve- 
ral? It  seemed  probable  that  the  use  of  in- 
sulin, controlled  by  careful  observations, 
would  not  only  still  further  establish  that 
fact,  but  would  also  help  to  mark  off,  much 
more  clearly  than  before,  certain  very  dif- 
ferent types  of  cases  of  diabetes  met  with 
in  practice."  Sir  Thomas  Horder  then 
said :  — 

"  One  result  of  this  segregation  we  are 
already  observing :  certain  cases  of  diabetes 
are  benefited  much  less  by  insulin  than  are 
others,  and  this  is  so  even  when  we  make 
due  allowance  for  all  those  collateral  points 
in  the  dietetic  part  of  the  treatment,  atten- 
tion to  which  we  know  to  be  so  important. 
Certain  caees  will  doubtless  be  found  not 
to  be  benefited  at  all.  And  if  we  do  not 
make  this  position  quite  clear  we  shall  see 
many  patients  suffer  the  bitter  nemesis  of 
disappointment  after  entertaining  a  false 
hope  for  which  we  may,  quite  unwittingly, 
have  been  partly  responsible." 

There  were  a  number  of  questions  which 
must  be  discussed.  Sir  Thomas  enunciated 
them  in  detail,  and  thereafter  called  on  Dr. 
Banting,  to  whom  he  extended  a  hearty 
welcome. 

Dr.  F.  G.  Banting,  of  Toronto,  the  dis- 
coverer of  insulin,  said  that  it  would  be 
several  years  before  the  limits  of  the  effec- 
tiveness of  insulin  were  known.  As  to 
patients  giving  themselves  insulin,  he 
quoted  the  case  of  the  American  commer- 
cial traveller  who  carried  his  own  insulin 
and  syringe,  and  described  the  daily  appli- 
cation of  it  as  being  no  i»"iore  difficult  than 
the  morning  shave.  After  a  warning  against 


this  practice,  Dr.  Banting  described  the  ex- 
periments which  led  to  the  discovery  of  in- 
sulin by  observing  that  a  dog  became  dia- 
betic after  its  pancreas  had  been  excised. 
It  was  then  found  that  if  they  ligatured  the 
duct  coming  from  the  pancreas  to  the  intes- 
tines they  would  necessarily  prevent  the 
passage  of  any  "external"  secretion. 
Nevertheless,  though  this  procedure  caused 
the  pancreas  to  become  atrophied  the  dog 
did  not  become  diabetic.  Evidently,  there- 
fore, there  was  an  "internal"  secretion 
which  went  straight  into  the  blood  stream. 
The  structure  of  the  pancreas  was  sub- 
mitted to  examination,  and  it  was  found  to 
consist  of  two  parts,  namely,  the  main 
gland  and  some  small  islands  of  cells.  The 
"internal"  secretion,  which  was  the  active 
principle,  "  insulin,"  came  from  these  cells. 
Further  experiments  were  still  being  made. 
He  pointed  out  that  the  discovery  of  insulin 
threw  no  light  on  the  causes  of  diabetes. 


DEATH  OF  EDWARD  KNOWLES 
MUSPRATT. 

Liverpool  has  lost  a  notable  scientist  and 
business  man  by  the  death,  on  the  1st  inst., 
of  the  above.  He  was  born  at  Linacre,  near 
Beetle,  on  November  6,  1833.  He  was  sent 
to  a  school  at  Worksop,  conducted  on  Pes- 
talozzi's  principles,  where  much  attention 
was  paid  to  science  and  modern  languages. 
In  the  holidays  he  saw  a  good  deal  of  his 
father's  friends,  who  included  Dickens, 
Lover,  Sheridan  Knowles,  the  dramatist 
(who  was  the  boy's  godfather),  Jerrold, 
Lemon,  Forster,  and  Charlotte  Cushman, 
the  actress,  and  her  sister  Susan,  who  mar- 
ried Muspratt's  brother. 

In  1850  he  was  sent  to  study  at  Giessen, 
the  university  of  the  great  chemist,  Justus 
von  Liehig,  who  became  an  intimate  friend 
of  the  family.  After  a  year's  preparation  he 
was  admitted  to  the  senior  laboratory,  and 
mixed  with  men  doing  original  research. 
Liebig  urged  him  to  specialise  in  physio- 
logical chemistry,  and  when  he  accepted  a 
chair  at  Munich,  Musprntt  went  with  him. 

In  the  'sixties  Weldon's  process  for  the 
recovery  of  manganese  and  I^udwig  Mond's 
process  for  the  extraction  of  sulphur  from 
alkali  waste  were  introduced  in  the  Mus- 
pratt  works.  In  1800  the  businesses  of 
James  Muspratt  and  Sons  and  ]\Tuspratt  nnd 
Huntley  were  incorporated  with  nihers  in 
the  United  Alkali  Company,  of  which  Mus- 
pratt was  vice-chairman  at  his  death. 


SEPTEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


159 


ELECTRICALLY  DEFLAGRATED 

MERCURY  FILAMENT  AS  A  FLASH 

LIGHT  FOR  INSTANTANEOUS 

PHOTOGRAPHY. 

By  Kyoji  Suyehiro. 

(Jap.  J.  Phys.,  I.  (1922),  97-100,  with  1 
fig.  and  2  pi.) 

Even  for  technical  researches  the  neces- 
sity- of  taking  an  instantaneous  photograph 
of  very  short  exposure  is  not  very  seldom 
experienced.  For  obvious  reasons,  how- 
ever, the  use  of  a  high  tension  spark  is  not 
convenient  in  a  workshop  or  in  a  similar 
place.  The  author  found  that  a  flash  light 
of  very  short  duration  could  he  obtained  by 
exploding  a  mercury  filament  sealed  in  a 
glass  capillary  tube  by  means  of  an  electric 
current  passed  through  it.  The  appHcd 
voltage  may  be  100  volts  or  so.  When  the 
filament  is  under  0.2  mm.  in  diameter  and 
the  wall  of  capillary  tube  is  very  thin,  the 
duration  of  the  flash  light  may  be  shortened 
even  to  a  hundred  thousandth  of  a  second. 
It  was  fq^und  that  this  flash  light  is  given 
out  from  the  mercury  arc  lit  up  for  a  short 
interval  just  after  the  exploeicxi  of  the 
^.apillary  tube. 

Apart  from  the  advantage  of  this  method 
over  the  high  tension  spark  with  regard  to 
its  simplicity  and  safety,  the  merit  of  it  lies 
in  the  fact  that  this  may  be  used  und<'r 
water  without  any  oonjplication  of  arrange- 
ment. 


NOTICES  OF  BOOKS. 

Materie,  ElektrizitHf  J.nergie,  von  Dr. 
Walther  Grrlach.  Pp.  195.  Dresden 
and  Leipzig:  Verlag  von  Theodor  Stein- 
kopff.     1923.     Price  3s.  3d. 

Prof.  G«rlach'8  volume  on  Matter,  Elec- 
tricity and  Energy  forms  one  of  the  series 
of  monographs  on  Natural  Science,  issued 
imder  the  direction  of  Prof.  Tiiesegang. 

The  author  has  undertaken  the  task  of 
summarising  the  advances  and  develop- 
ments in  Atomic  Science  from  the  enorni(nis 
volume  of  work  which  has  been  done  dur- 
ing the  last  ten  years.  A  good  account  is 
given  of  recent  work  on  Isotopy;  the  eluci- 
dation of  the  structure  of  the  Atom  and  the 
Atomic  Nucleus ;  the  changing  of  the  physi- 
cal state  of  the  Atom ;  the  application  of 
Tiine  and  X-ray  spectra ;  analysis  with  the 
aid  of  X-rays;  the  physical  basis  of  Photo- 


chemistry, etc.  Prominence  is  also  given 
to  the  author's  own  experimental  contri- 
butions. 

That  the  volume  contains  some  of  the 
most  recent  developments  will  be  gathered 
from  the  inclusion  of  an  account  of  the 
identification  of  the  occurrence  of  Hafnium 
in  Zirconium  minerals  by  Coster  and 
Hevesy.  This  has,  however,  been  taken 
from  Gemian  sources  (Naturwisseiischajtcn, 
1923,  Vol.  VIII).  It  is  indeed  noticeable 
that  much  recent  English  and  xlmerican 
research  work  has  evidently  escatped  the 
author's  attention.  Tliis  is  undoubtedly 
due  to  the  prohibitive  cost  of  English  books 
imd  periodicals  in  Germany  and  most  other 
European  countries.  Whilst  the  present 
unsettled  state  of  affairs  lasts,  English  pub- 
lishers cannot  hope  for  any  Continental  de- 
mand, and  the  dissemination  of  scientific 
knowledge  will  remain  retarded. 

As  it  is,  foreign  scientific  publications  are 
almost  inaccessible  to  German  scientists, 
who  are  obliged  to  rely  upon  the  meagre 
abstracts  in  their  Ccntralbliittcr  for  such 
information.  The  correctness  of  this  is  well 
illustrated  by  a  perusal  of  the  volume  under 
review. 

Prof.  Gerlach's  book  summarises  much 
recent  work  on  the  ultimate  structure  of 
matter,  and  should  prove  of  value  to  chem- 
ists, iphysicists,  and  others  interested  in  this 
subject. 


We  have  received  from  Messrs.  Robt. 
Boyle  &  Sons  a  booklet  dealing  with  the 
ventilation  of  public  buildings.* 

The  authors  have  devoted  themselves  to 
the  study  of  ventilation  on  truly  scientific 
lines,  and  have  had  a  world-wide  practical 
experience  in  the  subject. 

The  bcK)k  in  question  deals  exhaustively 
with  the  practical  application  of  ventila- 
tion, and  it  contains  a  fund  of  information 
as  to  the  methods  of  ventilation  adopted  for 
the  Houses  of  Parliament,  the  Guildhall, 
and  other  public  buildings.  The  relative 
merits  of  natural  and  artificial  ventilation 
are  fully  discussed,  and  the  opinions  of 
many  eminent  authorities  are  quoted. 

The  book  will  be  found  of  great  use  not 


*  The  Ventilation  of  Public  BuUdimja, 
by  Robert  Boylk.  Robert  Boyle  &  Sons, 
London.     Price  6s.  net. 


160 


THE  CHEMICAL  NE"WS. 


SEPTEMBER  7,  1923. 


only  to  architects  and  builders,  but  to 
those  responsible  for  public  buildings  gener- 
ally, as  it  explains  very  clearly  the  prin- 
ciples involved  in  a  successful  system  of 
ventilation,  and  also  explains  many  of  the 
failures  that  are  unhappily  often  apparent 
in  some  of  our  important  public  buildings. 

The  work  is  well  illustrated  with  draw- 
ings and  diagrams  that  help  greatly  in 
understanding  the  theories  advanced. 


1H18  list  is  specially  oompiled  for  The  Chemical 
News,  by  Messrs.  Rayner  «  Co.,  Registered  Patent 
Agents,  of  5.  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trada  Meixke, 
and  Designs  oan  be  obtained  gratuitously. 

Latest  Patent  Applications. 

20718— Canadian     Electro     Products     Co.,     Ltd.— 

Manufacture  of  ac-etaldehyde.     Aug.  15. 
21022 — Christenson,   0.   L. — Producing    ammonium 

chloride   from   aramoniaoal   hot   distillation 

or  generator  gases.    Aug.  18. 
20&49 — Neuss,   O. — Manufacture  of  products     from 

urea  and  formic  aldehyde.    Aug.  17. 
21006 — Pintsch     Akt-Ges.— Process     for     obtaining 

nitric  oxide.    Aug.  18. 

Specifications   Published   this    Week. 

201624— Galbraith,  W.  L.,  and  Leacock,  W.,  and 
Tallantyre,  S.  B.  Manufacture  of  conden- 
sation products  from  carbazole  and  p- 
nitrosophenol  and  its  derivatives. 

190448— Leggo,  A.  V.— Furnaces  or  the  like  for 
ore-roasting  or  like  operations. 

Abstract  Published  this  Week. 

199886— Catalytic  oxidation  of  organic  compounds. 
— Badische  Anilin  &  Soda  Fabrik,  Ludwig- 
shafen-on-Rhine,   Germany. 

Aldehydes;  ketones;  catalytic  agents,  prepara- 
tion of. — The  partial  oxidation  of  organic  com- 
pounds is  effected  by  passing  the  compwund  in  the 
gaseous  or  vapour  phase,  in  admixture  with  an 
oxygen-containing  gas,  over  borio  or  phosphoric 
acid  or  their  salts.  The  catalytic  materials  are 
preferably  mounted  on  a  carrier;  thus  clay,  fire- 
brick or  magnesia  is  soaked  with  boric  or  phos- 
phoric acid,  or  silica,  kieselguhr,  a  metallic 
oxide,  carlxjnate  or  nitrate  is  introduced  into 
molten  boric  acid.  Mixed  catalysts,  obtained  by 
adding  boric  or  phosphoric  acid  to  molten  metal 
salts  such  as  nitrates,  may  be  used.  According  to 
the  examples,  (1)  formaldehyde  is  produced  by 
passing  ethylene  and  oxygen  over  boric  or  phos- 
phoric acid  or  their  salts  mounted  on  burnt  clay 
or  diatomaceous  earth;  the  gases  may  circulate 
over  the  contact  mass,  the  formaldehyde  being 
absorbed  in  water  and  further  ethylene  and  oxy- 
gen being  introduced  continuously  or  at  intervals ; 
methane,  acetone,  ethyl  alcohol  and  cyclohexa- 
none  may  also  be  oxidised  to  formaldehyde  in  a 
similar  way;  (2)  anthracene  and  air  passed  over 
the  catalytic  material  yield  anthraquinone,  ben- 
zyl alcohol  gives  benzaldehyde,  ,and  ethyl  alcohol 
produces  acetaldehyde. 

Messrs.  Rayner  &  Co.  wiTl  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each. 


CITY  OF  CARDIFF  EDUCATION 
COMMITTEE. 

THE  TECHNICAL  COLLEGE. 

Principal  ^-  Charles  Coles,  B.Sc.  (Lond.). 

DEPARTMENT  OF  INDUSTRIAL 
CHEMISTRY. 
Head  of  Department  — 

H.  W.  Webb,  M.Sc,  F.I.C. 
Session    1923-24. 
(Commencing  on  Tuesday,  2nd  October, 
1923). 
Joint    Course 
(with  the  University  College  of  South 
Wales  and  Monmouthshire). 
COMPLETE  COURSE  in  Chemistry 
and  associated    subjects    is  provided 
for    those    wishing    to    become     industrial 
chemists.     The  Course  includes:  — 

Chemistry,  Physics,  Mathematics, 
Chemical  Engineering,  Utilisation  of 
Steam  and  Electrical  Power,  Cost  Ac- 
counting, together  with  a  specialised  prac- 
tical training  in  a  branch  of  industrial 
chemistry  chosen  from  the  following:  — 


Fuel. 


General  Iron  and  Steel  Manufacture. 
Gas  Manufacture. 
Foundry- work. 
Tin-plate  manufacture. 
Refractories  and  Cement. 

(7)  Electro  Chemistry. 

(8)  Brewing. 

(9)  Paper-making. 

Examinations  which  are  also  catered  for 
by  the  Course  include  :  — 

B.Sc.  (Lond.)  Ext. 

Associate,  Institute  of  Chemistry. 

F.I.C.  in  Chemical  Engineering. 

A  number  of  Part-time  Courses  are  also 
available  to  cover  requirements  of  Work's 
Chemist,  and  those  of  various  public 
examinations. 

OPEN .  SCHOLARSHIPS,  covering 
tuition  fees  and  maintenance  grants  of  £40 
per  annum  for  three  years,  are  offered  for 
competition  annually,  and  candidates  for 
entry  to  the  above  Department  are  eligible 
to  compete. 

For  further  particulars  of  Full-time  and 
Part-time  Courses,  Entrance  Examination, 
Scholarships,  Fees,  etc.,  apply  to  the 
Principal.  Forms  of  application  for  ad- 
mission to  the  Entrance  Scholarship  Ex- 
amination, duly  completed,  must  be  re- 
ceived by  the  ITth  September. 

JOHN  J.  JACKSON, 

Director  of  Education, 
City  Hall,  Cardiff. 


SEPTEMBER  14,  1923. 


THE  CHEMICAL  NEWS. 


161 


THE   CHEMICAL  NEWS, 

VOL.  CXXVII.      No.  3309. 

[British  Association  for  the  Advance- 
ment OF  Science:  Liverpool,  1923.] 

THE  PKESIDENTL\L  ADDRESS. 

THE    ELECTRICAL    STRUCTURE    OF 

MATTER. 

By  Professor  Sir  Ernest  Rutherford, 
D.Sc,  LL.D.,  Ph.D.,  F.R.S.. 

President  of  the  Association. 

It  was  in  1896  that  this  Association  last 
met  in  Liverpool,  under  the  presidency  of 
the  late  Lord  Lister,  that  groat  pioneer  in 
antiseptic  surgery,  whose  iiioinory  is  held 
in  affectionate  remembrance  by  all  nations. 
His  address,  which  dealt  mainly  with  the 
history  of  the  aipplication  of  antiseptic 
methods  to  surgery  and  its  connection  with 
the  work  of  Pasteur,  that  prince  of,  experi- 
menters, whose  birth  has  been  so  fittingly 
celebrated  this  year,  gave  us  in  a  sense  a 
completed  page  of  brilliant  scientific  his- 
tory. At  the  same  time,  in  his  opening  re- 
marks. Lister  emphusiHtd  the  importance 
of  the  discovery  by  Rontgen  of  a  new  type 
of  radiation,  the  X-rays,  which  we  now  see 
marked  the  beginning  of  a  new  and  fruitful 
era  in  another  branch  of  science. 

The  visit  to  your  city  in  '  "'^  was  for  me 
a  memorable  occasicm,  for  it  was  here  that 
I  first  attended  a  meetinfi  of  this  Associa- 
tion, and  here  that  I  read  my  first  scientific 
paper.  But  of  much  more  importance,  it 
was  here  that  I  benefited  by  the  opportun- 
ity, which  these  gatherings  so  amply  afford, 
of  meeting  for  the  first  time  many  of  the 
distinguished  scientific  men  of  this  country- 
and  the  foreign  representatives  of  science 
who  were  the  guests  of  this  city  on  that 
occasion.  The  yenr  1800  has  always 
seemed  to  me  a  memorable  one  for  other 
reasons,  for  on  looking  back  with  some 
sense  of  perspective  we  cannot  fail  to  recog- 
nise that  the  last  liivcrpool  meeting 
marked  the  beginning  of  what  has  b€<'n 
aptly  termed  the  heroic  age  of  Physical 
Science.  Never  before  in  the  history  of 
physics  hna  there  l)een  witnessed  such  a 
period  of  intense  activity  when  discoveries 
of  fundamental  importance  have  followed 
one  another  with  such  bewildering  rnjpidity. 

The  fUs<'overy  of  X-ray«  by  RSntgen  had 
been  published  to  the  world  in  1895,  while 


the  discovery  of  the  radioactivity  of  uranium 
by  Becquerel  was  annpunced  early  in  1896. 
Even  the  most  imaginative  of  our  scientific 
men  could  never  have  dreamed  at  that 
time  of  the  extension  of  our  knowledge  of 
the  structure  of  matter  that  was  to  develop 
from  these  two  fundamental  discoveries, 
but  in  the  records  of  the  Liverpool  meeting 
we  see  the  dawning  recog:nition  of  the  pos- 
sible consequences  of  the  discovery  of  X- 
rays,  not  only  in  their  application  to  medi- 
cine and  surgery,  but  as  a  new  and  powerful 
agent  for  attacking  some  of  the  funda- 
mental problems  of  physics.  The  address 
of  Professor  J,  J.  Thomson,  President  of 
Section  A,  was  devoted  mainly  to  a  discus- 
sion of  the  nature  of  the  X-rays,  and  the 
remarkable  properties  induced  in  gases  by 
the  ipassage  of  X-rays  through  them — the 
beginning  of  a  new  and  fruitful  branch  of 
study. 

In  applied  physics,  too,  this  year  marked 
the  beginning  of  another  advance.  In  the 
discussion  or  a  paper  which  I  had  the 
honour  to  read,  on  a  new  magnetic  detector 
of  electrical  waves,  the  late  Sir  William 
Preece  told  the  meeting  of  the  successful 
transmission  of  signals  for  a  few  hundred 
yards  by  electric  waves  which  had  been 
given  by  Sir  Oliver  Lodge  at  the  Oxford 
Meeting  of  this  Association  in  1894.  It  is 
startling  to  recall  the  rapidity  of  the  de- 
velopment from  such  small  beginnings  of 
the  new  uiethod  of  wireless  intercommimi- 
eation  over  the  greatest  terrestrial  dis- 
tances. In  the  last  few  years  this  has  been 
followed  by  the  even  more  rapid  growth  of 
the  allied  subject  of  radiotelephony  as  a 
practical  means  of  broadcasting  speech  and 
music  to  distances  only  limited  by  the 
•power  of  the  transmitting  station.  The 
rapidity  of  these  technical  advances  is  an 
illustration  of  the  close  interconnection 
that  must  exist  between  pure  and  applied 
science  if  rapid  and  sure  progress  is  to  be 
made.  The  electrical  engineer  has  been 
able  to  base  his  technical  development's  on 
the  solid  foimdation  of  Maxwell's  electro- 
magnetic theory  and  its  complete  verifica- 
tion by  the  researches  of  Hertz,  and  also  by 
the  experiments  of  Sir  Oliver  Lodge  in  this 
University — a  verification  which  was  com- 
pleted long  bt^fore  the  practical  possibilities 
o  this  new  methwl  of  signalling  had  been 
generally  recognised.  The  later  advances 
in  radiotelegraphy  and  radiotelephony  have 
largely  depended  on  the  application  of  the 
results  of  fimdaniental  researches  on  the 
properties  of  electrons,  as  illustrated  in  the 


162 


THE  CHEMICAL  NEWS 


SEPTEMBER  14,  1923. 


use  of  the  thermionic  valve  or  electron  tube 
which  has  proved  such  an  invaluable  agent 
both  for  the  transmission  and  reception  of 
electric  waves. 

It  is  of  great  interest  to  note  that  the 
benefits  of  this  union  of  pure  and  applied 
research  have  not  been  one-sided.  If  the 
fundamental  researches  of  the  workers  in 
pure  science  supply  the  foundations  on 
tvhich  the  applications  are  surely  built,  the 
successful  practical  application  in  turn 
quickens  and  extends  the  interest  of  the 
feivestigiator'  in  the  fundamental  problem, 
while  the  development  of  new  methods  and 
apipliances  required  for  technical  purposes 
often  provides  the  investigator  with  means 
of  attacking  still  mone  difficult  questions. 
This  important  reaction  between  pure  and 
applied  science  can  be  illustrated  in  many 
branches  of  knowledge.  It  is  particularly 
manifest  in  the  industrial  development  of 
X-ray  radiography  for  therapeutic  and  in- 
dustrial purposes,  where  the  development 
on  a  large  scale  of  special  X-ray  tubes  and 
improved  methods  of  excitation  has  given 
the  physicist  much  more  efficient  tools  to 
carry  out  his  researches  on  the  nature  of  the 
rays  themselves  and  on  the  structure  of 
the  atom.  In  this  age  no  one  can  draw  any 
sharp  line  of  distinction  between  the  im- 
portance of  so-called  pure  and  applied  re- 
search. Both  are  equally  essential  to  pro- 
gress, and  we  cannot  but  recognise  that 
without  flourishing  schools  of  research  on 
fundamental  matters  in  our  universities  and 
scientific  institutions  technical  research 
must  tend  to  wither.  Fortunately  there  is 
little  need  to  labour  this  point  at  the  mo- 
ment, for  the  importance  of  a  training  in 
pure  research  has  been  generafly  recognised. 
The  Department  of  Scientific  and  Industrial 
Research  has  made  a  generous  provision  of 
grants  to  train  qualified  young  men  of  pro- 
mise in  research  methods  in  our  scientific 
institutions,  and  has  aided  special  funda- 
mental researches  which  are  clearly  beyond 
the  capacity  of  a  laboratory  to  finance  from 
its  own  funds.  Those  who  have  the  respon- 
sibility of  administering  the  grants  in  aid  of 
research  both  for  pure  and  applied  science 
will  need  all  their  wisdom  and  experience  to 
make  a  wise  allocation  of  funds  to  secure 
the  maximum  of  results  for  the  minimum 
of  exipenditure.  It  is  fatally  easy  to  spend 
much  money  in  a  direct  frontal  attack  on 
some  technical  problem  of  importance  when 
the  solution  may  depend  on  some  addition 
to  knowledge  which  can  be  gained  in  s(  me 
other  field  of  scientific  inquiry  possibly  at 


a  trilling  cost.  It  is  not  in  any  sense  iny 
purpose  to  criticise  those  bodies  which  ad- 
minister funds  for  fostering  pure  and  up- 
plied  research,  but  to  emphasise  how  dilli- 
cult  it  is  to  strike  the  correct  balance  be- 
tween the  expenditure  on  pure  and  applied 
science  in  order  to  achieve  the  best  results 
in  the  long  run. 

It  is  my  intention  this  evening  to  refer 
very  briefly  to  some  of  the  main  features  of 
that  great  advance  in  knowledge  of  the 
nature  of  electricity  and  matter  which  is 
one  of  the  salient  features  of  the  interval 
since  the  last  meeting  of  this  Association  in 
Liverpool. 

In  order  to  view  the  extensive  territory 
which  has  been  conquered  by  science  in 
this  interval,  it  is  desirable  to  give  a  brief 
summary  of  the  state  of  knowledge  of  the 
constitution  of  matter  at  the  beginning  of 
this  epoc'i.  Ever  since  its  announcement 
by  Dalton  the  atomic  theory  has  stoacily 
gained  ground,  and  formed  the  philosophic 
basis  foi-  the  explanation  of  the  facts  of 
chemical  combination.  In  the  early  stages 
of  its  application  to  physics  an(i  chomisiry 
it  was  unnecessary  to  have  any  detailed 
knowledge  of  the  dimensions  or  structure  of 
the  atom.  It  was  only  necessary  to  assume 
that  the  atoms  acted  as  individual  ur  its, 
and  to  know  the  relative  masses  of  the 
atoms  of  the  different  elements.  In  the 
next  stage,  for  example,  in  the  kinetic 
theory  of  gases,  it  was  possible  to  explain 
the  main  properties  of  gases  by  supposing 
that  the  atom*  of  the  gas  acted  as  minute 
perfectly  elastic  spheres.  During  this 
period,  by  the  application  of  a  variety  of 
methods,  many  of  which  were  due  to  Ijord 
Kelvin,  rough  estimates  had  been  obtained 
of  the  absolute  dimensions  and  mass  of  the 
atoms.  These  brought  out  the  minute  size 
and  mass  of  the  atom  and  the  enormous 
number  .of  atoms  necessary  to  produce  a 
det<ectahle  effect  in  any  kind  of  measure- 
ment. From  this  arose  the  general  idea 
that  the  atomic  theory  must  of  necessity 
for  ever  remain  unverifiable  by  direct  ex- 
periment, and  for  this  reason  it  was  sug- 
gested by  one  school  of  thought  that  the 
atomic  theory  should  be  banished  from  the 
teaching  of  chemistry,  and  that  the  law  of 
multiple  proportions  should  be  accepted  as 
the  ultimate  fact  of  Chemistry. 

While  the  vaguest  ideas  were  held  as  to 
the  possible  structure  of  atoms,  there  was 
a  general  belief  among  the  more  philoso- 
phically minded  that  the  atoms  of  the  ele- 
ments could  not    be  regarded  as  simple  un- 


SEPTEMBER  14,  1023. 


THE  CHEMICAL  NEWS. 


163 


connected  units.  The  periodic  variations 
of  tlie  properties  of  the  elements  brought 
out  by  Mendeleef  were  only  exiplicablo  if 
atoms  were  similar  structures  in  some  way 
constructed  of  similar  material.  We  shall 
see  that  the  problem  of  the  constitution  of 
atoms  is  intimately  connected  with  our 
conception  f>f  the  nature  of  electricity.  The 
wonderful  success  of  the  electromagnetic 
theor}-  had  concentrat<;d  attention  on  the 
medium  or  ether  surrounding  the  con- 
ductor of  electricity,  and  little  attention 
had  been  paid  bo  the  actual  carriers  of  the 
electric  current  itself.  At  the  same  time 
the  idea  was  generally  gaining  ground  that 
an  explanation  of  the  results  of  Faraday's 
experiments  on  electrolysis  was  only  pos- 
sible on  the  assumption  that  electricity,  like 
matter,  was  atomic  in  nature  The  niime 
"electron"  had  even  been  given  to  this  fun- 
(lanu'ntal  unit  by  Johnstone  Stonev.  and 
its  magnittide  roughly  estimated,  but  the' 
full  recognition  of  the  significance  and  im- 
portance of  this  cmiception  belongs  to  the 
new  epoch. 

For  the  clarifying  of  these  somewhat 
vague  ideas,  the  proof  in  1807  of  the  in- 
fleipendent  existence  of  the  electron  as  a 
mobile  electrified  unit,  of  mass  minute 
compared  with  that  of  the  lightest  atom, 
was  of  extraordinary  importance.  It  was 
soon  seen  that  the  electron  must  be  ol  a 
constituent  of  all  the  atoms  of  matter,  and 
that  optical  spectra  had  their  origin  in  tluir 
vibrations.  The  discovery  of  me  electron 
and  the  proof  of  its  liberation  by  a  variety 
of  methorls  from  all  the  atoms  of  matti-r 
was  of  the  utmost  significance,  for  it 
str(»ngthened  the  view  that  the  electron  was 
probably  the  common  unit  in  the  struetim' 
of  atoms  which  the  periodic  variation  of 
the  chemical  properties  had  indicated.  It 
gave  for  the  first  time  some  hope  of  the 
success  of  an  attack  on  that  most  funda- 
mental of  all  problems — the  detailed  struc- 
ture of  the  atom.  In  the  early  develop- 
ment of  this  subject  science  owes  much  t-o 
the  work  of  Sir  J.  J.  Thomson,  both  for  the 
boldness  of  his  ideas  and  for  his  ingenuity 
in  developinjT  methods  for  estimating  the 
number  of  electrons  in  the  atom,  and  of 
probing  its  stnicture.  He  early  took  th<' 
view  that  the  atom  must  be  an  eleetncMl 
structure,  held  together  by  electrical  forces, 
and  showed  in  a  general  way  lines  of  pos- 
sible rvplanntion  of  the  variation  of  physi- 
cal and  chemical  properties  of  the  elements, 
exemplified  in  the  periodic  law. 

In  the  meantime  our  whole  conception 
of  the  atom  and  of    the  magnitude  of    the 


forces  which  held  it  together  were  revolu- 
tionised-by  the  study  of  radioactivity.  The 
discovery  of  radium  was  a  great  step  in 
advance,  for  it  provided  the  experimenter 
with  powerful  sources  of  radiation  specially 
suit-able  for  examining  the  nature  of  the 
characteristic  radiations  which  are  emitted 
by  the  radioactive  bodies  in  general.  It 
wa-s  soon  shown  that  the  atoms  of  radio- 
active matter  were  undergoing  spontaneous 
transformation,  and  that  the  characteristic 
radiations  emitted,  viz.,  the  a,  ft,  and  y 
rays,  were  an  accompaniment  and  conse- 
quence of  these  atomic  explosions.  The 
wonderful  succession  of  changes  that  occur 
in  uranium,  more  than  thirty  in  number, 
was  soon  disclosed  and  simply  int-eripreted 
on  the  transformation  theory.  The  radio- 
active elements  provide  us  for  the  first  time 
with  a  glimpse  into  Nature's  laboratory, 
and  allow  us  to  watch  and  study  but  not 
control  the  changes  that  have  their  origin 
in  the  heart  of  the  radioactive  atoms.  These 
atomic  explosions  involve  energies  which 
are  gigantic  compared  with  those  involved 
in  any  ordinary  physical  or  chemical  pro- 
cess. In  the  majority  of  cases  an  a  particle 
is  expelled  at  high  speed,  but  in  others  a 
swift  electron  is  ejected  often  accompanied 
by  a  y  ray,  which  is  a  very  penetrating  X- 
ray  of  high  frequency.  The  proof  that  the 
a  particle  is  a  charged  helium  atom  for  the 
first  time  disclosed  the  importance  of  he- 
lium as  one  of  the  units  in  the  structure  of 
the  radioactive  atoms,  and  probably  also 
in  that  of  the  atoms  of  most  of  the  ordinary 
elements.  Not  only  then  have  the  radio- 
active elements  had  the  greatest  direct  in- 
fluent on  natural  philosophy,  but  in  sub- 
sidiary ways  they  have  provided  us  with 
experimental  methods  of  almost  equal  im- 
portance. The  use  of  a  particles  as  projec- 
tiles with  which  to  explore  the  interior  of 
the  atom  has  definitely  exhibited  its  nuclear 
stnicture,  has  led  to  artificial  disintegration 
of  certain  light  atoms,  and  promises  to 
yield  more  information  yet  as  to  the  actual 
structure  of  the  nucleus  itself. 

The  influence  of  radioactivity  has  also 
extended  to  yet  another  field  of  study  of 
fascinating  interest.  We  have  seen  that 
the  first  rough  estimates  of  the  size  and 
mass  of  the  atom  gave  little  hope  that  we 
could  detect  the  effect  of  a  single  atom. 
The  discovery  that  the  radioactive  bodies 
expel  actual  charged  atoms  of  helium  with 
en^yrmous  energy  altered  this  aspect  of  the 
problem.  The  energy  associated  witli  a 
single  a  particle  is  so  great  that  it  can  read- 


164 


THE  CHEMICAL  NEWS. 


SEPTEMBER  14,  1923. 


ily  be    detected  by    a  variety    of    methods. 
Each  a  particle,     as  Sir  Win.  Crookes  first 
showed,    produces    a  flash    of  Hght    easily 
visible  in  a  dark    room  when    it  falls  on    a 
screen  coated  with  crystals  of  zinc  sulphide. 
This  scintillation  method    of  counting  indi- 
vidual particles    has  proved    invaluable    in 
many  researches,    for  it  gives  us  a  method 
of    unequalled    delicacy    for    studying  the 
ejects  of  single  atoms.     Ihe  a  particle  can 
also  be  detected  electrically  or  photographic- 
ally, but    the  most  powerful    and  beautiful 
of  all  methods  is  that    perfected  by  Mr.  C. 
T.     R.    Wilson     for    observing     the    track 
through  a  gas  not  only  of  an  a  particle  but 
of  any  type  of  penetrating    radiation  which 
produces  ions     or    of    electrified     particles 
along    its  path.       The  method    is  compara- 
tively simiple,  depending  on  the    fact,  first 
discovered  by  him,  that    if  a  gas  -saturated 
with    moisture  is    suddenlv  cooled    each  of 
the  ions  produced  by  the  radiation  becomes 
the  nucleus  of  a  visible  drop  of  water.    The 
water-drops  along  the  track  of  the  a  particle 
are  clearly  visible  to  the  eye,  and  can  be  re- 
corded photo«graphically.       These  beautiful 
photographs    of    the     effect    produced    by 
single  atoms    or  single    electrons  appeal,  I 
think,  greatly  to  all  scientific  men.       They 
not  only  afford  convincing  evidence  of  the 
discrete  nature  of  these  particles,    but  give 
us  new    courage    and    confidence    that  the 
scientific  methods  of  experiment  and  deduc- 
tion are  to  be  relied  upon  in  this  field  of  in- 
quiry;   for  many  of    the    essential    points 
brought  out    so  clearly    and    concretely    in 
these  photographs    were  correctly  deduced 
long  before  such    confirmatory  photographs 
were  available.      At  the  same  time,  a  min- 
ute study  of  the    detail  disclosed    in  these 
photographs  gives    us  most  valuable  infor- 
mation   and  new    clues  on  many    recondite 
effects  produced    by    the    passage    through 
matter  of  these  flying  projectiles  and  pene- 
trating radiations. 

In  the  meantime  a  number  of  new 
methods  had  been  devised  t^^  fix  with  some 
accuracy  the  mass  of  the  individual  atom 
and  the  number  in  any  given  quantity  of 
matter.  The  ^ncordant  results  obtained 
by  widely  different  physical  principles  gave 
great  confidence  in  the  correctness  of  the 
atomic  idea  of  matter.  The  method  found 
capable  of  most  accuracy  depends  on  the 
definite  proof  of  the  atomic  nature  of  elec- 
tricity and  the  exact  valuation  of  this  fun- 
damental unit  of  charge.  We  have  seen 
that  it  was  early  surmised  that  electricity 
was  atomic  in  nature.     This  view  was  eon- 


firmed  and  extended  by  a  study  of  the 
charges  carried  by  electrons,  a  particles, 
and  the  ions  produced  iu  gases  by  X-rays 
and  the  rays  from  radioactive  matter.  It 
was  first  shown  by  Tounsend  that  the  posi- 
tive or  negative  charge  carried  by  an  ion  in 
gases  was  invariably  equal  to  the  charge 
carried  by  the  hydrogen  ion  in  the  electro- 
lysis of  water,  which  we  have  seen  was 
assumed,  and  assumed  correctly,  by  John- 
stone Stoney  to  be  the  fundamental  unit  of 
charge.  Various  methods  were  devised  to 
measure  the  magnitude  of  this  fundamental 
unit;  the  best  known  and  most  accurate  is 
Millikan's,  which  depends  on  comparing 
the  pull  of  an  electric  field  on  a  chaiged 
droplet  of  oil  or  mercury  with  the  weight  of 
the  drop.  His  experiments  gave  a  most 
convincing  proof  of  the  correctness  of  the 
electronic  theory,  and  gave  a  measure  of 
this  unit,  the  most  fundamental  of  all  phy- 
sical units,  with  an  accuracy  of  about  one 
in  a  thousand.  Knowing  this  value,  we 
can  by  the  aid  of  electrochemical  data  easily 
deduce  the  mass  of  the  individual  atoms 
and  the  number  of  molecules  in  a  cubic  cen- 
timetre of  any  gas  with  an  accuracy  of  pos- 
sibly one  in  a  thousand,  but  certainly  better 
than  one  in  a  hundred.  When  we  consider 
the  minuteness  of  the  unit  of  electricity 
and  of  the  mass  of  the  atom  this  experi- 
mental achievement  is  one  of  the  most  not- 
able even  in  an  era  of  great  advances. 

The  idea  of  the  atomic  nature  of  electri- 
city is  very  closely  connected  with  the  at- 
tack on  the  problem  of  the  structure  of  the 
atom.  If  the  atom  is  an  electrical  struc- 
ture it  can  only  contain  an  integral  number 
of  charged  units,  and,  since  it  is  ordinarily 
neutral,  the  number  of  units  of  positive 
charge  must  equal  the  number  of  negative. 
One  of  the  main  difficulties  in  this  problem 
has  been  the  uncertainty  as  to  the  relative 
part  played  by  positive  and  negative  elec- 
tricity in  the  structure  of  the  atom.  We 
know  that  the  electron  has  a  negative 
charge  of  one  fundamental  unit,  while  the 
charged  hydrogen  atom,  whether  in  electro- 
lysis or  in  the  electric  discharge,  has  a 
charge  of  one  positive  unit.  But  the  mass 
of  the  electron  is  only  1/1840  of  the  mass  of 
the  hydrogen  atom,  and  though  an  exten- 
sive search  has  been  made,  not  the  slightest 
evidence  has  been  found  of  the  existence  of 
a  positive  electron  of  small  mass  like  the 
negative.  In  no  case  has  a  positive  charge 
been  found  associated  with  a  mass  less  than 
that  of  the  charged  atom  of  hydrogen.  This 
difference    between    positive    and    negative 


SEPTEMBER  14,  1923. 


THE  CHEMICAL  N2WS. 


165 


electricity  is  at  first  sight  very  surprising, 
but  the  deeper  we  pursue  our  inquiries  the 
more  this  fundamental  difference  between 
the  units  of  positive  and  negative  electri- 
city is  emphasised.  In  fact,  us  we  shall  see 
later,  the  atoms  are  quite  unsymmetrical 
structures  with  regard  to  the  positive  and 
negative  units  contained  in  them,  and  in- 
deed it  seems  certain  that  if  there  were  not 
this  difference  in  mass  between  the  two 
units',  matter,  as  we  know  it,  could  not 
e.xist. 

It  is  natural  to  inquire  what  ex|)lanati(Hi 
can  be  given  of  this  striking  difference  in 
mass  of  the  two  units.  I  think  all  scientific 
men  are  convinced  that  the  small  mass  of 
the  negative  electron  is  to  be  entirely  asso- 
ciated with  the  energy  of  its  electrical 
structure,  so  that  the  electron  may  be  re- 
garded as  a  disembodied  atom  of  negative 
electricity.  We  know  that  an  electron  in 
motion,  in  addition  to  possessing  an  elec- 
tric field,  also  generates  a  magnetic  field 
around  it,  and  energy  in  the  electromag- 
netic fonri  is  stored  in  the  medium  and 
moves  with  it.  This  gives  the  electron  an 
apparent  or  electrical  mass,  which,  while 
Dearly  constant  for  slow  speeds,  increases 
liipidly  !is  its  velocity  approaches  that  of 
light.  This  increase  of  mass  is  in  good 
accord  with  calculation,  whether  basea  <«i 
the  ordinary  electrical  theory  or  on  the 
theory  of  relativity.  Now  we  know  that 
the  hydrogen  atom  is  the  lightest  of  all 
atoms,  and  is  presumably  the  simplest  in 
structure,  and  that  the  charged  hydrogen 
atom,  which  we  shall  see  is  to  be  regarded 
as  the  hvdrogen  rmcleus,  carries  a  unit 
positive  charge.  It  is  thus  natural  to  sup- 
ipoae  that  the  hydrogen  nucleus  is  th*^  atom 
of  positive  electricity,  or  positive  electron, 
analogous  to  the  negative  electron,  but  dif- 
fering from  it  in  mass.  Electrical  theory 
shows  that  the  mass  of  a  given  charge  of 
electricitv  increases  with  the  concentra- 
tion, and  the  greater  mass  of  the  hydrogen 
nucleus  would  be  accounted  iar  if  its  size 
were  much  smaller  than  that  d  the  elec- 
tron. Such  a  conclusion  is  supported  by 
I'vidence  obtained  from  the  study  of  the 
close  collisions  of  a  particles  with  hydrogen 
nuclei.  It  is  found  that  the  hydrogen  nu- 
cleus must  be  of  minute  size,  of  radius  less 
than  the  electron,  which  is  usually  sup- 
posed to  be  about  10-'-^  cms.;  also  the  e.x- 
perimental  evidence  is  not  inconsistent  with 
the  view  fhat  the  hydrf>gon  nucleus  may 
actually  be  much  sjnnller  than  the  elec- 
tron.     While  the  greater  mass  of  the  posi- 


tive atom  of  electricity  may  be  explained  in 
this  way,  we  are  still  left  with  the  enigma 
why  the  two  units  of  electricity  should 
differ  so  markedly  in  this  respect.  In  the 
present  state  of  our  knowledge  it  does  not 
seem  possible  to  push  this  inquiry  further, 
or  to  discuss  the  problem  of  the  relation  of 
these  two  units. 

We  shall  see  that  there  is  the  strongest 
evidence  that  the  atoms  of  matter  are  built 
up  to  these  two  electrical  units,  viz.,  the 
electron  and  the  hydrogen  nucleus  or  pro- 
ton, as  it  is  usually  called  when  it  forms 
part  of  the  structure  of  any  atom.  It  is 
probable  that  these  two  are  the  fundamen- 
tal and  indivisible  units  which  build  up  our 
universe,  but  we  may  reserve  in  our  mind 
the  possibility  that  further  inquiry  may 
some  day  show  that  these  units  are  com- 
plex, and  divisible  into  even  mcyre  funda- 
mental entities.  On  the  views  we  have 
outlined  the  mass  of  the  atom  is  the  sum 
of  the  electrical  masses  of  the  individu;ii 
charged  units  composing  its  structure,  and 
there  is  no  need  to  assume  that  any  other 
kind  of  mass  exists.  At  the  same  time,  it 
is  to  be  borne  in  mind  that  the  actual  mass 
of  an  atom  may  be  somewhat  less  than  the 
sum  of  the  masses  of  component  positive 
and  negative  electrons  when  in  the  free 
state.  On  account  of  the  very  close  prox- 
imity of  the  charged  units  in  the  nucleus  of 
an  atom,  and  the  conseq\ient  disturbance 
()f  the  electric  and  magnetic  field  surround- 
ing them,  «uch  a  decrease  of  mass  is  to  be 
anticipated  on  general  theoretical  grounds. 

{To  he  continued.) 


THE  QUANTUM  THEORY. 

By  R.  F.  Hunter,  F.C.S. 

(Continued  from  Page  147.) 

When  T  >  0.9 

iSo' 


the  term 


^^o^/M    T 
(.  iSo'/T-l) 


approximates  to  the  value  1,  and  hence  onr 
older  exipression  is  merely  a  first  approxi- 
mation,  viz. : 

Cv   =  ,ST?. 


166 


TfiE  CHEMICAL  KEWS. 


SEPTEMBER  14.  1923. 


Unfortunately,  Einstein's  expression  was 
shown  to  hold  only  in  a  quantitative  man- 
ner, and  further  correction  was  necessary. 
This  was  undei-taken  by  Debye. 

The  fallacy  in  Einstein's  investigation 
lay  in  this  way :  Einstein  assumed  for  the 
sake  of  simplicity  that  a  vibrating  particle 
only  gives  rise  to  monochromatic  light  and 
absorbs  such;  Debye,  observing  tbis, 
worked  out  an  expression  for  atomic  heat 
on  the  basis  of  absorption  and  emission  of 
a  number  of  vibration  frequencies  covering, 
as  a  matter  of  fact,  the  whole  spectrum. 
He  assumed  firstly,  that  a  vibrating  atom 
in  a  soHd  cannot  vibrate  simply  in  S.H.M. 
with  one  frequency,  but  owing  to  the  effect 
of  other  neighbouring  atoms  and  the  prob- 
ability of  collision,  assumes  a  complex 
mode  of  vibration;  the  complex  vibration 
being  calculated  by  the  method  of  Fourier. 
If  the  temperature,    T,    be  a  multiiple  or  a 

T 
characteristic  constant  —  for  a  substance, 
6 

T 
Atomic  heat  is  a  nn'\<^'*c"'  function  of  — 

H 
Further,   at  low  temperature,   Debye  de- 
duced that  the  atomic  heat  of  solids  a  T\ 
Hence  the  atomic  heat  would  be  a  T". 
Debye 's  expression  fa-  the  tuergy,   U,  of 
a  solid  vol.  V  containing  N  atoms  is  of  the 
form 
U  =  9N       r   V„  hv 


1 


vMv       (1) 


Further,    giving     the     constant     6,     the 
meaning 

e  =  hv„ 

=  i8v„  (2) 

k 
and  introducing    into    (1)    a  new    variable, 

hv 
without  dimensions,  ^  = 


one  arrives  at 


U  =  9NkT 


KT 


^hv„/kT 


hv„j 


(3) 


c^-  I 


Substituting,  one  obtains 


3/0'T     3 


U  =  9NkT  1— 

ei 


(4) 


Differentiating,  one  obtains : 


la 
a  =  3Nk  h 


el- 1 


3x 
ey-1 


(5 


which  is  De bye's  equation. 

Debye 's  formula  subjected  to  experunen- 
tal  tests  proved  to  agree  exceedingly  well 
with  experimental  results. 

Two  theories  which  deserve  mention  be- 
fore we  pass  on  to  the  Eutherford  Bohr 
thcOTy,  are  the  t.heories  of  Bjerrum  and 
of  Kruger, 

The  Bjerrum  theory  has  been  of  con- 
siderable use  in  the  question  of  the  rota- 
tional spectrum  of  water  vapour  ccn- 
structed  by  Eucken. 

Ki*uger's  theory  can  be  regarded  av  a 
modification  of  the  liutherford  Bohr  theory 
or,  to  be  more  accurate,  an  application  of  it. 

Kruger  accepts  Rutherford's  theory  of 
atoms,  and  regards  gaseous  molecules  as 
gyroscopic  in  nature,  meaning  that  mole- 
cular rotation  is  regarded  as  impossible. 
and  molecules  are  only  capable  of  carrying 
out  precessional  vibrations.  These  vibra- 
tions are  regarded  as  being  fundamentally 
different  from  the  ordinary  vibrations  of 
atoms  along  the  line  forming  their  centres. 

Considering  molecular  collision,  Kruger 
postulates  that  the  ring  of  rotating  elec- 
trons of  a  Bohr  atom,  which  serve  to  hold 
two  atoms  in  union,  suffers  displacement  in 
a  direction  perpendicular  to  the  direction  of 
motion,  with  the  ultimate  result  that  the 
atoms  themselves  describe  small  circular  or 
approximately  circular  orbil-  and  thus  the 
molecule  as  one  whole  exhibits  a  preces- 
sional kind  of  motion. 

Further,  Kruger  points  out  that  such 
motion  is  wholly  kinetic  in  nature,  and  in- 
volves two  degrees  of  freedom.  Now  in  the 
range  of  temperature  in  which  the  principle 
of  equipartition  is  known  to  Hold  gf>od,  the 
energy  term  will  be  one  corresponding  to 
two  degrees  of  freedom,  and  one  degree  = 
1 

—  R  T;  therefore  the  energy  is  R.T.  which 
2 

is  identical  with  the  energy  which  Bjerrum 
postulated  for  diatomic  molecules  on  the 
basis  of  molecular  rotation  as  a  whole  over 
the  same  temiperature  region. 

Kruger's  theory  possesses  the  advantage 
that  it  furnishes  an  explanation  of  the  be- 
haviour of  monoatomio  gases,  viz.,  the  be- 
haviour of  inert  gases  such  as  argon. 


SKPTEMBUli  14,  1923. 


THE  CHEMICAL  NEWS. 


167 


We  now  come  to  one  of  the  most  impor- 
tant pieces  of  work  on  the  quantum  theory, 
namely,  Bohr's  application  of  the  quantum 
theory  to  the  Rutherford  Atom  Model :  and 
it  seems  necessary  to  give  first  a  vague  out- 
line of  the  Rutherford  liohr  theacy  of  the 
atom. 

Briefly  the  theory  can  be  described  as 
follows:  We  consider  the  atom  as  consist- 
ing of  a  nuclear  charge  surrounded  by  a 
series  of  electrons  rotating  in  definite  orbits, 
nearly  the  whole  mass  being  ascribed  to  the 
nucleus.  The  nucleus  is  very  small  in  it- 
self as  compared  with  the  whole  volume  of 
the  atom.  The  outer  row  of  electrons  are 
those  which  gave  the  atom  its  characteris- 
tic chemical  properties,  such  as  valency, 
etc.  The  electrons  on  Rutherford's  atom 
are  regarded  as  "atmosphere"  electrons. 
The  above  is  a  rough  postulation  of  the 
Kutherford  atom  as  conceived  by  its  inven- 
tor in  1911. 

Bohr  pointed  out  that  the  above  atom 
suffered  from  the  drawback  of  a  system  of 
"atmosphere"  electrons,  a  system  unstable 
from  the  point  of  viyw  of  classical  electro- 
dynamics, but  if  Planck's  conception  was 
introduced  the  trouble  vanished,  instability 
no  longer  would  exist  from  the  theoretical 
point  of  vifw. 

Rutherford  considered  the  hydrogen  atom 
ivs  follows :  as  consisting  of  a  nucleus  with 
ji  single  electron  describing  a  closed  orbit 
around  it.  Bohr  considers  while  the  elec- 
tron is  in  a  steady  state  of  rotating  motion 
in  the  aforesaid  orbit,  it  is  neither  radiating 
nor  absorbing  energy.  Radiation  he  con- 
siders to  be  the  result  of  electron  transfer- 
ence from  one  orbit  to  another.  The  quan- 
tum tiieory  assumes  that  during  the  pas- 
sage of  the  electron  from  one  stable  orbit 
to  another  homogeneous  radiation  is  given 
out  or  absorbed  at  a  definite  frequency,  and 
the  amount  given  out  or  absorbed  is  hv 
where  h  is  Planck's  constant. 

The  equations  deduced  from  this  are 
familiar  <mea,  viz. : 

2»rme»E='  (1) 

W  =  


W    - 


4n-^jne-E'" 


2&  =  -' 


2ff"meE 


(2) 

(a) 


where  W  is  energy  transference  during 
change ; 

e  is  charge  on  the  electron; 
E  is  charge  on  the  nucleus ; 
W  is  angular  velocity ; 
2a  major  axes  of  orbit. 
Finally  one  arrives  at  the  expression : 
2ffme*  r       X     -     X 

h^       I       r  =*  T  * 

which  gives  the  frequency  of  the  homo- 
geneous radiation  emitted  by  a  gas  when 
the  atomic  system  changes  from  a  station- 
ary state  defined  by  r^  to  one  r^. 

By  taking  the  expression  and  putting 
Tj  =  2  and  allowing  t^  to  vary,  we  get  the 
Balmar  series  of  lines  of  hydrogen  spec- 
trum. This  is  the  most  definite  proof  of 
the  Bohr  theory,  and  has  therefore  an 
effect  on  the  corresponding  quantum  theory. 
We  have  two  more  matters  to  consider 
briefly  with  regard  to  the  quantum  hyipo- 
thesis,  and  they  are :  the  photo  electric 
effect  and  the  Nemst  heat  theorem,  in 
their  relation  to  the  quantum  hypothesis  : 
these  we  shall  deal  briefly  with  in  the  re- 
spective order :  Photo-electric  effect  and 
Quantum  Theory;  Nemst  Heat  Theorem 
and  Quantum  Theory. 

Some  forty  years  ago  what  we  call  the 
"photo  electric  effect"  was  obtained  by 
Hallwachs,  who  showed  a  charged  body  ex- 
posed to  ultra  violet  light  loses  its  charge. 
In  the  photo-electric  effect  we  apparently 
deal  with  two  phenomena:  firstly,  the  nor- 
mal photo-electric  effect,  and  secondly  the 
selective  photo-electric  effect.  The  effect 
produced  moving  electrons  set  free  at  sur- 
face depends  on,  firstly,  the  number  of 
electrons  emitted  in  unit  time,  and  secondly 
on  the  spetni  of  these  electrons. 

One  of  the  most  striking  parts  of  the 
photo-electric  effect  is  that  the  speed  of 
electrons  is  the  same  for  a  given  frequency 
of  light  independent  of  the  intensity  of  the 
light,  and  more  than  this,  on  keeping  the 
intensitv  constant  and  varying  the  quality 
of  the  fight  the  speed  of  the  electrons  in- 
creases as  the  frequency  increases.  These 
facts  have  found  an  explanation  on  the 
quantum  theory,  in  which,  as  we  have  seen, 
we  regard  light  as  heterogeneous.  Sir  J.  J. 
Thomson  enunciated  the  view  we  hold  of 
the  problem  roughly  as  follows:  Radinnt 
cnergv  which  travels  out  from  a  source  with 
a  wave  is  not  spread  uniformly  over  the 
wave  front,  but  is  concentrated  on  those 
parts  of  the  front  where  the    pulsee  travel 


168 


THE  CHEMICAL  WEWS 


SEPTEMBER  14,  1923. 


aloag  the  lines  of  force.  TEe  energy  of  the 
wave,  therefore,  tends  to  become  collected 
into  regions,  these  regions  being  portions 
of  lines  of  force  occupied  by  pulses.  The 
distribution  of  energy  appears  to  be  analo- 
gous almost  to  the  old  emission  theory,  the 
energy  being  located  on  moving  particles 
sparsely  distributed  throughout  space.  The 
energy  appearing  in  bundles  and  the  energy 
content  of  such  bundles  being  constant 
during  travelling  along  lines  of  force.  Thus 
when  light  falls  on  a  metal  plate,  if  the  dis- 
tance of  the  source  is  increased,  we 
diminish  the  number  of  bundles  falling  on 
given  area,  but  the  energy  in  individual 
units  will  not  be  diminished,  but  any  effect 
which  is  produced  will  be  less  frequent  but 
of  the  same  character  as  before.  Laden- 
bm-g  recently  found  that  the  velocities  of 
corpuscles  emitted  under  the  action  of 
ultra  violet  light  of  varied  wave  lengths, 
varies  continuously  with  the  frequency, 
hence  the  velocity  is  proportional  to  the 
frequency,  hence  although  the  velocity  of 
corpuscles  is  independent  of  the  intensity 
of  the  lights,  it  varies  apparently  in  a  con- 
tinuous manner  with  the  quality  of  the 
light;  this  clearly  renders  it  impossible  to 
consider  the  corpuscles  as  being  expelled  by 
the  explosion  of  the  molecule 

Einstein  gave  the  exjpression : 

Ve  =  I  mv'  =  hv  -  hv,, 
to  the  quantitative  relation  between  the 
theory  of  quantum  and  the  photo-electric 
effect  where  ^  mv^  is  the  K.E.  of  an  elec- 
tron emitted  by  light  of  frequency,  v,  Vo  is 
the  threshold  frequency. 

Einstein's  law,  which  can  be  stated  as 
follows,  "  When  a  photochemical  reaction 
takes  place  owing  to  the  absorption  of 
radiation  in  terms  of  quanta,  each  single 
molecule  of  a  photosensitive  substance  re- 
quiring just  one  quantum  hv^.  in  order  that 
it  may  be  decomposed,"  has  been  investi- 
gated by  Bodenstein,  who  found  the  law  to 
break  down  badly,  because  one  quantum  is 
apparently  capable  of  decomposing  several 
molecules.  Baley  has  dealt  with  this  prob- 
lem, and  his  argument  is  essentially  as 
follows :  that  in  the  case  of  a  dissolved 
substance  which  reacts  photochemically, 
less  energy  is  required  per  molecule  than  is 
required  for  the  same  substance  in  a  gase- 
ous state,  and  hence  Einstein's  law  will 
only  hold  for  the  gaseous  state. 

We  now  consider  our  last  problem, 
namely :  the  relation  between  the  Nemst 
Heat  Theorem  and  the  Quantum  Hypothe- 
sis.    The  application  of  the  quantum  h;*  po- 


thesis  to  the  atomic  heats  of  bodies  in  a 
solid  state  lead  us  to  expect  that  at  low 
temperatures,  atomic  heats  would  become 
nearly  zero.  Further,  if  we  consider  chemi- 
cal reaction  at  low  temperatures,  the  hypo- 
thesis of  quantum  lead  us  to  the  conclusion 
that  for  low  temperatures  the  reaction  be- 
tween two  solids  will  be  given  by  : 


dU 


dT 


=  0 


This    is     in    agreement     with    the     Nernst 
theory,  which  states  that 

L    t  /dA  . 

T  =     o         d  T  J  ~ 


L     t 


T 


dU 
dT 


=  O 


The  i-elation 


dA 
dT 


=  0    is  in    agreement 


also  with  the  Plank-Einstein  hypothesis  re- 
garding energy  distribution  in  solids,  be- 
cause we  can  say  this :  as  molecules  or 
atoms  of  a  solid  body  at  low  temperature 
possess  infinitesimally  small  K.E.  of  vibra- 
tion, the  mutual  distance  apart  will  only 
change  slightly  with  temperature  over  a 
range  of  this  region,  and  hence  the  mutual 
potential  energy  of  the  atom  will  be  nearly 
constant,  hence  their  free  energy  will  be 
constant,  and  hence  mathematically  we 
have 


L    t 
T  =     o 


dA 
dT 


=    0. 


In  composing  this  article,  I  have  followed 
more  or  less  the  treatment  of  the  subject  by 
Lewisi  in  Vol.  III.  of  his  "  System  of  Phy- 
sical Chemistry."  Space  unfortunately  has 
prevented  the  production  of  anything  but 
the  mistiest  of  misty  outlines  of  the  sub- 
ject. Many  things  of  importance  have 
been  no  more  than  mentioned ;  many  more 
have  not  even  been  mentioned.  The  ixiathc- 
matics  I  have  openly  shirked.  The  only 
hope  which  I  express  for  the  article  is  that 
it  may  have  dispelled  amongst  some  chem- 
ists the  fear  and  awe  which  the  titlo, 
"  Quantum  Theory,"  appears  to  have  for 
many  of  us  who  are  research  organic 
chemists,  and  not  mathematical  physicis^ts. 


SEPTEMBEK  14.  1923. 


THE  CHEMICAL  NEWS 


169 


AMERICAN    DYE    PRODUCTION. 
The  Demand  for  Standardisation. 

Prior  to  the  war  Germany  dominated  the 
world's  dye  markets,  producing  about 
three-fourths  of  all  synthetic  dyes.  Of  the 
remaining  fourth  about  one-half  were  made 
of  German  intermediates,  and  eonsequontly 
the  production  of  these  dyes  was  dependent 
uipon  Germany.  Soon  after  the  declaration 
of  war  the  supply  of  German  dyes  was  cut 
off  from  the  world's  markets.  An  acute  dye 
famine  developed,  threatening  the  activities 
of  the  vast  textile  and  other  industries  de- 
pendent upon  dyes  for  their  operation. 
Prices  increased  to  previously  unheard  <  f 
levels,  and  certain  dyes  were  not  to  be  had 
at  any  price.  During  and  since  the  war  tin 
United  States,  the  United  Kingdom  and 
France  have  made  extensive  development-. 
in  the  manufacture  of  dyes,  and  have  ex- 
ported dyes  in  significant  quantities  sinci' 
the  signing  of  the  Armistice.  The  com- 
plete German  monqpoly  of  the  world's  dyt- 
production  has  been  broken  at  least  tem- 
porarily, if  not  permanently.  Extensive 
developments  in  dye  manufacture  in  the 
various  countries  have  resulted  in  an  ap- 
proximate doubling  of  the  world's  capacity 
to  produce  synthetic  dyes,  and  sharp  com- 
petition may  be  expected  in  the  world's  dve 
markets.  It  is  already  in  evidence  in  ttic 
Far  East. 

The  German  dye  industry  for  instjuu;*', 
offers  a  united  front  to  the  world  in  a  com- 
bination known  as  the  I.G.  (Interessen 
Gemeinschaft).  It  possesses  the  advantage 
of  cumulated  experience,  lower  manufac- 
turing costs,  and  a  unified  organisation  for 
buying  and  selling.  The  three  Swiss  dye 
manufacturers  have  also  formed  an  amal- 
gamation. China  leads  the  world  as  a  con- 
sumer of  dyes  with  a  consumption  esti- 
mated at  about  70  million  lbs.  per  annum  ; 
the  United  States  ranks  second  with  an 
average  consumption  of  about  56  million 
lbs.,  followed  by  the  United  Kingdom  with 
a  consumption  of  nearly  50  million  lbs.  per 
year.  It  is  expected  that  Germany  will 
make  every  endeavour  to  recover  a  part  of 
hor  former  trade  with  these  three  dye  con- 
suming nations.  In  case  protrctivc 
measures  are  retained  ,by  the  new  dye  ipro- 
ducing  countries  Germany  may  resort  to 
the  establishment  of  factories  or  seek  affilia- 
tions, as  hns  already  been  done  by  the  S\\nss 
manufacturers  in  establishing  plants  in 
poth  the  United  States  and  the  United 
Kingdom. 


The  foregoing  has  been  taken  from  an  ad- 
vance summary*  of  the  Report  on  the  an- 
nual Census  of  Dyes  and  other  Synthetic 
Organic  Chemicals  recently  completed  by 
the  United  States  Tariff  Commission.  The 
following  statement  of  the  dye  industry  of 
the  United  Slates  has  been  extracted  from 
the  same  source  :  — 

Growth  of  Dye  Production. 

The  Repoi-t  shows  that  during  the  year 
1922  the  domestic  dye  and  organic  chemical 
industry  made  notable  progress.  Many 
products  were  manufactured  for  the  first 
time  in  the  United  States,  and  there  were 
large  increases  in  the  quantity  of  produc- 
tion, with  conspicuous  reductions  in  prices. 

The  domestic  production  of  dyes  during 
the  year  by  87  firms  was  64,632,187  lb.,  an 
increase  of  66  per  cent,  over  that  of  1921. 
The  sales  for  1922  totalled  69,107,105  lb., 
valued  at  41,463,790  dols.  The  size  of  the 
industry  in  1922  was  in  sharp  contrast  with 
that  of  1914,  when  only  seven  firms  manu-- 
factured  a  total  of  6,619,  <ziv  lb.,  valued  at 
2,470,096  dols.  The  dye  industry  in  that 
period  was  in  no  sense  a  self-contained  one_, 
as  the  dyes  produced  were  made  almost  en- 
tirely of  intermediates  imported  chiefly 
from  Germany.  The  increase  in  production 
during  1922  was  largely  due  to  an  expan- 
sion in  general  business.  Beginning  about 
June  the  textile  and  other  dye-consuming 
industries  became  more  active  after  the 
depression,  and  during  the  remainder  of  the 
year  the  demand  for  dyes  steadily  Ihcreased. 

Large  Price  Reductions. 

The  average  selling  price  of  all  domestic 
ilyes  for  1922  was  60  cents,  per  lb.,  com- 
pared with  83  cents  in  1921  and  1  dol,  26 
cents  per  lb.  in  1917.  The  1922  figures  re- 
present a  28  per  cent,  decline  from  that  of 
1021.  There  were  price  reductions  for  both 
the  bulk  colours  and  dyes  consumed  in 
smaller  quantities.  The  average  price  of 
indigo  in  1921  was  45  cents  per  lb.,  com- 
pared with  24  cents  in  1922,  a  47  per  cent. 
decrease. 

Increased  Output  of  Vat  and  Alizarin 
Dyes. 

One  of  the  conspicuous  developments  of 
the  year  was  the  increased  production  of 
vat  and  alizarin  dyes.  The  vat  colours  are 
of  great  complexity  and  have  presented 
serious  difficulties  in  their  commercial  pro- 
duction. Their  use  is  on  the  increase,  as 
the  public    is  beginning    to  recognise    that 


170 


THE  CHEMICAL  NEWS. 


SEPTEMBER  14,  1028. 


fast  shades  are  obtainable  on  cotton  goods. 
The  alizarin  dyes  are  of  great  value  in  wool 
dyeing,  and  the  addition  to  this  field  of 
new  dyes  and  the  increased  production  of 
other  dyes  is  a  significant  step  in  the  de- 
velopment of  a  self-contained  dye  industry. 
The  total  production  in  1922  of  vat  dyes 
(not  including  indigo)  was  1,075,992  lb., 
compared  with  345,152  lb.  in  1921.  The 
production  of  the  anthraquinone  dyes, 
which  includes  alizarin  dyes  and  a  large 
part  of  the  vat  dyes,  was  1,234,963  lb. 

Production  of  New  Dyes. 
Many  important  dyes  were  produced  for 
the  first  time  on  a  commercial  scale  in  ]1)22. 
These  comprise  colours  of  great  value  f'>r 
the  dyeing  of  either  silk,  cotton,  or  wool, 
such  as  vat  dyes,  alizarin,  developed  cot- 
ton dyes,  mordant  and  acid  dyes.  The  pro- 
duction of  these  dyes  has  resulted  only 
after  large  expenditures  on  research  and 
most  painstaking  investigations.  There 
are,  however,  still  gaps  to  be  filled  in  cer- 
tain vat  dyes  and  some  of  the  mordant, 
acid  and  direct  dyes. 

Quality  and  Standardisation  of 
American  Dyes. 
Dye  for  dye,  with  relatively  few  excep- 
tions, domestic  products  are  now  found 
equal  to  pre-war  Gerftian  dyes.  In  the 
early  stages  of  the  United  States  dye  indus- 
try, after  the  outbreak  of  the  Great  War, 
many  dyes  were  lacking  in  uniformity  of 
strength  and  quality.  This  condition, 
however,  no  longer  prevails,  as  is  attested 
to  by  the  largest  silk  and  woollen  manufac- 
turers and  cotton  printers  and  dyers. 

Ratio  of  Production  to  Consumption. 

The  United  States  produces  about  93.5 
per  cent,  of  the  dyes  actually  consumed  in 
the  country.  The  imports  of  dyes  in  1922 
totalled  3,982,631  lb.,  the  .nroduction  was 
64,632,187  lb.,  and  the  exports  totalled 
6,956,593  lb.  Consumption  is  assumed  to 
equal  production,  plus  imports,  minus  ex- 
ports, or  61,658,225  lb.  The  imports  in 
1922  were  6.2  per  cent,  of  United  States 
production  and  6.5  per  cent,  of  consump- 
tion. In  1914  the  irmports  were  nearly  90 
per  cent,  of  consumption. 

Production  by  Classes. 

The  production  of  dyes  in  1922,  grou[)(d 
by  classes  according  to  their  method  of 
application  on  fibres,  were  as  follows:  — 


Acid  

Basic  dyes  

Direct  cotton  dyes         

Lake  and  spirit-soluble  dyes  ... 
Mordant  and  chrome  dyes 

Sulphur  dyes       

Vat  dyes  (not  including  indigo) 

Indigo 

Unclassified  dyes 


lb. 

9,880,014 

2,937,585 
11,931,737 
11,009,512 

8,749, a)- 
16,913,767 

1,075,992 
15,850,752 

1,283,127 


Dye  Imports  :  Amount  and  Sources. 

Imports  of  dyes  into  the  United  States 
last  year  amounted  to  3,982,631  W.,  valued 
at  5,243,258  dols.,  as  compared  vith 
4,252,011  lb.  in  1921  and  45,950,895  lb.  in 
1914.  Of  last  year's  imports,  44.58  per 
cent,  came  from  Germany,  43.72  per  cent, 
from  Switzerland,  5.25  per  cent,  from  the 
United  Kingdom,  and  4.i8  per  cent,  from 
Italy.  The  1922  figures  show  a  decline  of 
dye  imports  from  Germany,  as  during  the 
previous  year  48.84  per  cent,  and  in  1920 
51  per  cent,  came  from  there.  Vat  dyes  led 
in  quantity  of  imports,  totallinor  1,549,024 
lb.  (single  strength);  mordant  and  chrome 
dyes  amounted  to  716,790  lb.,  and  direct 
cotton  dyes  to  671,621  lb. 


Expenditure  on  Dye  Research. 
The    United     States     coal-tar    dje 


and 


chemical  industry  expended  over  21  million 
dols.  on  research  during  the  five  years 
1917-22.  The  accomplishments  of  that 
period  and  the  progress  of  the  dye  industry 
may  be  attributed  in  no  small  part  to  the 
enormous  expenditure  on  research.  New 
dyes  and  other  chernicals  of  great  economic 
value  have  been  developed,  and  the  costs  of 
production  have  been  materially  reduced. 

Dye  Exports. 

The  .e.vport  of  dyes  from  the  United 
States  in  1922  shows  a  decrease  in  value 
from  the  previous  year  from  6,270.155  dols. 
in  1921  to  3,023,127  dols.  Further,  the 
1922  figure  is  a  90  per  cent,  decline  from 
that  of  1920,  when  exports  reached  the 
maximum  value  of  29,823,591  dols.  The 
large  export  during  1920  was  due  to  the 
trade  boom  before  German  dyes  made  their 
appearance  in  the  large  dye  markets  of  the 
world.  The  official  import  figures  of  China. 
India,  and  Japan  show  that  large  quanti- 
ties of  German  dyes  were  exported  to  these 
coimtries  after  1920,  and,  in  addition, 
Swiss,  French,  and  British  dyes  have  been 
notable  factors  in  the  Far  Eastern  markets. 


SEPTEMBER  14,  1928. 


THE  CHEMICAL  NEWS. 


m 


Exports  of  dyes  for  the  first  four  months 
of  1923  show  a  recovery  in  value  and  quan- 
tity. This  increased  demand  for  American 
dyes,  largely  by  the  Far  Eastern  markets, 
may  be  attributed  in  part  to  the  reduced 
imports  of  German  dyes  on  account  of  the 
occuipation  of  the  Kuhr  by  the  French  in 
1923. 

Other  Fixisued  Coal-Tar  Products. 

The  total  output  of  dyes  and  other 
finished  coal-tar  chemicals  in  the  United 
States  in  1922  by  164  firms  was  88,368,131 
lb.,  compared  with  51, 457, 565  lb.  by  147 
firms  in  1921,  a  72  per  cent,  increase.  Pre- 
liminary figures  of  the  United  States  Geo- 
logical Survey  indicate  that  the  production 
of  coal  tar  and  by-products  from  the  by- 
product coke  industry  last  year  was  the 
greaU-'st  in  the  history  of  the  industry.  The 
output  of  by-product  coke  was  about  28A 
million  tons,  which  exceeded  the  produc- 
tion of  both  beehive  and  by,-product  coke 
during  the  previous  year. 

Chemicals  of  Non-Coal  Tar  Origin. 
Consipicuous  progress  has  also  been  made 
within  the  past  few  years  in  the  develop- 
ment and  manufacture  of  synthetic  organic 
clK'micals  of  non-coal  tar  origin.  The  pro- 
duction during  1922  was  79.202,155  lb.,  as 
compared  with  21.545,186  lb.  in  1921. 

Need  for  Standardisation. 
In  a  Memorandum*  issued  by  the  United 
State*  Bureau  of  Standards  on  its  work  in 
coimection  with  the  standardisation  of  dyes 
it  is  stated  that  the  lack  of  uniformity  of 
commercial  dyes  in  colour  strength,  quality 
and  money  value  is  well  gnown  to  the  trade. 
Before  the  war  the  dye  industry  was  con- 
trolled by  the  German  firms,  who  umin- 
tained  a  multiplicity  of  names,  strengths, 
and  qualities  of  dyes.  The  trade  was  ac- 
customed, therefore,  to  dyestulfs  of  vari- 
able quality,  so  that  when  the  field  was 
opened  to  American  manufacturers  oppor- 
tunity was  presented  for  the  wholesale 
adulteration  of  textile  colouring  matters  by 
jobbers  and  brokers,  whose  profits  entailed 


*  The  Sunnnanj  of  the  Kcpori  of  the 
Tariff  Cotnmisnion  and  the  Memorandum  of 
the  Bureau  of  StandardH,  tvhich  have  been 
forwarded  by  H.M.  KepreHeniaiive  at  Wash- 
ington, maif  be  consaJtrd  by  United  Kiiin- 
dom  firms  interested  on  application  to    the 

Department    of    Overseas    Trade,    85,    Old 

Queen  Street,  London,  S.W-l. 


■d  corresponding  loss  to  legitimate  industry. 
The  demand  for  standardisation  has  come 
mainly  from  the  dyers  and  textile  manufac- 
turers, who  believe  that  standardisation 
will  remedy  this  objectionable  condition. 
The  situation  with  resipect  to  the  enforce- 
ment of  the  standardisation  features  of  the 
Tariff  Act  of  1922  clearly  shows  that  there 
was  little  or  no  standardisation  in  the  past, 
and  that  it  is  needed  now. 

The  standardisation  of  dyes  is  in  accord 
with  modern  business  practice,  whereby 
buyer  and  seller  have  a  conmion  basis  of 
knowledge  of  the  products  of  trade.  Such 
practice  leads  to  more  economical  business 
and  better  business  to  legitimate  industry. 
The  manufacturer  of  dyes,  in  paiticular,  is 
coming  to  see  the  advantages  of  standardi- 
sation. In  fact,  standardisation  may  well 
become  a  distinctive  feature  of  the  Ameri- 
can Dye  Industry. 

The  problem  of  dye  standardisation  is 
first  to  devise  methods  for  :  — 

(1)  Identification  of  dye  sipecies. 

(2)  Determinafion  of  colour  strength  in 
t^enns  of  pure  dye  content  or  some 
arbitrarily  chosen  standard. 

(3)  Determination  of  quality  of  a  dye. 
This  includes  fastness  tests  and  bests 
for  suitability  of  a  given  product  for 
a  special  use. 

Then  the  problem  is  to  establish  stand- 
ards and  specifications  for  each  dye  which 
will  be  acceptable  to  manufacturer  and 
consumer. 


GENERAL    NOTES. 

SOUTH  AFIUCA— TAR  OR  TAR 
SUBSTITUTE. 

His  Mnjestv's  Senior  Trade  Commis- 
sioner in  South  Africa  (Mr.  W.  E.  G.  Wick- 
ham)  reports  a  call  for  tenders  for  the  sup- 
ply of  1 .800  tons  of  tar  or  tar  substitute. 

Applications  for  further  particulars 
should  be  addressed  to  the  Department  of 
Overseas  Trade,  35.  Old  Queen  Street, 
Westminster,  S.W.I. 

MEXICO. 

His  Majesty's  Consul-General  at  Mexico 
City  (Mr.  N.  King)  wishes  to  draw  the  at- 
tention of  British  traders  sending  catalogues 
to  Mexico  to  the  necessity  for  the  payment 
of  the  recontly  imposed  dutv  on  such  litera- 
ture. ,    ,   ,  ,.  .        . 

It  should  he  not^^d  that  delivery  is  not  per- 
mitted before  this  duty  has  been  paid. 


17^ 


TTtE  cnSMlCAL  NEWS. 


SEPTEMBER  14    1923. 


SODIUM  ACETATE  (COMMERCIAL) 
FOE  AUSTRALIA. 

Mr.  S.  W.  B.  McGregor,  H.M.  Senior 
Trade  Commissioner  in  Australia,  reports 
that  the  Victorian  Railways  Commissioners 
are  calling  for  tenders  to  be  presented  be- 
fore October  17,  1923,  for  the  supply  of  fif- 
teen tons  of  (commercial)  sodium  acetate. 

Applications  from  United  Kingdom  firms 
for  further  particulars  should  be  addressed 
to  the  Department  of  Overseas  Trade,  35, 
Old  Queen  Street,  London,  S.W.I,  quoting 
reference  No.  12039/E.D./C.P. 


CREOSOTE  FOR  BULGARIA. 

H.M.  Legation  at  Sofia  reports  that  the 
Bulgarian  State  Railways  are  desirous  of 
receiving  tenders  for  the  supply  of  500  tons 
of  creosote  to  the  approximate  value  of 
3,500,000  leva.  A  public  adjudication  of 
tenders  will  be  held  on  the  28th  September, 
1923. 

Reference  No.  11466/FE/CC(2). 


QUESTIONNAIRE  ON  FERTILISERS. 
The  International    Institute    of    Agi'icul- 
ture,-  Rome,   has  issued  a,  questionnaire  on 
Fertilisers,  which  is  to  be  sent  to  the  Gov- 
ernments of  all  the  adhering  States. 

The  Permanent  Committee  of  the  Insti- 
tute is  anxious  that  suitable  measures  be 
taken  to  increase  the  production  and  use  of 
fertilisers  in  agriculture. 


BRITISH  CATALOGUES  FOR 
CANADA. 

His    Majesty's     Senior    Trade    Commis 
sioner  in  Canada    (Mr.    R.  W.  Dalton)  has 
informed  the  Department  of  Overseas  Trade 
that  there  is  a  serious    lack  of  British  cata- 
logues in  the  various  Trade  Commissioners' 
Offices  in  Canada.    He  points  out  that  with 
out  such  catalogues,    it  is  often    a  difficult 
matter  to  advise  firms  in  Canada  as  to  pos 
sible  British  sources  of  supply,  and  that  thi 
necessity    of    referring    enquiries    to    head 
quarters    in    London    takes    time,     during 
which  business  that  might  otherwise  have 
gone  to  British  firms,  is  lost  to  them. 

United  Kingdom  firms  desirous  of  ensur- 
ing their  names  being  ^iven  to  suitable  en- 
quirers should  foi-ward  copies  of  their  cata- 
logues to  any,  or  all,  of  the  following:  — 

H.M.  Senior  Trade  Commissioner  in 
Canada,  285,  Beaver  Hall  Hill.  Montreal. 

H.M.  Trade  Commissioner,  24.  Adelaide 
Street  West,  Toronto. 


H.M.  Trade  Commissioner,  210,  Winch 
Building,  Vancouver. 

The  Chief  Clerk,  Office  of  H.M.  xrade 
Commissioner,  703,  Union  Bank  Buildings, 
Winnipeg. 

It  should  be  noted  that  Customs  duty  is 
levied  on  catalogues  entering  Canada,  find 
firms  desiring  to  send  them  by  parcel  post 
should  prepay  such  duty.  Foi*  this  purpose 
stamps  may  be  obtained  from  the  office  of 
the  High  Commissioner  for  Canada,  \\m- 
naird  House,  Pall  Mall  East,  London, 
S.W.I. 


THE  SIR  JOHN  CASS  TECHNICAL 

INSTITUTE,    JEWRY  STREET 

ALDGATE,  E.C.3. 

Session  1923-24. 

The  session  1923-24  will  commence  on 
Thursday,  September  20;  students  will  be 
enrolled  on  Monday,  Tuesday  and  Wednes- 
day, September  17,  18  and  19,  from  0  to 
8.30  p.m. 

The  courses  of  instruction  at  the  In^^i- 
tute,  which  are  held  from  6  to  10  (p.m,, 
meet  the  requirements  of  those  engaged  in 
chemical,  metallurgical,  electrical,  petro- 
leum and  the  fermentation  industries. 

Full  facilities  are  provided  in  the  well- 
equipped  laboratories  of  the  Institute  for 
special  investigations  and  research.  The 
instruction  in  experimental  science  also 
provides  systematic  courses  for  the  ex- 
aminations of  London  University,  the  City 
and  Guilds  of  London  Institute,  and  of  the 
Institutes  of  Physics,  Chemistry,  and 
Brewing. 

Special  courses  of  higher  technological  in- 
struction form  a  distinctive  feature  of  the 
work  of  the  Institute,  and  during  the  forth- 
coming session  the  following  courses  will  be 
included  in  the  syllabus:  — 

Brewing,  Malting,  Micro-Biology,  Bott- 
ling and  Cellar  Management,  Petroleum 
Technology,  Colloids,  Alternating  Currents 
and  Electrical  Oscillations,  Mathematical 
Statistics,  Metallography  and  Pyrometry, 
Heat  Treatment,  and  Mechanical  Testing 
of  Metals  and  Alloys,  Foundry  Practice, 
Mining  and  Surveying. 


I 


The  Postmaster-General  wishes  to  correct 
the  widespread  imipression  which  exists 
that  an  initial  charge  is  made  for  installing 
a  telephone. 

During  the  war  a  imiform  surcharge  of 
£4  on  new  installations  was  made;  but  this 
charge  was  abolished    more  than  two  years 


J|SEPTEMBEB  14,  1923.  THE  CHEMICAL  NEWS. 


173 


ago.  The  present  system  of  charging  is  i 
broadly  as  follows  :  The  rental  is  payable 
quarterly  in  advance,  and  the  fees  for  calls 
and  other  services,  such  as  telegrams  dic- 
tated over  subscribers'  oircuils,  are  pay- 
able quarterly  in  arrear.  On  the  completion 
of  an  installation,  a  new  subscriber  pays  on 
account  of  rental  the  proportionate  amoimt 
up  to  the  next  quarter  day,  together  with  a 
small  deposit  in  resipect  of  calls  t'>  be  made 
during  the  quarter.  The  rental  includes 
the  cost  of  installing  the  telephone,  and  no 
other  preliminary  charge  is  made  on  that 
accoimt. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  INSTITUTE  OF  METALS. 
Second  Autumn  Lecture, 

Delivered  by  Lieut. -Colonkl  Sir  Henry 
Fowler,  K.B.E.,  at  Manchester,  on  Mon- 
day, Septeml)er  10,  1923,  on  The  Uee  of 
Non-Ferrous  Metah  in  Engineering. 

There  are  very  many  articles  which  every 
day  use  has  so  familiarised  us  with  that  we 
look  up)on  them  as  common-place.  A  little 
thought,  however,  will  show  that  the  fact 
that  we  have  them  available  in  the  fcmn  we 
use  them  is  the  result  of  years  of  research 
and  patient  investigation.  It  is  probable 
that  it  was  some  such  thought  as  this  that 
led  the  Council  of  the  Institute  of  Metals  t( 
chf>ose  the  subject  of  the  autumn  lecture 
for  this  year,  and  to  place  it  in  the  hands 
of  an  enginet-r. 

The  subject  itself  is  so  extremely  com- 
prehensive that  it  is  only  in  the  form  of  a 
popular  lecture  that  it  could  iposgibly  be 
•  K'alt  with  in  a  single  a(l(iress.  It  may  be 
said  that  the  use  of  non-ferrous  metals  by 
engineers  is  the  ultimate  object  cf  all  papjTs 
read  before  the  Institute. 

Of  these  metals  the  one  which  has  been 
in  longest  use  is  copper,  and  it  is  at  present 
the  one  most  closely  associated  either  by 
itself  or  alloyed  with  engineering  work.  The 
uses  to  which  its  comparatively  simple  al- 
loys vvitii  tin  and  zinc  can  be  put  are  end- 
less. The  next  in  importance  is  iperhaps 
tin  which,  alloyed  with  con^'-v  lead  and 
antimony,  give  us  those  white  metals  which 
allow  bearings  to  be  a  practical  proposition. 

Aluminium  is  one  of  the  most  interest- 
ing of  the  series  of  metals  and  although 
from    an  engineering  standpoint    it  is  per- 


haps most  generally  used  in  connection 
with  aeronautics,  recent  investigations 
have  opened  up  a  new  field  for  its  use. 

There  still  remain  numbers  of  other 
metals  which,  as  alloys,  are  helping  to  solve 
the  problems  which  the  advances  in  recent 
engineering  practice  bring  in  their  train. 

Annual  Autumn  Meeting  of  the  Institute 
OF  Metals,  held  in  Manchestku,  ox 

Tuesday,  Sei'tkmber  11,  1928. 
The  Cause  of  Red  Stains  on  Sheet  Brass, 
by  E.  A.  lioLTON,  M.Sc. 

The  author  gave  an  account  of  work  car- 
ried out  to  elucidate  this  piobleni.  The 
various  theories  which  have  been  frtm  time 
to  time  put  forward  were  reviewed  and  ex- 
periment described  which  Ixnu-  upon  these 
theories.  Although  the  experiments  were 
carried  out  in  the  laboratory,  close  touch 
was  established  throughout  with  actual 
works'  practice.  The  outstanding  point  is 
that  the  stains  actually  occur  through  re- 
actions of  copper  oxides  in  the  scale  formed 
(hiring  anneiUing  and  the  pickling  medium. 
Cuprio  oxide,  contrary  to  the  usual  opinion, 
is  shown  to  be  jis  hamiful  as  cuprous  oxide. 

It  is  shown  that  oxides  of  copper  may  be 
present  from  various  causes,  such  as  care- 
less washing  after  the  pickling  operation 
resulting  in  the  presence  of  acid  and  salts 
during  the  subsequent  annealing,  the  pre- 
sence of  iron  in  the  brass  or  upon  its  sur- 
face, the  use  of  impure  rolling  oils,  etc.  It 
is  concluded,  however,  that  the  main  cause 
of  the  oxidation  of  the  copper  is  the  use  of 
o'd-fashioned  annealing  furnaces  in  which 
the  flames  impinge  directly  upon  the  brass. 

The  paper  concluded  with  an  account  of 
possible  remedies  for  the  red-stain  trouble. 

Brinell  Hardness  Numbers,  by  H,  W. 
Brownsdon,  M.Sc,  Ph.D.,  F.I.C,  Mem- 
l)er  of  Council. 

The  author  drew  attention  to  the  desir- 
ability of  Brinell  numbers  for  non-ferrous 
metafs  being  given  in  figures  that  may  be 
comparable. 

Stereoiijping,  by  A.  H.  Mundey  and  John 
I'artland,  M.C  M.Sc. 

The  authors  described  the  process  of 
stereotyping  which  is  generally  rogardinl  by 
printers  as  one  which  is  almost  a  trade 
secret.  The  authors  point  out  that  the  pro- 
cess was  invented  by  a  practical  metallur- 
gist, William  Ged,  an  Edinburgh  goldsmit'i, 
in  1750. 


174 


r 


THE  CHEMICAL  NEWS. 


SEPTEMBER  14,  1923. 


The  metallurgical  trials  and  diflB.culties 
were  briefly  dealt  with,  and  the  considei'a- 
tion  of  metallurgists  is  invited  to  some  of 
the  problems  involved.  The  authors  point 
out  with  truth  that  the  industry  is  much 
fore  important  than  is  usually  understood, 
and  they  call  attention  to  the  high  degree 
of  accuracy  demanded  in  the  mechanical 
and  metallurgical  details  in  order  to  rpro- 
duce  the  results  which  are  a  commonplace 
to  everyone. 

The  enormous  speed  and  absolute  relia- 
bility of  production  necessarv  in  the  case  of 
newspaper  work  was  referred  to,  in  addition 
to  the  fact  that  the  produ"^^  -*  this  metallur- 
gical process — the  printed  page — is  open  to 
the  criticism  of  the  whole  public. 

Crystallisation  Effect  on  Galvanised  Iron 
Sheets,  by  J.  D.  Hannah,  M.Sc.Tech., 
and  E.  L.  Rhead,  M.Sc.Tech. 

Manufacturers  of  galvanised  iron  and 
steel  goods,  specially  corrugated  sheets  in 
which  it  is  desired  to  obtain  the  best  ap- 
pearance, have  always  sought  to  produce  a 
zinc  covered  surface  having  large  charac- 
teristic spangles.  Failure  to  do  this  is  a 
frequently  recurring  source  of  trouble  and 
loss.  The  absence  of,  or  the  production  of, 
only  small  spangles  has  been  attributed  to 
many  causes.  The  quality  of  the  steel, 
either  the  presence  of  sulphides  and  other 
non-metallic  inclusions,  or  its  condition 
produced  by  rolling  and  subsequent  treat- 
ment, the  pickling,  either  caused  by  im- 
purities in  the  acid,  by  the  occlusion  of  gas 
by  the  metal,  the  temperature  of  the  bath, 
and  the  purity  of  the  zinc,  have  all  been 
blamed  for  the  failures. 

Messrs.  Hannah  and  Rhead  gave  an  ac- 
count of  a  research  to  ascertain  the  real 
causes.  Little  assistance  can  be  obtained 
from  literature  on  the  subject. 

The  research  shows  that  the  metal — iron 
or  steel — has  practically  no  influence  on 
the  result  if  the  temperatures  are  satisfac- 
torily maintained.  After  the  conditions  of 
good  work  had  been  establish <^'^  samples  of 
both  good  and  bad  sheet  from  which  the 
zinc  had  been  stripped,  gave  equally  good 
results.  It  was  shown  that  pure  zinc  did 
not  yield  the  desired  large  spangles,  and 
that  too  high  a  temperature  interfered  by 
producing  large  quantities  of  a  zin?  iron 
compound  which  crystallised  in  needles  on 
the  metal  and  interfered  witR  the  develop- 
ment of  the  spangle.  The  presence  of  tin 
or  aluminium — contrary  to  expectation  and 
as  commonly  stated — did  not    produce  the 


desired  result,  but  the  addition  of  lead  did 
so  immediately. 

Judging  from  the  known  relationships 
between  zinc  and  lead,  the  authors  irgued 
that  the  separation  of  the  impure  zinc  form- 
ing the  layer  on  the  metal  sheet  into  conju- 
gate solutions — lead  rich  and  zinc  rich — at 
the  dipping  temperature,  and  the  method 
of  subsequent  crystallisation  were  the 
causes  of  the  effects  obtained.  That  this 
occurred  was  proved  by  the  analysis  of  dif- 
ferent types  of  sipangle  occurring  on  the 
same  sheet,  and  by  the  observed  differences 
in  the  rate  of  attack  of  digerent  spangles 
forming  the  coating.  The  separation  is  at- 
tributed to  the  difference  in  the  surface  ten- 
sions of  the  two  solutions.  That  such  dif- 
ferences exist  was  proveu  by  experiment. 

Proof  of  the  hypothesis  is  furnished  by 
the  fact  that  Bismuth,  the  only  common 
metal  that  resembles  leacl  more  or  less,  in 
its  relations  with  zinc,  produces  similar 
effects.  The  temperature  at  which  good  re- 
sults can  bo  obtained  is  limited  by  the  ten- 
dency to  form  excessive  amoimts  of  the 
iron  zinc  compound  previously  referred  to, 
and  the  time  occupied  in  diipping  and  cool- 
ing. 

Effects  of  Rate  of  Cooling  on  the  Density 
and  Comjiosition  of  Metals  and  Alloys,  bv 
R.  C.  Reader,  Ph.D.,  M.Sc. 

This  note  was  concerned  chiefly  with  two 
rates  of  cooling,  fast  and  slow,  as  produced 
by  casting  in  chill  and  sand  moulds.  The 
results  recorded  show  that  the  densities  of 
pure  metals  are  not  affected  by  the  rate  at 
which  they  solidify,  and  a  similar  remark 
applies  to  those  alloys  which  solidify  at  a 
constant  temperature.  In  the  case,  how- 
over,  of  those  alloys  which  solidify  over  a 
range  of  temperature,  the  rate  at  which 
they  pass  through  this  range  seriously  af- 
fects the  density,  the  slower  the  rate  of 
solidification  the  lower  being  the  density. 
Also  when  alloys  which  possess  a  long 
solidifying  range  are  prepared  in  cylindrical 
chill  moulds  they  are  less  dense  in  the 
centre  than  at  the  outside.  Rapid  solidifi- 
cation has  a  pronounced  effect  on  the  com- 
position throughout  the  mass  of  those  al- 
loys which  solidify  over  a  range  of  tem^iera- 
ture.  When  prepared  in  chill  these  alloys 
are  found  to  be  richer  on  the  outside  in  the 
component  of  the  lower  melting  point  and 
richer  in  the  centre  in  the  component  of  the 
higher  melting  point.  Sand  castings  in 
these  alloys  are  uniform  throughout.  Alloys 
which     solidify  at  a  constant    temperature 


SEPTEMBER  14,  1923. 


THE  CHEMICAL  NEWS. 


175 


aie    uniform    in    composition     throughout, 
whether  prtipared  in  sand  or  chill  moulds. 

The  Effect  of  Small  Quantities  of  Nicket 
upon  High-grade  Bearing  Metal,  by  A.  H. 
MuxDEY  and  C.  C.  Bissett,  B.A.,  B.Sc, 
B.Met. 

This  note  gave  an  account  of  a  practical 
trial  of  the  effect  of  varyin<r  small  quanti- 
ties of  nickel  upon  a  tough  and  well-reputed 
bearing  metal. 

There  was  chosen  for  test  the  well  known 
alloy  consisting  of: 

Tin  93  per  cent.,  Antimony  3.5  per  cent., 
Copper  3.5  per  cent. 

The  authors  state  that  nickel  is  now 
found  to  he  added  to  some  considerable  ex- 
tent, possibly  as  a  means  f)f  identification, 
but  some  merit  is  als  >  claimed  for  it. 

The  results  of  the  usual  iphysical  tests 
are  detailed.  Tensile,  compression  and 
hardness  tests  gave  no  indication  of  im- 
provement due  to  the  nickel :  in  fact,  the 
alloys  were  rather  inferior  when  containing 
nickel.  Running  trials  on  the  Thurston 
machine  aa  strictly  comparative  lines 
showed  practically  no  change  as  between 
nickel  and  non-nickel  alloys. 

The  comparison  of  hardness  at  varying 
increased  temperatures  exhibited  no  "im- 
provement. Probably  the  mo«t  inttmsfing 
feature  is  the  structure  as  shown  under  the 
microscope.  In  the  case  of  the  alloy  with 
no  nickel  the  hard  copper-tin  constituent  is 
very  marked  in  its  characteristic  crystalline 
formation.  The  presence  of  nickel'eveu  in 
small  quantities  results  in  a  great  diminu- 
tion of  this  crystalline  structure,  and  the 
structure  is  only  in  a  measure  restored  by 
the  addition  of  mon'  copper. 

The  authors  conclude  from  their  experi- 
ments that  the  beneficial  results  of  nickel 
in  alloys  of  the  character  employed  are  yet 
to  be  demonstrated. 

The  Measurement  of  the  Change  of  Vol- 
ume in  Metals  during  Solutification,  by 
HiKozo  Endo. 

In  the  casting  process  it  is  very  impor- 
tant to  know  to  what  extent  a  change  of 
volume  occurs  during  solidification.  Not- 
withstanding this  great  necessity,  the  liter- 
ature concerning  the  phenomena  is  very- 
scanty,  because  of  the  lack  of  a  suitable 
method  for  arriving  at  an  accurate  deter- 
mination. In  1888,  Vincentini  and"  Omwlei 
calculated  the  change  of  volume  of  some 
fusible  metals  during  solidification  from  the 
change  of  density  at  the  ineltinrr  point.  The 
measurement    of  the    density  of    different 


metals  in  the  vicinity  of  their  melting 
points  has  been  the  subject  of  inquiry  by 
several  investigators  among  which  are  to 
be  mentioned  E.  Wiedemann,  Paul  Pascal, 
,and  Louis  Hackspill.  M.  Toepler,  who 
studied  the  change  of  volume  by  means  of 
a  dilatometer,  suggested  a  relation  of  the 
change  of  volume  of  a  metal  at  melting 
point  to  its  atomic  weight,  similar  to  that 
of  the  atomic  volume  to  the  atomic  weight. 
Recently  K.  Bomemann  and  F.  Sauerwafd 
also  measured  the  density  of  metals  at 
various  high  tt^mperatures  by  means  of  the 
Archimedes  iprinciple,  using  a  mixture  of 
sodium  and  potassium  chlorides  as  liquid. 

The  present  investigation  was  started  in 
April,  1921,  and  the  measurement  of  the 
change  of  volume  during  solidification  or 
melting  for  a  number  of  metals  having  low 
melting  points  up  to  1100°  C.  has  now  been 
finished.  This  paper  contains  the  results 
of  the  measurements,  and  forms  the  first 
report  of  the  results  of  the  investigation  of 
a  long  series  of  experiments  which  are  to 
be  extended  to  other  metals  having  higher 
melting  points. 

The  method  of  investigation,  which  was 
suggested  by  Professor  K.  Honda,  consists 
in  the  measurement  j>f  the  change  of  buoy- 
ancy of  a  metal  suspended  in  an  inactive 
liquid  during  its  solidification  or  melting  by 
means  of  a  thermobalance. 


CORRESPONDENCE. 


THE  BRAILLE  AND  "SERVERS  OF 
THE    BLIND""    LEAGUE. 

To  the  Editors  of  The  Chemical  News. 

Sir, — As  the  President  of  the  Braille  and 
"Servers  of  the  Blind"  League,  may  I  ask 
the  sympathy  of  your  readers  for  a  unique 
work  of  help? 

Up  to  the  present  no  provision  has  been 
made  for  the  defective  blind  children — 
thosc>  unfortunate  babies  who,  in  addition 
to  blindness,  have  some  other  disaoiiity, 
such  as  backward  mentality,  deafness, 
dumbness. 

The  Braille  and  "Servers  of  the  Blind" 
League  has  undertaken  to  make  this  provi- 
sion, and  is  establishing  the  Ellen  Terry 
National  Homes  for  Defective  Blind  Chil- 
dren, having  purchased  a  home  at  Reigate, 
Surrey,  where  these  little  children,  who  are 
mentally  and  physically  blind,  will  have  the 
mcfst  skilful  nursing  and  treatment,  speci- 
ally    adapted     educational    facilities,      and 


176 


THE  CHEMICAL  NEWS. 


SEPTEMBER  14,  1923. 


training  in  trades    suited  to  their    varying 
capacities. 

The  Junior  Home  for  children  under 
seven  is  to  do  a  splendid  work,  but  money 
is  badly  needed  ^  pay  the  mortgage  and  to 
obtain  the  necessary  equipment.  If  funds 
are  provided,  the  Home  can  be  quickly  en- 
larged to  take  in  more  than  is  at  present 
possible. 

Negotiations  are  taking  pla^^e  for  addi- 
tional homes  in  the  north  of  England,  but 
the  scheme  cannot  be  complete  unless  the 
public  come  to  our  aid. 

Buildings  exist  in  the  grounds  already 
purchased  which  can  easily  be  adapted,  if 
the  money  can  be  found  for  the  alterations, 
for  training  defectives  In  light  employment 
suited  to  their  capacities. 

The  Ministry  of  Health  gives  the  heai-ti- 
est  welcome  and  support  to  our  scheme, 
and  is  most  anxious  that  we  should  bring  it 
to  an  early  fruition  so  as  to  extend  it  to  the 
care  of  adult  defectives.  In  addition,  local 
authorities  and  blind  institutions  accord 
warmest  co-operation  to  our  plan,  which 
fills  a  long-existing  need.  There  is  a  con- 
stant enquiry  regarding  the  admission  of 
double  defectives  known  to  them. 

No  more  deserving  charity  could  be  found 
than  the  kindly  care  of  these  little  ones — 
bom  into  the  world  without  light  and  with- 
out hope  unless  we  come  to  their  aid — 
doubly  blind.  May  I  ask  for  all  who  feel 
for  these  lonely  babes — the  parents  and  re- 
latives of  those  children  who  are  blessed 
vnth  sight — to  share  in  a  great  national 
thank-offering  for  the  power  to  see  by  send- 
ing their  contribution  to  me  at  the  address 
of  the  Braille  and  "Servers  of  the  Blind" 
League,  3,  Upper  Woburn  Place,  W.C.I. 

Thanking  you  in  the  name  of  these  little 
ones,        Yours  sincerely,     Ellen  Terry. 


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all  information  relating  to  Patents.  Trade  Marks, 
and  Designs  can  he  obtainpd  trratuitonsly. 
Latest  Patent  Applications. 
21136 — Cocksedge,  H.  E. — Manufacture     of  sodium 

carbonate.    Aug.  21. 
21072 — Badische  Anilin  &  Soda  Fabrik. — Manufac- 
ture of  formic  acid.    Aug.  20. 
Specifications  Published   this    Week. 
202078— Imison,  C.  S.,  Bligh.  J.  A.,  Wright,  R.  R., 
and  Carmichael  &  Co.,     Ltd.,  J.  P.— Fur- 
naces producing  sulphurous   gases. 
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CITY  OF  CARDIFF  EDUCATION 
COMMITTEE. 

THE  TECHNICAL  COLLEGE. 

Principal  —  Charles  Coles,  B.Sc.  (Lond.). 

DEPARTMENT  OF  INDUSTRIAL 
CHEMISTRY. 
Head  of  Department  — 

H.  W.  Webb,  M.Sc,  F.I.C. 
Session    1923-24. 
(Commencing  on  Tuesday,  2nd  October, 
1923). 
Joint    Course 
(with  the  University  College  of  South 
Wales  and  Monmouthshire). 
COMPLETE  COURSE  in  Chemistry 
and  associated    subjects    is  provided 
for    those    wishing    to    become     industrial 
chemists.     The  Course  includes:  — 

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Examinations  which  are  also  catered  for 
by  the  Course  include  :  — 

B.Sc.  (Lond.)  Ext. 

Associate,  Institute  of  Chemistry. 

F.I.C.  in  Chemical  Engineering. 

A  number  of  Part-time  Courses  are  also 
available  to  cover  requirements  of  Work's 
Chemist,  and  those  of  various  public 
examinations. 

OPEN  SCHOLARSHIPS,  covering 
tuition  fees  and  maintenance  grants  of  £40 
per  annum  for  three  years,  arc  offered  for 
competition  annually,  and  candidates  for 
entry  to  the  above  Department  are  eligible 
to  compete. 

For  further  particulars  of  Full-time  and 
Part-time  Courses,  Entrance  Examination, 
Scholarships,  Fees,  etc.,  apply  to  the 
Principal.  Forms  of  application  for  ad- 
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amination, duly  completed,  must  be  re- 
ceived by  the  17th  September. 

JOHN  J.  JACKSON, 
Director  of  Education, 
City  Hall,  Cardiff. 


SEPTEMBEH  21,  1923. 


THE  CHEMICAL  NEWS. 


177 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3310. 


[British    Association  for  the    Advance- 
ment OF  Science  :  Liverpool,  1923.] 

THE  PRESIDENTIAL  ADDRESS. 

THE    ELECTRICAL    STRUCTURE    OF 

MATTER. 

By  Professor  Sir  Ernest  Rutherford, 
D.Sc,  J.L.D.,  Ph.D.,  F.R.S., 

President  of  the  Association. 

{Continued  from  Page  165.) 

We  must  now  look  baqk  again  to  the 
earUer  stages  of  the  present  tpoch  in  order 
to  trace  the  development  of  our  ideas  on 
the  detailed  structure  of  the  atom.  That 
electrons  ks  such  were  inipoitant  constitu- 
ents was  clear  by  1900,  but  little  real  pro- 
gress followed  until  the  part  played  by  the 
positive  charges  was  made  clear.  New 
light  was  thrown  on  this  subject  by  examin- 
ing the  deviation  of  a  particles  when  they 
passed  through  the  atoms  of  matter.  It 
was  found  that  occasionally  a  swift  a  par- 
ticle was  deflected  from  its  rectilinear  path 
through  more  than  a  right  angle  by  an  en- 
counter with  a  single  atom.  In  such  a 
collision  the  laws  of  dynamics  ordinarily 
apply,  and  the  relation  between  the  veloci- 
ties of  the  colliding  atoms  before  and  aft^r 
collision  are  exactly  the  same  as  if  the  two 
colliding  particles  are  regarded  as  perfectly 
elastic  spheres  of  minute  dimensions.  It 
must,  however,  be  borne  in  mind  that  in 
these  atf>mic  collisions  there  is  no  question 
of  mechanical  impacts  such  as  we  observe 
with  ordinary  matter.  The  reaction  be- 
tween the  two  particles  occurs  through  the 
intermediary  of  the  powerful  electric  fields 
that  surround  them.  Beautiful  photo- 
graphs illustrating  the  accuracy  of  these 
laws  of  collision  between  an  a  particle  and 
an  atom  have  been  obtained  by  Messrs. 
Wilson,  Blackett,  and  others,  while  Mr. 
Wilson  has  recently  obtained  many  striking 
illustrations  of  collisions  between  two 
electrons.  Remembering  the  great  kinetic 
energy  of  the  a  particle,  its  deflection 
through  a  large  angle  in  a  single  atomic  en- 
counter shows  clearly  that  very  intense 
deflecting  forces  exist  inside  the  atom.  It 
seemed  clear  that  electric  fields  of  the  re- 
quired magnitude  could  be  obtained  only  if 


the  main  charge  of  the  atom  were  concen- 
trated in  a  minute  nucleus.  From  this 
arose  the  conceiption  of  the  nuclear  atom, 
now  so  well  known,  in  which  the  heart  of 
the  atom  is  supposed  to  consist  of  a  minute 
but  massive  nucleus,  carrying  a  positive 
chsirge  of  electricity,  and  surrounded  at  a 
distance  by  the  requisite  number  of  elec- 
trons to  form  a  neutral  atom. 

A  detailed  study  of  the  scattering  of  a 
particles  at  different  angles,  by  Geiger  and 
Marsden,  showed  that  the  results  were  in 
close  accord  with  this  theory,  and  that  the 
intense  electric  forces  near  the  nucleus 
varied  according  to  the  ordinary  inverse 
square  law.  In  addition,  the  experiments 
allowed  us  to  fix  an  upper  limit  for  the 
dimensions  of  the  nucleus.  For  a  heavy 
atom  like  that  of  gold  the  radius  of  the 
nucleus,  if  supposed  to  be  spherical,  was 
less  than  one-thousandth  of  the  radius  of 
the  complete  atom  surrounded  by  its  elec- 
trons, and  certainly  less  than  4  x  10-"  cms. 
All  the  atoms  were  found  to  show  this  nu- 
clear structure,  and  an  aipproximate  esti- 
mate was  made  of  the  nuclear  charge  of  dif- 
ferent atoms.  This  type  of  nuclear  atom, 
based  on  direct  experimental  evidence, 
possesses  some  very  simple  properties.  It 
is  obvious  that  the  number  of  units  of  re- 
sultant positive  charge  in  the  nucleus  fixes 
the  number  of  the  outer  planetary  electrons 
in  the  neutral  atom.  In  addition,  since 
these  outer  electrons  are  in  some  way  held 
in  equilibrium  by  the  attractive  forces 
from  the  nucleus,  and,  since  we  arc  confi- 
dent from  general  physical  and  chemical 
evidence  that  all  atoms  of  any  one  element 
are  identical  in  their  external  structure,  it 
is  clear  that  their  arrangement  and  motion 
must  be  governed  entirely  by  the  magni- 
tude of  the  nuclear  charge.  Since  the  or- 
dinary chemical  and  physical  properties  are 
to  be  ascribed  mainly  to  the  configuration 
and  motion  of  the  outer  electrons,  it  fol- 
lows that  the  properties  of  an  atom  are  de- 
fined by  a  whole  number  representing  its 
nuclear  charge.  It  thus  becomes  of  great 
importance  to  determine  the  value  of  this 
nuclear  charge  for  the  atoms  of  all  the 
elements. 

Data  obtained  from  the  scattering  of  a 
particles,  and  also  from  the  scattering  of 
X-rays  by  light  elements,  indicated  that 
the  nuclear  charge  of  an  element  was 
numerically  equal  to  about  half  the  atomic 
weight  in  terms  of  hydrogen.  It  was  fairly 
clear  from  general  evidence  that  the  hydro- 
gen   nucleus    had  a  charge    one,    and    the 


178 


THE  CHEMICAL  NEWS. 


SEPTEMBER  21,  1923. 


helium    nucleus    (the  a  particle)  a    charge 
two.     At  this  stage    another  discovery    of 
great     importance      provided     a     powerful 
method  of  attack  on  this  iproblem.     The  in- 
vestigation by  Laue  on  fhe  diffraction  of  X- 
rays  by  crystals    had  shown  definitely    that 
X-rays     were      electromagnetic     waves     of 
much  shorter  wave-length  than  light,    and 
the  experiments  of  Sir  William  Bragg  and 
W,  L.  Bragg  had  provided  simple  methods 
for  studying    the  spectra  of    a  beam  of  X- 
rays.       It  was  found  that  the  spectrum  in 
general  shows  a  continuous  background  on 
which    is     superimposed     a    spectrum     of 
bright  lines.    At  this  stage  H.  G.  J.  Mose- 
ley  began  a  research  with    the  intention  of 
deciding  whether  the    properties  of  an  ele- 
ment depended  on  its  nuclear  charge  rather 
than  on  its  atomic  weight  as  ordinarily  sup- 
posed.    For  this  purpose  the  X-ray  spectra 
emitted  by  a  number    of  elements  were  ex- 
amined and  found  to  be  all  similar  in  type. 
The  frequency  of  a  given  line  was  found  to 
vary  very    nearly  as  the  square    of  a  whole 
number  which  varied    by  unity  in    passing 
from  one    element  to   the    next.       Moseley 
identified    this    whole     number    with    the 
atomic    or  ordinal  number  of    the  elements 
when  arranged  in  increasing  order  of  atomic 
weight,     allowance     being    made     for    the 
known  anomalies    in  the  periodic  table  and 
for  certain    gaps  corresponding    to  possible 
but  missing  elements.     He  concluded  that 
the  atomic    number  of    an  element    was  a 
measure  of  its  nuclear  charge,  and  the  cor- 
rectness of  this  deduction  has  been  recently 
verified  by  Chadwick  by  direct  experiments 
on  the  scattering  of  a  iparticles.     Moseley 's 
discovery  is  of  fundamental  importance,  for 
it  not  only  fixes  the  number  of  electrons  in 
all  the  atoms,  but  shows  conclusively  that 
the  properties  of  an  atom,  as  had  been  sur- 
mised,   are  determined    not  by  its    atomic 
weight  but  by  its  nuclear  charge,      A  rela- 
tion of  unexpected  simplicity  is  thus  found 
to    hold    between    the  elements.       No    one 
could  have  anticipated  that  with  few  excep- 
tions all  atomic  numbers  between  hydrogen 
1,    and  uranium  92.    would  correspond    to 
known    elements.       The    great     power     of 
Moseley 's  law  in  fixing  the  atomic  number 
of  an  element  is  well  illustrated  by  the  re- 
cent discovery    by  Coster    and  Hevesy    in 
Copenhagen     of    the    missing     element    of 
atomic  number  72,  which  they  have  named 
"  hafnium." 

Once  the  salient  features  of  the  structure 
of  atoms  have  been  fixed  and  the  number 
of  electrons  known,  the  further  study  of 
the  structure    of  the  atom    falls    naturally 


into  two  great  divisions :   one,  the  arrange- 
ment of  the  outer  electrons  which  controls 
the  main  physical  and    chemical  properties 
of  an  element,  and  the  other  the  structure 
of    the    nucleus    on    which    the    mass    and 
radioactivity  of  the  atom  depends.     On  the 
nuclear  theory  the  hydrogen  atom  is  of  ex- 
treme simplicity,    consisting    of    a    singly- 
charged  positive  nucleus    with  only  one  at- 
tendant electron.   The  position  and  motions 
of  the  single  electron  must  account  for  the 
complicated    optical  spectrum,     and  what- 
ever physical    and  chemical    properties  are 
to  be  attributed  to  the  hydrogen  atom.  The 
first  definite  attack    on  the  iproblem  of  the 
electronic  skucture  of  the  atom  was  made 
by  Niels  Bohr.     He  saw  clearly  that,  if  this 
simple  constitution  was  assumed,  it  is  im- 
possible   to    account  for    the  spectrum    of 
hydrogen  on  the  classical  electrical  theories, 
but  that  a  radical  departure  from    existing 
views  was  necessary.     For  this  purpose  he 
applied  to  the  atom    the  essential  ideas  of 
the  Quantum    Theory  which  had    been  de- 
veloped by  Planck  for  other  purposes,   and 
had  been  found  of  great  service  in  exiplain- 
ing  many  fundamental    difficulties  in  other 
branches  of  science.       On  Planck's    theory 
radiation     is    emitted    in  definite    units    or 
quanta,  in  which  the  energy    E  of  a  radia- 
tion is  equal  to  hv  where  v  is  the  frequency 
of  the  radiation  measured  by  the   ordinary 
methods    and    /i  is  a    universal    constant. 
This  quantum  of  radiation    is  not  a  definite 
fixed  unit    like  the  atom  of  electricity,    for 
its  magnitude  depends  on  the  frequency  of 
the  radiation.     For  example,  the  energy  of 
a  quantum  is  small  for    visible  light,     but 
becomes  large    for  radiation    of    high    fre- 
quency corresponding  to  the  X-rays  or  the  y 
rays  from  radium. 

Time  does  not  allow  me  to  discuss  the 
underlying  meaning  of  the  quantum  theory 
or  the  difficulties  connected  with  it.  Cer- 
tain aspects  of  the  difficulties  were  dis- 
cussed in  the  Presidential  Address  before 
this  Association  by  Sir  Oliver  Lodge  at  Bir- 
mingham in  1913.  It  suffices  to  say  that 
this  theory  has  proved  of  great  value  in 
several  branches  of  science,  and  is  sup- 
ported by  a  large  mass  of  direct  experimen- 
tal evidence. 

In  applying  the  quantum  theory  to  the 
structure  of  the  hydrogen  atom,  Bohr  sup- 
posed that  the  single  electron  could  move 
in  a  number  of  stable  orbits,  controlled  by 
the  attractive  force  of  the  nucleus,  without 
losing  energy  by  radiation.  The  position 
and  character  of  these  orbits  were  defined 
by  certain  quantum  relations  depending  on 


SEPTEMBER  21,  1923. 


THE  CHEMICAL  NEWS 


179 


one  or  more  whole    numbers.      It    was  as- 
sumed   that  radiation    was    only    emitted 
when  the    electron    for  some    reason    wiu^ 
transferred  from  one  stable  orbit  to  another 
of  lower  energy.     In  such  a  case  it  was  sup- 
posed that     a  homt^eneous  radiation    was 
emitted  of  frequency  v  determined  by  the 
quantum  relation  E  =  hv,    where  E  was  the 
difference    of  the  energy  of  the    electron  in 
the  two  orbits.        Some    of  these    possiblr 
orbits    are  circular,    others  elliiptical,    with 
the  nucleus  as  a  focus,  while  if  the  change 
of  mass  of    the  electron    with    velocity    is 
taken  into  accovmt  the  orbits,  as  Sommer- 
feld  showed,  depend  on  two  quantum  num- 
bers, and  are  not  closed,    but  consist    of  a 
nearly  elliptical  orbit  slowly  rotating  round 
the  nucleus.     In  this  way  it  is  possible  not 
only  to  account    for  the  series  relations  be- 
tween the  bright  lines  of  the  bydrogen  spec- 
trum, but  also  to  explain  the  fine  structure 
of    the    lines    and    the    very    complicat<Ml 
changes  observed  when  the  radiating  atoms 
are  exposed  in  a  strong  magnetic  or  electeic 
field.     Under  ordinary  conditions  the  elec- 
tron in  the  hydrogen  atom  rotates  in  a  cir- 
cular orbit  close  to  the  nucleus,  but  if  the 
atoms  are  excited    by  an  electric  discharge 
or  other  suitable  method,  the  electron  may 
be  displaced    and  occupy    any  one  of    the 
stable  positions  specified  by  the  theory.    I?i 
a  radiating  gas    giving  the  complete  hydro- 
gen spectrum  there    will  be  present    many 
different  kinds  of  hydrogen  atoms,  in  eacli 
of  which    the  electi-on  describes  one  of  the 
possible  orbits  specified  by  the  theory.     On 
this  view  it  is  seen  that  the  variety  of  mndes 
of      vibration    of    the    hydrogen    atom     is 
ascribed,  not  to  complexity  of  the  structure 
of  the  atom,    but  to  the    variety  of    stable 
orl)its  which    an  electron  may  occupy  rela- 
tive to  the  nucleus.       This  novel  theory  of 
the  origin  of  spectra  has  been  developed  so 
as  to  apply  not  only  to  hydrogen  but  to  all 
the  elements,     and  has  been    instrumental 
in  throwing  a  flood  of  light  on  the  relations 
and  origin  of  their  spectra,  both  X-ray  and 
optical.     The  information  thus  gained   has 
l^en  applied  by  Bohr  to  determine  the  dis- 
tribution of  the  electrons  round  the  nucleus 
of  any    atom.       The    problem  is    obviously 
much  less  complicated    for  hydrogen  than 
for  a  heavy  atom,  where  each  of  the  larg*- 
ninnber    of    electrons    present  acts    on  the 
other,     and  where  the  orbits  described    are 
much  more  intricate    than  the  orbit  of  the 
single  electron  in  hydrogen.     Notwithstand- 
ing the  great  difficulties    of  such  a  compli- 
cated svstem  of  electrons  in  motion,  it  has 


been  possible  to  fix  the  quantum  numbers 
that  characterise  the  motion  of  each  elec- 
tron, and  to  form  at  any  rate  a  rough  idea 
of  the  character  of  the  orbit. 

These  planetary  electrons  divide  them- 
selves up  into  groups,  according  as  their 
orbits  are  characterised  by  one  or  more 
equal  quantum  numbers.  ^  Without  going 
into  detail,  a  few  examples  may  be  given  to 
illustrate  the  conclusions  which  have  been 
reached.  As  we  have  seen,  the  first  ele- 
ment, hydrogen,  has  a  nuclear  charge  of  1 
and  1  electron;  the  second,  helium,  has  a 
charge  2  and  2  electrons,  moving  in  couipled 
orbits  on  the  detailed  nature  of  which  there 
is  still  some  uncertainty.  These  two  elec- 
trMis  form  a  definite  group,  known  as  the  K 
group,  which  is  common  to  all  the  elements 
except  hydrogen.  For  increasing  nuclear 
charge  the  K  group  of  electrons  retain  their 
characteristics,  but  move  with  increasing 
speed,  and  approjieh  closer  to  the  nucleus. 
As  we  pass  from  helium  of  atomic  number 
2  to  neon,  number  10,  a  new  group  of  elec- 
trons is  added  consisting  of  two  sub- 
groups, each  of  four  electrons,  together 
called  the  L  group.  This  L  grouip  appears 
in  all  atoms  of  higher  atomic  number,  and, 
as  in  the  case  of  the  K  group,  the  speed  of 
motion  of  the  electrons  increases,  and  the 
size  of  their  orbits  diminishes  with  the 
atomic  number.  When  once  the  L  group 
has  been  completed,  a  new  and  still  more 
complicated  M  group  of  electrons  begins 
forming  outside  it,  and  a  similar  process 
goes  on  until  uranium,  which  has  the  high- 
est atomic  number,  is  reached. 

It  may  be  of  interest  to  try  to  visualise 
the  conception  of  the  atom  we  have  so  far 
reached  by  taking  for  illustration  the  heavi- 
est atom,  lU'anium.  At  the  centre  of  the 
atom  is  a  minut<^  nucleus  surrfumded  by  a 
swirling  group  of  02  electrons,  all  in  motion 
in  definite  orbits,  and  occupying  but  by  no 
means  filling  a  volume  verj'  large  compared 
with  that  of  the  nucleus.  Some  of  the 
electrons  describe  nearly  circular  orbits 
round  the  nucleus ;  others,  orbits  of  a  more 
elliptical  shape  whose  axes  rotate  rapidly 
roimd  the  nucleus.  The  motion  of  the  elec- 
trons in  the  different  groups  is  not  neces- 
sarily confined  to  a  definite  region  of  the 
atom,  but  the  electrons  of  one  group  may 
penetrate  deeply  into  the  region  mainly 
occupied  by  another  group,  thus  giving  a 
type  of  inter-connection  or  coupling  be- 
tween the  various  groups.  The  maximum 
speed  of  any  electron  depends  on  the  close- 
ness   of  the  approach    to  the  nucleus,    but 


180 


THE  CHEMICAL  NEWS. 


SEPTEMBER  21,  1923. 


the  outermost  electron  will  have  a  mini- 
iiium  speed  of  more  than  1,000  kilometres 
per  second,  while  the  innermost  K  electrons 
have  an  average  speed  of  more  than  150,000 
kilometres  per  second,  or  half  the  speed  of 
Ught.  When  we  visualise  the  extraordi- 
nary complexity  of  the  electronic  system 
we  may  be  surprised  that  it  has  been  pos- 
sible to  find  any  order  in  the  apparent  med- 
ley of  motions. 

In  reaching  these  conclusions,  which  we 
owe  largely  to  Professor  Bohr  and  his  co- 
workers, every  available  kind  of  data  about 
the  different  atoms  has  been  taken  into 
consideration.  A  study  of  the  X-ray  spec- 
tra, in  particular,  affords  information  of 
great  value  as  to  the  arrangement  of  the 
various  groups  in  the  atom,  while  the  opti- 
cal spectrum  and  general  chemical  proper- 
ties are  of  great  importance  in  deciding  the 
arrangements  of  the  suiperficial  electrons. 
While  the  solution  of  the  grouping  of  the 
electrons  proposed  by  Bohr  has  been  as- 
sisted by  considerations  of  this  kind,  it  is 
not  empirical  in  character,  but  has  been 
largely  based  on  general  theoretical  con- 
siderations of  the  orbits  of  electrons  that 
are  physically  possible  on  the  generalised 
quantum  theory.  The  real  problem  in- 
volved may  be  illustrated  in  the  following 
way.  Suppose  the  gold  nucleus  be  in  some 
way  stripped  of  its  attendant  seventy-nine 
electrons,  and  that  the  atom  is  reconsti- 
tuted by  the  successive  addition  of  elec- 
trons one  by  one.  According  to  Bohr,  the 
atom  will  be  reorganised  in  one  way  only, 
and  one  group  after  another  will  succes- 
sively form  and  be  filled  up  in  the  manner 
outlined.  The  nucleus  atom  has  often  been 
likened  to  a  solar  system  where  the  sun 
corresponds  to  the  nucleus  and  the  planets 
to  the  electrons.  The  analogy,  however, 
must  not  be  pressed  too  far.  Suppose,  for 
example,  we  imagined  that  some  large  and 
swift  celestial  visitor  traverses  and  escapes 
from  our  solar  system  without  any  catas- 
trophe to  itself  or  the  planets.  There  will 
inevitably  result  permanent  changes  in  the 
lengths  of  the  month  and  year^  and  our 
system  will  never  return  to  its  original 
state.  Contrast  this  with  the  effect  of 
shooting  an  electron  or  a  particle  through 
the  electronic  structure  of  the  atom.  The 
motion  of  many  of  the  electrons  will  be  dis- 
turbed by  its  passage,  and  in  special  cases 
an  electron  may  be  removed  from  its  orbit 
and  hurled  out  of  its  atomic  system.  In  a 
short  time  another  electron  will  fall  into  the 
vacant  place  from  one  of  the  outer  groups, 
and  this  vacant  place  in  turn  will  be  filled 


up,  and  so  on  until  the  atom  is  again  re- 
organised. In  all  cases  the  final  state  of 
the  electronic  system  is  the  same  as  in  the 
begirming.  This  illustration  also  serves  to 
indicate  the  origin  of  the  X-rays  excited  in 
the  atom,  for  these  arise  in  the  process  of 
reformation  of  an  atom  from  which  an  elec- 
tron has  been  ejected,  and  the  radiation  of 
highest  frequency  arises  when  the  electron 
is  removed  from  the  K  group. 

It  is  possibly  too  soon  to  express  a  final 
opinion  on  the  accuracy  of  this  theory 
which  defines  the  outer  structure  of  the 
atom,  but  there  can  be  no  doubt  that  it 
constitutes  a  great  advance.  Not  only  does 
it  offer  a  general  exiplanation  of  the  6ptical 
and  X-ray  spectra  of  the  atom,  but  it  ac- 
counts in  detail  for  many  of  the  most  char- 
acteristic features  of  the  periodic  law  of 
Mendel^f.  It  gives  us  for  the  first  time  a 
clear  idea  of  the  reason  for  the  appearance 
in  the  family  of  elements  of  groups  of  con- 
secutive elements  with  similar  chemical 
properties,  such  as  the  groups  analogous  to 
the  iron  group  and  the  unique  group  of 
rare  earths.  The  theory  of  Bohr,  like  all 
living  theories,  has  not  only  correlated  a 
multitude  of  isolated  facts  known  about 
the  atom,  but  has  shown  its  power  to  pre- 
dict new  relations  which  can  be  verified  by 
experiment.  For  example,  the  theory  pre- 
dicted the  relations  which  must  subsist  be- 
tween the  Rydberg  constants  of  the  arc  and 
spark  spectra,  and  generally  between  all 
the  successive  optical  spectra  of  an  ele- 
ment, a  prediction  so  strikingly  confirmed 
by  Paschen's  work  on  the  spectrum  of 
doubly  ionised  aluminium  and  Fowler's 
work  on  the  spectrum  of  trebly  ionised  sili- 
con. Finally,  it  predicted  with  such  great 
confidence  the  chemical  properties  of  the 
missing  element,  number  72,  that  it  gave 
the  necessary  incentive  for  its  recent  dis- 
covery. 

While  the  progress  of  our  knowledge  of 
the  outer  structure  of  atoms  has  been  much 
more  rapid  than  could  have  been  antici- 
pated, we  clearly  see  that  only  a  beginning 
has  been  made  on  this  great  problem,  and 
that  an  enormous  amount  of  work  is  still 
required  before  we  can  hope  to  form  any- 
thing like  a  complete  picture  even  of  the 
outer  structure  of  the  atom.  We  may  be 
confident  that  the  main  features  of  the 
structure  are  clear,  but  in  a  problem  of 
such  great  complexity  progress  in  detail 
must  of  necessity  be  diflficult  and  slow. 

We  have  not  so  far  referred  to  the  very 
difficult  question  of  the  explanation  on  this 
theory    of    the    chemical    combination    of 


SEPTEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


181 


atoms.  In  fact,  as  yet  the  theory  has 
hardly  concerDed  itself  with  molecular 
structure.  On  the  chemical  side,  however, 
certain  advances  have  already  been  made, 
notably  by  G.  N.  Lewis,  Kossel,  and  Lang- 
muir,  in  the  interpretation  of  the  chemical 
evidence  by  the  idea  of  shared  electrons, 
which  play  a  part  in  the  electronic  struc- 
ture of  two  combined  atoms.  There  can 
be  little  doubt  that  the  next  decade  will  see 
an  intensified  attack  by  physicists  and 
chemists  on  this  very  important  but  un- 
doubtedly very  complicated  question. 

Before  leaving  this  subject,  it  may  be  of 
interest  to  refer  to  certain  points  in  Bohr's 
theory  of  a  more  philosophical  nature.  It 
is  seen  that  the  orbits  and  energies  of  the 
various  groups  of  electrons  can  be  specified 
by  certain  quantum  numbers,  and  the 
nature  of  the  radiation  associated  with  a 
change  of  orbit  can  be  defined.  But  at  the 
same  time  we  cannot  explain  why  these  or- 
bits are  alone  permissible  under  normal 
conditions,  or  understand  the  mechanism 
by  which  radiation  is  emitted.  It  may  be 
quite  possible  to  formulate  accurately  the 
energy  relation  of  the  electrons  in  the  atom 
on  a  simple  theory,  and  to  explain  in  con- 
siderable detail  all  the  properties  of  an 
atom,  without  any  clear  understanding  of 
the  underlying  processes  which  lead  to 
these  results.  It  is  natural  to  hope  that 
with  advance  of  knowledge  we  may  be  able 
to  grasp  the  details  of  the  piocess  which 
leads  to  the  emission  of  radiation,  and  to 
understand  why  the  orbits  of  the  electrons 
in  the  atom  arc  defined  by  the  quantimi 
relations.  Some,  however,  are  inclined  to 
take  the  view  that  in  the  present  state  of 
knowledge  it  may  be  quite  impossible  in 
the  nature  of  things  to  form  that  detailed 
picture  in  space  and  time  of  successive 
events  that  we  have  been  accustomed  to 
consider  as  so  important  a  part  of  a  com- 
plete theory.  The  atom  is  naturally  the 
most  fundamental  structure  presented  to 
us.  Its  properties  must  explain  the  pro- 
perties of  all  more  complicated  structures, 
including  nuatter  in  bulk,  but  we  may  not, 
therefore,  be  justified  in  expecting  that  its 
processes  can  be  explained  in  terms  of  con- 
cepts derived  entirely  from  a  study  of  molar 
properties.  The  atomic  processes  involved 
may  be  so  fundamental  that  a  complete 
understanding  may  be  denied  us.  It  is 
early  yet  to  be  pessimistic  on  this  question, 
for  we  may  hope  that  our  difficulties  may 
any  day  be  resolved  by  further  discoveries. 

We  must   now  turn  our  attention  to  that 


new  and  comparatively  unexplored  terri- 
tory, the  nucleus  of  the  atom.  In  a  dis- 
cussion on  the  structure  of  the  nucleus,  I 
was  rash  enough  to  say  that  it  was  a  prob- 
lem that  might  well  be  left  to  the  next 
generation,  for  at  that  time  there  seemed  to 
be  few  obvious  methods  of  attack  to  throw 
light  on  its  constitution.  While  much  more 
progress  has  been  made  than  appeared  pos- 
sible at  that  time,  the  problem  of  the  struc- 
ture of  the  nucleus  is  inherently  more  diffi- 
cult than  the  allied  problem  already  con- 
sidered of  the  structure  of  the  outer  atom, 
where  we  have  a  wealth  of  information  ob- 
tained from  the  study  of  light  and  X-ray 
spectra  and  from  the  chemical  properties 
to  test  the  accuracy  of  our  theories. 

In  the  case  of  the  nucleus,  we  know  its 
resultant  charge,  fixed  by  Moseley's  law, 
and  its  mass,  which  is  very  nearly  equal  to 
the  mass  of  the  whole  atom,  since  the  mass 
of  the  planetary  electrons  is  relatively  very 
small  and  may  for  most  purposes  be  neg- 
lected. We  know  that  the  nucleus  is  of 
size  minute  compared  with  that  of  the 
whole  atom,  and  can  with  some  confidence 
set  a  maximum  limit  to  its  size.  The 
study  of  radioactive  bodies  has  provided  us 
with  very  valuable  information  on  the 
structure  of  the  nucleus,  for  we  know  that 
the  a  and  /3  particles  must  be  expelled  from 
it,  and  there  is  strong  evidence  that  the 
very  penetrating  y  rays  represent  modes  of 
vibration  of  the  electrons  contained  in  its 
structure.  In  the  long  series  of  transfor- 
mations which  occur  in  the  uranium  atom, 
eight  a  particles  are  emitted  and  six  elec- 
trons, and  it  seems  clear  that  the  nucleus 
of  a  heavy  atom  is  built  up,  in  part  at  least, 
of  helium  nuclei  and  electrons.  It  is 
natural  to  suppose  that  many  of  the  ordi- 
nary stable  atoms  are  constituted  in  a 
similar  way.  It  is  a  matter  of  remark  that 
no  indication  has  been  obtained  that  the 
lightest  nucleus,  viz.,  that  of  hydrogen,  is 
liberated  in  these  transformations,  where 
the  processes  occuning  are  of  so  fundamen- 
tal a  character.  At  the  same  time,  it  is 
evident  that  the  hydrogen  nucleus  must 
be  a  unit  in  the  structure  of  some  atoms, 
and  this  has  been  confirmed  by  direct  ex- 
periment. Dr.  Chadwick  and  I  have  ob- 
served that  swift  hydrogen  nuclei  are  re- 
leased from  the  elements  boron,  nitrogen, 
fluorine,  sodium,  aluminium,  and  phos- 
phorus when  they  are  bombarded  by  swift 
a  particles,  and  there  is  little  room  for 
doubt  that  these  hydrogen  nuclei  form  an 
essential  part  of  the  nuclear  structure.  The 


182 


THE  CHEMICAL  NEWS. 


SEPTEMBEE  21,  192B. 


speed  of  ejection  of  these  nuclei  depends  on 
the  velocity    of  the  a  particle    and  on    the 
element  bombarded.       It  is  of  interest    to 
note  that  the  hydrogen  nuclei  are  liberated 
in  all  directions,  but  the  speed  in  the  back- 
ward  direction    is   always    somewhat    less 
than  in    the  direction    of    the    a    particle. 
Such  a  result  receives  a  simple  explanation 
if  we  suppose  that  the  hydrogen  nuclei  are 
not  built  into  the  main  nucleus  but  exist  as 
satellites  probably  in  motion  round  a  cen- 
tral core.     There  can  be  no  doubt  that  bom- 
bardment by  a  particles  has  effected  a  verit- 
able   disintegration  of    the  nuclei    of    this 
group  of  elements.   It  is  significant  that  the 
liberation  of  hydroyen  nuclei  only  occurs  in 
elements  of  odd  atomic  number,  viz.,  5,  7, 
9,  11,  13,  15,  the  elements  of  even  number 
appearing  quite  unaffected.     For  a  collision 
of  an    a  particle    to  be    effective,    it  must 
either  pass  close  to  the  nucleus  or  actually 
penetrate  its  structure.     The  chance  of  this 
is  _  excessively    small    on     account    of    the 
minute  size  of  the  nucleus.     For  example, 
although    each    individual    a  particle    will 
pass  through    the  outer  structure  of    more 
than    100,000  atoms    of  aluminium    in  its 
pa,th,    it  is  only    about  one    a  particle    in  a 
million  that  gets  close  enough  to  the  nucleus 
to    effect    the    liberation    of     its    hydrogen 
satellite. 

(To  be  continued.) 


[British  Association  for  the  Advance- 
ment OF  Science. — Sectional 
Transactions.] 

SECTION    A.— MATHEIVTATICAL     AND 
PHYSICAL  SCIENCE. 
Thursday,  September  13. 
Prof.  C.  G.  Darwin,  F.K.S.— T/ie    Re- 
cent Worh  of  Prof.  A.  H.  Compton  on  the 
Scattering  of  X-rays. 

Prof.  C.  G.  Barkla,  F.B.S.— X-ray  Ab- 
sorption and  the  J  Discontinuities. 

Dr.  W.  M.  Smart. — Navigation. 

Friday,  September  14, 

Senatore    Vito    Volterra,    For.    Mem. 
R.S. — Liquid  Jets. 

Prof.  R.  A.  Millikan. — The  Penetrating 
Radiations  from  the  Upper  Air. 

Sir  Oliver  Lodge,  F.B..S.— Matter  and 
Radiation. 


Mr.  G.  Stead  and  Miss  B.  Trevblyan. 
— The  Production  of  Triatomic  Hydro- 
gen (•?). 

Hydrogen  is  subjected  to  intense  elec- 
tronic bombardment  in  a  cylindrical  ther- 
mionic tube  with  open  grid  and  no  anode. 
With  a  grid  potential  of  30  volts  and  over, 
a  blue  glow,  consisting  of  primary  and 
secondary  hydrogen  lines,  is  observed  near 
the  filament.  The  glow  spreads  progres- 
sively along  the  tube,  the  current  increas- 
ing similarly  till  it  suddenly  falls  to  a  small 
value,  and  the  glow  simultaneously  runs 
back.  A  regular  oscillation  of  the  glow  and 
current  is  maintained,  and  the  pressure  in 
the  tube  follows  the  current  changes. 

It  a^ppears  that  a  polymerised  modifica- 
tion of  hydrogen  is  periodically  formed  and 
decomposed.  If  a  tube  surrounded  by 
liquid  air  is  attached  no  oscillation  takes 
place,  but  nearly  all  the  gas  disappears 
rapidly.  It  is  re-liberated  on  removing  the 
liquid  air,  and  is  stable,  but  easily  decom- 
posed by  electric  discharge,  showing  an  in- 
crease in  volume  in  the  ratio  of  1.5  to  1. 
The  decomposed  gas  shows  bright  primary 
and  secondary  spectra  of  hydrogen.  The 
optimum  pressure  in  the  tube  is  about  0.05 
mm.  of  mercury. 

Capt.  D.  Brunt. — Energy  of  the  Circu- 
lation of  the  Atmosphere. 

Mr.  F.  J.  W.  Whipple. — Notes  on  the 
Transmission  of  Sound  through  the  Atmos- 
phere. 

Dr.  a.  T.  Doodson. — Meteorological  Ef- 
fects on  Sea  Level  and  Tides. 

Mr.  T.  Smith. — Apocoptic  Expansions. 

Prof.  H.  Levy  and  Mr.  W.  H.  Moore. 
— Notes  on  the  Approximate  Expression  of 
Empirical  Results. 

Rev.  a,  L.  Cortie. — Series  in  Magnetic 
Disturbances. 

Mr.  W.  M.  Mordey. — Some  Recent 
Studies  in  Alternating  Magnetis^n.  (Illus- 
trated by  Experiments  and  Lantern  SUdes). 

Mr.  S.  G.  Brown,  F.R.S. — Demonstra- 
tion of  the  '  Frenophone,'  or  Friction  Oper- 
ated Loud-Speaker. 


I 


SEPTEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


183 


Monday,  September  17. 

PKESIDENTIAL  ADDRESS,  by  Prof. 
■J.  C.  McLennan,  F.R.S.,  on  Origin  of 
Spectra  (an  account  of  which  will  be  pub- 
lished subsequently  in  The  Chemical  News). 


Bohr. — The     Correspondence 


Prof.    N. 
Principle. 

The  quantum  theory  of  atomic  constitu- 
tion rests  upon  the  following  two  postu- 
lates :  — 

I. — ^Among  the  conceivably  possible 
states  of  motion  in  an  atomic  system  there 
exist  a  number  of  so-called  "stationary 
states"  which,  in  sipite  of  thu  fact  that  the 
motion  of  the  particles  in  these  states  obeys 
the  laws  of  classical  mechanics  to  a  con- 
siderable extent,  possess  a  peculiar 
meohanically  unexplainable  stability,  of 
such  a  sort  that  every  perraan(  nt  change  in 
the  motion  of  the  system  must  consist  of  a 
complete  transition  from  one  stationary 
state  to  another. 

II. — While  in  contradiction  to  the  classi- 
cal electromagnetic  theory  no  radiation 
takes  place  from  the  atom  in  the  stationary 
states  thcMselves,  a  process  of  transition 
between  two  stationary  states  can  be  ac- 
companied by  the  omission  of  electromag- 
netio  radiation,  which  will  have  the  same 
properties  as  that  which  would  be  sent  out 
according  to  the  classical  theory  from  an 
electrified  particle  executing  a  harmonic 
vibration  with  constant  frequency.  This 
frequency  v  has,  however,  no  simple  rela- 
tion to  the  motion  of  the  particles  of  the 
atom,  but  is  given  by  the  quantum  relation 


hv  =  E'— E", 


(1) 


where  h  is  Planck's  constant,  and  E'  and 
E"  are  the  values  of  the  energy  of  the 
atom  in  the  two  stationary  states  that  form 
the  initial  and  final  states  of  the  radiation 
process. 

It  will  be  the  purpose  of  these  remarks 
to  show  how,  notwithstanding  the  funda- 
mental departure  from  the  ideas  of  the 
classical  theories  of  mechanics  and  elec- 
trodynamics involved  in  these  postulates, 
it  has  been  possible  to  trace  a  connection 
between  the  radiation  emitted  by  an  atom 
and  the  motion  of  the  particles  which  ex- 
hibits a  far-reaching  analogy  to  that 
claimi'd  by  the  classical  ideas  of  the  origin 
of  radiation. 


It  was  shown  by  examples  from  the  in- 
vestigation of  the  spectra  oi  the  elements 
and  of  the  effects  of  electric  and  magnetic 
fields  on  sipectral  lines,  how  the  correspon- 
dence principle  has  been  supported  to  an 
extent  that  seems  to  justify  us  in  using  it 
as  a  guide  also  in  more  complicated  cases, 
which  we  meet  in  liie  theory  of  atomic  con- 
stitution, and  where  it  has  not  yet  been 
possible  to  fix  the  stationary  states  in  an 
unambiguous  way  by  use  of  symbols  bor- 
rowed from  classical  mechanics. 


Prof.    P.     Ehrenfest. 
Quantisation. 


Remarks     on 


Prof.  P.  Langevin. — The  Structure  of 
Atoms  and  their  Magnetic  Properties. 

To  account  for  magnetic  properties  it  is 
assumed  that  each  atom  or  molecule  nor- 
mally possesses  a  definite  magnetic  mo- 
ment prQportional  to  the  total  moment  of 
the  quantity  of  electron  movement.  This 
can  be  zero  when  the  symmetry  of  the  edi- 
fice is  sufttcient,  and  always  becomes  modi- 
fied in  the  diamagnetio  sense  under  the 
action  of  an  external  field. 

The  laws  of  quanta  allow  us  to  predict 
the  existence  of  molecular  magnetic  mo- 
ments which  are  integral  multiples  of  the 
Bohr  magneton,  and  they  alone  permit  us 
to  develop  coherently  an  electronic  theory 
of  magnetism  in  the  same  way  as  they  have 
rendered  possible  a  theory  of  atomic  struc- 
ture and  of  the  emission  of  spectra. 

Prof.  R.  W.  Wood,  For.  Mem.  R.S., 
and  Dr.  A.  Ellett. — The  Effects  of  Weak 
Magnetic  Fields  on  the  Polarisation  of  Re- 
sonance Radiation. 

Mr.  I.  0.  Griffith. — Experiments  in 
very  High  Temperatures. 

Tuesday,  September  18. 

Discussion  on  The  Spectra  of  the  Lighter 
Elements.  Opener,  the  President,  Prof. 
J.  C.  McLennan,  F.R.S.  Sipeakers :  Prof. 
N.  Bohr,  Prof.  R.  A.  Millikan,  Prof.  A. 
Fowler,  F.R.S. ,  and  others. 

Dr.  F.  W.  Aston,  F.R.S. — Further  De- 
terminations of  the  Constitution  of  the  Ele- 
ments by  the  method  of  Accelerated  Anode 
Rays. 

Mr.  R.  W.  Roberts. — The  Magnetic 
llotanj  Dispersion  in  certain  Paramagnetic 
Liquids. 


184 


THE  CHEMICAL  "NEWS. 


SEPTEMBEK  21,  1923. 


Mr.  R.  Ablett. — The  Angle  of  Contact 
— Variation  with  Relative  Motion  of  Solid 
and  Liquid. 

Eeport  of  the   Seismology  Committee. 

SECTION  B.— CHEMISTRY. 

Thursday,  September  13. 

JOINT  DISCUSSION  with  Sections  A 
and  G  (in  rooms  of  Section  B),  on  Cohesion 
and  Molecular  Forces.  Sir  William  H. 
Bragg,  F.R.S.,  Dr.  W.  Rosenhain, 
F.R.S.,  Dr.  A.  A.  Griffith,  and  other 
speakers. 

Prof.  Sven  Oden. — The  Formation  of 
Precipitates. 

Prof.  G.  S.  Whitby. — The  Nature  and 
Significance  of  the  Reain  of  Hevea  Rubber. 

The  resin  of  raw  rubber,  which  consti- 
tutes about  3  per  cent,  of  the  material,  con- 
tains liquid  unsaturated  acids,  a  new  solid 
fatty  acid  (Heveic  acid),  a  phytosterol  glu- 
coside,  a  phytosterol  ester,  a  free  phytos- 
terol, quebrachitol,  and  d- valine.  The 
acids  have  a  marked  influence  on  the  vul- 
canisation of  rubber  r  in  the  presence  of 
catalysts.  The  introduotion  into  the  rub- 
ber of  strong  bases  increases  the  rate  of  vul- 
canisation with  catalysts  and  enhances  the 
tensile  strength  of  the  product.  This  effect 
is  not  due  merely  or  mostly  to  the  elimina- 
tion, by  neutralisation,  of  the  retarding  in- 
kuence  of  acids,  but  largely  to  the  dispers- 
ing action  on  the  caoutchouc  of  the  soaps 
produced.  The  total  resin-acid-content  of 
different  samples  of  raw  rubber  varies 
greatly.  Such  variation  is  probably  an  im- 
portant factor  in  vulcanisation.  The  abil- 
ity of  organic  substances  to  swell  rubber 
was  studied  in  relation  to  the  question  of 
the  mode  of  occurrence  of  the  resin  con- 
stituents in  latex  and  in  rubber, 

Friday,  September  14. 

PRESIDENTIAL  ADDRESS,  by  Prof. 
F.  Cf.  BoNNAN,  F.R.S.,  on  The  Physical 
Chemistry  of  Interfaces  (an  account  of 
which  will  be  published  later  in  The  Chemi- 
cal News). 


Prof.  G.  N.  Lewis. 
ory  in  Chemistry. 


-The  Quantum  The- 


Dr.  N.  V.  SiDGwiCK,  F.R.S. 
Atom,  and  the  Periodic  Law. 


-The  Bohr 


Dr.  D.  Coster.— On  High  Frequency 
Spectra  and  the  Theory  of  Atomic  Struc- 
ture. 

Moseley  showed  that  the  characteristic 
X-ray  spectra  have  a  very  simple  structure. 
The  square  root  of  the  frequency  of  a  given 
X-raj  line  is  a  linear  function  of  the  atomic 
number.  The  great  changes  in  physical 
and  chemical  properties,  which  mostly 
occur  when  proceeding  from  one  element 
to  the  next  one  in  the  periodic  table,  are 
not  expressed  in  the  X-ray  spectrum. 

Recent  researches  have  revealed  that 
some  peculiarities  of  the  periodic  table  find 
expression  in  the  X-ray  spectrum.  If  we 
plot  Moseley  curves  not  for  the  lines  them- 
selves but  for  the  spectral  terms,  we  ob- 
serve at  different  stages  sudden  changes  in 
the  slope  of  the  curves.  These  irregulari- 
ties correspond  with  regions  of  the  periodic 
table  where,  according  to  Bohr,  an  inner 
group  of  electrons  is  being  completed. 

Recently  X-ray  spectroscopy  has  led  to  a 
confirmation  of  the  Bohr  theory.  Accord- 
ing to  Bohr,  the  element  of  atomic  number 
72  should  not  belong  to  the  rare  earth 
metals,  but  must  be  a  homologue  of  zir- 
conium. This  is  verified  by  the  discovery 
of  hafnium. 

Miss  Edith  H.  Usherwood. — The  Acti- 
vation of  Hydrogen  in  Organic  Compounds. 

A  great  variety  of  organic  chemical 
phenomena  depend  upon  one  and  the  same 
molecular  condition.  This  condition  is  de- 
fined in  terms  of  molecular  structure,  and 
the  result  follows  that  tendency  to  undergo 
reactions  of  many  different  kinds  is  referred 
to  certain  definite  and  easily  recognised 
structural  features. 

JOINT  DISCUSSION  with  Section  I  (in 
the  rooms  of  Section  B),  on  The  Physical 
Che^nistry  of  Membranes  in  Relation  to 
Physiological  Science.  Prof.  H.  E.  Roaf, 
Prof.  F.  G.  Donnan,  and  other  speakers. 

Dr.  E.  B.  R.  Prideaux. — Membrane  Po- 
tentials considered  as  Diffusion  Potentials. 

Through  most  ordinary  membranes, 
such  as  parchment,  a  slow  diffusion  of  elec- 
trolyte takes  place,  and  the  membrane  po- 
tentials at  these  are  not  due  to  the  imper- 
meability, but  to  the  selective  permeabil- 
ity, of  either  anion  or  kation.  These  po- 
tentials are  generally  higher  than  the  cor- 
responding diffusion  potentials,  and  may  be 
considered  as  diffusion  potentials  in  which 


I 


SEPTEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


185 


the  trsinsport  numbers  or  the  relative 
mobilities  of  one  ion  ar^  modified  by  the 
membrane.  A  comparison  of  the  mobility 
of  the  anion  in  the  case  of  Na  and  K  benzo- 
ates  and  salicylate  determined  by  conduc- 
tivity with  the  present  measurements  of 
diffusion  potentials,  viscosities,  and  mem- 
brane potentials,  shows  that  the  mobility 
of  the  benzoic  anjpn  has  indeed  been 
diminished  by  the  parchment  to  a  value 
which  is  apparently  definite  both  for  K  and 
for  Na  salts.  The  mobility  of  the  salicylic 
ion  was  diminished  in  a  higher  ratio. 

Monday,  September  17. 

Dr.  E.  F.  Armstrong,  F.R.S.— En- 
xymes. 

Enzymes  are  to  be  regarded  as  colloid 
catalysts.  It  is  customary  to  think  of  them 
as  definite  chemical  entities,  but  the  activ- 
ity associated  with  them  is  connected  with 
certain  aggregates  of  groups  in  a  very  much 
larger  mofeoule.  Probably  the  enzyme,  as 
such,  is  incapable  of  existing,  and  the  larger 
molecule  may  well  be  variable  in  its  nature. 
Their  activity  in  the  main  is  hydrolytic — 
that  is,  they  activate  water  molecule*,  and 
in  special  cases  they  also  bring  about  syn- 
thetic action;  there  is  also  the  class  of 
oxidising  and  reducing  enzymes  which  act 
again  in  activating  water  so  as  to  give  oxy- 
gen to  one  and  hydrogen  to  another  ac- 
ceptor. The  study  of  enzymes  is  thus  inti- 
mately bound  up  with  that  of  the  behnvi'  »ir 
of  water  in  solutions. 

Enzymes  are  obtained  from  nnimal  and 
vegetable  tissues  in  a  concentrated,  as  op- 
posed to  a  purified,  condition;  their  out- 
standing and  indeed  remarkable  property  is 
their  very  highly  specific  character.  In 
every  instance  their  action  is  restricted  to 
one  or  to  a  few  substances  very  closely  re- 
lated in  structure,  and  there  is  obviously 
the  most  intimafe  correlation  between  the 
structure  of  the  substrate  and  of  the  enzyme 
complex. 

Dr.  K.  G.  Falk.— T^je  Belation  of  Cer- 
tain Enzyme  Actions  to  Tissue  Differentia- 
tion and  Tumour  Orowth. 

The  comparative  lipase  actions  on  a  num- 
ber of  different  esters  and  protease  actions 
on  several  protein  preparations,  of  diffi-rent 
tissues  and  organs  of  rats  as  well  as  of  the 
Flexner-.Tobling  rat  carcinoma,  were 
studied.  Well-defined  rlifferences  in  the 
actions  were  found.  A  number  of  tumours 
of  human  origin  and  somr  normal  human 
tissues  were    studied    similarly.       A    more 


connplete  study  of  the  enzyme  actions  of 
fibromyoma  of  the  uterus  indicated  in  some 
cases  enzyme  actions  of  the  growths  simi- 
lar to  those  of  uterus  muscle,  and  in  some 
cases  both  types  of  actions  present  in  the 
material  obtained  fi'om  different  parts  of 
the  same  specimen.  The  enzyme  results 
corresponded  to  the  histological  examina- 
tions of  the  same  materials. 

Mr.  W.  G.  Palmer. — Catalytic  Actions  in 
the  System  Copper,  Copper-Oxide,  Oxygen, 
and  Gaseous  Reducing  Agent. 

The  rate  of  oxidation    of  a  copper    film 

about mm.  in  thickness  can  readily  be 

1000 
found  from  observations  on  the  increasing 
electrical  resistance;  similarly  the  rate  of 
reduction  of  oxide  can  be  followed  by  ob- 
serving the  decrease  of  resistance.  Such  a 
film  conducts  electricity  normally,  but  is 
sutiiciently  thin  for  the  effects  of  gaseous 
diffusion  to  be  absent. 

Mixtures  of  reducing  gas  (such  as  carbon 
monoxide  or  hydrogen)  with  oxygen,  when 
brought  into  contact  with  copper  at  250° 
C,  oxidise  the  metal  m«e  rapidly  thsui 
does  pure  oxygen.  This  effect  is  very 
nuirked  even  when  equal  volumes  of  reduc- 
ing gas  and  oxygen  are  used.  The  reduc- 
tion of  copper  ( xide  by  carbon  monoxide  or 
by  hydrogen  at  low  temperatures  takes 
place  only  in  the  presence  of  copper,  and 
the  rate  of  reduction  is  simply  proiportional 
to  the  amount  of  metal  present. 

When  hydrogen  is  used  for  reduction  the 
water  fwmed  acts  as  a  "negative"  catalyst, 
and  the  reduction  is  soon  brought  to  a 
standstill  unless  the  water  is  removed  by 
exhaustion. 

Prok.   W.    Vernadsky — Alumosilicates. 
We    can     distinguish    in     alumosilicates 
Ixxiies  of  different  chemical  functions : 

anhydrides :  AljSiOj,  sillimanite 
AljSiaOr  leverrierite 
AljSiO^Fj  topaz,  &c. 
acids  :   HjALSijOg  .  HgO — kaolinite 
HjAljSi^Ojj — pyrophyllite,   &c. 
salts:   KoAlgSijOj, — orthoclase,   &c. 

All  these  bodies  in  the  solid  condition  can 
give  addition  products,  e.g., 

zoisite  SCaAljSijOg  .  CaCOH)^ 
grossularite  CaAl2Si20„  .  Cii.SiO^ 
where  the    alumosilicate  group    dominates 
the  properties  of  the  compound, 


186 


THBl  CHEMICAL  NEWS. 


SEPTEMBER  21.  1923. 


+  nO«  +  2 


the  salts  and  their  addition  products  can  be 
divided  into  three  groups : 

1. — Sillimanite  salts — of  acid  H2Al2Si06 
and  their  addition  products :  group  of 
chloritoids. 

2. — Leverrierite  salts — of  acids  HjAljSia- 
n=  0,  2,  4,  6,  8. 
KgAlgSiaOg — phacellite 
KaAlaSi^Ojj — leucite. 
These     compounds    have     a   chromogene 
constitution. 

3. — Salts  of  'polyhasic  acids  of  anhydrides 
ALSiO.,  Al^Si^O,,  Al^Si^O^     .     .     . 
Al2SiO,-„(HO), 
Al^Si^O.-^CHO); 
Chlorites 
Mostly  hydrated  Mg  and  Fe  compounds. 

Dr.  G.  Hevesy. — The  Chemistry  of  Haf- 
nium. 
Though  hafnium  is  placed  in  the  periodic 

table  between  zirconium  and  thorium,  its 
chemical  properties  are  not  intermediate  be- 
tween those  of  zirconium  and  thcH-ium,  but 
much  nearer  to  Zr. 

While  the  fluorides  and  double  fluorides 
of  thorium  are  practically  insoluble,  the 
coKrespouding  zirconium  compounds,  and 
still  more  the  hafnium  compounds,  are 
fairly  soluble  in  cold,  very  soluble  in  hot 
water.  By  this  method  zirconium  can  easily 
be  separated  from  hafnium.  The  mineral 
is  melted  with  KFHF,  and  by  crystallising 
the  potassium  double  fluorides  the  hafnium 
concentrates  in  the  mother-liquor. 

Hafnium  oxalate  is  soluble  in  excess  of 
oxalic  acid.  The  oxychloride  is  less  soluble 
than  zirconium  oixyohloride.  Hafnium  is 
more  basic  than  zirconium;  accordingly  the 
latter  is  more  easily  precipitated  by  am- 
monia, sodium  thiosulphate,  &c. ;  and 
while  zirconium  sulphate  begins  to  decom- 
pose above  400°,  the  temperature  at  which 
hafnium  sulphate  undergoes  marked  de- 
composition lies  about  100°  higher.  Thor- 
ium phosphate  is  easily  dissolved  by  strong 
acids,  zirconium  phosphate  much  less, 
whereas  hafnium  phosphate  is  found  to  be 
still  less  soluble. 

Zirconium  extracted  from  different 
minerals  always  contains  i-30  per  cent, 
hafnium.  We  must  conclude  that  "  zir- 
conium," hitherto  thought  to  be  an  ele- 
ment, is  a  mixture  of  zirconium  and  haf- 
nium. 

Tuesday,  September  18. 
Sbnatore    Ginori    Conti. — The     Utilisa- 
tion   of  Volcanic    Steam.        (With    lantern 
slides.) 


Miss  Elizabeth  S.  Semmens. — The  Bio- 
chemical Effect  of  Polarised  Light. 

That  plane  polarised  light  has  a  distinct 
accelerating  effect  on  the  breaking  up  of 
starch  grains  in  the  presence  of  diastase 
can  be  shown  under  the  microscope.  At 
laboratory  temperatures  below  20°  and 
with  small  concentration  of  diastase,  starch 
grains  exposed  to  light  polarised  by  reflec- 
tion or  by  a  Nicol  prism  erode  quickly  and 
give  crystals  of  sugar,  controls  in  ordinary 
light  or  in  the  dark  remaining  almost  in- 
tact. 

Dr.  K.  G.  Faegher. — Cotton  Wax. 

The  term  "cotton  wax"  has  been  aip- 
plied  by  different  writers  to  the  extracts 
obtained  from  cotton  by  means  of  organic 
solvents,  and  even  to  the  material  removed 
by  boiling  the  cotton  with  dilute  sodium 
hydroxide.  It  includes  fat,  wax,  and  the 
more  readily  soluble  portion  of  the  resin 
present  in  the  cotton,  the  proportion  of  fat 
being  relatively  small. 

Comparison  of  the  extracts  obtained  with 
a  number  of  organic  solvents  indicated  that 
carbon  tetrachloride  removed  the  fat  and 
wax  and  left  the  major  portion  of  the  resin 
unldissolved ;  whilst  chloroform  dissolved 
fat,  wax  and  resin. 

Dr.  D.  a.  Clibbens — The  Absorption  of 
Methylene  Blue  by  Cotton. 

A  quantitative  investigation  of  the  con- 
ditions which  determine  the  absorption  of 
methylene  blue  by  bleached  cotton  from 
neutral  solutions  of  methylene  blue  hydro- 
chloride. The  object  of  the  work  was  to 
provide  a  method  for  determining  the  effi- 
ciency of  cotton-bleaching  processes  with 
respect  to  their  production  of  pure  cotton 
cellulose.  Measurements  of  the  absorption 
of  methylene  blue  at  various  stages  of  a 
bleaching  process  show  :  — 

The  absorption  by  raw  cotton  is  high,  and 
is  a  property  of  certain  acidic  non-cellulose 
impurities. 

The  absorption  diminishes  progressively, 
and  measures  the  progressibe  purification  of 
the  cotton  cellulose. 

The  absorption  by  scoured  cotton  is  not 
further  affected  by  normal  bleaching, 
agents,  so-called  "over-bleaching,"  causes 
chemical  attack  of  the  cellulose  itself  and 
though  excessive  treatment  with  oxidising 
results  in  an  increased  absorption  of  the 
basic  dye  due  to  the  presence  of  acidic  oxi- 
dation products  ("oxjcellulose"). 


SEPTEMBEK  21,  1923. 


THE  CHEMICAL  NEWS. 


187 


Prof.  H.  E.  Fiebz. — The    Sulphonation 
and  Nitration  of  Naphthalene. 

The  author  has  investigated  the  inter- 
action of  naphthalene  and  sulphuric  acid, 
and  has  been  able  to  show  that  the  rule 
established  first  by  Armstrong  and  Wynne 
holds  good  in  every  case  where  the  system 
uujphthalene  and  sulphuric  acid  is  involved. 
Several  free  naphthalene-mono  and  di- 
sulphonic  acids  and  nitration  products  have 
been  prepared  and  described.  The  crystals 
were  measured  and  compared  with  the  cor- 
responding metal  salts.  Over  100  were 
investigated. 


GENERAL    NOTES. 


PRODUCTION  OF  METALS  OF  THE 
PL.VTINUM  GROUP  IN  CAN.\DA. 

The  High  Commissioner  for  Cftna^la  in 
London  has  just  received  from  the  Do- 
minicm  Bureau  of  Statistics  at  Ottawa,  re- 
vised statistics  dated  July  23,  on  the  pro- 
duction of  metals  on  the  platinum  group  in 
Canada. 

The  production  of  metals  of  the  platinum 
group  in  Canada  for  1022  was  derived  al- 
ujost  entirely  from  the  nickel-copper  ores 
of  the  Sudbury  district.  In  accordance 
with  the  low  production  of  nickel-oopper, 
the  amounts  of  metals  of  the  platinum 
group  recovered  were  comparatively  small. 
The  actual  production  figures  have  been 
augmented  by  the  addition  of  quantities 
prwluced  prior  to  1922,  but  reportcJd  for  the 
first  time  in  that  year. 

The  [production  was  valued  at  the  average 
New  York  quotations  for  the  year,  which 
were  as  follows :  platinum  $97,618  per  fine 
ounce,  palladium  $65.00  per  fine  ounce, 
ond  osmium  group  $80.00  per  fine  ounce. 

Metals  of  the  Platinum 


GYPSUM. 

The  Dominion  Bureau  of  Statistics, 
Canada,  issues  the  finally  revised  statistics 
on  the  production  of  gypsum  in  Canada 
during  1922. 

The  total  output  of  gypsum  rock  in 
Canada  during  1922  amounted  to  484,629 
twis,  of  which  quantity  145,954  tons,  or  30 
per  cent.,  was  calcined.  The  quantity 
quuri'ied  by  provinces  was :  Nova  Scotia, 
281,861  tons;  New  Brunswick,  56,692  tons; 
Ontario,  106,829  tons;  Manitoba,  39,147 
tons;  and  British  Columbia,   100  tons. 

For  statistical  purposes  the  production 
of  gypsum  is  considered  to  be  the  sum  of 
the  quantities  disposed  of  in  the  different 
marketable  forms,  care  being  taken  to 
avoid  duplication;  the  values  used  are 
those  at  point  of  shipment. 

Shipments  of  al!  grades  totalled  559,265 
tons,  valued  at  $2,160,898,  an  increase  of 
172.715  tons  and  $375,360  over  the  1921 
production.  The  1922  production  included 
lump  or  mine  run,  crushed,  fine  ground  and 
calcined  gypsum  sold ;  calcined  gypsum 
used  in  the  calcining  plants  for  the  produc- 
tion of  wall  plaster,  alabastine  and  other 
gxpsum  products  was  also  included.  The 
average  value  per  ton  received  by  operators 
throughout  Canada  was,  by  grades :  lump, 
$1.52;  crushed,  $2.26;  fine  ground  $6.22; 
and  calcined,  $10.67.  Prices  during  the 
previous  year  averaged  as  follows :  lump, 
$1.78;  crushed,  $2.56;  fine  ground,  $3.42, 
and  calcined,  $10.61. 

The  Dominion  Bureau  of  Statistics  has 
also  issued  finally  revised  statistics  on  the 
production  of  salt  in  Canada  for  last  year. 

The  output  of  salt  from  all  .sources  in 
Canada  rjuring  1922  totalled  183,438  tons, 


Group,  Canada,    1922. 


Rhodium, 

Osmium. 

Ruthonium 


Platinum.  Palladium.  Iridium. 
Produced  by  Canadian  and  United 
States     nickel     refineries     from 

Canadian   ores    fine  07.8.             458  724  891 

Value  $        44.700        $  47.060          $  331,280 

B.C.    Pincers     fin(>  nzs.               H  •  1 

Vnlne  $         1.074  ...  80 

Total  for  Caniidn    fine  ozi*.             4r)9  f.i)  724  (b)  302  fc) 

Value  $        45,78.*}        $  47,(»60          $  31.360 
(i\)  includes — 282  ounces  platinum                ) 

(b)  includes— 383  ounces  palladium  )  Produced  but  not  reported  previous  to  1922. 

(c)  includes — 266  ounces  of  others  ) 


188 


THE  CHEMICAL  NEWS. 


SEPTEMBEE  21,  1923. 


of  which  quantity  aipproximately  99  per 
cent.,  or  181,794  tons,  valued  at  $1,628,323, 
was  marketed.  Compared  with  the  sales 
for  the  previous  year,  the  1922  records 
showed  an  increase  of  10,811  tons,  or  6.6 
per  c€nt.  in  quantity,  and  a  decrease  of 
$45,362  or  2.7  per  cent,  in  value. 

Ontario  continued  to  be  the  chief  pro- 
ducer, contributing  97.2  per  cent,  of  the 
total  sales.  Nova  Scotia  shipments,  from 
the  Melagash  Mine,  amounted  to  5,053 
tons  of  common  coarse,  land  and  rock  salt. 


BRITISH  MALAYA. 
Consumption  of  Acetic  Acid. 

With  the  exception  of  native  rubber 
holdings  and  possibly  of  one  or  two  large 
estates,  all  rubber  latex  produced  in 
British  Malaya  is  coagulated  with  acetic 
acid.  During  the  war,  when  supplies  of 
acetic  acid  were  difficult  to  obtain,  sul- 
phuric acid  came  into  general  use.  This 
acid  is  cheaper  than  acetic,  but  its  use  has 
been  condemned  by  the  Department  of 
Agriculture  of  the  Straits  Settlements  and 
Federated  Malay  States,  and  also  by  the 
Rubber  Growers'  Association, 

The  value  of  acetic  acid  imiports  has 
risen  enormously  since  1920.  The  sourci-s 
from  which  the  acid  has  been  imported  are 
interesting.  In  1921  Canada  furnished  al- 
most 50  per  cent,  of  the  supply,  but  by 
1923  she  has  altogether  ceased  from  com- 
petition in  the  market.  The  bulk  of  the 
acid  is  now  supplied  by  European  Continen- 
tal countries.  Details  as  to  the  respective 
quantities  exported  by  the  different  coun- 
tries of  the  Continent  in  1922  and  1923  arc 
not  yet  available,  but  in  1921  the  Nether- 
lands and  Germany  were  the  only  two 
European  Continental  countries  exporting 
the  acid  to  Malaya.  The  value  of  Japanese 
acetic  acid  rose  enormously  in  1922,  but 
has  fallen  again  during  the  first  half  of  the 
current  year. 


BOARD  OF  TRADE  ANNOUNCEMENT. 

Dyestuffs  (Import  Regulation)  Act,  1920. 
Applications  for  Licence  during  August. 
The  total  number  of  applications  received 
during  the  month  was  391,  of  which  269 
were  from  merchants  or  importers.  To 
these  should  be  added  the  29  cases  out- 
standing on  August  1,    making  a  total  for 


the  month  of  420.     These  were  dealt  with 
as  follows :  — 

Granted — 282  (of  which  248  were  dealt 
with  within  seven  days  of  receipt). 

Referred  to  British  makers  of  similar 
products — 74  (of  which  63  were  dealt 
with  within  seven  days  of  receipt). 

Referred  to  Reparation  suppHes  avail- 
able— 30  (all  dealt  with  within  two  days 
of  receipt). 

Outstanding  on  August  31 — 34  (mostly 
dealt  with  at    the  meeting  of    the  Com- 
mittee held  on  August  31), 
Of  t^he  total  of  420  applications  received, 
341,  or  81  per  cent.,  were  dealt  with  within 
seven  days  of  receipt. 


APPEAL  FOR  BRITISH  EMPIRE 
CANCER  CAMPAIGN. 

"  Help  to  Stamp  out  Cancer!" 
Following  the  announcement  last  week 
that  the  new  Emipire  campaign  against 
cancer  was  in  need  of  voluntary  workers, 
many  offers  of  help  have  reached  the  head- 
quarters of  the  British  Red  Cross  Society, 
19,  Berkeley  Street,  W,l.  The  county 
branches  of  the  Red  Cross  also  report  muon 
enthusiasm  amongst  their  workers  who  are 
enrolling  thousands  for  active  canvassing 
during  the  autumn  campaign. 

The  example  of  Mr.  Reuben  Wood,  of 
Sheffield,  who  recently  lost  his  son  through 
cancer,  in  collecting  a  sum  of  money  for  the 
campaign,  a  course  he  suggested  to  all  who 
had  lost  relations  or  friends  through  this 
dreadful  scourge,  has  been  followed  widely. 
Many  requests  have  reached  19,  Berkeley 
Street  for  books  of  stamps  (of  Is.  and  6d. 
denominations)  to  be  sold  for  the  benefit  of 
the  campaign,  and  for  literature  in  the 
shape  of  leaflets  and  pamphlets  describing 
the  aims'  of  the  campaign.  One  enthusias- 
tic young  worker  called  on  a  recent  morning 
at  19,  Berkeley  Street  for  a  book  of  stamps 
valued  at  £1,  and  returned  twice  during  the 
day  for  further  supplies,  having  sold  the 
others  to  his  friends. 

"Help  to  Stamp  Out  Cancer"  is  the  slo- 
gan adopted  for  the  cards  of  stamps  which 
will  be  shortly  on  sale  in  many  retail  shops 
and  other  institutions.  It  is  hoped  that  by 
the  purchase  of  these  stamps,  which  are  of 
a  striking  design  and  may  be  affixed  to  cor- 
respondence, will  afford  the  public  an  easy 
and  convenient  way  of  subscribing  small 
amounts  to  this  great  cause. 


SEPTEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


189 


'  Meantime  larger  subscriptions  continue 
to  be  made  to  this  fund,  and  it  is  hoped  that 
the  total  sum  required,  £1,000.000,  to  sub- 
sidise and  initiate  further  rebearch  through- 
out the  Empire  will  eventually  be  secured. 
Subscriptions  should  be  sent  to  the  Hon. 
Sir  Arthur  Stanley,  G.B.E.,  C.B.,  M.V.6., 
British  Empire  Cancer  Campaign  Dept., 
British  Red  Cross  Society,  19,  Berkeley 
Street,  W.l,  or  to  any  of  the  branches  of 
Lloyds  Bank,  Ltd. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


INSTITUTE    OF    METALS. 

Annual  Autumn  Mekting,  Held  at 

Manchester,  on  Wednesday,  September 

12. 

(Continued  from  Page  175.) 

The  Constitution  and  Age-Hardening  of 
the  Quaternary  Alloys  of  Aluminium,  Cop- 
per, Magnesium  and  Magnesium  Silicide, 
by  Marie  L.  V.  Caylek,  M.Sc. 

The  constitution  and  age-hardening  of 
the  quaternary  alloys  of  aluminium,  cop- 
per, magnesium,  magnesium  silicide,  con. 
taining  up  to  0  per  cent,  copper,  4  per  cent, 
magnesium,  and  4  per  cent,  magnesium 
silicide,   were  considered. 

In  a  quaternary  system  it  is  cmly  possible 
to  represent  the  equilibrium  of  the  system 
at  any  single  temperature,  and  the  isother- 
mal sections  take  the  form  of  regular  tctra- 
hedra.  For  the  above  investigation  iso- 
therms at  -100°  C.  and  2r)0°  C.  have  been 
determined  from  the  results  of  thermal  anrj 
microscopic  examination,  and  wire  mrxlels 
have  been  constructed. 

The  results  show  that  when  copper, 
magnesium,  magnesium  silicide  are  present 
in  aluminium,  any  two  of  these  compo- 
nents have  a  marked  effect  on  the  solubility 
of  the  third.  The  sum  of  these  effects  is 
that  ultimately  CuAl,  and  MgjSi  are  both 
thrown  out  of  solution.  Also,  if  copper 
and  magnesium  are  present  in  a  ratio 
greater  than  12  to  5  approximately,  then 
alloys,  when  (pienched  from  high  tempera- 
tures, age-harden  at  room  temperature, 
owing  to  the  difference  in  the  solubility  of 
MgjSi  at  the  quenching  and  ageing  tem- 
p(!rature.  If,  however,  the  ratio  of  copper 
to  magnesium  is  less  than  12  to  5,  then  no 
age-hardening  takes  place,  since  there  is 
little  difference  in  the  solul)ility    of  Mg^Si 


at  high  and  low  temperatures.  The  slight 
increase  in  hardness  obtained  on  further 
heat-treating  these  quenched  and  aged  al- 
loys is  attributed  to  the  small  difference  in 
solubility  of  copper  at  the  quenching  and 
ageing  temperature.  It  is  shown,  there- 
fore, that  the  age-hardening  of  alloys  of 
the  "Duralumin"  type  is  due  primarily  to 
MgjSi,  copper  causing  very  little  age- 
hardening,  and  that  the  addition  of  magne- 
sium and  copper  is  important,  since  both 
reduce  the  solubility  of  MgjSi  at  high  and 
low  temperatures,  and  consequently  reduce 
•  the  maximum  age-hardness  due  to  MgjSi. 

The   Electro-Chemical  Character  of  Cor- 
rosion, by  Click  R.  Evans,  M.A. 

Experiments  have  indicated  that  the  cor- 
rosion   of  metals    in  mainly — probably  en- 
tirey^ — electro-chemical  in  character.      Cor- 
rosion aco(Mnpaniecl    by  evolution  of  hydro- 
gen gas  is  characteristic  of  reactive  metals 
■placed    in  acid  solutions,    but  the  velocity 
varies  greatly  with  the  purity  of  the  metal. 
Where  this  type  is  impossible,   slower  cor- 
rosion can  take  place  at  a  rate  determined 
by  the  diffusion  of  oxygen  to  the  metal,  an3 
comparatively   independent     of  the   purity. 
When  a  metal  is  immersed  in  a  solution  of 
potassium    chloride,     one  can  observe    the 
production    of  alkali    at  the    cathodic  por- 
tions, the  production  of  the  chloride  of  the 
metal  at  the  anodic  portions,  and  the  pre- 
cipitation of  hydroxide    where  these  meet. 
The    electric    current  can    be  trapped    and 
measured,  and  is  found  (by  applying  Fara- 
day's law)  to    account  for  the  greater  part 
of  the  corrosion  actually  observed.      Gener- 
ally the  cathodic  areas  are  those  to  which 
air  has  free  access,  whilst  the  anodic  areas 
are  those    protected  from  aeration.       It  is 
significant  that  corrosion  usually  proceeds 
most  rapidly    at    the    comparatively    "un- 
aerated"    places — hence   the   intense   corro- 
sion observed    in    "pits"    and    over    areas 
covered  up  by  porous  corrosion-products. 

Experiments  with  some  Copper  Wire; 
Cohesion  a  Function  of  both  Temperature 
and  Cold  Work,  by  Douglas  H.  Ingall, 
M.Sc. 

Five  samiples  of  copper  wire  were  used, 
representing  soft  annealed  and  four  degrees 
of  cold  work  given  by  25,  40,  50  and  75  per 
cent,  reduction  of  area  by  drawing.  Each 
sample  of  cold  worked  wire  was  obtained  by 
drawing  in  one  pass  from  the  next  thicker 
wire.  The  cohesion  at  elevated  tempera- 
tures was  determined  by  placing  given  loads 


190 


THE  CHEMICAL  NEWS. 


PTEMBEE  21,  1923. 


on  the  wire  at  atmospheric  temperature, 
heating  the  yire  and  determining  the  tem- 
perature at  which  it  broke.  All  the  samples 
gave  similar  graphs  (plotting  cohesion 
against  temperature)  in  which  with  r':Se  of 
temperature  the  cohesion  decreased  along  a 
straight  line  to  a  constant  critical  tempera- 
ture of  350°  C,  beyond  which  the  cohesion 
was  represented  by  a  sharply  descending 
curve. 

Investigation  of  the  Effects  of  Impurities 
on  Copper.  Part  I.  :  The  Effect  of  Oxygen 
on  Copper,  by  D.  Hanson,  D.Sc,  C.  B. 
Marryat,  B.Sc,  and  Grace  W.  Ford,. 
B.Sc. 

The  effect  of  oxygen,  utp  to  a  concentra- 
tion of  0.36  per  cent.,  on  the  properties  of 
pure  copper  was  described.  The  investiga- 
tion deals  with  the  casting  of  the  metal, 
cold  rolling,  hot  rolling,  density  of  chill- 
castings  and  rolled  bars,  tensile  tests  at 
ordinary  and  at  elevated  temperatures, 
hardness  tests,  fatigue  tests,  notched-bar 
impact  tests,  electrical  conductivity,  micro- 
structure  of  castings,  and  microstructures 
of  the  alloys  in  various  conditions,  and  de- 
termination of  the  solubility  of  oxygen  in 
solid  copper. 

The  results  indicate  that  oxygen  has  a 
relatively  small  effect  on  the  properties  of 
copper,  and  is  neither  seriously  deleterious 
nor  remarkably  beneficial.  The  mechanical 
properties  are  not  much  affected  by  small 
quantities  of  oxygen,  and  copper  containmg 
as  much  as  0.1  per  cent,  differs  very 
slightly  from  pure  copper.  The  electrical 
conductivity,  which  is  usually  profoundly 
affected  by  the  addition  of  small  quantities 
of  an  impurity  to  a  pure  metal,  does  not 
fall  rapidly,  and  values  exceeding  100  per 
cent,  of  the  International  Standard  are  ob- 
tained in  all  annealed  materials  containing 
loss  than  0.1  per  cent,  of  oxygen.  The  re- 
latively small  effect  of  oxygen  is  without 
doubt  due  to  the  fact  that  the  solubility  of 
the  oxide  in  sohd  copper  is  extremely  low, 
so  low  in  fact  that  for  all  practical  purposes 
oxygen  may  be  regarded  as  insoluble  in 
solid  copper.  The  oxygen- bearing  metals 
must,  therefore,  be  considered  as  a  hetero- 
geneous mixture  of  pure  copper  and  finely 
divided  particles  of  cuprous  oxide,  and 
within  the  range  of  composition  investi- 
gated the  percentage  of  copper  greatly  ex- 
ceeds that  of  cuprous  oxide.  The  materials 
consist  essentially  of  a-  soft  ductile  copper 
matrix,  in  which  harder  particles  of  cuprous 
oxide  are  distributed,  and  the  properties  of 
the  series  are  such    as  would    be  expected 


from  a  mechanical    mixture    of  such    con- 
stituents. 

These  conclusions,  however,  are  applic- 
able strictly  only  to  pure  copper  containing 
oxygen  and  free  from  other  impurities.  The 
effect  of  the  simultaneous  presence  of  other 
impurities  may  be  very  appreciable,  and 
requires  special  investigation,  foi'  which  the 
present  Report  furnishes  a  necessary  basis. 

Hardness  Tests  on  Crystals  of  Alu- 
minium, by  Hugh  O'Neill,  M.Met. 

In  the  Brinell  hardness  test  the  relation 
between  the  applied  load  (L)  and  the  dia- 
meter (d)  of  the  indentation  produced  on  a 
specimen  is  given  by  L  =  ad°  (Mayer's  for- 
mula). Many^  workers  have  determined  the 
values  of  a  and  n  for  different  metals,  and 
the  author  has  recently  shown  that  for  an 
amorphous  substance  n:=2.0.  The  present 
work  deals  with  completely  crystalhne 
material,  single  crystals  of  aluminium  hav- 
ing been  chosen  since  the  technique  of  their 
production  has  been  worked  out  by  Profes- 
sor Carpenter  and  Miss  Elam. 

Two  pieces  of  aluminium  strip  were 
treated  separately  by  their  process,  but  only 
the  first  became  a  single  crystal.  By  acci- 
dent it  was  annealed  for  a  short  time  just 
below  its  melting  point  and  upon  its  upper 
surface  three  series  of  parallel  ridged  mark- 
ings were  visible.  X-ray  examination 
showed  that  this  surface  was  a  rhombic- 
dodecahedral  (Oil)  face,  whilst  two  crystals 
chosen  from  the  second  piece  proved  like- 
wise to  be  presenting  octahedral  (111)  and 
cube   (001)  faces  respectively. 

Brinell  tests  showed  that  at  low  loads 
the  different  crystallographic  planes  resist 
penetration  to  different  degrees,  and  give 
indentations  of  different  shapes.  In  the 
Brinell  sense  the  (110)  face  is  the  "hard- 
est" arid  the  cube  (001)  face  appears  to  be 
the  "  softest."  But  the  load  required  to 
immerse  the  ball — and  probably  eventually 
to  make  it  perforate  the  metal — is  appar- 
ently the  same  in  all  cases.  Crystal  boun- 
daries were  also  found  to  be  without  any 
appreciable  effect  in  increasing  the  resist- 
ance of  aluminium  to  penetration.  In 
terms  of  Meyer's  formula,  if  a  1  mm.  hall  he 
used  then  whilst  n  varies  from  2.483  for  the 
(001)  face  to  2.274  for  the  (Oil)  face,  a  is  a 
constant  for  annealed  aluminium.  It  is  in- 
dependent of  the  presence  of  grain  boun- 
daries and,  in  single  crystals,  of  grain 
orientation. 


d 


SEPTEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


191 


The  Behaviour  of  Metals  under  Compres- 
sive Stresses,  by  H.  I.  Coe,  M.Sc. 

Compression  tests  carried  out  on  small 
cylinders  of  metals  show  that  with  succes- 
sive increments  of  loads  iplastic  flow  occurs, 
after  the  elastic  limit  has  been  exceeded,  at 
an  increasing  rate.  Graphical  representa- 
tion shows  that  at  a  certain  load  the  rate  of 
flow  for  a  given  increment  of  load  under- 
goes a  more  or  less  abrupt  change,  very 
soft  metals,  such  as  tin  and  lead,  becoming 
perfectly  plastic,  harder  metals  becoming 
more  plastic  than  under  preceding  loads 
and  immediately  succeeding  loads. 

Annealed  metals  appear  to  commence 
flowing  at  a  comparatively  low  load,  and 
continue  doing  so  at  an  increasing  rate  up 
to  the  load  corresiponding  to  critical  plas- 
ticity; the  same  metals,  however,  in  the 
worked  condition  are  much  more  resistant  f 
to  compressive  stresses  until  they  approach  ' 
near  the  load  corresponding  to  critical  plas- 
ticity when  they  suddenly  collapse  and  a 
marked  temporary  flow  occurs. 

A  Dilato metric  Study  of  the  Transforma- 
tions and  Thermal  Treatment  of  Light  Al- 
loys of  Aluminium,  by  Albert  M.  Poktk- 
viN  and  Pierre  Cheven.'vrd. 

Amongst  the  light  alloys  of  aluminium 
capable  of  being  hardened  by  quenching 
followed  by  tempering,  is  the  group  known 
under  the  naine  of  Duriihmiin,  whose  es- 
sential characteristic  is  their  magnesium 
content.  The  eflfect  of  the  addition  of  this 
metal  to  aluminium  was  first  pointed  out 
by  Wilm. 

The  investigations  of  Rosenhain,  Arch- 
butt,  Hanson  and  Gayler  have  linked  uip 
the  phenomena  of  quenching  shown  bv 
these  alloys,  with  the  variation  of  the  solu- 
bility, in  solid  alumininin,  of  Mg.Si.  wiiich 
is  always  present  in  commercial  afuininium. 
Rut  the  solubility  curves  of  MgjSi,  in  solid 
aluminium,  have  only  been  indirectiv 
traced  by  the  examination  of  alloys 
quenched   at  different  temperatures. 

The  authors  conclude  that  (1)  the  appli- 
cation of  dilatometric  methods,  judiciouslv 
using  the  recording  differential  dilatometer, 
permits  of  the  study  of  the  transformations 
and  the  mechanism  of  heat-treatment  of 
the  light  alloys  of  aluminium-magnesium- 
silieon,  and  in  general,  of  alloys  containing 
two  phase,  univarient  transformations,  a 
stufly  which  had  not  been  carried  out  up  to 
the  present.  (2)  The  study  of  the  con- 
stantant  temperature  transformations  by 
stant     temperature  transformations  by  the 


differential  dilatometer,  using  a  high 
the  differential  dilatometer,  using  a  high 
sensitivity  aipparatus,  leads  to  general  ex- 
pressions representing  the  phenomena  as 
functions  of  time  and  temperature.  (3) 
The  phenomena  of  quenching  and  temper- 
ing in  the  aluminium-magnesium-silicon  al- 
Io\s  can  be  interpreted  by  the  known  varia- 
tions in  the  solubility  of  Mg^Si  in  the  solid 
state,  without  it  being  necessary  to  assume 
anj-^  further  transformations  in  these  alloys. 
Equilibrium  in  the  System  Gold-Zinc 
{based  on  Investigations  of  electrical  con- 
ductivity at  high  temperatures),    by  Prof. 

P.    SOLDAU. 

Alloys  of  gold  and  zinc  belong  to  the 
type  of  AR-brasses,  where  A  is  a  metal  be- 
longing to  the  first,  and  R  to  the  second 
group  of  the  periodic  system.  These  alloys 
are  of  considerable  importance,  as  their 
chemical  nature  is  very  close  to  the  alloys 
of  copper  with  zinc,  i.e.,  to  the  ordinary 
brasses. 

The  system  gold-zinc  was  investigated  by 
R.  Vogel  in  1906,  and  no  transformations 
were  detected.  However,  the  results  of  the 
investigation  of  the  system  gold-cadmium 
led  the  author  to  undertake  the  investiga- 
tion of  alloys  of  gold  and  zinc,  taking  ad- 
vantage of  several  different  methods  of 
physico-chemical  analyses,  which  would 
check  and  complement  one  another. 

Special  attention  was  paid  to  the  deter- 
mination of  electrical  conductivity  at  high 
temperatures,  which  necessitated  the  con- 
struction of  a  special  apparatus. 

When  the  results  obtained  by  the  elec- 
trical conductivity  method  at  high  tem- 
peratures and  by  q[uenching  showed  a  com- 
plete concordance,  then  that  former  method 
could  be  recommended  with  sufficient 
guarantee  for  the  investigation  of  other 
metallic  systems,  and  in  the  first  instance 
such  practically  important  ones  as  those 
belonging  to  the  type  of  brasses. 


NOTICES  OF  BOOKS. 
Physikalische  Chernie,  von  Dr.  Alfrel 

Benrath.     Pp.  VIII.  +  107.     Dresden  & 

Leipzig:   Verlag  von  Theodor  Steinkopff. 

1923.     Price  2s. 

Prof.  Benrath 's  concise  volume  aims  at 
being  a  monograph  on  the  development  of 
physical  chemistry  during  the  last  decade. 

He  has  divided  his  book  into  two  parts. 
The  first  part,  entitled  Chemically  pure 
Bodies,  is  very  brief,  occupying  only  22 
pages,    and  being  concerned  with  the  rela- 


102 


THE  CHEMICAL  NEWS. 


SEPTEMBER  21,  1923. 


tions  between  elements  and  compounds  and 
the  theory  of  allotropy.  A  good  account  of 
the  researches  of  the  Dutch  physicists  on 
this  subject  is  given. 

Part  II.  deals  with  Solutions,  and  com- 
mences with  remarks  on  Van't  Hoff's 
Theory  of  Solution  in  the  case  of  the  solu- 
tion of  indifferent  bodies.  The  case  of 
Binary  Mixtures  is  also  described. 

The  solution  of  electrolytes  receives 
fuller  treatment,  commencing  with  a  de- 
scription of  the  theory  of  electrolytic  dis- 
sociation. Its  position  in  1914  and  its  sub- 
sequent development  are  traced,  and  an 
extensive  bibliography  is  given.  The  theory^ 
of  indicators  and  of  completely  dissociated 
electrolytes  are  discussed.  There  are  also 
sections  on  the  electrolytic  dissociation  of 
fused  and  of  crystallised  salts. 

The  development  of  the  Solvate  Theory 
of  s.olutions  is  also  traced,  especially  in 
connection  with  the  question  of  the 
existence  of  hydrates  in  aqueous  solutions. 

In  a  small  volume  of  this  kind  it  is  essen- 
tial that  a  selection  of  the  literature  avail- 
able must  be  made,  and  this  has,  in  the 
main,  been  done  with  discrimination,  but 
references  to  British  work  later  than  1914 
are  inadequate.  This  is  probably  not  the 
author's  intention,  but  is  a  consequence  of 
the  inability  of  German  scientists  and  in- 
stitutions to  purchase  foreign  publications. 

At  the  low  price  of  2s.,  Prof.  Benrath's 
book,  which  is  Vol.  VIII.  of  the  Naturwis- 
senschaftliche  Reihe,  published  under  the 
general  editorship  of  Prof.  Liesegang, 
should  find  a  wide  public  among  chemists 
and  physicists,  and  especially  advanced 
students,  for  whom  it  is  evidently  intended. 


Messrs.  David  Bridge  &  Co.,  Ltd., 
Castleton,  Manchester,  have  sent  a  copy  of 
Bridge's  Modem  MiUgearing,  pp.  132.  This 
work,  which  treats  the  subject  more  deeply 
than  is  usual  in  catalogues,  contains  many 
illustrations,  diagrams,  and  working  formu- 
la, and  an  index.  It  is  clearly  printed  on 
art  paper,  and  prices  for  all  classes  of  mill- 
gearing  are  quoted.  There  is  also  an  ap- 
pendix covering  the  field  of  power  trans- 
mission, and  should  be  of  special  interest 
to  engineers  and  draughtsmen.  A  copy  of 
the  work  may  be  obtained  gratis  on  request. 


BOOKS  RECEIVED. 

Field  Crops  in  South  Africa,  by  H.  D. 
Leppan,  B.Sc.A.,  and  G.  J.  Bosman, 
B.Sc.A.  Pp.  IX.  +  358.  1923.  Central 
News  Agency,  Ltd.,  South  Africa.  21s.  net. 


iHis  lisL  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Eegistered  Patent 
Agents,  of  5.  Chanoe.-y  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trada  Marks, 

and  Designs  can  be  obtained  gratuitously. 
202181— Coplan,  A.  H.— Production  and  refining  of 
nickel-ohrome  steels. 

Abstract  Published  this  Week. 
200175 — Cleaneing-compositions ;  sodium  aluminium 
silicates.— Ouernsey,  F.  H.,  of  7,  Bewley 
Parkway,  and  Electric  Smelting  &  Alu- 
minium Co.,  both  in  Lockport,  New  York, 
U.S.A. 
A  crystalline  detergent  compound  which  is 
solid  at  ordinary  temperatures,  and  having  the 
formula  Al  0  (SiO  )  x  (Nu  O)  x-1  (H  0)y,  where 
X  represents  any  number  greater  than  seven,  is 
made  by  boiling  together  a  mixture  of  aluminium 
silicate,  sodium  silicate,  and  caustic  lye.  Tlie 
boiled  mixture  is  preferably  chilled  to  a  semi- 
plastic  condition,  and  allowed  to  solidify.  When 
X  has  the  value  75,  the  compound  is  completely 
soluble  and  has  a  melting-point  of  126°  F.  To  en- 
hance the  water-softening  properties  of  the  com- 
pound, alkali  metal  salts  of  weak  acids  such  as 
sodium  or  potassium  carbonates,  or  other  car- 
bonates, or  phosphates  or  borates  may  be  mixed 
with  it.  An  emulsifying  agent  such  as  sulphon- 
ated  or  saiwnified  oils  or  fats  may  also  be  added, 
preferably  in  amounts  of  about  5  per  cent.  To 
provide  for  loss  of  alkali  oxide  during  cleansing 
operations,  a  further  amoimt  of  oxide,  up  to  2 
molecules  for  each  molecule  of  detergent,  may  be 
mixed  with  the  compound. 

Latest  Patent   Applications. 
21733— Badische   Anilin   &   Soda-Fabrik.— Manufac- 
ture    of   oxygenated     organic     compounds. 
Aug.   28. 
^1659 — Pellegrini,     G. — Manufacture       of       meta- 

phenylene-diamine.    Aug.    27. 
21916 — Pico,    L. — Destructive    fermentation    of    or- 
ganic  residues.    Aug.  30. 
22029— Scottish   Dyes,  Ltd.— Production  of  anthra- 
quinone    sulphonic   acids.     Aug.    31. 
Specifications   Published   this    Week. 
202333 — Mosicki,  I. — Processes  for  the  dry  distilla- 
tion of  bituminous  or  cellulose  containing 
material. 
202883— Air     Reduction     Co.,     Inc.— Process       of 

manufacture   of   alkali    cyanides. 
202,532 — Germot,  A. — Process     for   the     direct  ob- 
taining of  antimony. 

Abstract  Published  this  Week. 
200739— Dyes,  dyeing.— Cliemische  Fabrik  Greis- 
heim-Elektron,  Frankfurt-on-Main,  Ger- 
many. 
Monoazo  dyes  are  prepared  in  substance  or  on 
the  fibre  by  coupling  diazotized  5-nitro-2-toluidine 
with  a  p-alkyloxyarylide  of  2 :3-oxynaphthoio 
acid,  the  p-anisidide  and  p-phenetidide  being 
mentioned;  bluish-red,  or  in  light  tones,  pink 
shades  fast  to  light  are  thus  obtained  on  the 
fibre;  the  products  may  also  be  used  in  the  pro- 
duction of  lakes.  An  example  is  given  of  the 
manufacture  in  substance  of  the  dyestuff  from  5- 
nitro-2-toluidine  and  the  p-anisidide  of  2 :3-oxy- 
nitro-2-toluidine  and  the  p-ansidide  of  2 :3-oxy- 
naphthoic  acid  and  of  the  production  of  pink  and 
red  shades  on  the  fibre  by  padding  with  a  solu- 
tion containing  the  p-anisidide,  caustic  soda,  tni- 
key-red  oil,  and  formaldehyde,  and  developing 
with  the  diazo  compound. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d> 
each. 


4 


SEPTEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


198 


THE   CHEMICAL  NEWS, 

VOL.  CXXVII.      No.  3311. 


[British    Association  for  the    Advance- 
ment OF  Science  :  Liverpool,  1923.] 

THE  PRESIDENTL\L  ADDRESS. 

TUK    ELECTRICAL    STRUCTURE    OF 

MATTER. 

By  Professor  Sir  Ernest  Rutherford, 
D.Sc,  LL.D.,  Ph.D.,  F.R.S., 

President  of  the  Association. 

{Continued  from  Page  182.) 

This  artifirial  di.sintegration -of  elements 
by  a  particles  takes  place  only  on  a  minute 
scale,  and  its  observation  has  only  been 
possible  by  the  counting  of  individual  swift 
hydrogen  nuclei  by  the  scintillations  they 
produce  in  zinc  sulphide. 

These     experiments     sugj^^est     that     the 
hydrogen  nucleus  or  proton  must  be  one  of 
the    fundamental    units    which    build    up    a 
nucleus,  and  it  seems  highly  probable  that 
the  helium  nucleus  is  a  secondary  building 
unit  composed   of  the   very  close  union  of 
four  protons  and  two  electrons.     The  view 
that  the  nuclei  of  all  atoms  are  ultimately 
built  up  of  protons  of  mass  nearly  one  and 
of  electrons  has  been  strongly  supported  and 
extended  by  the  study  of  isotopes.     It  was 
early  observed  that  some  of  the  radioactive 
elements  which  showed  distinct  radioactive 
properties  were  chemically  so  alike  that   it 
was   impossible   to  effect     their    separation 
when  mixed  together.     Similar  elements  of 
this  kind  were  calTed  '  isotopes  '  by  Soddy, 
since    they    appeared    to    occupy   the    same 
place  in  the  periodic  table.      For  example,  a 
number     of     radioactive     elements     in     the 
uranium  and  thorium  series  Have  been  found 
to    have    physical    and    chemical   properties 
i<lentical  with  those  of  ordinary  lead,  but  yet 
to  have  atomic  weights  differing  from  ordi- 
nary  lead,    and   also  distinctive  radioactive 
properties.     The  nuclear  theory  of  the  atom 
offers  at  once  a  simple  interpretation  of  the 
relation   between    isotopic  elements.      Since 
the  chemical   properties  of  an   element   are 
controlled   by   its   nuclear  charge  and   little 
influenced  by  its  mass,  isotopes  must  corre- 
spond   to    atoms    with    the    same    nuclear 
charge  but  of  different  nuclear  mass.     Such 
a  view  also  offers  a  simple  ex()lanation  why 


the  radioactive  isotopes  show  different 
radioactive  properties,  for  it  is  to  be  antici- 
pated that  the  stability  of  a  nucleus  will  be 
nuuli  influenced  by  its  mass  and  arrange- 
ment. 

C)ur    knowledge    of    isotopes    has    been 
widely   extended   in   the   last   few  years   by 
Aston,   who  has  devised  an  accurate  direct 
method  for  showing  the  presence  of  isotopes 
in  the  ordinary  elements.    He  has  found  that 
some  of  the  elements  are  '  pure  ' — i.e.,  con- 
sist of  atoms  of  identical  mass — while  others 
contain  a  mixture  of  two  or  more  isotopes. 
In  the   case   of  the   isotopic    elements,    the 
atomic  mass,  as  ordinarily  measured  by  the 
chemist,  is  a  mean  value  depending  on  the 
atomic  masses  of  the  individual  isotopes  and 
their  relative  abundance.     These  investiga- 
tions have  not  only  shown  clearly  that  the 
number  of  distinct  species  of  atoms  is  much 
greater     than     was     supposed,     but     have 
brought  out  a  relation  between  the  elements 
of    great     interest    and     importance.     The 
atomic  masses  of  the  isotopes  of  most  of 
the  elements  examined  have  been  found,  to 
an  accuracy  of  about  one  in  a  thousand,  to 
be  whole  numbers  in  terms  of  oxygen,   16. 
This  indicates  that  the  nuclei  are  ultimately 
built  up  of  protons  of  mass  very  nearly  one 
and  of  electrons.     It  is  natural  to  suppose 
that    this    building    unit    is    the    hydrogen 
nucleus,   but  that  its  average  mass  in  the 
complex  nucleus  is  somewhat  less  than  its 
mass  in   the  free  state  owing  to  the  close 
packing  of  the  charged  units  in  the  nuclear 
structure.     We  have  already  seen  that  the 
helium  nucleus  of  mass  4  is  probably  a  unit 
of  great   importance  in   the  building  up  of 
many  atoms,  and  it  may  be  that  other  sim- 
ple combinations  of  protons  and  electrons  of 
mass  2  and  3  occur  in  the  nucleus,  but  these 
have  not  been  observed  in  the  free  state. 

While  the  mass  of  the  majority  of  the 
isotopes  are  nearly  whole  numbers,  certain 
cases  have  been  observed  by  Aston  where 
this  rule  is  slightly  departed  from.  Such 
variations  in  mass  may  ultimately  prove  of 
great  importance  in  throwing  light  on  the 
arrangement  and  closeness  of  packing  of  the 
protons  anfl  electrons,  and  for  this  reason  it 
is  to  be  hoped  that  it  may  soon  prove  pos- 
sible to  compare  atomic  masses  of  the  ele- 
ments with  much  greater  precision  even 
than  at  present. 

While  we  may  he  confident  that  the  pro- 
ton and  the  electron  are  the  ultimate  units 
which   take  pnrt   in   the  building   up  of  all 


194 


THE  CHEMICAL  NEWS. 


SEPTEMBER  28.  1923. 


nuclei,  and  can  deduce  with  some  certainty 
the  number  of  protons  and  electrons  in  the 
nuclei  of  all  atoms,  we  have  little,  if  any, 
information  on  the  distribution  of  these 
units  in  the  atom  or  on  the  nature  of  the 
forces  that  hold  them  in  equilibrium.  While 
it  is  known  that  the  law  of  the  inverse 
square  holds  for  the  electrical  forces  some 
distance  from  the  nucleus,  it  seems  certain 
that  this  law  breaks  down  inside  the 
nucleus.  A  detailed  study  of  the  collisions 
between  a  particles  and  hydrogen  atoms, 
where  the  nuclei  approach  very  close  to  each 
other,  shows  that  the  forces  between  nuclei 
increase  ultimately  much  more  rapidly  than 
is  to  be  expected  from  the  law  of  the  inverse 
square,  and  it  may  be  that  new  and  un- 
pected  forces  may  come  into  importance  at 
the  very  small  distances  separating  the  pro- 
tons and  electrons  in  the  nucleus.  Until  we 
gain  more  information  on  the  nature  and 
law  of  variation  of  the  forces  inside  the 
nucleus,  further  progress  on  the  detailed 
structure  of  the  nucleus  may  be  difficult.  At 
the  same  time,  there  are  still  a  number  of 
hopeful  directions  in  which  an  attack  may 
be  made  on  this  most  difficult  of  problems. 
A  detailed  study  of  the  y  rays  from  radio- 
active bodies  may  be  expected  to  yield  in- 
formation as  to  the  motion  of  the  electrons 
inside  the  nucleus,  and  it  may  be,  as  Ellis 
has  suggested,  that  quantum  laws  are 
operative  inside  as  well  as  outside  the 
nucleus.  From  a  study  of  the  relative  pro- 
portions of  the  elements  in  the  earth's  crust, 
Harkins  has  shown  that  elements  of  even 
atomic  number  are  much  more  abundant 
than  elements  of  odd  number,  suggesting  a 
marked  difference  of  stability  in  these  two 
classes  of  elements.  It  seems  probable  that 
any  process  of  stellar  evolution  must  be  inti- 
mately connected  with  the  building  up  of 
complex  nuclei  from  simpler  ones,  and  its 
study  may  thus  be  expected  to  throw  much 
light  on  the  evolution  of  the  elements. 

The  nucleus  of  a  heavy  atom  is  un- 
doubtedly a  very  complicated  system,  and  in 
a  sense  a  world  of  its  own,  little,  if  at  all, 
influenced  by  the  ordinary  physical  and 
chemical  agencies  at  our  command.  When 
we  consider  the  mass  of  a  nucleus  compared 
with  its  volume  it  seems  certain  that  its 
density  is  many  billions  of  times  that  of  our 
heaviest  element.  Yet,  if  we  could  form  a 
magnified  picture  of  the  nucleus,  we  should 
expect  that  it  would  show  a  discontinuous 
structure,    occupied    but    not    filled    by    the 


minute  building  units,  the  protons  and  elec- 
trons, in  ceaseless  rapid  motion  controlled 
by  their  mutual  forces. 

Before  leaving  this  subject  it  is  desirable 
to  say  a  few  words  on  the  important  ques- 
tion of  the  energy  relations  involved  in  the 
formation  and  disintegration  of  atomic 
nuclei,  first  opened  up  by  the  study  of  radio- 
activity. For  example,  it  is  well  known 
that  the  total  evolution  of  energy  during  the 
complete  disintegration  of  one  gramme  of 
radium  is  many  millions  of  times  greater 
than  in  the  complete  combustion  of  an  equal 
weight  of  coal.  It  is  known  that  this 
energy  is  initially  mostly  emitted  in  the 
kinetic  form  of  swift  a  and  ^  particles,  and 
the  energy  of  motion  of  these  bodies  is  ulti- 
mately con\erted  into  heat  when  they  are 
stopped  by  matter.  Since  is  believed  that 
the  radioactive  elements  were  analogous  in 
structure  to  the  ordinary  inactive  elements 
the  idea  naturally  arose  that  the  atoms  of  all 
the  elements  contained  a  similar  concentra- 
tion of  energy,  which  would  be  available  for 
use  if  only  some  simple  method  could  be  dis- 
covered of  promoting  and  controlling  their 
disintegration.  This  possibility  of  obtain- 
ing new  and  cheap  sources  of  energy  for 
practical  purposes  was  naturally  an  alluring 
prospect  to  the  lay  and  scientific  man  alike. 
It  is  quite  true  that,  if  we  were  able  to 
hasten  the  radioactive  processes  in  uranium 
and  thorium  so  that  the  whole  cycle  of  their 
disintegration  could  be  confined  to  a  few 
days  instead  of  being  spread  over  thousands 
of  millions  of  years,  these  elements  would 
provide  very  convenient  sources  of  energy 
on  a  sufficient  scale  to  be  of  considerable 
practical  importance.  Unfortunately,  al- 
though many  experiments  have  been  tried, 
there  is  no  evidence  that  the  rate  of  dis- 
integration of  these  elements  can  be  altered 
in  the  slightest  degree  by  the  most  powerful 
laboratory  agencies.  With  increase  in  our 
knowledge  of  atomic  structure  there  has 
been  a  gradual  change  of  our  point  of  view 
on  this  important  question,  and  there  is  by 
no  means  the  same  certainty  to-day  as  a  de- 
cade ago  that  the  atoms  of  an  element  con- 
tain hidden  stores  of  energy.  It  may  be 
worth  while  to  spend  a  few  minutes  in 
discussing  the  reason  for  this  change  In 
outlook.  This  can  best  be  illustrated  by 
considering  an  interesting  analogy  between 
the  transformation  of  a  radioactive  nucleus 
and  the  changes  in  the  electron  arrangement 
of  an  ordinary  atom.     It  is  now  well  Icnown 


SEPTEMBER  28,  1923. 


THE  CHEMICAL  NEWS 


195 


that  it  is  possible  by  means  of  electron  bom- 
bardment or  by  appropriate  radiation  to  ex- 
cite an  atom  in  such  a  way  that  one  of  its 
superficial  electrons  is  displaced  from  its 
ordinary  stable  position  to  another  tem- 
porarily stable  position  further  removed 
from  the  nucleus.  This  electron  in  course 
of  time  falls  back  into  its  old  position,  and 
its  potential  energy  is  converted  into  radia- 
tion in  the  process.  There  is  some  reason 
for  believingf  that  the  electron  has  a  definite 
average  life  in  the  displaced  position,  and 
that  the  chance  of  its  return  to  its  original 
position  is  governed  by  the  laws  of  proba- 
bility. In  some  respects  an  '  excited  '  atom 
of  this  kind  is  thus  analogous  to  a  radio- 
active atom,  but  of  course  the  energy  re- 
leased in  the  disintegration  of  a  nucleus  is 
of  an  entirely  different  order  of  magnitude 
from  the  energy  released  by  return  of  the 
electron  in  the  excited  atom.  It  may  be 
that  the  elements,  uranium  anc!  thorium, 
represent  the  sole  survivals  in  the  earth 
to-<lay  of  types  of  elements  that  were  com- 
mon in  the  long  distant  ages,  when  the 
atoms  now  composing  the  earth  were  in 
course  of  formation.  A  fraction  of  the 
atoms  of  uranium  and  thorium  formed  at 
that  time  has  survived  over  the  long  interval 
on  account  of  their  very  slow  rate  of  trans- 
formation. It  is  thus  possible  to  regard 
these  atoms  as  having  not  yet  completed  the 
cycle  of  changes  which  the  ordinary  atoms 
have  long  since  passed  through,  and  that 
the  atoms  are  still  in  the  '  excited  '  state 
where  the  nuclear  units  have  not  yet 
arranged  themselves  in  positions  of  ultimate 
equilibrium,  but  still  have  a  surplus  of 
energy  which  can  only  be  released  in  the 
form  of  the  characteristic  radiation  from 
active  matter.  On  such  a  view,  the  pre- 
sence of  a  store  of  energy  ready  for  release 
is  not  a  property  of  all  atoms,  but  only  of 
a  special  class  of  atoms  like  the  radioactive 
atoms  which  have  not  yet  reached  the  final 
state  for  equilibrium. 

It  may  be  urged  that  the  artificial  dis- 
integration of  certain  elements  by  bombard- 
ment with  swift  a  particles  gives  definite 
evidence  of  a  store  of  energy  in  some  of  the 
ordinary  elements,  for  it  is  known  that  a 
few  of  the  hydrogen  nuclei,  released  from 
aluminium  for  example,  are  expelled  with 
such  swiftness  that  the  particle  has  a 
greater  inflividual  energy  that  the  a  particle 
which  causes  their  liberation.  Unfortu- 
nately, it  is  very  difficult  to  give  a  definite 


answer  on  this  point  until  we  know  more  of 
the  details  of  this  disintegration. 

On  the  other  hand,  another  method  of 
attack  on  this  question  has  become  im- 
portant during  the  last  few  years,  based  on 
the  comparison  of  the  relative  masses  of  the 
elements.  This  new  point  of  view  can  best 
be  illustrated  by  a  comparison  of  the  atomic 
masses  of  hydrogen  and  helium.  As  we 
have  seen,  it  seems  very  probable  that 
helium  is  not  an  ultimate  unit  in  the  struc- 
ture of  nuclei,  but  it  is  a  very  close  com- 
bination of  four  hydrogen  nuclei  and  two 
electrons.  The  mass  of  the  helium  nucleus, 
4.00  in  terms  of  0  =  16,  is  considerably  less 
than  the  mass  4.03  of  four  hydrogen  nuclei. 
On  modern  views  there  is  believed  to  be  a 
very  close  connection  between  mass  and 
energy,  and  this  loss  in  mass  in  the  syn- 
thesis of  the  helium  nucleus  from  hydrogen 
nuclei  indicates  that  a  large  amount  of 
energy  in  the  form  of  radiation  has  been 
released  in  the  building  of  the  helium 
nucleus  from  iis  components.  It  is  easy  to 
calculate  from  this  loss  of  mass  that  the 
energy  set  free  in  forming  one  gramme  of 
helium  is  large  even  compared  with  that 
liberated  in  the  total  disintegration  of  one 
gramme  of  radium.  For  example,  calcula- 
tion shows  that  the  energy  released  in  the 
formation  of  one  pound  of  helium  gas  is 
equivalent  to  the  energy  emitted  in  the  com- 
plete combustion  of  about  eight  thousand 
tons  of  pure  carl>on.  It  has  been  suggested 
by  Kddington  and  Perrin  that  it  is  mainly 
to  this  source  of  energy  that  we  must  look 
to  maintain  the  heat  emission  of  the  sun  and 
hot  stars  over  long  periods  of  time.  Calcu- 
lations of  the  loss  of  heat  from  the  sun  show 
that  this  synthesis  of  helium  need  only  take 
place  slowly  in  order  to  maintain  the  present 
rate  of  radiation  for  periods  of  the  order  of 
one  thousand  million  years.  It  must  be 
acknowledged  that  these  arguments  are 
somewhat  speculative  in  character,  for  no 
certain  experimental  evidence  has  yet  been 
obtained  that  helium  can  be  formed  from 
hydrogen. 

The  evidence  of  the  slow  rate  of  stellar 
evolution,  however,  certainly  indicates  that 
the  synthesis  of  helium,  and  perhaps  other 
elements  of  higher  atomic  weight,  may  take 
place  slowly  in  the  interior  of  hot  stars. 
While  in  the  electric  discharge  through 
hydrogen  at  low  pressure  we  can  easily  re- 
produce the  conditions  of  the  interior  of  the 
hottest  star  as  far  as  regards  the  energy  of 


196 


I'HE  CHEMICAL  NEWS. 


SEPTEMBER  28,  1923 


motion  of  the  electrons  and  hydrog^en  nuclei, 
we  cannot  hope  to  reproduce  that  enormous 
density  of  radiation  which  must  exist  in  the 
interior  of  a  g^iant  star.  For  this  and  other 
reasons  it  may  be  very  difficult,  or  even  im- 
possible, to  produce  helium  from  hydrogen 
under  laboratory  conditions. 

If  this  view  of  the  great  heat  emission  in 
the  formation  of  helium  be  correct,  it  is  clear 
that  the  helium  nucleus  is  the  most  stable  of 
all  nuclei,   for   an  amount  of  energy  conie- 
sponding  to  three  or  four  a  particles  would 
be  required  to  disrupt  it  into  its  components. 
In  addition,  since  the  mass  of  the  proton  in 
nuclei   is   nearly   1.000   instead   of  its   mass 
1.0072  in  the  free  state,  it  follows  that  much 
more  energy  must  be  put  into  the  atom  than 
will  be  liberated  by  its  disintegration  into  its 
ultimate  units.     At  the  same  time,  if  we  con- 
sider an  atom  of  oxygen,  which  may  be  sup- 
posed to  be  built  up  of  four  helium  nuclei  as 
secondary  units,  the  change  of  mass,  if  any, 
in  its  synthesis  from  already  formed  helium 
nuclei   is   so   small   that   we   cannot   yet    be 
certain  whether  there  will  be  a  gain  or  loss 
of      energy     by      its     disintegration      into 
helium     nuclei,     but      in     any      case      wc 
are    certain    that     the    magniture     of     the 
energy      will     be      much     less     than      for 
the     synthesis    of    helium    from    hydrogen. 
Our   information    on   this  subject  of  energy 
changes  in  the  formation  or  disintegration 
of  atoms  in  general  is  as  yet  too  uncertain 
and  speculative  to  give  any  decided  opinion 
on  future  possibilities  in  this  direction,  but 
I  have  endeavoured  to  outline  some  of  the 
main  arguments  which  should  be  taken  into 
account. 

I  must  now  bring  to  an  end  my  survey, 
I  am  afraid  all  too  brief  and  inadequate,  of 
this  great  period  of  advance  in  physical 
science.  In  the  short  time  at  my  disposal  it 
has  been  impossible  for  me,  even  if  I  had  the 
knowledge,  to  refer  to  the  great  advances 
made  during  the  period  under  consideration 
in  all  branches  of  pure  and  applied  science. 
I  am  well  aware  that  in  some  departments 
the  progress  made  may  justly  compare  with 
that  of  my  own  subject.  In  these  great 
additions  to  our  knowledge  of  the  structure 
of  matter  every  civilised  nation  has  taken  on 
active  part,  but  we  may  be  justly  proud  that 
this  country  has  made  many  fundamental 
contributions.  With  this  country  I  must 
properly  include  our  Dominions  overseas, 
for  they  have  not  been  behindhand  in  their 
contributions  to  this  new  knowledge.  It  is, 
I  am  sure,  a  matter  of  pride  to  this  country 


that  the  scientific  men  of  our  Dominions 
have  been  responsible  for  some  of  the  most 
fundamental  discoveries  of  this  epoch,  par- 
ticularly in  radioactivity. 

This  tide  of  advance  was  continuous  from 
1896,  but  there  was  an  inevitable  slackening 
during  the  War.  It  is  a  matter  of  good 
omen  that,  in  the  last  few  years,  the  old  rate 
of  progress  has  not  only  been  maintained 
but  even  intensified,  and  there  appears  to  be 
no  obvious  sign  that  this  period  of  great 
advances  has  come  to  an  end.  There  has 
never  been  a  time  when  the  enthusiasm  of 
the  scientific  workers  was  greater,  or  when 
there  was  a  more  hopeful  feeling  that  great 
advances  were  imminent.  This  feeling  is 
no  doubt  in  part  due  to  the  great  improve- 
ment during  this  epoch  of  the  technical 
metliods  of  attack,  for  problems  that  at  one 
time  seemed  unattackable  are  now  seen  to 
be  likely  to  fall  before  the  new  methods.  In 
the  main,  the  epoch  under  consideration  has 
been  an  age  of  experiment,  where  the  ex- 
perimenter has  been  the  pioneer  in  the 
attack  on  new  problems.  At  the  same  time, 
it  has  been  also  an  age  of  bold  ideas  in 
theory,  as  the  Quantum  Theory  and  the 
Theory  of  Relativity  so  well  illustrate. 

I  feel  it  is  a  great  privilege  to  have  wit- 
nessed this  period,  which    may    almost    be 
termed  the  Renaissance  of  Physics.      It  has 
been  of  extarordinary  intellectual  interest  to 
watch  the  gradual  unfolding  of  new  ideas 
and  the  ever-changing  methods  of  attack  on 
difficult    problems.       It   has    been    of   great 
interest,   too,  to  note  the  comparative  sim- 
plicity   of    the    ideas    that    has    ultimately 
emerged.      For  example,  no  one  could  have 
anticipated  that  the  the  general  relation  be- 
tween the  elements  would  prove  to  be  of  so 
simple  a  character  as  we  now  believe  it  to 
be.     Ft   is   an   illustration    of   the   fact    th;it 
Nature  appears  to  work   in  a   simple  way, 
and  that  the  more  fundamental  the  problem 
often  simpler  are  the  conceptions  needed  for 
its  explanation.      The  rapidity  and  certitude 
of  the   advance   in    this   epoch  have   largely 
j      depended  on  the  fact  that  it  has  been  pos- 
sible to  devise  experiments  so  that  few  vari- 
ables   were    involved.       For    example,    the 
study  of  the  structure  of  the  atom  has  been 
much    fr.rilitated   by   the   possibility   of   ex- 
amining the  effects  due  to  a  single  atom  of 
matter,  or,  as  in  radioactivity  of  X-rays,  of 
studying    processes   going   on    in    the   indi- 
vidual atom  which  were  quite  uninfluenced 
by  external  conditions. 


SEPTEMBER  28,  1923. 


THE  CflSMlCAL  KEWB. 


197 


In  watching-  the  rapidity  of  this  tide  of  ad- 
vance in  physics  I  have  become  more  and 
more  impressed  by  the  power  of  the 
scientific  method  of  extending  our  know- 
ledge of  Nature.  Experiment,  directed  by 
the  discipHned  imagination  either  of  an  indi- 
vidual, or  still  better,  of  a  group  of  indi- 
viduals of  varied  mental  outlook,  is  able  to 
achieve  results  which  far  transcend  the 
imagination  alone  of  the  greatest  natural 
philosopher.  Experiment  without  imagina- 
tion, or  imagination  without  recourse  to  ex- 
periment, can  accomplish  little,  but,  for 
effective  progress,  a  happy  blend  of  these 
two  powers  is  necessary.  The  unknown 
appears  as  a  dense  mist  before  the  eyes  of 
men.  In  penetrating  this  obscurity  we  can- 
not invoke  the  aid  of  supermen,  but  must 
depend  on  the  combined  efforts  of  a  number 
of  adequately  trained  ordinary  men  of 
scientific  imagination.  Each  in  his  own 
.special  field  of  inquiry  is  enabled  by  the 
scientific  method  to  penetrate  a  short  dis- 
tance, and  his  work  reacts  upon  and  influ- 
ences the  whole  body  of  other  workers. 
From  time  to  time  there  arises  an  illuminat- 
ing conception,  based  on  accumulated  know- 
ledge, which  lights  up  a  large  region  and 
shows  tlu'  connection  between  these  indivi- 
dual efforts,  so  that  a  general  advance 
follows.  The  attack  begins  anew  on  a 
wider  front,  and  often  with  improved  techni- 
cal weapons.  The  conception  which  led  to 
this  advance  often  appears  simple  and  ob- 
vious when  once  it  has  been  put  forward. 
This  is  a  common  experience,  and  the 
scientific  man  often  feels  a  sense  of  dis- 
appointment that  he  himself  had  not  fore- 
seen a  development  which  ultimately  seems 
so  clear  and  inevitable. 

The  intellectual  interest  due  to  the  rapid 
growth  of  science  to-day  cannot  fail  to  act 
as  a  stimulus  to  young  men  to  join  in 
scientific  investigation.  In  every  branch  of 
science  there  are  numerous  problems  of 
fundamental  interest  and  importance  which 
await  solution.  We  may  confidently  pre- 
dict an  accelerated  rate  of  progress  of 
scientific  discovery,  beneficial  to  mankind 
certainly  in  a  material  but  possibly  even 
more  so  in  an  intellectual  sense.  In  order 
to  obtain  the  best  results  certain  conditions 
must,  however,  be  fulfilled.  It  is  necessary 
that  our  universities  and  other  specific  insti- 
tutions should  be  liberally  supported,  so  as 
not  only  to  be  in  a  position  to  train  ade- 
(juately  young  investigators  of  promise,  but 


also  to  serve  themselves  as  active  centres 
of  research.  At  the  same  time  there  must 
be  a  reasonable  competence  for  those  who 
have  shown  a  capacity  for  original  investi- 
gation. Not  least,  peace  throughout  the 
civilised  world  is  as  important  for  rapid 
scientific  development  as  for  general  com- 
mercial prosperity.  Indeed,  science  is  truly 
international,  and  for  progress  in  many 
directions  the  co-operation  of  nations  is  as 
essential  as  the  co-operation  of  individuals. 
Science,  no  less  than  industry,  desires  a 
stability  not  yet  achieved  in  world  con- 
ditions. 

There  is  an  error  far  too  prevalent  to-day 
that  science  progresses  by  the  demolition 
of  former  well-established  theories.  Such  is 
very  rarely  the  case.  For  example,  it  is 
often  stated  that  Einstein's  general  theory 
of  relativity  has  overthrown  the  work  of 
Newton  on  gravitation.  No  statement 
could  be  farther  from  the  truth.  Their 
works,  in  fact,  are  hardly  comparable,  for 
they  deal  with  different  fields  of  thought. 
So  far  as  the  work  of  Einstein  is  relevant 
to  that  of  Newton,  it  is  simply  a  generalisa- 
tion and  broadening  of  its  basis;  in  fact, 
a  typical  case  of  mathematical  and  physical 
development.  In  general,  a  great  principle 
is  not  discarded  but  so  modified  that  it  rests 
on  a  broader  and  more  stable  basis. 

It  is  clear  that  the  splendid  period  of 
scientific  activity  which  we  have  reviewed 
to-night  owes  much  of  its  success  and  intel- 
lectual appeal  to  the  labours  of  those  great 
men  in  the  past,  who  wisely  laid  the  sure 
foundations  on  which  the  scientific  worker 
builds  to-day,  or  to  quote  from  the  words 
inscribed  in  the  dome  of  the  National 
Gallery,  '  The  works  of  those  who  have 
stood  the  test  of  ages  have  a  claim  to  that 
respect  and  veneration  to  which  no  modern 
can  pretend. ' 


[British  Association,  Liverpool,  1023.] 

RECTTOX    T.     PHYSIOLOGY. 

SYMBIOSIS    IN    ANIMALS    AND 

PLANTS. 

.\DnRK.ss  BY  Gkorge  H.  F.  Nuttall, 
M.D..   Ph.D..   So.D.,  F.R.S. 

The  ndflross  flonlt  with  Symbiofiis  in 
Lichens,  Root-nrxliiles  of  Leguminou'S 
Plants,  the  significnnce  of  Mycorhizn  in 
various  Plants,  and  Symbiosis  in  Animals. 

The  temj  "symbiosis"    denotes  a  oondi- 


198 


1?HE  CHEMICAL  NEWS. 


SEPTEMBER  28,  1923. 


tion  of  conjoint  life  existing  between  differ- 
ent organisms  that  in  a  var^'ing  degree  are 
benefited  by  the  partnership.  The  term 
"  symbiont,"  strictly  speaking,  applies 
equally  to  both  the  partners;  it  "has,  how- 
ever, come  to  be  used  also  in  a  restricted 
sense  as  meaning  the  microscopic  member 
or  members  of  the  partnership  in  contra- 
distinction to  the  piiysically  larger  partners 
which  are  conveniently  termed  the  "hosts" 
m  conformity  with  parasifcological  usage. 

The  condition  of  life  defined  as  symbiosis 
may  be  regarded  as  balancing  between  two 
extremes — complete  immunity  and  deadly 
infective  disease.  A  condition  of  perfect 
symbiosis  or  balance  is  realised' with  com- 
parative rarity  because  of  the  many  difficul- 
ties of  its  establishment  in  organisms  that 
are  either  capable  of  living  independently 
or  are  incapable  of  resisting  the  invasion  of 
organisms  imperfectly  adapted  to  com- 
munal life.  In  these  respects  the  conclu- 
sions of  Bernard  and  Magrou  in  relation  to 
plants  apply  equally  to  animals.  It  is  diffi- 
cult to  imagine  that  symbiosis  originated 
otherwise  than  through  a  preliminary  stage 
of  parasitism  on  the  part  of  one  or  other  of 
the  associated  organisms,  the  conflict  be- 
tween them  in  the  course  of  time  ending  in 
mutual  adaptation.  It  is,  indeed,  probable 
that  some  supposed  symbionts  may  prove 
to  be  parasites  on  further  investigation. 

In  perfect  symbiosis  the  associated  or- 
ganisms are  completely  adapted  to  a  life  in 
common.  In  parasitism  the  degree  of 
adaptation  varies  greatly;  it  may  approach 
symbiotic  conditions  on  the  one  hand,  or 
range  to  vanishing  point  on  the  other  by 
leading  to  the  death  of  the  organism  that  is 
invaded  by  a  highly  pathogenic  animal  or 
vegetable  disease  agent.  There  is  no  defi- 
nite boundary  between  symbiosis  and  para- 
sitism. The  factors  governing  immunity 
from  symbionts  or  parasites  are  essentially 
the  same. 

No  final  conclusions  can  a&  yet  be 
reached  regarding  the  function  of  sym- 
bionts in  many  invertebrate  animals  owing 
to  our  ignorance  of  the  physiological  pro- 
cesses in  the  associated  organisms.  The 
investigation  of  these  problems  is  one 
fraught  with  difficulties  which  we  must 
hope  will  be  surmounted. 

New  knowledge  is  continually  being 
acquired,  and  a  glance  into  new  and  even 
recent  publications  shows  that  symbionts 
have  been  repeatedly  seen  and  interpreted 
as  mitochondria  or  chromidia.  The  increas- 
ing number  of  infective    diseases  of  animals 


and  plants,  moreover,  which  have  been 
traced,  especially  of  recent  years,  to  appar- 
ently ultramicroscQpic  organisms,  cannot 
but  suggest  that  there  may  exist  ultra- 
microsoopic  symbionts. 

We  are  on  the  threshold  of  further  dis- 
coveries, and  that  a  wide  field  of  fruitful 
research  is  open  to  those  who  enter  upon  it. 
In  closing,  it  seems  but  fitting  to  express 
the  hope  that  British  workers  may  take  a 
more  active  part  in  the  elucidation  of  the  in- 
teresting biological  problems  that  lie  before 
us  in  the  study  of  symbiosis  and  the  allied 
subject  of  parasitism. 


[BiiiTisH  Association  for  the  Advance- 
ment OF  Science.     Liverpool,   1923.] 

SECTION  A.— MATHEMATICS  AND 

PHYSICS. 

ON  THE  ORIGIN  OF  SPECTRA 

(RECENT   PROGRESS). 

Address  by  Professor  J.  C.  McLennan, 

F.R.S.,  President  of  the  Section. 

I. — Introduction. 

The  problem  of  the  origin  of  spectra  is 
intimately  bound  up  with  that  of  the  con- 
stitution and  structure  of  atoms.  Models 
of  atoms  of  different  types  have  been  pro- 
posed from  time  to  time,  and  these  all  have 
served,  in  a  measure,  to  explain  some  at 
least  of  the  chemical,  optical,  and  mechani- 
cal properties  of  matter.  The  conception, 
however,  that  inspires  and  co-ordinates  the 
whole  of  modern  atomic  physics  in  so  far 
as  radiation  is  concerned  is  the  remarkably 
simple  atomic  model  of  Rutherford  and 
Bohr. 

According  to  this  model  the  neutral 
atom  consists  of  a  central  positively 
charged  nucleus  with  dimensions  of  the 
same  order  as  those  of  the  electron  itself 
(10-13  cm.),  and  surrounded  by  a  system 
of  electrons  whose  aggregate  negative 
charge  is  equal  in  amount  to  that  of  the 
positive  charge  carried  by  the  nucleus. 
The  atomic  number  gives  for  a  neutral 
atom  the  number  of  electrons  surrounding 
the  nucleus,  and  is  at  the  same  time  a 
measure  of  the  positive  electric  charge  car- 
ried by  the  latter. 

Rutherford  has  shown  that  the  electric 
field  due  to  the  charge  on  the  nucleus  is 
central,  and  that  it  follows  the  inverse 
square  law  practically  up  to  the  effective 
boundary  of  the  nucleus.     Close  to  the  nu- 


SElPTEMBEK  28,  1923. 


THE  CHEMICAL  NEWS. 


199 


cleus  the  electric  field  is  very  intense,  and 
therefore  sufficient  to  produce  those  le- 
markably  interesting  deflections  of  alpha 
rays  that  are  being  studied  so  widely  and 
so  successfully  at  the  present  time  by  the 
use  of  C.  T.  11.  Wilson's  beautiful  metho<l 
of  photographing  cloud  tracks. 

With  the  introduction  of  the  theory  of 
quanta  into  the  mechanics  of  the  atom  it 
became  possible  to  analyse  in  detail  the 
structure  of  atoms  and  to  make  quantita- 
tive comparisons  between  the  properties  of 
matter  and  those  deducible  from  the  differ- 
ent atomic  models.  In  the  develoipments 
that  have  taken  place  in  this  direction 
Niels  Bohr  has  been  the  leader;  but  very 
notable  and  important  contributions  to  the 
theory  have  been  made  by  Wilson,  Som- 
merfeld,  Ehrenfest,  Kramers,  Lande,  and 
others. 

Bohr,  in  his  theory,  supposes  that  each 
electron  in  an  atom  describes  a  central  or 
quasi-central  orbit  under  the  attraction  of 
the  nucleus  in  combination  with  the  fields 
of  the  other  extra-nuclear  electrons  present 
in  the  atom.  He  imposes,  moreover,  upon 
those  motions  of  the  electrons  in  atoms 
s'unethini^'  in  the  nature  of  a  quantum  cen- 
sorship. 

From  the  continuous  manifold  of  all 
conceivable  states  of  motion  that  may  be 
ascribed  to  an  atomic  system  there  exists  a 
definable  number  of  stationary  states  that 
possess  a  peculiar  stability,  and  that  are  of 
such  a  kind  that  every  permanent  change 
of  motion  within  the  system  must  involve 
a  comiplete  transition  from  one  stationary 
state  to  another. 

It  is  postulated  further  that  while  no 
radiation  is  emitted  by  the  atomic  system 
when  it  is  in  one  of  its  stationary  states, 
the  process  of  transition  from  one  station- 
ary state  to  another  is  accompanied  by  the 
omission  of  monochromatic  radiation  with 
a  frequency  given  by  the  relation 
V  h  =  E,  -  Ea, 

where  h  is  Planck's  constant  and  Ej  and  Ej 
are  the  values  of  the  energy  of  the  atom  in 
the  initial  and  final  stationary  states  be- 
tween which  the  transition  takes  place. 
Conversely,  it  is  to  be  understood  that  the 
absorption  by  the  atomic  system  of  radia- 
tion with  the  frequency  given  above  results 
in  a  transition  back  from  the  final  station- 
ary state  to  the  initial  one.  These  postu- 
lates, it  will  be  seen,  form  the  basis  of  an 
interpretation  of  the  laws  of  series  spectr.-i, 
for  the  most    general    of  these — the    com- 


bination principle  of  Ritz — asserts  that 
the  frequency  v  of  each  of  the  lines  in  the 
spectrum  of  a  selected  element  can  be  re- 
presented  by  the  formula 

V  =  T,  -  T„ 
where    T^    and  T2    are  two    spectral    terms 
taken  from  a  number  that  are  characteris- 
tic of  the  element  in  question. 

On  Bohr's  theory  the  interpretation  of 
the  law  of  Kitz  would  be  that  the  spectrum 
of  the  element  referred  to  must  originate 
in  transitions  between  stationary  states  for 
which  the  atomic  energy  values  are  ob- 
tained sunply  by  multiplying  by  Planck's 
constant  the  values  of  those  spectral  terms 
of  which  Tj  and  T^  are  types. 

This,  it  is  evident,  indicates  the  feasibil- 
ity of  establishing  a  connection  between 
the  series  spectrum  of  an  element  and  the 
constitution  and  structure  of  its  atoms. 
From  the  spectrum  of  the  element  the 
series  spectral  terms  can  be  selected  and 
evaluated,  and  these  values  when  multi- 
plied by  Planck's  constant  will  give  tlie 
various  energy  levels  within  and  associated 
with  the  atom  of  the  element.  As  the 
number  of  electrons  within  the  said  atom 
is  given  by  the  atomic  number  of  the  ele- 
ment, the  problem  becomes  one  of  assign- 
ing to  these  constituent  electrons  orbits  of 
a  size  and  form  that  will  provide  the  values 
of  the  energy  levels  determined  by  the 
spectral  series  terms. 

The  reciprocal  nature  of  this  relationship 
between  the  series  spectrum  of  an  element 
and  its  atomic  structure  will  be  evident.  In 
a  case  where  the  series  spectrum  of  an  ele- 
ment is  not  known  a  knowledge  of  it  may 
be  obtained  by  determining  the  energy 
levels  in  the  atoms  of  this  element  inde- 
pendently. This  can  be  done  after  the 
manner  of  Moseley  and  Franck  and  Hertz 
by  causing  atoms  to  emit  limited  portions 
of  its  spectrum  vmder  bombardment  by 
electrons  of  selected  speeds. 
Stationary  States — Quantum  Conditions. 

We  may  take  the  simple  case  of  an 
atom  of  hydrogen  which  consists  of  a  nu- 
cleus with  charge  +e  and  an  electron  with 
charge  ~c.  The  frequencies  of  the  series 
si>ectra  of  this  element  are  given  with  great 
accuracy  by  the  Balmer  formula 

/I             ^  V 

V  =  K      I I   .     .      (1) 

V  n"-  nli  / 

whore  n"  and  »'  are  two  integers  and  K  is 
the  Hydberg  constant.  All  the  spectral 
terms  are  of  the  form  K/n'*,  and  the  energy 


200 


THE  CHEMiCAL  l^BWS. 


SEPTEMBEll  28,  1923. 


corresponding  to  the  various  stationary 
states  of  the  atom  of  hydrogen  must  be 
given  by  Khjn^  with  n  having  all  possible 
integral  values. 

When  an  electron  describes  an  elliptic 
orbit  about  the  nucleus  of  a  hydrogen  atom 
the  major  axis  of  the  orbit  described  is  in- 
versely proportional  to  w  the  work  required 
completely  to  remove  the  electron  from  the 
field  of  the  nucleus.       The    major  axis    is 

c2 
given  by  2a  =  — .      If,  therefore,    we  take 
w 
e-n 
2a  =  —  we  have  determined    for  the  hy- 

K/i 
dix>gen  atom  a  set  of  clearly  defined  sta- 
tionary states  consisting  of  a  series  of  ellip- 
tical orbits  for  which  the  major  axis  takes 
on  discrete  values  proportional  to  the 
squares  of  the  whole  numbers.  Transitions 
from  one  to  another  of  such  a  set  of  sta- 
tionary states  will  suffice  on  Bohr's  theory 
to  account  for  all  the  lines  in  the  series 
sipectinim  of  atomic  hydrogen. 

Though  tlie  single  principal  quantum 
number  suffices  to  define  the  energy  levels 
for  the  atom  of  hydmgen,  the  introduction 
of  the  subordinate  quantum  numbers  7l^ 
and  n^  extended  the  basis  of  the  theory, 
and,  as  is  well  known,  led  to  developments 
by  Sommerfeld  of  profound  importance  in 
dealing  with  the  questi<Mi  of  the  fine  struc- 
ture of  spectral  lines. 

Bohr's  theory  of  the  origin  of  spectra  as 
it  exists  to-day  is  approached  from  a  some- 
what different  angle  from  that  given  above. 
Through  extensions  initiated  indepen- 
dently by  Wilson  and  by  Sommerfeld  the 
quantising  conditions  are  made  to  apply  to 
momentum  rather  than  to  energy,  and  in 
dealing  with  the  problem  of  the  stationary 
states  of  a  system  such  as  that  of  the  hy- 
drogen atom  the  angular  and  radial  mo- 
menta of  the  electron  in  its  orbit  are  both 
quantised. 

Quantum  Numbers  and  Their 
Significance. 

For  a  given  atomic  system  the  quantum 
numbers  define  the  stationary  states,  and 
the  energy  values  and  moments  of  momen- 
tum of  the  system  in  these  states.  More- 
over, they  define  the  kineiriatical  charac- 
ter of  the  electron  orbits  in  the  atomic  edi- 
fice, and  on  accc^nt  of  the  simple  relation 
connecting  the  values  of  spectral  terms  in 
the  series  spectrum  of  an  element  with  the 
energy  of  the  atom  of  this  element  in  its 
various  stationary  states,  they  define  these 


spectral  terms  and    enable  us  to    calculate 
their  values. 

In  the  simplest  possible  treatment  of  a 
system  such  as  that  of  the  atom  of  hydro- 
gen one  quantum  number  n  suffices  to  de- 
fine the  various  factors  just  mentioned.  In 
the  theory  of  the  fine  structure  of  the  spec- 
tral lines  of  hydrogen  two  quantum  num- 
bers n  and  k  were  required.  In  the  case  of 
a  series  spectrum  of  single  lines  two  quan- 
tum numbers  n  and  k  are  requisite  to  de- 
fine its  terms  and  the  orbits  corresponding 
to  them.  For  a  series  spectrum  consisting 
of  doublets,  triplets  or  multiplets,  three 
quantum  numbers  are  required,  n,  k  and  /, 
to  define  its  spectral  terms  and  the  corres- 
ponding electronic  orbits.  In  the  case  of 
the  resolution  of  a  spectral  line  by  the  ap- 
plication of  an  external  magnetic  field  a 
fourth  (quantum  number  m  is  necessary  in 
order  to  distinguish  the  stationary  states 
and  too  valuate  the  spectral  terms  corres- 
ponding to  the  Zeeman  components. 

In  spectroscoipy  it  has  become  custom- 
ary, in  order  to  distinguish  series  of  differ- 
ent kinds,  to  designate  singlet  systems  by 
the  use  of  capital  letters,  doublet  series  by 
Greek  letters,  and  triplet  series  by  small 
letters.     Thus : 

P  S  D  F  =  singlet  systems, 
a-  (T  8   f     =  doublet  systems. 
p    8    d    f  =  triplet  systems. 

In  the  same  way  it  has  become  custom- 
ary to  use  the  same  letters  to  designate  the 
spectral  terms  whose  differences  deter- 
mine the  frequencies  of  the  lines  in  a  series. 
As  example  we  may  cite  IS,  2S,  &c.,  Itt, 
2k,  &c.  ;  Id,  2d,  &c. ;  and  1/,  2/,  &c. 

Principles  of  Selection — The 
Correspondence  Principle. 

In  the  early  development  of  Bohr's 
theory  it  was  found  that  the  censorship 
imposed-  by  the  quantum  conditions  re- 
ferred to  above  were  not  sufficiently  dras- 
tic to  account  completely  either  for  the 
observed  complexity  of  the  fine  structure  of 
spectral  lines  originating  in  the  variation  of 
the  mass  of  an  electron  with  its  velocity  or 
for  the  observed  complexity  and  state  of 
polarisation  of  the  components  of  spectral 
lines  that  had  their  origin  in  the  applica- 
tion of  an  external  electric  or  magnetic 
field. 

To  make  up  for  this  deficiency  arbitrary 
Principles  of  Selection,  involving  such  fac- 
tors as  intensity  and  polarisation,  were 
brought  forward  by  Eubinowicz  and  by 
Sommerfeld,   that    found    immediate    and 


SEPTEMBER  28,  1923. 


THE  CHEMICAL  NEWS 


201 


remarkable  verifications  in  the  relativity 
fine  structure  of  the  Balmer  lines,  in  the 
Stark  effect,  in  the  Zeeniau  effect,  and  in 
the  spectra  of  rotation. 

Although  these  (principles  at  selection 
furnished  rules  that  have  served  as  useful 
guides  in  unravelling  the  intricacies  of 
various  types  of  spectral  resolution,  it  has 
all  along  been  recognised  by  the  proposers, 
as  well  as  by  others,  that  the  principles  as 
formulated  rested  upon  a  (l\namical  basis 
that  was  rather  limited  anj  scarcely  ade- 
quate. 

The  whole  matter,  how.vrr,  was  given 
an  entirely  new  orientation  and  an  en- 
hanced significance  by  Bolii  s  enunciation 
of  the  Correspondence  Principle. 

The  explicit  hypothesis  made  by  Bohr  in 
his  Corresipondence  Principle  is  that  what 
has  been  shown  above  to  be  true  necessar- 
ily for  very  great  orbital  periods  is  also 
sensibly  true  for  finite  ones  as  well.  To 
put  the  matter  in  anothc  rway — if  the  orbit 
described  by  an  electron  were  carried  out 
under  a  law  of  action  proi)ortional  to  the 
distance,  the  development  of  the  law  of 
motion  in  a  Fourier  series  would  permit  the 
use  of  a  fundamental  term  only.  The  Cor- 
respondence Principle  would  under  these 
conditi(His  demand  that  the  olectrcm  could 
pass  spontaneously  only  liom  the  nth 
quantum  orbit  to  the  n — 1  (luantuni  orbit 
immediately  below  it.  If  tin  so  conditions 
were  to  apply  in  the  case  of  the  hydr<^eu 
atom,  for  example,  it  would  limit  each 
series  to  a  single  wave- length,  and  the 
Balmer  series  would  be  reduced  to  its  first 
component. 

The  existence  of  series  made  up  of 
numerous  terms  shows  that  the  electronic 
orbits  of  an  atom  cannot  be  described 
under  a  central  force  varying  as  the  direct 
distance,  but  points  rather  in  the  direction 
of  the  orbits  being  ellipses  following  ap- 
proximately the  Keplerian  law. 

In  general,  if  the  electronic  motion  with- 
in an  atom  is  periodic  and  not  gimply  of  a  I 
pure  sinusoidal  character,  Fourier's  theory  ' 
shows  that  the  vibration  of  the  electron  is 
repn^sented  by  a  superposition  of  pure 
periodic  motions  that  arc  harmonics  of  a 
fundamental  one.  To  this  classical  notion 
therec  orresponds  in  the  theory  of  quanta 
the  notion  of  transitions  from  one  station- 
ary state  to  another  with  variations  in  the 
quantum  numl)er  no  longer  equal  to  one 
only.  If  the  Fourier  series  representing 
the  inotioncon  tains  effectively  an  harmo- 
nic of  rank,  1,    2,    3    .     .  .     or  m,  for  ex- 


ample, the  Correspondence  Principle  pos- 
tulatt-s  that  the  atom  can  be  the  seat  of 
transitions  corresiponding  to  differences  in 
the  characterising  quantum  number  of  1, 
2,  3  .  .  .  or  ?n.  If,  on  the  contrary, 
the  coefficient  of  a  term  in  the  Fourier 
series  under  consideration  is  small  or  equal 
to  zero,  this  signifies  that  the  probability 
of  corresponding  transitions  in  the  atom 
beccMnes  small  or  vanishes. 

The  Correspondence  Principle  co-ordi- 
nates every  transition  process  between  two 
stationai-y  states  with  a  corresponding  har- 
m(;nic  vibration  conii)onent  in  such  a  way 
that  the  probability  of  the  occun*ence  of 
the  tnmsition  is  dependent  on  the  ampli- 
tude of  this  particular  vibration. 

The  Genesis  of  Atoms. 

One  of  the  more  interesting  of  the  recent 
developments  of  Bohr's  theory  is  that 
which  concerns  the  genesis  of  atoms  of  dif- 
ferent types.  Bohr  has  put  fwward  the 
view  that  the  fundamental  process  that 
must  apply  consists  in  the  successive 
binding  of  electrons  one  after  another  by  a 
nucleus  originally  naked. 

On  this  view  the  electrons  as  they  are 
successively  bound  to  the  nucleus  take  up 
certain  final  and  definite  orbits  that  are 
characteristic  of  the  particular  atom 
selected  in  its  normal  state,  and  that  can 
to  a  first  approximation  be  specified  by  two 
quantum  numbers — njuiiely,  the  princiipal 
and  subordinate  quantum  numbers  n  and  k. 
This  Mu  auis  that  the  motion  of  each  single 
electron  of  the  atomic  system  can  be  ap- 
proximately described  as  a  plane  periodic 
motion  on  which  is  superimposed  a  uni- 
form rotation  in  the  plane  of  the  orbit. 

It  is  assumed  as  a  general  postulate  that 
during  the  binding  of  an  electron  by  a  nu- 
cleus the  values  of  the  quantum  numbers 
n  and  k  that  characterise  the  orbits  of  the 
earlier  bound  electrons  remain  unchanged, 
and  that  at  most,  apart  from  a  few  excep- 
tional cases,  the  addition  of  the  later  bound 
electrons  merely  results  in  slight  altera- 
tions in  the  orientations  in  sipace  of  the  or- 
bits of  the  electrons  already   bound. 

The  Fine  Structure  of  the  Balmer  Lines 
OF  Hydrogen. 
In  the  simplest  treatment  by  the  quan- 
tum theory  of  the  wigin  of  the  spectrum  of 
atomic  hydrogen  no  allowance  is  made  for 
a  variation  in  the  rna.ss  of  the  electron  with 
its  speed.  If  this  factor  be  taken  into  ac- 
o*>unt,  as  it  has  been  i)y  Sommerfeld,  it  is 
found  that  the    motion  of  the    electron  is 


202 


THE  CHEMICAL  NEWS. 


SEPTEMBER  28,  1023. 


reducible  to    a  motion    in  an  elliptic    orbit 
upon  which  is  imposed    a  slow  rotation  in 
its  own  plane    about  the  nucleus  as  focus. 
The  resulting  orbit    has  the  form    of  a  ro- 
sette, and  is  similar  to  that  shown  in  Fig.  o. 
In  this  treatment  the  chief  factor  in  dc- 
temiining  the  stationary  states  is  the  prin- 
cipal quantum  number  n,  but  the  subordi- 
nate quantum  number  k    is  also  contribu- 
tory.      The  former  practically   determines 
the  major  axis  and  the  period  of  the  ellipti- 
cal orbit,  while  the  latter  defines  the  para- 
meter   of    the    ellipse — i.e.,     the     shortest 
chord  through  its  focus.     The  subordinate 
quantum  number    k  also    determines^    the 
period  of  rotation  of  the  elliptic  orbit  in  its 
plane.      The  energy  corresponding  to  each 
stationary  state  is  in  the  main  determined 
by    the  value  of  the    quantum  number    n, 
but    stationary    states  determined    by  the 
same  value  of  n  are  characterised  by  energy 
values    that  vary    slightly     with     different 
values  of  the  quantum  number  k. 

Model  of  the  Atom  of  Helium. 

From  the  chemical  point  of  view,  helium 
is  considered  to  be  inert.  Of  all  atoms  it 
is  the  most  stable,  for  it  has  the  highest 
ionisation  potential,  namely,  24.5  volts.  A 
study  of  the  X-radiation  emitted  by  the 
elements  generally  makes  it  appear  inat 
the  configuration  we  assign  to  the  electro- 
nic orbits  in  helium  atoms  is  nuiintained 
intact  throughout  the  whole  of  the  remain- 
ing heavier  elements.  These  orbits,  as 
already  shown,  constitute  for  all  atoms  the 
K  X-ray  grouip  the  innermost  and  most 
stable  system.  For  these  reasons  it  is 
highly  desirable  that  a  model  of  the  atom 
of  helium  be  realised  possessing  high  sta- 
bility endowed  with  the  capacity  to  emit 
radiation  exhibiting  the  chai-acteristic  fea- 
tures of  the  helium  spectrum,  and  having 
energy  values  for  its  normal  and  temporary 
stationary  states  that  fit  in  with  the  ex- 
perimentally determined  values  of  its  ioni- 
sation, resonance,  and  other  critical  excita- 
tion potentials. 
The  Kossel-Sommerfeld  Displacemekt 
Law. 

In  arriving  at  his  scheme  of  atomic  orbits, 
Bohr  was  guided  by  the- view  that  the  fun- 
damental process  to  keeip  in  mind  was  that 
when  a  nucleus  originally  naked  acquired 
electrons  sufficient  in  number  to  neutralise 
its  charge,  it  did  so  by  binding  them  accord- 
ing to  a  programme  that  was  definite  and 
fixed  for  each  value  of  the  nuclear  charge. 

{To  be  continued.) 


ORGANIC  MERCURY  COMPOUNDS. 

Part  I. 

By  R.  F.  Hunter,  F.C.S. 

Some  few  days  ago  a  short  review  was 
given  of  our  present  knowledge  of  organic 
arsenic  compounds,  with  particular  refer- 
ence to  their  immense  value  in  dealing  with 
protozoal  diseases,  mainly  in  reference  to 
their  use  in  venereal  work.  This  leads  to 
the  consideration  of  organic  mercury  com- 
pounds owing  to  the  fact  that  it  has  become 
customary  in  recent  years  to  use  non-ionised 
mercury  compounds  in  conjunction  with 
aromatic  arsenicals,  such  as  salvarean.  In 
view  of  this,  no  apology  is  called  for  in  con- 
nection with  this  article,  which  is  intended 
only  as  the  roughest  of  outlines  on  a  subject 
which  has  been  attracting  the  attention  of 
some  of  our  leading  researchers  for  many 
years. 

The  study  of  organic  compounds  of  mer- 
cury carries  us  back  to  the  year  1843,  when 
A.  W.  von  Hofmann,  later  professor  of 
chemistry  at  the  Royal  College  of  Science, 
discovei'ed  a  mercuz*y  compound  which  he 
prepared  from  aniline  and  mercuric  chlor- 
ide, and  to  this  day  the  nature  of  the  afore- 
said compound,  prepared  as  above,  is  a 
matter  for  discussion.  Seven  years  later, 
Frankland  discovered  the  reaction  between 
alkyl  halides  and  mercury.  Four  years 
after  this  Strieker  prepared  ethyl  mercuric 
iodide. 

In  1868  mercury  dinaphthyl  was  dis- 
covered, followed  the  next  year  by  Wurtz's 
discovery  of  mercury  diphenyl.  Subse- 
quently Reynolds,  Cahours,  Meyer  and 
Michaelis  studied  various  compounds  and 
preparations.  1892  saw  the  publication  of 
Pesci's  researches  on  mercury  derivatives 
of  aromatic  amino  compounds  (aniline),  re- 
searches of  immense  importance.  In  1894 
researches  on  the  preparation  of  mercury 
derivatives  of  phenol  and  corresponding 
naphthalene  compounds  were  published  by 
Desesquelle,  and  three  years  later  Bamber- 
ger discovered  his  reaction  between  N2O3 
and  the  diphenyl  of  mercury.  Dimroth  the 
following  year  showed  that  mercuration  of 
aromatics  is  a  process  of  nitration  or  sulpho- 
nation. 

Of  more  recent  date,  we  have  had  such 
researches  as  Pesci's  action  between  mer- 
curic acetate  and  phthalic  acid,  'published  in 
1901,  the  ajpplication  of  Grignard's  reaction 
to  organic  mercury  compounds  by  Pfeiffer, 
1904,  the  study    of  mercury    derivatives    of 


SEPTEMBER  28,  1923. 


THE  CHEMICAL  NBWS. 


203 


nitrophenol  by  Hantrich  in  1908.  The  long 
and  academic  researches  of  Sohoeller  and 
Sehrauth  started  in  the  same  year  as  Han- 
trich's  results,  and  in  1913  the  electrolysis 
of  solutions  of  alkyl  mercuric  halides  in 
liquid  ammonia. 

It  will  be  advisable  to  nienti(m  the  chief 
methods  of  preparation  of  organic  mercury 
compounds.  We  can  enumerate  the 
methods  by  means  of  examples,  as  follows : 
(a)  CH3l  +  Hg^CH3  -  Hgl 

2  CH3  1+2  Na+Hg  ->CH3  HgCH,+Nal 

Sodium  Amalgam 

CH3  Mgl+Hg  I,->Ch3  Hgl+Hgl 
2  CH3  Mgl  +  Hgl.-^-CH,  Hg  CH,+2  MgL 

(b)  Preparation  by  means  of  mercuric 
oxides,  for  instance,  if  one  treats  alcohol 
with  mercuric  oxide  and  sfxlium  hydrate, 
ethane  hexamer  carbide,  CaHg,  O^H,,  is 
produced,  in  which  we  have  hydroj^en 
atoms  of  methyl  groups  replaced  by  mer- 
cury atoms.  Similar  cumpounds  can  lu' 
obtained  from  the  action  of  mercuric  oxide 
on  aldehydes  and  ketones. 

(c)  A  third  method  of  jmparation  is  to 
treat  unsaturated  compounds  with  mer- 
curic salts  in  aqueous  or  alcohoho  solution. 
Thus  from  ethylene 

CH  •  CH,  +  HgX,  +  H,0->- 

X  Hg  GH,  CH,  Uki 
and  from  acetylene  >/ 

CH  :  CH-VCl  Hg  -  CH  :  CH  CI      (Gl  Hg), 
CH.  CH  CI,->^(CI  Hg),  CH  Cl!0-> 
(CI  Hg),  C.  CHO. 

(d)  A  fruitful  reaction  has  been  that  of 
the  direct  action  of  mercuric  acetate  on  aro- 
matic compounds.  Thus  benzene  under 
ipre»sure  reacts  in  this  way 

C.  H.  +  Hg  (0  AcL-> 

d,  H,  Hg  0  Ac  +  H  O  .\e 
Certain  phenyl  5  pyrazolones  have  also 
been  mercuratod  by  this  method,  eome  three 
or  four  mercury  atoms  being  introduced, 
some  of  which  go  into  ben/.ene  nucleus  and 
some  of  which  go  into  the  pyrazolone  ring. 

(e)  The  last  reaction  we  shall  mention 
is  the  action  of  mercuric  chloride  solution 
on  aromatic  boric  and  sulfinic  acids,  when 
we  have,  for  instance  : 

C.H,  B(OH),  +  Hg  CI,  +  H,(>-> 

C  AHg  CI  +  H'ClT  H,  BO3 
C.H.SOjH  +  Hg  Cl,->- 

C.H.Hg  CI  +  SO,  +  H  CI. 

Before  proceeding  to  study    some  of  the 

mercury  compounds,  it  will  be  advisable  to 

pay  some  attention  to  the  general  properties 

and  reactions.     Whitmorc,  in  his  "Organic 


Compounds  of  Mercury,"  classified  the  re- 
actions under  the  headings  of 

(a)  Action  of  acids. 

(b)  Action  of  bases. 

(c)  Action  of  sulphides. 

(d)  Change  of  compounds  of  type  11  Hg  X 
to  R,  Hg. 

(e)  The  reverse  change  of  RaHg  to  R  Hg  X. 

(f)  Action  of  halogens. 

(g)  Action  of  halides  and  cyanides  of  metals. 
(h)  Action  of  halides  of  non-metals. 

(i)    Action  of  alkyl  and  aryl  halides. 
(j)    Action  of  acid  halides. 
(k)  Action  of  metals. 

Before  proceeding  to  examples  of  these, 
there  is  one  point  necessary  to  be  noted, 
and  that  is :  the  linkage  of  mercury  to  car- 
bon is  capable  of  far  greater  stability  than 
that  of  any  other  metal. 

For  instance,  a  compound  CH,  Hg  I,  un- 
like the  corresponding  magnesium  com- 
pound, is  not  acted  upon  by  water,  amines 
and  alcohols.  Also  organic  mercury  halides 
do  not  react  with  compounds  containing 
carbonyl.  Further,  the  mercury  in  organic 
compounds  reacts  differently  from  ionised 
mercury,  and  the  organic  mercury  halides 
can  give  double  decomposition  reactions  in 
the  same  way  as  inorganic  halides.  We 
now  consider  the  typical  reactions  under 
Dr.  Whitmorc 's  classification,  as  enumer- 
ated above : 

(a)  (CH),  Hg  +  H  CI  =  CH,  Hg  CI  +  CH, 
(C,H,),  Hg  +  CH,  CO,  ll^ 

C,H.  +  C,H;Hg  O  C  O  CH, 
C,H,  Hg  0  CO  CH,^ 

Hg  +  C.H^O  C  0  CH, 

(b)  Many  compounds  dissolve  in  solu- 
tions of  the  bases,  and  are  recovered  un- 
changed by  allowing  to  cool,  also  bases  do 
not  normally  break  the  carbon  mercury 
linkage.  Compounds  having  a  free  phenol 
or  C0,H  group  are  soluble  in  bfises.  Many 
mercury  compounds  of  these  types  readily 
yield  anhydrides,  or  rather  inner  salts, 
which  are  insoluble  in  water.  These  com- 
pounds dissolve  in  alkalis  yielding  solutions 
of  oorresi)onding  salts. 

(o)     The    "reactions    of  organic    mercury 
compounds    with    sulphides    vary    greatly. 
Thus  we  may  have  this  scheme  : 
R  HgX-XR  Hg),  S 

^R,Hg  +  Hg  S 

Certain  compounds,  such  as  alkyl  mer- 
curic iodide,  react  instantly  with  suljihides. 
Tt  has  been  noticed  that  the  compounds 
which  react  most  readily  are  those  in  whicli 
the  nu>rcury  atom  is  alpha  w.  carboxyl  or 
phenyl,  this  giving  the  alpha  atom  its  high 
reactivity. 


204 


TfiB  CHfiMlCAL  NEWS. 


SIJPTEMBER  28,  1923. 


The  beta  compounds  react  very  slowly,  if 
at  all,  and  in  most  cases  do  not  react  at  all. 

Thus  hydroxy  mercury  methyl  maluuic 
ester  is  unacted  upon  by  ammonium  sul- 
phide. 

(d)     Change  from  R  Hg  X  to  R  Hg  R. 

We  usually  have  to  carry  out  the  change 
in  presence  of  a  reagent;  we  can  represent 
it  as 

2RHgX  =  R^Hg  +  HgX,. 

The  a  thiophene  mercuric  iodides  under- 
go the  change  without  the  addition  of  re- 
agents. If  we  treat  the  chloride  with  Nal 
in  the  usual  way,  a  quantity  of  mercury  di- 
thionyl  crystallises  out,  and  the  iodide  is 
left  in  the  mother  liquors. 

The  iodides  which  change  t©  RaHg  com- 
pounds on  heating  are  a  thiophene  mercuric 
iodide  and  a  iodo  a  iodo  mercuric  thiophene. 
When  dealing  with  substituted  anilides  the 
action  of  an  excess  of  alcoholic  Nal  is  the 
best  method  for  ipreparing  RjHg  compound, 
thios  o.  acetoxy  mercuri  p.  bromodimethyl- 
aniline  yields  quantities  of  mercury  di- 
phenyl  on  refluxing  some  eight  hours  with 
potassium  iodide  or  sodium  iodide.  A  point 
of  interest  is  the  formation  of  a  mercury  di 
ft  phenylanhydro  hydracrylic  acid  from  an- 
hydro  a  hydroxy  mercuric  P  methoxy  hydro- 
cinnamic  acid  and  potassium  iodide. 

The  most  general  method  for  producing 
RjHg  compound  from  R  Hg  X  compounds 
is  by  the  sodium  thio  sulphate  method. 
The  reaction  has  been  made  use  of  in  the 
case  of 

(1)  Phenyl  mercury  compounds. 

(2)  Substituted  aniline    and  toluidine  mer- 
cury comipounds. 

(3)  Mercury  compounds  of  diphenylamine. 

(4)  Phenol  mercury  compounds. 

(5)  Aminobenzoio  acid  mercury  derivatives. 

(6)  Salicylic  ester  mercury  derivatives. 
Another  method  of  obtaining  the  change 

is  by  means  of  the  scheme : 
2  R  Hg  X  +  2  NaO  H  +  Na^  Sn  0,+R.,Hg-> 
Na.  Sn  O3  +  Hg  +  2  NaX  +  H^O, 
which  "has  been  applied  to  such  cases  as 
ethyl  mercuri  chloride  diepi  iodhydrine  di- 
mercuric  bromide.  Mercurated  nitro  and 
dinitro  benzoic  acid,  and  others. 

(e)     Reaction  between  RjHg  compounds 
and  mercuric  salts.     The  scheme  is : 
R^Hg  +  Hg  X,->-2  R  Hg  X. 
This  reaction    has    been    carried  out    with 
such  compounds  as 
Mercury  dimethyl ; 
, ,         diethyl ; 
,,  di  isoamvl ; 

,,         di  cyclohexyl; 


Cyclomercuri  pentamethylene ; 
Mercury  diphenyl ; 

, ,         di  benzyl ; 

,,         di  anilines; 

,,         di  anisoles; 

,,         di  phenc'toles ; 

di  thionyl  compounds, 
(f)     Reaction  with  halogens. 

The  scheme  is : 

R,  Hg  +  X2    =  R  X  +  R  Hg  X 
R  Hg  X  +  X,  =  R  X  +  Hg  X,. 
ihe  reaction    carried  out  in    such  cases    as 
mercury  diniethyl. 

Mercury  di  n  propyl ; 
,,  di  isobutyl; 
,,  di  isoamyl ; 
,,  di  octyl; 

also  with  lodornethyliiiercuric  iodide. 

Chloromethyl  mercuric  iodide; 

Diethyl  ether  dimercuric  iodide ; 

Di  epi  iodohydrine  di  mercuric  iodide; 

fi  Acetoxy  mej-curiethyl  methyl  ether. 

Mercury  bis  mono  chloruacetylene  reacts 
with  iodine  in  ethereal  solution  to  give 
chiorotri  iodoethylene. 

Mercury  bis  "^tri  chloroethylene  reacts 
with  chlorine  to  give  perchloroethane  and 
Hg  CI3.  Anhydro  hydroxy  mercuri  nitro 
acetic  ester  reacts  with  bromine  to  give  di- 
bromo  nitro  acetic  ester. 

Mercui7  diazo  acetic  ester  with  iodine 
gives  an  explosive  organic  compound. 

The  reaction  has  also  been  applied  in 
cases  of 

Penta  methylene  di  mercuric  iodide; 

Penta  methylene  di  mercuri  phenyl; 

Tolyl  mercuric  chlorides; 

Monomercurated  phenols ; 

Mercurated  nitro  phenols; 

Mercurated  benzoic  acid ; 

Mercurated  Salicylic  acid. 

Acetoxy  mercuric  iphenyl  glycine  ethyl 
ester. 

Mercurated  quaternary  ammonium  com- 
pounds. 

Mercurated  anthra  nilic  acid  and  mercury 
dinaphthyl. 

Mercurated  ft  naiphthol  carboxylic  acid. 
Also  mercurated  camphor  in  benzene  solu- 
tion of  iodine  gives  di  iodo  camphor,  which 
can  be  converted  into  a  quinone  of  camphor. 

Cineol  mercuric  iodide  reacts  with  iodide 
in  ether  to  give  a  liquid  iodide,  which  we 
l)e]ieve  to  be  cineol  iodide,  but  where  com- 
pr).sition  has  yet  to  be  proved. 

(g)  The  reaction.^  with  halides  and  cy- 
anides of  metals  are  indicated  by  the 
scheme  : 


SEPTEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


205 


R  Hg  X  +  KI  +  H.,0-^R  Hg  +  Hg  I3+KOH 
R  C  H  O  H  OH  (Hg  I)  CO,  K  +  KI 
-^►R  CH :  CH  CO2  K  +  Hg  I^  +  K  0  H,  , 
the  reaction  of  ioditUs  in  foimatiou  of 
R2Hg  compounds  having  had  previous 
treatment. 

The  reactions  above  are  clearly  those  of 
Hg  -  C  linkage  splitting. 

K  C  N  has  the  effect  of  stplitting  many 
C  -  Hg  linkages  which  are  unaffected  by 
K  I,  for  instance,  ethanol  mercuric  com- 
pounds react  with  K  C  N  yielding  CjH^  on 
warming. 

Tetra  aoetoxy  mercuri  di  acetone  hydrate 
reacts  with  K  CN  to  give  acetone. 

(h^  The  reaction  with  non-metallic 
halifles  is  worthy  of  mention. 

B  CI3,  for  instance,  reacts  giving  mercuri 
halides  and  compounds  of  type  R  B  Clj. 

P  Clj  reacts  with  mercury  dimethyl, 
yielding  methyl  mercuric  chloride. 

As  CI3  reacts  with  mercury  dipropyl  to 
give  tri  propylarsine,  thionyl  chloride  re- 
acts with  mercury  aromatic  compounds, 
giving  corresponding  aromatic  mercuric 
chloride. 

(i)  The  reaction  with  nlkyl  and  aryl 
halides  is  not  of  very  great  importance. 

Examples  are : 

Methylene  di  mercuric  chloride  reacts 
with  CjHjI  lo  give  methvl  mercuric  iodide 
at  140^ 

Mercury  diphenyl  heated  at  200°  with 
CjH^Brj  gives  iphenyl  mercuric  bromide. 

(j)  The  reaction  with  acid  halides  is 
likewise  not  very  important.  We  might 
mention  that  mercury  compounds  contain- 
ing amine  or  hydroxy!  groups  can  be  acetyl- 
ated  without  affecting  thi'  mercury,  and 
that  the  mercury  addition  pro^lucts  of  ethyl- 
ene compounds  are  capable  of  benzoylation. 

(k)  The  reaction  with  metals  is  well 
known,  for  instance,  sodium  reacts  with 
mercury,  dimethyl  and  diethyl,  to  give  cor- 
responding sodium  compounds. 

The  methods  of  preparation  and  the 
grneral  properties  an!  re.ictions  of  the  or- 
ganic mercury  compounds  having  been 
given  n  brief  review,  it  is  proposed  to  now 
study  some  of  the  more  important  typical 
compounds  in  some  detail,  following  more 
or  less  the  system  of  Whitmore,  which  ap- 
pears to  be  the  best  at  the  present  time. 


GENERAL    NOTES. 


STORES  REQUIRED  FOR  THE 
NETHE RT AN DS  COLONI A L 
GOVERNMENT  SERVICE. 
Mr.  R.  V.  Laming,  O.B.E,,  Commercial 
Secretary  at  The  Hague,    reports  that    the 
Kolonial  Etablissement,  2,  Westeraoksdijk, 
Amsterdam,    is  inviting  tenders  to  be  pre- 
sented by  1  o'clock  on  September  19  for  the 
suipply    and  delivery  of    various  goods,    in- 
cluding 700  K.G.  dyestuff,  ultramarine;  50 
K.G.  dyestuff,  "Kogelblauw"  (wash  blue); 
7,000  K.G.  carbonate  of  soda;    8,000  K.G. 
yellow  soap. 

The  conditions  of  tenders  and  deliveries 
are  contained  in  the  "Algemeene  Bepalin- 
gen  betreffende  de  aanschaffing  van  goede- 
ren  ten  behoeve  van  's  Lands  dienst  in  de 
Kolonien,"  a  copy  of  which  is  in  the  posses- 
sion of  the  British  Chamber  of  Commerce 
for  the  Netherlands  East  Indies,  Abbey 
House,  1,  Victoria  Street,  London,  S.W.I, 
who  have  expressed  their  willingness  to  al- 
low interested  British  firms  to  consult  it. 

Copies  of  the  specifications  (in  Dutch), 
which  also  contain  the  special  conditions  of 
tender,  may  be  consulted  by  British  firms 
on  applicaticm  to  the  Enquiry  Room,  De- 
partment of  Overseas  Trade,  35,  Old  Queen 
Street,  London,  S.W.I. 

I      The    possession    of    a    representative    in 
1  Holland  is  an  essential  condition  of  tender- 
ing, and  British    firms    not    locally    repre- 
sented should  apply    to  the  Department  of 
'  Overseas    Trade    for    the  names    of    likely 
agents  to  act  for  them  in  this  matter. 


CZECHO-SLOVAKIA'S  FOREIGN 
TRADE  IN  JULY. 

The  Officer  in  Charge  for  the  Commercial 
Secretary  at  Prague  informs  the  Depart- 
ment of  Overseas  Trade  that,  according  to 
the  official  figures  just  published  by  the 
State  Office  of  Statistics,  the  value  of  the 
Czecho- Slovak  exports  for  July  amounted 
to  1,008  million  crowns,  and  the  imports  to 
744  million  crowns,  thus  showing  a  balance 
of  264  million  crowns  in  favour  of  exports. 
The  exports  for  the  first  seven  months  of 
this  year  totalled  6,621  million  crowns,  and 
the  imports  4,816  millions,  an  excess  of 
1,704  million  of  crowns  of  exports  over 
imports. 


206 


THE  CHEMICAL  NEWS. 


SEPTEMBER  28,  1028. 


AUSTRALIA'S  FOREIGN  TRADE  FOR 
THE  YEAR  ENDED  30  JUNE,  1923. 

Mr.  S.  W.  B.  MciGegor,  H.M.  Senior 
Trade  Commissioner  in  Australia,  has  in- 
formed the  Department  of  Overseas  Trade 
that  the  statistics  of  Australian  trade  for 
the  year  ending  30  June,  1923,  show  that 
the  imports  were  £131,808,673,  as  com- 
pared with  £127,846,535  for  the  previous 
year,  a  decrease  of  £9,923,452. 

The  balance  of  trade  favourable  to  Aus- 
tralia in  1921-22,  amounting  to  £24,780,099. 
has  become  an  adverse  balance  of 
£13,895,590  in  1922-23. 

The  accumulation  of  Australian  funds  in 
London,  together  with  new  loan  money, 
has  had  a  stimulating  effect  on  imports 
and  some  reaction,  temporarily  unfavour- 
able to  British  trade,  must  be  expected. 

The  decrease  in  the  value  of  exports  in 
1922-23  is  largely  due  to  the  fall  in  the 
value  of  wheat,  which  accounts  for 
£20,136,000  of  the  decrease  as  compared 
with  1921-22.  The  increase  in  the  value  of 
wool  exported  was  £9,163,0(X). 

There  has  been  a  marked  increase  in  the 
value  of  imported  manufactured  apparel 
and  in  textiles  generally,  the  total  for  this 
class  being  £44,914,128  compared  with 
£34,149,710  in  1921-22.  Some  falling  off 
in  these  lines  of  trade  must  now  be  antici- 
pated. 

The  total  value  of  imports  of  metals, 
metal  manufactures,  and  machinery  was 
£35,195,931,  compared  with  £25,096,571 
in  1921-22,  of  which  chassis  for  motor  cars 
are  valued  at  £6,117,179,  compared  with 
£2,927,759  in  the  previous  year.  This  ex- 
traordinary increase  in  the  value  of  the  im- 
ports of  motor  cars  is  an  indication  of  the 
prosperty  of  Australia  generally,  and  a 
growing  feeling  that  a  motor  car  is  a  neces- 
sity for  the  ethciont  conduct  of  town  or 
country  avocations. 

Information  as  to  countries  of  origin  and 
destination  of  imports  and  exports  respec- 
tively will  not  be  available  for  several 
months. 


NOTICES  OF  BOOKS. 
Redwood  and  Eastlake's  Petroleuw 
Technologist's  Pochet-Book,  Revised  by 
A.  W.  E'astlake,  M.I.Min.E.,  A.M.I.'- 
Mech.E.  Pp.  546.  Second  Edition. 
London:  Charles  Griflfin  k  Co.,  T^td.. 
Exeter  Street,  Strand,  W.C.2.  1923. 
Price  15s, 


The  need  for  a  small  handy  work  of  re- 
ference on  petroleum  has  been  met  by  the 
publication,  in  1915,  of  this  pocket-book. 
Its  proved  usefulness  has  led  to  the  appear- 
ance of  a  second  and  revised  edition  by  Mr. 
Eastlake,  to  which  Sir  Thomas  H.  Hol- 
land, Vice-President  of  the  Institution  of 
Petroleum  Technologists,  etc.,  has  contri- 
buted a  Foreword. 

Chemists  and  technologists  may  be  re- 
minded that  the  volume  contains  much 
condensed  information  concerning  the  Geo- 
logy, Physics,  and  Chemistry  of  Petroleum. 
A  good  deal  of  space  is  devoted  to  produc- 
tion, which  is  followed  by  a  section  on  re- 
fining, transiport,  storage  and  testing.  In 
addition  to  statistical  tables,  weights  and 
measures,  there  is  also  a  miscellaneous 
section,  which  gives  a  list  of  the  Courses  of 
Instiniction  in  Petroleum  Technology  in 
various  centres;  an  inclusive  list  of  petro- 
leum periodicals;  Passport  Regulations; 
Numerals,  etc.,  in  eight  languages;  etc. 

Eight  small  but  useful  maps,  indicating 
the  sources  of  petroleum  and  other  deposits, 
are  contained  in  a  pocket  at  the  end. 

The  extent  of  the  revision  of  this  edition 
may  be  gauged  by  the  fact  that  over  100 
pages  have  been  added,  but  the  bulk  of  the 
book  is  the  same,  since  it  is  printed  on 
thinner  (but  very  good)  paper. 

The  book  reflects  credit  upon  all  con- 
cerned with  its  publication,  and  should 
prove  to  be  of  especial  value  to  petroleum 
technologists. 


The  Phase  Rule  and  ihe  Study  of 
Heterogeneous  Equilibria.  An  Introduc- 
tory Study,  by  A.  C.  D.  Rivett,  M.A., 
D.Sc,  Pp.  204.  Oxford:  At  the  Claren- 
don Press.     Price  10s.  6d.  net. 

The  theoretical  importance  of  the  Phase 
Rule  is  not  likely  to  he  under-estimated  so 
long  as  the  work  of  Professor  Ostwald  is 
remembered.  But  the  Phase  Rule  is  not 
only  important  from  the  theoretical  point 
of  view.  As  Professor  Rivett  writes:  "The 
study  of  heterogeneous  equilibria,  from  the 
standpoint  of  the  Phase  Rule  and  the  Prin- 
ciple of  Le  Chatelier  and  Braun,  is  one 
which  every  manufacturer  would  do  well  to 
require  from  his  chemical  staff.  Whether 
or  not  costly  evaporations  are  necessary, 
or    recrystaiiisations,     or    extractions    with 


I 


SEPTEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


20V 


solvents,  only  systematic  work  will  show. 
The  cost  of  such  investigation  will  usually 
be  slight  compared  with  the  gains  that  will 
be  Hiadc  possible."  In  view  of  these  facts, 
the  small  number  of  text-books  dealing 
with  the  subject  of  the  Phase  Rule  that  are 
available  seems  to  be  totally  incommen- 
surate with  the  imtportance  of  the  subject, 
and  a  very  hearty  welcome  is  therefore  ex- 
tended to  this  introductory  study  by  Pro- 
fessor Rivett,  which  it  is  hoped  will  tend  to 
stimulate  further  interest  therein. 

The  work  is  strictly  in  the  nature  of  an 
introduction,  and,  as  the  author  points  out, 
must  not  be  regarded  as  constituting  either 
a  treatise  or  a  book  of  reference;  which 
fact,  perhaps,  exjplains  the  absence  of  an  in- 
dex. The  author's  aim  has  been  to  discuss 
types  of  systems  which  may  be  met,  and 
ways  in  which  such  sy&tems  may  be  gra- 
phically represented,  and  to  giving  some 
examples  of  the  manner  in  which  conclu- 
sions of  practical  importance  may  be  de- 
duced. 

The  author  commences  his  treatment  of 
the  graiphical  representation  of  various  sys- 
tems by  means  of  three  dimensioned 
models,  from  which  the  more  usual  two  di- 
mensioned graphs  are  obtained  by  con- 
sidering special  planes.  This  is,  as  he 
points  out,  not  the  usual  procedure,  but, 
although  students  may  have  s(Mne  little 
difficulty  in  dealing  with  the  three  dimen- 
sioned models,  the  method  certainly  has 
the  advantage  of  being  more  logical  than 
the  more  customary  one.  In  fact,  the  logi- 
cal quality  of  Dr.  Rivett 's>  treatment 
throughout  calls  for  favourable  notice.  In 
the  Preface,  for  example,  he  calls  attention 
to  the  fact  that  when  we  are  dealing  with 
mixtures  containing  more  than  one  compo- 
nent there  cannot  be  equilibrium  between 
two  phases  unless  each  component  is  pre- 
sent in  (>ach  phase.  A.<*  concerns  solid 
iphases,  this  fact  is  (except  in  special  cases) 
usually  ignored,  owing  to  the  very  small 
solvent  power  of  solids.  Unless,  however, 
the  formation  of  solid  solutions  is  recog- 
nised, the  subject  cannot  be  presented  in 
such  a  way  that  conclusions  shall  strictly 
conform  throughout  to  the  basic  principles 
summarised  in  the  Phase  Rule. 

In  dealing  with  mixtures  of  three  com- 
ponents, considerable  use  is  made  of  Gibb's 
equilateral  triangle  diagrams.  There  is 
also  a  long  chapter  dealing  with  four  com- 
ponent systems,  and  another  containing 
dome  simple  thermo-dynamical  considera- 
tions relavent  to  the  subject. 

H.  S.  Rbdgrovk. 


Rhus  Dcniintitis  (Poison  Ivy)  —  Its 
Pathology  and  Clicmofhcrapy,  by  James 
B.  McNair.  Pp.  IX.  +  298.  The  Uni- 
versity of  Chicago  Press,  5750,  Ellis 
Avenue,  Chicago,  Illinois,  U.S.A.  $4.00 
(post  paid  $4.15). 

Of  all  cutaneous  eruptions  caused  acci- 
dentally by  plant  substances,  that  resulting 
from  the  poison  oak  or  poison  ivy  is  the 
most  common  in  North  America.  The  lack 
of  any  rational  treatment  for  this  common 
poisoning  has  led  JMr.  McNair  into  a  pro- 
tracted study  of  the  isolated  principle,  in 
the  hope  that  knowledge  of  its  characteris- 
tic properties  may  starve  as  a  basis  for  such 
treatment. 

From  a  general  botanical  description  of 
the  plants,  Hhus  Toxicodendron,  R.  radi- 
rans,  and  especially  R.  diversiloba,  which 
have  long  been  known  under  the  names  of 
poison  ivy  or  poison  oak,  it  is  shown  that 
the  fresh  sap  emulsion  from  the  resin 
canals  alone  is  dangerous.  All  other  parts 
of  the  plant  have  been  shown  to  be  non- 
toxic. The  poisonous  proiperties  also  de- 
crease as  the  fruit  ripens. 

The  author  has  traced  the  chemical  in- 
vestigations into  the  nature  of  the  poison- 
ous principle  —  lobinol  —  which  has  been 
shown  to  contain  only  carbon,  hydrogen, 
and  oxygen,  and  which  is  a  phenolic  com- 
pound. An  exact  knowledge  of  its  chemi- 
cal nature  is  of  supreme  importance  if  a 
rational  remedy  for  its  action  is  to  be 
sought.  The  substance  was  originally  re- 
garded as  a  volatile  alkaloid,  and  later  as 
an  acid  until  the  absence  of  any  carboxyl 
group  was  proved.  Consequently  the  early 
remedies  adopted  were  quite  empirical. 

The  volume  contains  much  interesting 
matter  relating  to  pathological  cases,  im- 
munity, and  the  chemo-therapy  of  the  sub- 
ject, and  concludes  with  a  comprehensive 
bibliography  of  botanical,  chemical  and 
pathological  references. 


We  have  received  a  copy  of  the 
Announcements  of  the  Northamipton  Poly- 
technic Institute,  giving  particulars  of  the 
courses  of  instruction  in  the  different 
branches  of  Scientific  and  Engineering  In- 
dustries. 

On  this  occasion  the  new  issue  deals 
with  the  evening  work  only.  The  well- 
known  work  dealt  with  in  the  day  section 
of  the  Announcements  will  be  practically 
the  same  as  last  session,  there  being  only 
small  changes  in  details  of  syllabuses 
which  can  be  made  as  the  work  develops. 


208 


THE  CHEMICAL  NEWS. 


SEPTEMBER  28,  1023. 


The  whole  of  the  work  includes  day  and 
evening  courses  in  Engineering  (Civil, 
Mechanical  and  Electrical),  in  Optical  En- 
gineering and  Applied  Optics,  and  in  Horo- 
logy. The  Engineering  courses  include 
sub-sections  in  Automobile  work,  Aeronau- 
tics, and  Eadio-Telegraphy.  In  addition 
there  are  evening  courses  in  Electro- 
chemistry, Metallurgy,  and  Domestic  Eco- 
nomy and  Women's  Trades.  The  classes 
for  the  day  courses  commence  on  Monday, 
October  1,  and  those  for  the  evening 
courses  on  Monday,  September  24.  Enrol- 
ments for  the  latter  commenced  on  Mon- 
day, the  17th  inst. 

Full  details  of  the  syllabuses  and  the 
equipment  are  also  given. 

PUBLICATIONS    RECEIVED. 

The  U.S.  Department  of  the  Interior, 
Bureau  of  Mines,  has  just  issued  the  fol- 
lowing pamphlets  : 

Ez'plo.sives — Their  Materials,  Constitu- 
tion and  Analysis,  by  C.  A.  Taylor  and 
Wm.  H.  Rinkbnbach.     Pp.  XI.  +  188. 

Progress  of  Investigations  on  Liquid- 
Oxygen  Explosives,  by  S.  P.  Howell,  J. 
W,  Paul  and  J.  L.  Sherrick.  Pip.  VII.  + 
91. 

Anhydrous  Aluminium  Chloride,  by  Oli- 
ver C.  Ralston.     Pp.  IV.  +  38. 

Fires  in  Steamship  Blinker  and  Cnrqo 
Coal,  by  H.  H.  Stoek.     Pp.  IV.  +51. 

The  Motor  Gasoline  Surveys  of  1920  and 
1921  (A  sequel  to  Bulletin  191),  by  N.  A. 
C.  Smith.     Pp.  41. 

Mine  Rescue  Standards — A  Tentative 
Study,  prepared  by  a  Committee  appointed 
at  the  International  Mine  Rescue  Stand- 
ardisation Conference,  September,  1921. 
Pp.  IV.  +  43. 

Permissible  Explosives,  Mining  Equip- 
ment and  Apparatus  approved  prior  to 
January  1,  1923,  by  S.  P.  Howell,  L.  C. 
Ilsley,  D.  J.  Parker  and  A.  C.  Fieldner. 
Pp.  22. 

Sodium  Sulphate  :  Its  Sources  and  Uses, 
by  Roger  C.  Wells.     Pp.  IV.  +  43. 

Geology  and  Ore  Deposits  of  the  Creede 
District,  Colorado,  by  Wm.  H.  Emmons 
and  Esper  S.  Larsen.     Pp.  IX.  +  198. 

The  Commercial  Granites  of  Neiv  Eng- 
land, by  T.  Nelson  Dale.    Pp.  XV.  +  488. 

The  Kotsina-Kuskulana  District,  Alaska, 
by  Fred  H.  Moffit  and  J.  B.  Mertie,  Jr. 
Pp.  VII.  +149. 

Ilsemannite  at  Ouray,  Utah,  by  Frank 
L.  Hess.     Pp.  16. 


Mineral  Resources  of  the  United  States, 
1920— Part  I. 

Mineral  Resources  of  the  United  States 
in  1920 — Introduction,  by  G.  F.  Loughlin. 
Pp.   15oa. 

Coke  and  By-products  in  1921,  by  R.  S. 
McBride.     Pp.  444. 

Peat  in  1922,  by  K.  W.  Cottrkll.  Pp.  6. 

Surface  Waters  of  Wyoyning  and  Their 
Utilisation,  by  Robert  Follansbee.  Pp. 
X.  +  331. 

Geology  and  Ground-ivater  Resources  of 
Sacramento  Valley,  California,  by  Kirk 
Bryan.     Pp.  XI.  +  285. 

The  Industrial  Utility  of  Public  Water 
Supplied  in  the  United  States,  by  W.  D. 
Collins.     Pp.  59. 

Comparative  Tests  of  By-Product  Coke 
and  Other  Fuels  for  House-Heating  Boilers, 
by  Hhnuy  Kreisinger,  John  Blizard,  H.' 
W.  Jarrktt  and  J.  J.  McKitterick.  Pp. 
21. 

Tests  of  Low-Grade  and  Complex  Ores 
in  Colorado,  by  Will  H.  Coghill  and  CO. 
Anderson.     Pp.  67. 


t'His  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chancecy  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and   Designs  can  be  obtained  gratuitously. 

Latest  Patent   Applications. 
2216&-Beckett,  E.  G.— Production     of    anthraqui- 

none  derivatives.    Sept.  3. 
2262.5— Helbronner,  A. — Manufacture  of  chromates, 

etc.    Sept.  8. 
22429 — Keller,  A. — Manufacture  of  sulpliurio  acid. 

Sept.  6: 
22447 — Tokalon,  Ltd. — Manufacture     of  oleo  stear- 

ate  or  glyceryl.    Sept.  6. 

Specifications  Published  this  Week. 
175987 — Silica  Gel  Corporation. — Process  of  re- 
covering liquid  solutes  from  non-aqueous 
solutions. 
202664-Saltrick,  W.  A.— Manufacture  of  iron- 
cliromium  alloys. 
Alkali  thin  sulphates,  carbonates,  and  sulphocy- 
anides. — Liquors  containing  alkali  thiosulphatos 
and  other  loss  soluble  alkali  salts  such  as  carbon- 
ates, which  may  be  products  of  gas-i>urifying  pro- 
cesses such  as  those  described  in  Specifications 
169,996  and  170,572,  are  evaporated  until  the  boil- 
ing point  roaches  120°  ('.  at  atmospheric  pressure, 
when  the  salts  such  as  alkali  carbonates  separate, 
and  the  crystals  are  removed  in  a  centrifugal 
apparatus.  The  solution  is  then  cooled  to  obtain 
crystals  of  thiosulphate.  The  mother  liquor  may 
Ije  further  concentrated  to  obtain  a  second  crop  of 
thiosulphate  crystals;  the  final  mother  liquor  con- 
tains sulphocyanides.  The  thiosulphate  crystals 
are  washed  and  recrystallised,  the  mother  liquor 
being  returned  to  the  evaporator. 

Messrs,  Rayner  &  Co.  will  o))tain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each. 


OCTOBER  5,  1928. 


THE  CHEMICAL  NEWS. 


209 


THE   CHEMICAL  NEWS, 

VOL.  CXXVII.      Ko.  3312. 

[British  Association  for  the  Advance- 
ment OF  Science:  Liverpool,  1923.] 

SECTION  B— CHEMISTRY. 

SOME   ASPECTS    OF  THE    PHYSICAL 

CHEMISTRY    OF    INTERFACES. 

By  Professor  F.  G.  Donnan,  C.B.E., 
F.R.S.,  President  of  the  Section. 

It  was  at  the  last  meeting  at  Liverpool, 
in  1896,  that  I  first  had  tlie  honour  of  at- 
tending" a  gathering  of  the  P»iitish  Associa- 
tion. On  that  occasion  Dr.  l>udwig  Mond, 
F.R.S.,  wa.H  President  of  Section  B,  and  I 
shall  never  forget  the  interest  and  pleasure 
I  felt  in  listening  to  the  AcMress  of  that 
great  master  of  science  and  scientific 
method.  Little  did  I  dream  that  in  1923  1 
should  have  the  honour  and  privilege  of 
occupying  the  Chair  of  Section  B  at  Liver- 
pool. 

Looking  back  on  the  Liverpool  Meeting 
of  1896,  one  can  say  now  that  it  came  at 
the  dawn  of  a  new  era  in  the  development 
of  physico-chemical  science.  The  X-rays 
had  just  hern  discovered  by  Rontgen.  Per- 
rin  had  proved  experimentally  (1895)  that  a 
negative  electric  charge  was  associated  with 
the  cathode  rays  and  had  surmised  that 
these  so-called  "rays"  were  constituted  by 
electricity  in  motion,  thus  corroborating 
('rookos'  brilliant  views  of  a  decade  earlier 
and  demonstrating  that  Lenard  was  wrong. 
Sir  J.  J.  Thorn- on  had  just  begun  that 
siplendid  series  of  researches  which  re- 
suIUmI  not  only  in  the  complete  elucidation 
of  the  nature  of  the  cath<xle  "  rays,"  but 
also  in  the  discovery  of  the  negative  elec- 
tron as  a  constant,  imiversal,  and  funda- 
mental constituent  of  all  matter. 

The  discovery  of  the  chemically  inert  ele- 
mentary gases  by  Raleigh  and  Ramsay  had 
begun  in  1894.  and  the  series,  of  investiga- 
tions which  finally  led  to  the  recognition  of 
the  radio-active  transformations  of  atoms 
and  to  the  di^scovery  of  the  nature  and  con- 
stitution of  the  atom  itself,  were  jiust  begin- 
tving.  During  the  last  twenty-five  years 
the  influence  of  these  discoveries  on  chemi- 
cal Hoienco  has  been  enormous.  There  has 
come  about  a  fresih  reimion  of  physics  and 
chemistry,  somewhat  analogous  to  that 
which  occurred    in  the  days    of  Volta    and 


Davy.  During  the  two  decades  preceding 
1896,  physical  science  had  been  largely 
concerned    with    the     phenomena    of     the 

ether,"  with  electric  and  magnetic  fields, 
electromagnetic  waves,  and  the  identifica- 
tion of  light  and  other  forms  of  radiant 
energy  as  electromagnetic  phenomena. 
Now  that  the  physicists  have  brought  phy- 
sical science  back  to  the  close  and  intimate 
study  of  matter,  physics  and  chemistry 
have  come  together  again,  and  the  old  and 
hom<^eneous  science  of  "natural  philoso- 
phy" has  been  reconstituted.  It  is  time 
that  the  walls  which  divide  our  chemical 
and  physical  laboratories  were  broken 
down,  and  that  the  young  men  and  women 
who  come  to  our  Universities  to  study  phy- 
sics or  chemistry,  should  study  the  facts 
and  principles  of  a  fundamental  science 
which  includes  both. 

In  recent  years  a  great  deal  of  attention 
has  been  paid  to  the  phenomena  which 
occur  at  the  surfaces  or  interfaces  which 
separate  different  sorts  of  matter  in  bulk. 
During  the  last  quarter  of  the  nineteenth 
century,  both  J.  Willard  Gibbs  and  J.  J. 
Thomson  had  shown  the  peculiar  nature  of 
these  interfacial  or  transitional  layers. 
Things  could  happen  in  these  x-egions  which 
did  not  occur  in  the  more  homogeneous 
and  uniform  regions  well  inside  the  volume 
of  matter  in  bulk.  Such  happenings  might, 
if  they  could  be  investigated,  reveal  mole- 
cular or  atomic  peculiarities  which  would 
bo  imdetectable  in  the  jostling  throng  of 
individuals  inside.  A  surface  or  surface 
layer  represents  a  sort  of  thin  cross  section 
which  can  be  probed  and  examined  much 
more  readily  than  any  part  of  the  inside 
bulk.  It  is  indeed  only  within  compara- 
tively recent  years  that  the  X-rays  have 
provided  a  sufficiently  fine  probe  for  exam- 
ining this  bulk  in  the  case  of  crvstalline 
matter. 

In  the  theories  of  Laplace,  Gauss,  and 
Pois«on,  the  field  of  force  surrounding  an 
attracting  element  or  molecule  was  re- 
garded as  essentially  uniform  in  its  spatial 
relations,  i.e.,  the  equipotential  surfaces 
wen'  regarded  as  concentric  sipheres  with 
the  molecule  as  a  small  element  at  the 
centre.  The  molecules  were  thought  of  as 
prvssesfiing  what  one  might  call  a  very 
rounded  and  somewhat  monotonous  "phy- 
sical" character  as  regards  their  fields  of 
force.  In  recent  years  our  views  have 
undergone  a  radical  transformation.  The 
field  force  surrounding  a  molecule  may  be 
\ery    "  irregular,"    and  specially   localised 


210 


THE  CHEMICAL  NEWS. 


OCTOBER  5,  1923. 


around  oei*tain  active  or  "polar"  groups. 
Its  region  of  sensible  magnitude  may  be 
very  variable  and  relatively  small  compared 
with  molecular  dimensions.  The  chemical 
constitution  of  the  molecule  is  now  regarded 
as  determining  the  varying  nature,  of  the 
field  of  force  surrounding  it,  so  that  parts  of 
the  molecule  possessing  high  "  residual 
chemical  affinity  "  give  rise  to  specially 
powerful  regions  of  force.  In  this  way  the 
older  "physical"  theories  of  cohesion 
according  to  central  forces  with  uniform 
orientation  have  been  to  some  extent  re- 
placed, or  at  all  events  supplemented,  by 
"chemical"  theoriesi  according  to  which  the 
attractive  force-fields  are  highly  localised 
round  active  chemical  groups  and  atoms, 
are  relatively  minute  in  range,  and  can  be 
saturated  or  "neutralised"  by  the  atoms  or 
groups  of  neighbouring  or  juxtaposed  mole- 
cules. 

Dr.  W.  B.  Hardy  has  been  the  chief 
pioneer  in  the  development  of  these  newer 
theories,  having  been  led  thereto  by  his  re- 
searches on  surface  tension,  surface  films, 
composite  Uquid  surfaces  and  static  friction 
and  lubrication. 

His  ideas  are  clearly  expressed  in  the  fol- 
lowing-:  "  If  the  field  force  about  a  mole- 
cule be  not  symmetrical,  that  is  to  say,  if 
the  equipotential  surfaces  do  not  form 
spheres  about  the  centre  of  mass,  the  ar- 
rangement of  the  molecules  of  a  pure  fluid 
must  be  different  at  the  surface  from  the 
purely  random  distribution  which  obtains 
on  the  average  in  the  interior.  The  in- 
wardly directed  attractive  force  along  the 
normal  to  the  surface  will  orientate  the 
molecules  there.  The  surface  film  must 
therefore  have  a  characteristic  molecular 
architecture,  and  the  condition  of  minimal 
potential  involves  two  terms — one  relating 
to  the  variation  in  density,  the  other  to  the 
orientation  of  the  fields  of  force."     (1913.) 

These  conclusions  have  been  confirmed 
by  W.  D.  Harkins,  who  has  found  that  in 
the  case  of  very  many  organic  liquids  the 
"adhesional  work"  towards  water  is  greatly 
increased  by  the  presence  of  oxygen  atoms 
(as  in  alcohols,  acids,  and  aldehydes).  The 
very  symmetrical  halogen  derivatives,  CCl^ 
and  CjH^Brg,  give  markedly  low  values  for 
their  adhesional  work  towards  water,  and 
that  in  the  case  of  unsymmetrical  mole- 
cules, the  adhesional  work  towardsi  water  is 
determined  by  the  presence  of  certain  active 
atoms  or  atomic  groups. 

The  question  of  the  orientation  of  mole- 
cules at  the  surfaces  of  liquids  has  been 
grently  extended  by  a  study  of  the  extreme- 


ly thin  and  invisible  films  formed  by  the 
primary  spreading  of  oily  substances  on  the 
siurface  of  water.  In  a  continuation  and 
development  of  the  work  of  Miss  Tockels, 
the  late  Lord  Rayleigh  showed  many  years 
ago  that  when  olive  oil  forms  one  of  these 
invisible  films  on  water,  there  is  no  fall  in 
surface  tension  until  the  surface  concentra- 
tion reaches  a  certain  very  small  value.  He 
made  the  highly  interesting  and  important 
suggestion  that  this  concentration  marks 
the  point  where  there  is  formed  a  con- 
tinuous layer  just  one  molecule  thick.  This 
work  was  repeated  and  extended  by  H,  De- 
vaux  and  A-.  Marcelin,  who  sliowed  the 
correctness  of  his  suggestion  that  the  pri- 
mary film  oonsists  of  a  unimolecular  layer. 
It  appears,  however,  that  the  fall  in  surface 
tension  which  he  ascribed  to  the  building 
up  of  a  bimolecular  layer,  is  due  to  the 
closer  packing  of  the  molecules  of  the  uni- 
molecular layer. 

Let  us  now  consider  another  type  of  for- 
mation of  surface  layers  at  the  surfaces  of 
liquids — namely,  the  case  where  a  sub- 
stance dissolved  in  a  liquid  concentrates 
preferentially  at  the  liquid-air  or  liquid- 
va^pour  interface.  Gibbs,  and  later  J.  J. 
Thomson,  have  s^hown  that  if  a  dissolved 
substance  (in  relatively  dilute  solution) 
lowers  the  surface  tension,  it  will  concen- 
trate at  the  surface.  That  such  a  phenome- 
non actually  occurs  has  been  qualitatively 
demonstrated  in  the  experiments  of  D.  H. 
Hall,  J.  von  Zawidski,  and  F.  B.  Kenrick 
and  C.  Benson,  by  the  analysis  of  foams 
and  froths.  In  1908  S.  R.  Milner  used  the 
same  method  in  the  case  of  aqueous  solu- 
tions of  sodium  oleate,  and  arrived  at  a 
mean  value  of  1.2x10-"  gram  mols.  ex- 
cess concentration  per  sq.  cm.  of  surface. 
Now,  in  the  case  of  dilute  solution,  we  can 
calculate  q,  the  amount  concentrated  or 
"adsorbed"  ^n  the  surface  per  sq.  cm.  (ex- 
cess surface  concentration)  I  y  making  use 
of  the  equation  of  Gibbs, 

dy 
q  = 

dn 
where  y  =  surface  tension  and  fx  =  chemi- 
cal potential  of  the  adsorbed  substance  in 
the  bulk  of  the  solution.  Writing  /x  =  RT 
log  a  -t-  k,  where  a  =  "activity"  of  the  so- 
lute, and  /r  is  a  quantity  dependent  only  on 
the  temperature  and  nature  of  the  solute 
and  solvent,  d/x.  =  H  T  d  log  a,  and  so 
Gibbs'  equation  can  be  written  in  the  form 
■  1         dy 

RT  d  log  a 


OCTOBER  5,  1923. 


THE  CHEMICAL  NEWS. 


21] 


If  for  very  dilute  solutions  (or  "ideal"  solu- 
tions') we  can  write 

1       dy  c  dy 

KT  d  log  c  RT  dc 

In  this  way  Milner  has  calculated  from 
Whatrnough's  data  for  aqueous  solutions  of 
acetic  acid  that  the  "saturation"  value  of 
q  Is  3.3x10-'"  mols.  per  sq.  cm.,  from 
which  it  follows  that  the  aria  per  molecule 
in  the  surface  is  50  x  10-'*  sq.  cm.  In  a 
similar  manner,  Langmuir  has  calculated 
from  B.  de  Szyszkowski's  rial  a  for  aqueous 
solutions  of  proipionic,  butyric,  valeric,  and 
caproic  acids  that  tlie  surface  area  per 
molecule  adsorbed  in  the  saturated  layer  is 
equal  to  31  x  10-'*  sq.  cm.,  whikt  Harkins 
has  arrived  from  his  own  measurements  for 
butyric  acid  at  the  value  30  x  10- '•  sq,  cm. 

In  1911  Dr.  J.  T.  Barker  and  myself 
made  a  direct  determination  of  q  for  a  solu- 
tion of  nonylic  acid  in  wnt^r.  For  a  practi- 
cally saturated  surface  layer  it  was  found 
that  q  was  about  1.0x10-^  grm.  per  sq. 
cm.,  or  3.1x10'*  molecules  per  sq.  cm. 
From  this  result  it  follows  that  the  surface 
area  per  molecule  is  26  x  10- *•  sq.  cm. 

If  we  consider  these  various  values,  it  will 
be  at  once  evident  that  they  are  not  very 
different  from  the  values  found  by  Lang- 
muir and  by  Adam  for  the  oriented  uni- 
molecular  layers  of  practically  insoluble 
fatty  acids  resting  on  the  surface  of  water. 
That  in  the  present  case  some  of  the  valuer 
are  larger  might  easily  be  explained  on  the 
ground  that  these  adsorption  layers  are  (par- 
tially, or  completely,  in  the  state  of  "sur- 
face vapours."  For  Adam  and  Marcelin 
have  recently  made  the  important  discovery 
that  the  unimolecular  surface  films  investi- 
gated by  them  may  pass  rapidly  on  in 
crease  of  temperature  from  the  .stat<'  of 
"s:)lid"  or  "liquid"  surface  films  to  the 
state  of  "vaporised"  surface  films,  in  which 
the  juxtaposed  molecules  become  detached 
from  each  other  and  move  about  with  a 
Brownian  or  qua-si-molecular  motion,  prob- 
ably oommimicated  to  them  hv  the  thermal 
agitation  of  the  water  moleoules  to  which 
they  are  attached. 

It  is.  indeed,  highly  probable  that  the 
molecules  which  ai*e  concentrated  in  the 
surface  from  the  state  of  solution  in  the 
liquid  iphase  are  not  in  quite  the  same  situa- 
tion as  the  molecules  of  prncticaily  in- 
soluble substances  which  are  placed  on  the 
surface.  In  the  former  case  the  molecules 
are  still  "  dissolved,"  so  that  they  will  be 
more  subject  to  thermal    agitation  and  less 


able  to  form  a  juxtaposed  unimolecular 
layer.  They  may  also  be  "  hydrated." 
The  difference  between  the  two  cases  is 
rendered  very  evident  from  the  fact  that  in 
the  production  of  surface  layers  from  dis- 
solved^ molecules  of  the  fatty  acids  (and 
other  "surface  active"  substances)  there  is 
a  verj-  marked  fall  of  surface  tension,  whilst 
the  uncompressed  unimolecular  surface 
films  placed  on  the  surface  from  outside  do 
not  affect  the  surface  tension  of  the  water. 
Thus  th^  moleculas  of  the  surface-active 
substance  in  the  former  case  are  in  much 
closer  relation  to  the  solvent  molecules,  and 
are  in  kinetic  equilibrium  with  the  mole- 
cules of  both  solvent  and  solute  in  the  bulk 
of  the  liquid.  Nevertheless,  the  agi-eement 
as  regards  order  of  magnitude  in  the  values 
of  the  surface  area  })er  molecule  in  the  two 
types  of  case  is  certainly  very  suggestive 
and  significant.  Moreover,  the  experiments 
of  Mr.  Iredale  show  that  molecules  which 
are  adsorbed  on  the  surface  from  the 
vapour  phase  lower  the  surface  tension, 
and  are  therefore  from  this  ipoint  of  view 
comparable  with  molecules  concentrated  in 
the  surface  from  the  bulk  of  the  liquid 
phase. 

The  question  as  to  whether  the  simiplified 
form  of  Gibbs'  equation  yields  a  sufficiently 
accurate  value  for  the  excess  surface  con- 
centration can  .';o4ircely  be  decided  without 
more  experimental  data.  In  the  experi- 
ments made  by  Dr.  Barker  and  myself,  the 
values  calculated  from  the  surface  tension- 
cpncentration  curve  were  1.3x10-'  and 
0.6x10-'  grm.  per  sq.  cm.,  according  as 
the  value  of  the  van't  Hoflf  factor  t  for  the 
.very  dilute  solutions  of  nonylic  acid  was 
taken  as  1  or  2  respectively ;  whilst  the  cor- 
responding directly  detennined  value  was 
about  1.0 X  10-'  grm.  per  sq.  cm.  This  dis- 
crepancy was  probably  well  within  the  ex- 
perimental error  of  our  measurements. 

Within  the  last  few  years  H.  A.  McTag- 
gart  has  made  a  number  of  experiments  on 
the  electric  cataphoresis  of  gas  bubbles  in 
aqueous  solutions  and  other  liquids.  He 
finds  that  aliiphatic  acids  and  alcohols  in 
aqueous  solution  reduce  *the  surface  P.D., 
and  that  this  effect  runs  parallel  with  their 
influence  on  the  surface  tension  of  water. 
He  also  finds  that  acids  reduce  the  P.D. 
These  results  may  be  regarded  as  a  corro- 
boration of  those  obtained  by  Kenrick.  Mc- 
Taggart  has  found  that  the  nitrates  of  tri- 
and  tetravalent  cations  have  a  powerful 
effect  in  not  only  reducing  but  reversing  the 
r.D.    (i.e.,    the  bubble  becomes  positively 


212 


THE  CHEMICAL  NEWS. 


OCTOBER  5,  1923. 


charged).  His  experiments  also  show  that 
polyvalent  negative  ions,  such  as  tJie  ferio- 
cyanide  ion,  act  in  tlie  opposite  ilirection  to 
the  polyvalent  cations — i.e.,  they  increase 
the  negative  charge  on  the  bubble  or  dimin- 
ish a  previously  existing  positive  one.  These 
results  are  of  great  interest,  inasmuch  as 
they  shovi^  the  powerful  effects  iproduoed  by 
polyvalent  ions  on  the  P.D.  existing  in  the 
surface  layer  of  an  aqueous  solution.  As 
we  shall  see  presently,  very  similar  results 
have  been  obtained  at  liqufd-liquid  and 
solid-liquid  interfaces.  But  it  is  of  great 
importance  to  know  what  happens  at  the 
air-liquid  interface,  since  we  can  largely 
discount  the  chemical  and  physical  in- 
fluence of  the  gas  phase. 

Although  the  electrometric  method  em- 
ployed by  Kenrick  and  Thorwaldson  only 
gives  comparative  results  (since  two  inter- 
faces must  always  be  simultaneously  used), 
whilst  the  cataphoresis  method  gives  re- 
sults for  a  single  interface,  it  is  necessary  to 
observe  that  the  electrometric  method 
measures  the  total  fall  of  potential  from  the 
bulk  of  one  phase  to  the  bulk  of  another. 
The  cataphoresis  method  measures  what 
Freundlich  has  called  the  "electrokinetic'' 
P.D. — that  is  to  say,  the  potential  drop 
between  the  limiting  surface  of  the  "fixed" 
part  of  the  double  layer  and  the  rest  of  the 
liquid.  The  two  values  need  not  neces- 
sarily coincide. 

Let  us  now  inquire  kow  far  the  pheno- 
mena which  we  have  seen  to  be  characteris- 
tic of  a  gas- liquid  interface  occur  abo  at  tlie 
interface  between  two  immiscible  or  pai'- 
tially  miscible  liquids.  Many  years  ago  it 
was  shown  by  Gad  and  by  Quincke  that  a 
fatty  oil  is  very  readily  dispersed  in  the 
form  of  an  emulsion  by  a  dilute  solution  of 
caustic  soda.  A  neutral  hydrocarbon  f>il 
can  be  similarly  emulsified  in  a  dilute  aque- 
ous solution  of  alkali  if  one  of  the  higher 
fatty  acids  was  di&solve'd  in  it,  whilst  the 
lower  fatty  acids  do  not  produce  a  similar 
action.  It  was  shown  that  the  action  runs 
parallel  to  the  lowering  of  interfacial  ten- 
sion and  must  be  ascribed  to  the  formation 
of  a  soap,  which  lowers  the  interfacial  ten- 
sion and  concentrates  at  the  interface. 

I  cannot  conclude  this  account  of  certain 
asipects  of  surface  actions  and  properties 
without  making  a  passing,  though  all  too 
brief,  reference  to  the  beautiful  investiga- 
tions of  Sir  George  Beilby  on  the  amor- 
phous layer.  He  has  shown  that  when  the 
surface  of  crystalline  matter  is  subjected  to 
shearing  stress,  there  is  produced  a  surface 


layer    of  a  vitreous  or  amorphous  character 
— a  "flowed"  surface — in    which  the  parti- 
cular ordered.  aiTangement  of  the  molecules 
or  atoms  which    is  characteristic  of  the  cry- 
stalline   matter     largely    disappears.       Dr. 
Travers  and    Mr.  R.    C.  Ray  have    recently 
obtained  a  very  interesting  confirmation  of 
the  Beilby  EflEect.     The    heats  of    solution 
(in  kilogram  calories  per  gram  mol)  of  vitre- 
ous silica  and  silver  sand    (silica  as  crystal- 
line quartz)    in  aqueous    hydrofluoric    acid 
were  found  to  be    37.24  and    30.29    respec- 
tibely.      After  grinding  for  fifteen  hours  the 
corresponding  values    were  36.95  and  32.46 
respectively.     If  we  assume  that  the  inter- 
nal   energy  of  the    amoiiphous  phase    pro- 
duced by  grinding  is  the  same  as  that  of  the 
vitreous  silica  (silica  glass),    we  can  calcu- 
late from  these    results  that    about  31    per 
cent,  of  the  crystalline    silica  has  been  con- 
verted by  grinding  into    "amorphous"  sili- 
ca. '  The  densities  of  silica  glass  arid  silver 
sand  were  found  to  be    2.208  and    2.638  re- 
spectively.       After    fifteen  hours'  grinding- 
the    density  of    the  latter    was  I'owered    to 
2.528.      On  the  same  assumption  as  before, 
it  follows    that  about    26  per    cent,  of    the 
quartz  has  been  converted  into  the  vitreous 
condition.        The    difference    between     the 
figures  31  and  26  is  doubtless  due  to  the  ap- 
proximate     character    of     the    assumption 
underlying  the  calculations    and  to  experi- 
mental errors.       There  seems  little  doubt, 
however,    about  the  soundness  of  the  main 
conclusion — namely,     that  the    mechnnical 
action  of  shearing  stress  on  crystalline  mat- 
ter is    to  produce  a    random    molecular   or 
atomic  distribution  in  the  surface  layers. 

This  discussion,  necessarily  brief  and 
limited,  of  certain  aspects  of  the  properties 
of  surfaces — molecular  orientation,  surface 
concentration  or  adsorption,  electrical  or 
ionic  polarisation — ^has  dealt  very  largely 
with  states  o^f  thermodynamic  equilibrium. 


[British  Association  fou  the  x^dvanck- 
MENT  OF  Science.     Liverpool,   1923.] 

SECTION  A.— MATHEMATICS  AND 
PHYSICS. 

ON    THE    ORIGIN     OF    SPECTRA 
(RECENT      PROGRESS). 

Address  by  Professor  J.  C.  McLennan, 
F.R.S.,   President  of  the  Section. 

(Continued  from  Page  202.) 

If  this  view  be  accepted,  it  follows  that  if 
we  were  to  detach  from  the  neutral  atom  ol 


OCTOBER  5,  1923. 


THE  CHEMICAL  NEWS. 


313 


an  element  its  most  loosely  bound  electron, 
we    should  expect    to  find    that  the    orbits 
which  remained  were    characterised  by  the 
same  quantum  numbers  as  defined  them  io, 
the  neutral  atom.     Moreover,  except  in  cer- 
tain special  cases,    these    orbits    would    be 
identical  in  type  with  those  of  the    neutral 
atoms  of  the  next  lighter  element.    Ihe  ex- 
ceptional cases  would    include    those    ele- 
ments whose  atomic    structure  involved  the 
commencement    of  the  development    of  an 
inner  system  of  orbits,  such  as  those  of  the 
83,  43,  4^,  &c.,  groups.       Subject   to   these 
limitations,  we  should  expect  to  find  that  if 
the    n  last-bound    electrons  were    removed 
from  a  neutral    atom  of  an  element  the  or- 
bits that    remained    in  this  atom  would    be 
identical  in  tyipe  with    those  of  the  neutral 
atoms    of  the    nth  lighter   element.      This 
would  mean  that    the  arc  spectrum    of  the 
monovalent    positive    ion    of    arc    element 
would  be  identical    as  to  types  of  series  in- 
volved with  the  arc  spectrum  of  the  neutral 
atoms  of  the  next  lighter  elerhent.     There 
would  be  this  difference,    however,    that  in 
the  series    formulae  of  the  spectrum  of    the 
ion   the    Rydberg    constant    would    be  4K, 
whereas  in  the  series  of  the  spectrum  of  the 
neutral    atoms    of  the    lighter    element    it 
would  be  K.       Putting  the    niatt<^r  as  it    Is 
ordinarily  stated,  the  spark  spectrum  of  an 
element  should  be  made  up  of  series  of  the 
same  type    as  those  of  the  arc   spectrum  of 
the  next  lighter  element.     This  is  known  as 
the  Kossel-S'>tnmerfeId  Disiphicement  Law. 
In  t«rms    of    Bohr's    theory    the    fl-fold 
value  of  the  Rydberg  constant  would  be  in- 
terprt^ted  as  meaning  that  aluminium  atoms 
which  emitted    this  spectrum  had    lo«t  two 
electrons,  and  were  represented  by  A1  +  +  +  , 
or,    as  it  is    now  written,    Al(in).      The  16- 
fold  Rydberg  constant  would,  on  the  same 
theory,  also  be  interpreted  as  meaning  that 
the  atoms    of    silicon    wliich    cmitti'd    this 
spectrum    were    those  that    had  lost    three 
electrons,  i.e.,  Si(iv).     These  results,  it  will 
be  seen,    amply  confirm  the  view  that    the 
bound  electrons    in  the    neutral    atoms    of 
sodium  Na(i),  are  of  the  same  type  and  are 
characterised  by  the    same  (jnantum  num- 
bers as  those   of  the  singly  ionised    atom  of 
nuignesium,  Mg(ii),    of  the    doubly-ionised 
atom    of    aluminium,    AUiri).    and    of    the 
trebly-ionised  atom  of  silicon,  Si(iv), 

What  has  been  found  to  be  true  of  the 
spectra  of  sodium,  magnesium,  aluminium. 
;ind  silicon,  will  no  dmiht  he  found  to  be 
true  of  the  spectra  elements  lithium,  lieryl- 
lium,  boron,  and  carbon.  The  spectra  of 
beryllium  and  boron    are  extremely  meagre 


in  wave-lengths,  and  but  little  is  known  of 
their  spectral  series.  The  sipectrum  of  car- 
bon, however,  especially  in  the  extreme 
ultra-violet,  has  been  well  worked  out  by  a 
number  of  observers,  and  particularly  so  by 
Simeon. 

In  the  spectrum  of  beryllium  the  doublet 
A  =  3131.194  A,  A  =  3130.546  A,  has  been 
shown  to  be  the  first  member  of  a  principal 
and  a  second  subordinate  series  of  doublets. 
Moreover,  Back,  who  rec  ntiy  investigated 
its  magnetic  resolution,  has  found  that  the 
magnetic  components  are  of  the  D,  and  Dj 
type,  just  as  Kent  has  shown  the  magnetic 
components  of  the  close  lithium  doublet 
A  =  6708  A  to  be.  It  will,  therefore,  prob- 
ably be  found  when  the  spectrum  of  beryl- 
lium has  been  extended  that  the  doublet  A 
=  3131.194  A,  A  =  3130.546  A,  will  prove 
to  be  the  first  member  of  the  doublet  series 
of  the  positive  singly-charged  atom  of  beryl- 
lium, with  a  Rydberg  constant  for  the 
series  of  4K.  In  the  spectrum  of  boron  the 
doublets  A  =  2497.73  A,  A  =  2496.78  A, 
and  A  =  2089.49  A,  A  =  2088.84  A,  parti- 
cularly the  latter,  merit  attention  in  look- 
ing for  a  9K  series.  In  the  ultra-violet 
spectrum  of  carbon  there  is  a  strong  doublet 
at  A  =  1335.66  A.  A  =  1334.44  A,  and  an- 
other nearly  as  strong  at  A  =1329.60  A, 
A  =  1329.07  A.  These  twoa  Iso  merit  at- 
tention in  any  attempt  to  identify  16K  series 
for  this  element. 

In  ccMisidering  the  general  validity  of  the 
Koesel-Sommerfeld  Displacement  Law  the 
recent  work  of  Catalan  on  the  series  spectra 
of  manganese,  chromium  and  molybdenum 
is  of  interest. 

In  this  paper  an  attempt  has  been  made 
to  outline  some  of  the  leading  features  of 
the  quantum,  theory  as  it  is  being  used  to 
solve  the  problems  of  atomic  structure  as 
well  as  of  those  connected  with  the  origin  of 
radiations  emitted  by  atoms.  Other  illus- 
trations of  sipecial  interest  might  have  been 
drawn  from  the  treatment  of  problems  that 
have  arisen  in  a  study  of  band  spectra  and 
of  fluorescence  phenomena.  The  recent 
work  of  Cabrera,  Epstein,  and  Dauvillier, 
on  paramagnetism,  too,  has  a  most  interest- 
ing cf>nnection  with  the  development  of 
inner  systems  of  electronic  orbits  in  atoms 
in  liohr's  scheme  of  the  genesis  of  atoms. 

I  venture  to  think,  however,  that  the  few 
illustrations  presented  may  serve,  in  a 
measure,  to  indieat^  the  power  and  also  the 
beauty  of  the  methcxls  being  put  forward  to 
elucidate  the  problem  of  the  origin  of 
radiation. 


214 


THE  CHEMICAL  NEWS. 


OCTOBER  5,  1923. 


ORGANIC  MERCURY  COMPOUNDS. 

Part  II. 

By  R.  F.  Hunter,  F.C.S. 

(Continued  from  Page  205.) 

Mercury  dimethyl  is  t&e  first  alkyl  mer- 
cury cortupound  we  shall  consider. 

It  can  be  prepared  in  several  ways,  for 
instance,  by  the  action  of  sodium  amalgam 
on  methyl  iodide,  from  zinc  dimethyl  and 
methyl  mercuric  iodide,  fi'om  methyl  mer- 
curic iodide  and  potassium  cyanide,  from 
mercuric  chloride  and  ether  methyl  mag- 
nesium iodide  or  alundnium  carbide.  It  is 
a  colourless,  highly  refractive  and  exces- 
sively pois'onous  liquid,  and  reacts  with 
halogens,  acids,  metals,  iodocyanogen, 
stannous  chloride,  'phosphorus  and  anti- 
mony trichloride,  with  potassium  perman- 
ganate and  Witt  mercuric  salts. 

The  important  synthetical  compound 
methyl  mercuric  acetate  is  prepared  from 
it  by  heating  it  with  glacial  acetic  acid  in  a 
sealed  tube  for  some  time  at  130° ;  methane 
is  produced  in  this  reaction. 

The  homologue,  mercury  diethyl,  is  pre- 
pared by  similar  methods,  e.g.,  from  zinc 
diethyl  and  mercuric  ohloride,  from  ethyl 
bromide  and  sodium  amalgam,  from  ethyl 
mercuric  iodide  and  potassium  cyanide, 
etc.  It  reacts  in  a  similar  manner  with 
halogens,  metals,  acids,  potassium  per- 
manganate, mercuric  salts,  etc.,  with  ar- 
senobenzene,  on  heating  at  150°,  a  reaction 
takes  place  in  which  phenyl  diethyl  arsinc 
is  foniied  and  metallic  mercury  produced. 

Among  the  other  aJkyl  mercury  com- 
pounds which  have  been  prepared,  we 
might  mention:  mercury  dipropyl,  di  iso- 
butyl,  di  sec.  butyl,  di  isoamyl,  di  octyl, 
the  preparations  of  which  can  be  found  in 
Whitmore's  excellent  book  on  the  subject. 

A  number  of  mercury  compounds  have 
been  prepared  from  the  olefines.  For  in- 
stance, efchylene  reacts  with  aqueous  solu- 
tions of  mercuric  salts,  giving  a  variety  of 
complex  mercury  compounds.  These  have 
been  classified  as : 

Ethanol  mercuric  salts; 

Ethyl  ether  mercuric  salts; 

and  products  of  the  form  CgHgHg  (OR)X. 

As  derivatives  of  ethylene  we  might 
mention  Ethenol  mercuric  chloride,  bro- 
mide and  iodide;  Ethanol  mercuric  nitrate 
and  sulphide ;  /3^'  di  ohloro  mercuric  di- 
ethyl ether;  Mercurous  and  mercuric  di 
ethylene  oxides. 


Certain  prtxiucts  obtained  from  ethylene 
and  alcohohc  solutions  of  mercuric  salts, 
such  as  a  Acetoxymercuri,  (3  methoxy 
ethane,  and  a  Acetoxy  mercuri  (3  ethoxy 
ethane.  Mercury  compounds  have  also 
been  prepared  from  propylene,  for  instance, 
a  Acetoxymercuri  ft  hydroxy  propane,  and 
from  isobutylene:  chloromercuri  hydroxy 
isobutane. 

The  mercui7  compounds  of  acetylene 
are  of  interest  from  the  synthetical  produc- 
tion of  acetaldehyde  from  acetylene  in  the 
presence  of  salts  of  mercury.  We  might 
mention  mercury  bis  mono  chloro  acetylene 
as  an  acetylene  derivative  of  particular  in- 
terest. 

Ethyl  alcohol  in  the  presence  of  alkali  re- 
acts with  mercuric  salts  producing  a  variety 
of  compounds,  of  which  the  most  impor- 
tant are  the  mercarbides,  which  are  com- 
pounds in  which  the  hydrogen  of  a  CH, 
group  is  completely  replaced  by  mercury. 
Ethane  hexamercarbide,  C. Jig fi 2(^11)2,  is 
typical,  and  is  produced  by  the  refiuxing  of 
yellow  HgO,  K  0  H,  and  alcohol  for  several 
hours. 

The  dichloride  and  corresponding  nitrate 
and  suliphate  of  ethane  hexamercai-bide 
have  been  prepared. 

Mercury  ccanpounds  of  unsaturated  alco- 
hol, such  as  vinyl,  allyl  alcohols,  have  been 
prepared,  and  quite  a  large  amount  of  re- 
search has  been  carried  out  on  the  action  of 
mercuric  salts  on  allyl  alcohol. 

The  mercury  derivatives  of  the  fatty 
acids,  aldehydes,  ketones,  and  acid  amides 
have  been  subject  to  much  investigation. 
A  variety  of  compounds  are  prepared  from 
carbon  monoxide  and  alcoholic  solutions  of 
mercuric  salts.  We  might  mention  acetoxy 
mercuri  fonnic  methyl  ester  and  the  cor- 
responding ethyl  compounds  as  examples. 
Among  the  mercurated  acetic  acids  we  have 

Bromo  mercuri  acetic  acid ; 

Anhydro  hydroxy  mercuri  acetic  acid ; 

Nitrate  mercuri  acetic  acid; 

Mercui-i  nitrate  mercuri  acetic  acid ; 

Dichloromercuri  acetic  acid ; 

Trichloromercuri  acetic  acid ;  and 

Tri  hydroxy  mercuri  acetic  acid. 

Among  the  mercurated  propionic  acids, 
we  have  (3  mercury  bis  propionic  acid  and 
its  corresponding  anhydride,  and  the  anhy- 
dride of  a  hydroxy  mercuri  propionic  acid. 

Compounds  from  unsaturated  acids  have 
also  been  prepared  such  as  the  anhydride  of 
a  hydroxy  mercuri,  [3  hydroxy  propionic 
acid,  and  the  anhydride  of  hydroxy  mer- 
cuii  a  hydroxy  (3  butyric  acid. 


OCTOBER  5,  1923. 


THE  CHEMICAL  NEWS. 


215 


The  mercury  salts  of  a  acetoxy  mercuri  (3 
hydroxy  mercuri  and  ^  hydroxy  methyl  suc- 
cinic acid  have  been  pretpared. 

As  examples  of  mercury  aldehyde  com- 
pounds we  have 

Mercuri  chlorate,  mercuri  aldehyde,  mer- 
curi nitric,   mercuri  acetaldehyde. 

A  variety  of  compounds  are  obtained 
when  acetone  reacts  with  mercury  com- 
pounds.     \\v  might  state 

Tetra  acetoxy  mercuri  diacetone  hy- 
drate; and 

Tri  mercuri  diacetone  hydrate  as  ex- 
amples. 

Mercury  acetamide,  (CH3  CON  H),  Hg, 
is  typical  of  the  mercury  derivatives  of 
acid  amides,  and  is  prepared  by  adding  yel- 
low HgO  to  melted  acetamide  and  allowing 
the  temperature  to  rise  slowly  to  180°. 
Among  the  other  amide  derivatives  which 
have  been  prepared  by  various  workers  at 
different  times,  we  might  mentioa 

Mercury  monochloro  acetamide; 
,,         nitro  acetamide; 
, ,         propionamide ; 
,,         oxamide; 
,,         suocinamide; 
,,         tartamide  and  fumaramid£. 

The  mercury  derivatives  of  aromatic 
hydrocarbons  and  nitro  cv^>iii  pounds  have 
been  dealt  with  fully  by  Whitmore,  and 
hence  nothing  more  than  the  briefest  of  re- 
views will  be  given. 

A  typical  example  is  mercury  diphonvl. 
which  can  be  prepared  by  several  methods : 

1. — By  action  of  sodium  amalgam  on 
C.H.Br. 

2. — From  C.H^Br,  Kg  Cl^,  and  sodium. 

8. — From  Phenyl  arsenious  oxide  and 
Hg  CI,. 

4. — From  phenyl  magnesmm  bromide 
and  Hg  CI3. 

5. — From  phenyl  hydrazine  and  iiun- 
curic  oxide. 

6. — From  phenyl  mercuric  iodide  and 
sodium  amalgam. 

Also  from  phenyl  mercuric  bromide  and 
KjS,  and  from  phenyl  mercuric  acetate  and 
sodium  stannite. 

The  compounds  react  in  muioli  the  same 
way  as  thi'  alkyl  compounds  rto;  thvis  it  n>- 
acts  with  halogens,  metals,  and  chlorides, 
non-mctallic  halides,  acids,  mercuric  salts. 
organic  halides,  acid  anhydrides,  with  sul- 
phur and  with  oxidising  agents. 

Other  phenyl    mercuric    compounds    di- 
sserving mention    are    phenyl    mercuric  hy- 
droxide, chloride,  bromide.   i<xli(l.'  fnnn.i,. 


propionate,  acetate,  cyanide,  nitrate,  sul- 
phate, carbonate  and  suliphocyanide. 

Among  the  tolyhiiercuric  compounds  we 
have  o  mercury  di  tolyl,  o  tolyl  mercuric 
chloride  and  nitrate,  m  mercury  di  tolyl, 
m  tolyl  mercuric  nitrate,  m  mercury  di 
tolyl,  m  tolyl  mercuric  chloride  and  bro- 
mide, p  mercury  di  tolyl,  p  tolylmercuric 
chloride,  bromide  and  iodide,  and  p  tolyl- 
mercuric acetate  and  corresponding  nitrate. 

The  benzyl  nic'rt!iu*j-  compounds  worthy 
of  note  are :  mercury  di  benzyl  prepared 
from  benzyl  magnesium,  chloride  and  mer- 
curic chloride,  and  benzyl  mercuric  chlor- 
ide prepared  from  mercury  di  benzyl  and 
alcoholic  Hg  Clj.  The  corresiponding  bro- 
mide, iodide,  and  acetate  have  been  de- 
scribed. 

Mercury  derivatives  of  higher  benzene 
homologues  are  known,  for  instance : 

Mercuri  bis  3,  4  dimethyl  benzene, 
2,  4 
».  2,  0         ,,  ,, 

,,  2,  4,  6  tri  methyl  benzene. 

Mercuri  bis  penta  methyl  benzene,  and 
mercuri  bis  2  methyl  5  isopropylbenzene 
have  been  described. 

Mercury  derivatives  of  cyclo  hexane  are 
known ;  for  instance,  we  are  acquainted 
with  cyclo  hexylmercuri  chloride,  the  cor- 
responding bromide,  cyanide,  and  sulphide. 
.\mong  the  mercury  derivatives*  of  aromatic 
nitro  compounds,  we  have  o  nitro  phenyl 
mercuric  chloride  prepared  from  nitro  ben- 
zene and  mercuric  acetate;  m  and  p  nitro 
phenyl  mercuric  chloride.  A  compound  of 
this  class  worthy  of  note  is  anhydride  of  o 
nitro  benzal  dimercurio  hydroxide. 

Mercury  derivatives  of  sulphonic  acids 
have  be*n  prepared,  and  mercury  deriva- 
tives of  phenylacetylene  are  described  by 
various  workers,  but  compounds  which  do 
deserve  mention  are  the  derivatives  of 
naphthalene.  A  typical  example  of  these 
is  a  mercury  di  naphthyl,  which  is  obtained 
when  a  bromonaphthalene  is  heated  with 
xylene  and  sodium  amalgam  in  a  pasty  con- 
dition on  an  oil  bath  for  some  20  hours.  It 
reacts  with  acids,  metals,  halogens,  mer- 
curic salts,  oxides  of  nitrogen,  with  arseni- 
ous chloride  and  thionyl  chloride. 

Other  compounds  of  this  class  worthy  of 
mention  are :  a  Naphthyl  mercuric  chlor- 
ide bromide,  iodide,  formate,  acetate,  buty- 
rate,  nitrate  and  sulphide,  p  naphthyl- 
mereuric  halides  and  sulphide. 

We  have  now  to  consider  one  of  the  most 
interesting  groups  of  organic  mercury  com- 


2l6 


THE  CHEMICAL  l^EWS. 


OCTOBER  5,  192^. 


pounds,  namely,  the  mercury  compounds 
of  aromatic  amines,  which  constitute  one 
of  the  largest  families  of  the  mercury  com- 
pounds. 

The  first  compounds  to  be  considered  are 
the  double  compounds  of  aniline  and  mer- 
cury salts.  Typical  of  thisi  class  are  what 
are  known  as  "  mercuric  chloride  com- 
pounds." When  aniline  and  HgClj  in  al- 
cohol are  mixed,  we  obtain  a  white  crystal- 
line compound,  (CeH.N  H,)^  (Hg  G\^),; 
other  compounds  of  this  kind  are : 
(C.H^NH,),  Hg  Cl„  CeH^N  H,  Hg  Cl„ 
and  CeH^N  H^  H  CI  Hg  Cl^.  Correspond- 
ing mercuric  bromide,  iodide,  nitrate,  cy- 
anide and  chlorate  compounds  are  men- 
tioned in  the  literature  of  the  subject.  In 
1875,  while  studying  the  action  of  aniline 
on  alcoholic  solutions  of  mercuric  chloride, 
Wislicenus  prepared  a  yellow  white,  very 
insoluble  compound,  CgHgN  CI  Hg.  The 
compound  was  named  "pEenylated  white 
precipitate,"  and  was  studied  very  thor- 
oughly by  Forster. 

This  brings  us.  to  the  study  of  the  true 
compounds  of  aromatic  amines,  p  amino 
phenylmercuric  acetate  is  a  typical  com- 
pound and  can  be  prepared  from  N.  mer- 
curi  aniline  and  acetic  acid,  aniline  acetate, 
mercuric  acetate,  or  from  aniline  acetate 
and  mercuric  oxide,  or  from  aniline  and 
mercuric  acetate,  the  last  being  the  usual 
method  of  preparation ;  it  is  essential  to  use 
freshly  distilled  aniline.  The  compound 
reacts  with  halides,  can  be  acetylated,  fur- 
ther, it  can  be  diazotlzed  and  coupled,  also 
it  reacts  with  dinitro  phenylyddine  and  with 
propargylacetal. 

p  Mercuri  bis  aniline  is  another  aniline 
derivative  of  note,  and  can  be  prepared 
from  p  amino  phenyl  mercuric  acetate  and 
sodium  thiosulphate,  from  p  aminophenyl- 
arsenious  oxide  and  sodium  hydrate  and 
mercuric  chloride,  also  from  ip  mercuric  bis 
acetanilide,  by  heating  with  alcoholic  potas- 
sium hydroxide. 

p  Amino  phenyl  mercuric  hydroxide  and 
its  anhydride  are  obtained  by  dissolving  p 
amino  phenyl  mercuric  acetate  in  dilute 
K  0  H  and  treating  with  concentrated  (30 
per  cent.)  caustic  potash. 

p  Amino  phenyl  mercuric  chloride  exists 
in  both  crystalline  and  amorphous  forms, 
and  reacts  with  sodium  thiosulphate,  di- 
nitro diiphenyl  pyridine  chloride,  propargyl- 
acetate,  and  also  with  ethoxv  acrolein  ace- 
tal. 

Other  aniline  derivatives  are  p  amino, 
phenylmercuric    bromide,     iodide,     nitrate 


acid  sulphate,  sodium  p  aminophenyl  mer- 
curic thiosulphate,  o  aminophenyl  mer- 
curic acetate  and  chloride,  2  amino  5  nitro- 
sophenyl  mercuric  chloride,  2,  4  diacetoxy- 
mercuri  aniline. 

Mercury  compounds  of  nitroanilines  are 
known;  for  instance,  nitro  aniline  reacts  to 
yield  4  acetoxy  mercuri  2  nitro  aniline,  and 
4,  6  diaet'toxy  mercuri  2  nitroaniline.  Mer- 
cury derivatiyes  of  monomethylaniiine  and 
dimethylaniline  are  known.  Examples  are, 
p  methyl  aminophenyl  mercuric  acetate,  p 
mercuri  bis  monomethylaniiine,  p  nitro  o 
acetoxymercuri  monomethylaniiine  of  the 
first,  and  p  mercuri  bis  dimethylaniline  p 
dimethyl  amino  phenylmercuri  acetate,  hy- 
droxide chloride,  and  of  the  second,  p 
bromo  dimethylaniline  reacts  to  yield  o  ace- 
toxy mercuri  p  bromo  dimethylanihne  is 
prepared  from  o  nitro  dimethylaniline. 

In  a  similar  manner,  as  examples  of  deri- 
vatives of  ethyl  aniline,  we  have : 

p  Mercuri  bis  monoethylaniline,  ip  ethyl- 
aminophenyl  mercuric  acetate,  hydroxide 
and  chloride. 

For  derivatives  of  diethylaniline  we  have 
p  mercuri  bis  diethylaniline,  p  diethyl- 
aminophenyl  mercuric  acetate,  hydroxide 
and  chloride. 

As  examples  of  mercury  derivatives  of 
acid  anihdes  we  have : 

N  mercuri  bis  formanilide; 

N  mercuri  bis  acetanilide;  and 

p  Acetaminophenyl  mercuric  acetate,  p 
mercuri  bis  diphenylamine,  p  hydroxy  mer- 
curi diphenylamine,  p  mercuri  bis  metliyl 
diphenylamine  are  derivatives  of  diphenyl- 
amine, 2  acetoxy  mercuri  phenylglycine 
ethyl  ester. 

Ac  O  Hg  GJI,  N  H  CH^  CO^  C^H^  is  an 
example  of  an  anilide  fatty  acid  derivative. 

2  Chloromercuri  phenyl  a  aminopropiouio 
ethyl  ester  CI  Hg  GJI,  N  H  CH  (CH3) 
CO2  C2H5  is  another  example. 

Mercury  derivatives  of  the  three  tolui- 
dines  have  been  described ;  as  examples  of 
such  we  have : 

3  Methyl  4  aminophenyl  mercuric  ace- 
tate; 

Dihydroxy  mercuri  o  toluidine; 
Diacetoxy  mercuri  m  toluidine; 
Tri  acetoxy  mercuri  m  toluidine. 
Acetoxy  mercuri  p  toluidine; 
Hydroxy  mercuri  p  toluidine; 
Chloro  mercuri  p  toluidine. 
Other     amino    aromatic     derivatives      of 
mercury  are : 

Acetoxy  mercuri  dimethyl   p  toluidine ; 
p  Acetoxy  mercuri  o  aceto  tcluidide, 


OGTOBEK  5,  1923. 


THE  CHEMICAL  NEWS 


217 


Dichloro  mercuri  o  aceto  toluidide ; 

p  Aoetoxy  mercuri  m  aceiotoluidide. 

The  anhydride  of  o  hydroxy  mercuri  ,  p 
acetofcoluidide. 

Di  acefcoxy  mercuri  o  bolyglycine  ethyl 
ester;       ^ 

o  Acetoxy  mercuri  p  tolylglycine  ethyl 
ester; 

p  Benzylamino  phenyl  mercuric  acetate; 

2,  4  Diacetoxy  mercuri  and  naphthyl- 
amine;  and 

2  Acetoxy  mercuri  naphthionic  acid. 


ODOUR   CONDniONS. 
By  John  MrssioxnEN. 

To  place  into  categories  the  various  sub- 
stances which  produce  (dour,  to  enumerate 
definite  values  for  thest'  substances,  and  to 
define  some  tangible  link  between  odiferous 
bodies  and  their  chemical  j' roperties,  a  cer- 
tain amount  of  postulatiou  i>  essential.  K«  ■ 
ferring  to  the  works  of  Berthelot,  Kremer, 
J)urrans,  Tyndall,  Linne,  and  others,  oni- 
finds  such  a  wide  div"r<,'ence  of  views  as  t  • 
render  these  problems  s<('mingly  incapabl< 
of  solution.     Indeed,  li  lions  of  sonx 

that  no  measureable  i  ^  exist  are  al- 
most justifiable.  If,  however,  all  these  in- 
\\  stigations  and  opinions  are  collated,  and 
their  substance  oombiutKl  with  the  results  of 
later  resejirch,  a  working  hypothesis  and 
tabulation  becomes  ipracticable,  and  might 
form  the  base  of  more  intensive  and  exptirt 
examinations  wityhin  the  next  few  years. 

The  first  consideration  is  I  hat  of  the  phy- 
siological condifions  govern  iiig  the  organs 
of  smell,  with  the  chemical  conditions  being 
interdependent.  In  the  first  place,  all  sub- 
stances bhat  can  be  detected  by  the  olfac- 
tory senses  must  be  volatile;'  conse- 
quently, the  intensity  of  odour  may  be 
practically  determined  b\  degrees  of  vola- 
tility. In  the  second  place ,  the  substances 
in  their  volatile  state  must  be  capable  of 
solution  in  the  lipinous  fluid  of  the  olfactory 
organs,  and  their  degree  of  solubility  there- 
in determines  the  remaining  component  of 
intensity.  And,  in  the  third  place,  there 
must  be  some  chemical  reaction  with  the 
lipinous  fluid;  this  would  determine  the 
quality  of  the  odour. 

Three  conditions,  then,  based  mpon  the 
most  fundamental  facts  which  are  already 
common  knowledge,  provide  working  data. 
Their  tabulati<Mi  is  as  follows:  — 


(a)  degree  of  volatility :  ) 

(b)  degree  of  solubility  in  lipms  :)  intensity; 

(c)  chemical  reaction  with  lipU3d  :     quality. 

(a) — Degree  op  Volatility 

While  a  substance,  to  be  odiferous,  must 
be  volatile,  it  does  not  follow  that  ai  vola- 
tile substances  are  odiferous.  Water,  for 
instance,    is  volatile;    yet    i'  ' 

odourless.     If  this  datum  is 
a  relative  standpoint,    water    i  n- 

ferous,  inasmuch  that  it  diluii  s  i  his 

fluid,  thereby    causing  quite    a  pe; 
olfactory    state  when    present    in  sb 
quantities. 

Volatility  may  be  meas'ured  by  i^s 
weight  over  a  standard  period  of  time.  If 
this  period  be  taken  as  1  x  10'"  hours,  and 
the  amount  of  the  substance  be  standard- 
ised as  1,000  grams,  a  range  of  numerical 
values  would  result  under  uniform  condi- 
tions of  temperature  and  pressure.  Sup- 
pose trinitrobutyltoluene  be  selected  as  an 
example.  According  to  Berthelot's  calcu- 
lations, 1  gram  of  this  body  will  lose  about 
1 

—  grams  of  its  weight  in  one  hour  in  order 
10>* 

to  be  detected  by  the  olfactory  senses. 
That  is  to  say,  if  the  suggested  standard  be 
adopted,    the  degree    of    solubility    would 

1 

iw..    o  01.        Iodoform,      losing     about 

10>  = 
grams  per  hour,  would  lose  about  10  grams 
of  its  weight  (1,000  grams)  in  1  x  10'"  hours 
in  simple  rate,  or  lOe  grams  at  compound 
rate,  where  e  is  the  exponential.  This  is 
the  value  when  iodoform  is  just  discern- 
ible, and  would  obviously  vary  according  to 
the  sensitiveness  of  the  olfactory  organs. 
The  difficulty  may  be  overcome  by  calculat- 
ing the  value  at  mazimuvi  volatility  at 
N.T.P. 

Peisse"  has  arranged  all  known  perfumes 
in  graded  degrees  of  volatifity,  and  a  useful 
indication  of  relative  losses  of  weight  may 
bo  derived  therefrom.  Woker'  made  some 
observations  upon  the  dependence  of  vola- 
tility uipon  intramolecular  tension,  and  sug- 
gested that  the  intensity  of  odour  was  in- 
creased in  direct  ratio.  This  is  so  to  a  cer- 
tain extent,  but  due  allowance  must  be 
made  for  the  solubility  of  a  substance  in 
th{^  lipinoas  fluid,  as  it  has  been  found  that 
some  highly  volatile  bodies  arc  almost  in- 
soluble in  lipin — hence  practically  odour- 
less. Pyrocatechin,  C6H,(OH2)  :(i  :2),  is  a 
case  in  point. 


218 


THE  CHEMICAL  NEWS. 


OCTOBER  5,  1923. 


(b) — Degree  of  Solubility  in  Lipins. 

The  theory,  part  of  which  has  since  be- 
come an  incontrovertible  fact,  that  an  odi- 
ferous  substance  must  be  soluble  in  water 
and  lipins,  emanated  from  Backman.*  His 
theory  is  correct  in  the  case  of  water,  other- 
wise how  can  he  account  for  the  odour  of 
volatile  oils?  Whereas  these  oils  are  known 
to  be  soluble  in  lipins.  they  are  totally  in- 
soluble jn  water.  Both  water  and  the  Jipin- 
ous  fluid  undoubtedly  ass^ist  each  other,  but 
they  are  by  no  means  indispensable  to  each 
ot^w^  for  all  substances,  if  for  some. 

Investigation  has  not  provided  one  in- 
stance of  where  a  substance,  either  concen- 
trated or  dilute,  which  is  insoluble  in  lipin- 
ous  fluid,  iposses  odour;  while  there  is  much 
evidence  to  show  that  Hpin-soluble  sub- 
stances always  affect  the  olfactory  nerves  in 
a  perceptible  degree,  providing  a  sufficient 
quantity  be  present.  Such  substances  as 
bomyl  acetate,  phenol,  aad  thiocyauide 
compounds  stand  in  good  contrast  to  mer- 
cury (odourless)  and  pyrocatechin  (scarcely 
perceptible). 

There  are  a  number  of  prpperties,  too 
numerous  to  discuss  in  detail  within  such  a 
paper  as  this,  which  govern  the  activities  of 
lipin.  One  finds,  for  instance,  that  chlor- 
ine, on  conversion  into  a  chloride,  loses  the 
greater  part  (if  not  all)  of  its  odour;  and 
solubility,  combined  with  volatility,  ac- 
counts for  the  decrease.  The  reasons  for  the 
change  have  been  discussed  by  Teudt,^  and 
by  Ungerer  and  Stoddard,"  who  more  or 
less  claim  that  odour  is  dependent  upon  the 
rate  of  molecular  vibration.  Heller^  ener- 
getically condemns  the  hypothesis;  never- 
theless, it  is  a  sound  one — but  only  as  one 
of  the  conditions  producing  odour,  and  gov- 
erning intensity. 

(c) — Chemical  Reaction  with  Lipins. 

Some  very  interesting  postulatory  work 
has  been  executed  by  Linn6,  and  Zwaarde- 
maker,  who  endeavoured  to  classify  the 
qualities  of  odours.  The  term  "odoriphor"* 
was  introduced,  which  correstponded  with 
the  "osmophoric  group"  of  Rupe  and 
Majewski,^  and  the  aromatophors"  of  Kli- 
mont.^°  Many  other  terms  have  been  in- 
troduced. 

The  quality  of  an  odour  {i.e.,  whether  it 
is  aromatic,  repulsive,  and  so  forth)  may  be 
determined  by  the  results,  of  interaction 
with  lipinous  fluid,  and  not  by  the  rate  of  in- 
teraction. At  the  same  time,  some  over- 
lap in  these  definitions  is  unavoidable  :  as 
in  the  instance  of  ammonia.  AiruTionia 
produces    a  pungent  odour  which    is  objec- 


tionable; firstly  because  of  the  vibratory 
speed  of  interaction,  and  secondly  because 
the  residual  products  of  interaction  violent- 
ly attack  the  subcutaneous  tissue  through 
the  ipores.  The  first,  which  imparts  a  sen- 
sation of  burning,  denotes  intensity;  the 
second  is  quality.  ^^ 

The  determination  of  residual  products 
after  interaction  with  the  lipinous  fluid  is 
of  great  importance,  therefore,  and  all  too 
little  work  has  been  carried  out  in  this  di- 
rection. Some  observations  have  been 
made  very  much  along  the  lines  of  Zwaar- 
demaker's  postulations,  except  that  the  no- 
menclature has  been  adjusted  to  corres- 
pond with  that  of  Rupe,  Majewski,  Klimont, 
and  others.  The  names  have  been  placed 
in  columns,  as  under,  the  first  of  which  re- 
presents the  new  nomenclature,  the  second 
is  that  of  Zwaardemaker,  the  third  con. 
tains  exemplary  compounds,  and  the  fourth 
the  obsolete  name. 


Etherqphors. 
Aromatophors. 

(a)  Camphoraceoui 

(b)  Almond, 

(c)  Citral. 
Enosmophors. 
Ambrosophors. 
Aldylophors. 
Empyreunuit  (>y)hors. 
Hircinophoi's. 

K  akosmophors . 
Foetidophors. 

III. 
Ether,  etc. 
Eucalyptol. 
Acetophenol. 
Cyclic  limonene. 
Floral  extracts. 
Trinitrobutyltoluene. 
Ally  Is  and  cacodyls. 
Durene,  etc. 
Fatty  acids. 
Quinoline,  etc. 
Skatol,  etc. 


II. 

Ethereal  odours. 
Aromatic  odours. 


Fragrant  odours. 
Ambrosaics. 
Allyl  (xiours. 
Empyreumatics. 
Hircon  odours. 
Reipulsive  (xlours. 
Foetid  odours. 

IV. 

Aromatophors., 

Enosmophors. 


Kakosmophors. 

Odoriphors. 

Kakosmophors. 


It  will  be  appreciated  that  any  attenript 
at  sharp  classification  has  not  been  at- 
tempted, although  the  various  qualities  are 
clearly  seiparated  on  the  whole.  M.  Appui, 
of  St.  Etienne  (to  whf)m  I  am  much  in- 
debted for  very  valua})le  assistance,  and 
who  is  now  engaged  uj.on  the  lipin  re- 
actions) has  suggested  that  the  foetidophors 
be  sub-divided  into  "pungent"     and  "irri- 


1 


OCTOBER  5,  1923. 


THE  CHEMICAL  NEWS. 


219 


tant,"  but  I  do  not  think  that  the  two 
classes  would  be  sufficiently  defined,  as  the 
majority  of  pungent  odours  are  also  irritant. 

(d) — General    Observations. 

Although  it  is  impossible  to  trace  any 
connection  between  odour  and  one  chemical 
condition,  the  correlation  of  several  c</n- 
ditions  renders  classification  more  practic- 
able. The  intensity  of  an  odour  can  be 
measured,  once  standards  are  adopted,  as 
the  product  of  the  values  of  -volatility  and 
solubility ;  while  the  classes  under  which 
the  residual  products  fall  after  interaction 
with  the  lipinous  fluid  dett  )inin6s  quality. 
In  the  evolution  of  some  slmdard  hyipothe- 
sis,  full  credulence  can  hv  given  to  Teudt's 
theory,  although  this  is  but  a  subsidiary 
factor.  The  known  laws  governing  volatil- 
ity, solubility,  and  chemic.]  change  will. 
regarded  en  masse,  be  tht  laws  which  gov- 
ern odour,  and  it  is  hopid  that  this  may 
prove  to  be  the  correct  foundation  for  a 
more  omplete  survey  of  the  subject;  in 
addition  to  which  some  satisfactory  conclu- 
sions on  the  question  of  taste  may  be 
f(«Tned. 

References . 

*  A  gas  is  classed  as  a  volatile  snbsiance. 
'  Des  Odeurs  des  Parfums  ei  des  Cosmc- 

titpies,   1865;  Perfumery  Hvoord,  1019.    p. 
268. 
»  J.  Physik.  Chem.,  190('),  p.  466. 

*  J.  Phys.  Path,  gen.,  1917,  p.  1. 

*  Chcm.  Cen.,  1919,  p.  138. 

•  Ung.  Bull,  1922.  III.,  7. 
'  Amer.  Per.,  1920,  p.  865. 

•  Arch.  Necr.  Phys.,  1920,  p.  224;  Ahs. 
Chem.  Soc,  1920,  II.,  75. 

•  Ber.  Deut.,  1900,  p.  3,401. 

'*•  Die  syn.  und  iso.  Arotn.,  1899. 

[British  Science  Guild  Publicity 
Service. — Pamphlet  No.  2.] 

THERMIONIC    VAl.VES.* 
By  Dr.  J.  A.  Fleming,  F.K.S. 
Early  Discoveries. 
In  the  history    and  development    of  the 


*  Readers  of  "The  Che7nical  News"  will 
no  doubt  he  interested  in  one  of  the  practi- 
cal applications  of  electronn  as  apart  from 
their  functions  in  chemical  processes.  We 
have  pleasure  in  here  publishing  "in  toio" 
Pamphlet  No.  2,  issued  hy  the  BiHish 
Science  Guild,  being  "  Thrrmionie  VaUus 
and  Their  Uses,"  by  Prof.  J.  A.  Fleming, 
F.R.S. 


wonderful  instrument  called  the  Thermionic 
valve  is  to  be  found  a  striking  example  of 
the  important  industrial  applications  that 
sometimes  follow  from  discoveries  which 
take  place  in  the  course  of  purely  scientific 
researches.  In  1883  Edison  sealed  into  the 
ordinary  electric  iueaudescvnt  lamp  in  use 
for  domestic  lighting  purposes- a  metal  plate 
between  the  legs  of  its  carbon  filament. 
This  plate  was  carried  on  a  "'-v  ^"aled 
through  the  wall    of  the    glass  He 

noticed  that  when  the    filament   ^  ..>... 

incandescent  .  by     a     direct     cunt 
through  it,  simultaneously  a  small 
current  could    be    observed    to    be 
through  any  delicate    eurrent-detectiug    ui- 
strument  joined  up  in  a  circuit  between  the 
positive  terminal  of  the    filament  and  the 
win.'  carrying    the     metal  plates;     on    the 
other  hand,  when  the  same  instrument  was 
in  a  circuit  between  the  negative  end  of  the 
filament  and    the  plate,    there  was   no  sen- 
sible current.     This  phenomenon  was  called 
the    "  Edison  Effect,"    but  no  explanation 
of  it  was  given    by  its  discoverer,    nor  was 
any  practical  use  made  of  it  at  the  time. 

Scientific  investigations  on  the  nature  of 
this  "Edison  Effect"  were  undertaken  by 
nje,  beginning  in  1883,  and  the  discovery 
was  soon  made  that  this  effect  was  con- 
uected  with  the  projection  in  straight  lines 
of  particles  from  the  filament.  Sir  William 
Preeoe,  in  1885,  communicated  to  the  Royal 
Society  a  paper  on  this  effect,  and  there 
was  another  paper  by  me  in  1889,  in  which 
last  it  was  shown  that  these  projected  par- 
ticles carried  a  charge  of  negative  electricity 
and  could  convey  negative  electricity  froin 
the  filament  to  the  plate,  but  not  in  the 
()|)po8ite  direction.  A  long  paper  on  this 
subject  was  sent  by  the  present  author  in 
1896  to  the  Physical  Society  of  Ix>ndon. 

A  "further  step  in  advance  was  made 
about  1897  by  Sir  Joseph  Thomson,  the 
present  master  of  Trinity  College,  Cam- 
bridge, who,  whilst  carrying  out  his  re- 
markable researches  in  the  Cavendish 
Laboratory,  found  that  the  chemical  atoms 
of  nuitter  which  at  the  time  were  thought 
to  be  incapable  of  being  divided,  were  built 
up  of  still  smaller  atoms  of  electricity,  now 
called  electrons,  and  it  was  soon  definitely 
ascertained  that  the  incandescent  filament 
of  the  ordinary  electric  lamp  is  contintiously 
sending  out  a  vast  number  of  these  little 
electrons  in  all  directions. 

All  those  achievements  were  purely  scien- 
tific, and  attracted  no  poipular  attention. 

About  1897  the  application    by  Senators 


220 


THE  CHEMICAL  NEWS. 


OCTOBER  5,  1923. 


Marooni  of  Hertzian  Electric  Waves  for  the 
purposes  of  wireless  telegraphj?  began  to 
create  public  interest.  For  detecting  these 
waves  he  first  used  his  improved  form  of 
the  coherer  of  Branly  and  Sir  Oliver  Lodge. 
It  was,  however,  rather  capricious  and 
somewhat  difficult  to  manage,  and  Marconi 
soon  replaced  it  by  his  magnetic  detector  in 
190L 

Invention  of  the  Thermionic  Valve. 
In   Marconi'si    system    of  wireless     tele- 
graphy, the  electric  waves  ai-e  generated  by 
cremating     powerful     vibratory    currents    of 
^^ectricity  in  a  wire    called  an  aerial    wire 
"  stretched  up  through  the  air.     The  electric 
oscillations    in  this    wire  produce    in    sur- 
rounding space  an  effect  called  an  Electric 
Wave,     which    travels    outwards  with    the 
speed    of    Kght,    viz.,    186,000    miles    per 
seoond.     When  these  waves  cut  across  an- 
other similar  wire,  called  a  receiving  aerial, 
they  create  in  it  feeble  electric  vibrations  of 
the  same  type. 

In  considering  this  matter,    in  researches 
carried  out  at  Unibersity  College,  London, 
on  Wireless  Telegraphy,  in  1904,  I  saw  that 
if  means  could  be  found    of  converting  the 
very  rapid  to  and  fro,  or  alternating,  move- 
ments of  electricity  in  the  receiving  circuits 
into  a  uniform  motion    of  electricity  in  one 
direction,  it  would  then    be  possible  to  de- 
tect them,  and  therefore  the  electric  waves, 
by  the  use    of  the    telephone    or    galvano- 
meter aa  in    ordinary    telegraphy,    without 
the  use  of    a  coherer.       The    \abrations    of 
electricity  in  wireless  telegraph  aerials  are, 
however,  bery  rapid,    even  up  to  a  million 
per  second,  and    none    of    the  devices    for 
"rectifying"  or  converting  slow  alternating 
electric  currents    into  direct  currents  are  of 
any  use.     Recalling  to  mind,  however^    my 
scientific     investigations     on     the     Edison 
Effect,    I  found    on    experiment  that,    if  a 
metal  cylinder  was  placed    around  the  fila- 
ment inside  the  vacuous  bulb  of  an  electric 
lamp  carried  on  a  wire    sealed  through  the 
bulb,  this  appliance    could    "rectify"    and 
therefore  detect  by  the    aid  of  a  telephone 
or  galvanometer  the  feeble    high  frequency 
oscillations    of    electricity.       These    cannot 
directly  affect  a  telephone,  because  of  their 
rapid  reversals    of  directions    thousands  of 
times  per  second,  but  the  instrument  above 
described  acts  as  a  valve  when  placed  in  the 
path    of    these    oscillations,     and    converts 
them  into  motions  of  electricity  in  one  di- 
rection in  virtue  of  the    fact  that  negative 
electrons  are  passing    in  the  vacuous  space 


only  from  the  filament  to  the  surrounding 
metal  cylinder. 

I  therefore  named  this  appliance  an  oscil- 
lation valve  and  subsequently  a  thermionic 
valve. 

Later,  in  1909,  I  suggested  the  use  of 
tungsten  as  the  material  for  the  filament  in 
place  of  carbon,  as  it  withstands  a  higher 
temperature  and  emits  more  electrons. 

The  above  described  two-electrode  or  hot 
and  cold  electrode  thermionic  valve  was 
soon  etensively  adopted  as  a  means  of  rec- 
tifying and  detecting  electric  oscillations 
and  detecting  wireless  waves. 

In  the  spark  system  of  wireless  tele- 
graphy then  exclusively  used,  the  waves 
come  in  little  groups  of  20  or  30  with  longer 
intervals  of  time  between  the  groups.  The 
Fleming  valve  rectifies  the  groups  of  oscil- 
lations produced  in  the  receiving  aerial  into 
short  gushes  of  electricity  in  one  direction, 
and  when  these  are  passed  through  a  tele- 
phone they  gave  rise  to  a  more  or  less  musi- 
cal iSound  which  can  be  cut  up  by  a  key  in 
the  transmitter  into  dot  and  dash,  or  short 
and  long  sounds  making  signals  in  the 
Morse  Code. 

Subsequent  Improvements. 

In  1907  an  addition  was  made  to  the 
author's  O'scillation  valve  by  Dr.  Lee  de 
Forest,  who  had  been  following  in  the 
United  States  very  carefully  the  work  done 
on  this  subject.  Dr.  de  Forest  introduced 
into  a  low  vacuum  valve  a  grid  or  zig-zag  of 
wire  between  the  filament  and  the  plate. 
This  started  a  new  line  of  development, 
and  it  was  found  that,  if  a  cylinder  of  metal 
gauze  or  spiral  of  wire  was  introduced  into 
the  hard  or  high  vacuum  Fleming  Valve  be 
tween  the  cylinder  and  the  filament,  it  en- 
abled the  device  to  act  as  an  amplifier  of 
oscillations  as  well  as  a  detector,  so  that 
very  feeble  high  frequency  oscillations  could 
be  magnified  five  or  ten  times  by  its  aid. 
This  sukgesticMi  was  deaeloped  practically 
by  the  resources  of  the  Western  Electric 
and  General  Electric  Companies  of 
America. 

This  modified  form  then  became  known 
as  a  three-electrode  valve,  and  is  sometimes 
called  for  shortness  a  triode,  or  other  trade 
names.  To  employ  it  as  an  amplified  we 
have  to  connect  a  high  tension  battery  giv- 
ing, say,  40  to  140  volts  with  its  negative 
polo  joined  to  the  filament  and  its  positive 
pole  to  the  plate.  A  torrent  of  electrons  is 
then  forced  from  the  filament,  through  the 
holes  in  the  grid  or  gauze  to  the  plate.     If, 


OCTOBER  5,  1923. 


THE  CHEMICAL  NEWS. 


221 


however,  a  feeble  electrification  is  given  to 
the  grid  positive  or  negative  it  increases  or 
decreases  this  electron  ciuTt-nt.  The  grit  I 
potential  electrification  can  be  obtainod 
from  anj  two  points  on  a  circuit  in  which..! 
feeble  hikh  frequency  current  flows,  and  the 
variation  of  the  plate  current  of  the  valve 
will  follow  the  variations  of  its  grid  poten- 
tial. A  number  of  such  valves  can  be  used 
in  st'ries  and  inter-connected  by  suitable 
induction  coils  or  transformers  and  the 
plate  current  variations  in  one  valve  made 
to  create  changes  of  grid  pf>tential  in  the 
next  valve.  By  a  series  of  such  coupled 
amplifying  valves,  we  can  t-hen  magnify  in 
any  required  proportion  feeble  electric'  os- 
cillations. It  is  the  invention  of  this  de- 
tector comprising  a  series  of  amplifying 
valves  which  has  given  us  a  detector  of 
electric  oscillations  so  enormously  sensitivi 
that  wireless  signals  can  b<'  detected  by  it 
at  the  antipodes  of  the  sending  station  and 
enabled  us  to  signal  half  round  the  world  by 
its  aid. 

(To  be  Continued.) 


FLASHING    POINTS. 
By   Frank  Brownk,    F.l.C. 

Attention  is  drawn  to  the  dangerous 
nature  of  highly  infl[an)mablc  liquids  of  low 
flashing  point,  of  which  class  other,  benzol, 
carbon  disulphide,  benzol inc  and  petrol  are 
typical.  Their  flashing  points  (close  test) 
are  between  -11°  and  -30°.  Liquids  with 
such  low  flashing  points  continuously  give 
off  inflammable  vapour.  The  vapour  from 
each  is  about  2.5  times  heavier  than  air. 
('onsequently,  on  a  warm,  still,  day,  this 
vajpour  floNV's  from  an  open  tin  of  the  liquid 
on  to  the  floor,  and  may  be  drawn  towards 
a  flame  situated  at  a  distance  of  30  feet  by 
the  air  current  pr<xluced  by  the  heat.  Then 
also  tile  heavy  vapour  may  pass  through 
flooring  into  a  danger  zone  in  a  room  below, 
f>r  it  may  flow  downstairs.  Users  and  the 
public,  both  on  land  and  sea,  should  recog- 
nise these  dangerous  properties,  and  take 
measures  accordingly.  Where  such  a  liquid 
is  being  used  there  should  be  no  flame  with- 
in a  distance  of  50  feet.  A  store  should  be 
ventilated  both  at  top  and  bottom.  Water 
iM'ing  useless,  a  good  supply  of  sand  should 
be  available  for  putting  out  a  fire.  Vessels 
oontaining  these  liquidis  might  usefully  be 
labelled  "  In  case  of  accident,  smother 
fire  with  sand,  earth  or  cloth."- — (From  the 
"  Pharmaceutical  Journal,"    1928,  p.  305.) 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

A  meeting  of  the  Society  was  held  on 
Wednesday,  October  3rd,  at  the  Chemical 
Society's  Rooms,  Burlington  House,  W. 

Papers  read :  — 

The  Sampling  of  Coal;  the  General  Prob- 
lem and  some  Experiments,  by  J.  H.  Coste, 
F.l.C,  E.  R.  Andrews,  F.I.C,  and  W.  E. 
F.  POWNEY,  F.l.C. 

A  New  Teat  for  distinguishing  Castor  Oil, 
by  H.  G.  Stocks,  F.l.C. 

The  Volumetric  Eslimation  of  Vanadium 
in  Steel,  by  A.  E.  ExHEKmaEi  B.Sc, 
F.l.C,  M.B.E. 

The  lodimetric  Determination  of  Sugars, 
by  C  L.  HiNTON,  F.l.C,  and  T.  Macara, 
F.l.C. 


THE    CHEMICAL    SOCIETY. 

Ordinary  Scientific  Meeting,    Thursday, 
October  4. 

The  following  papers  were  read :  — 

A  Revision  of  the  Dissociation  Constants 
of  Weak  Inorganic  Acids.  Part  I. :  Boric 
Acid,  by  E.  B.  R.  Prideaux  and  A.  T. 
Ward. 

A  Revision  of  the  Dissociation  Constants 
of  Weak  Inorganic  Acids.  Part  II. :  Phos- 
phoric Acid,  by  E.  B.  R.  Prideaux  and  A. 
T.  Ward. 

Two  Heterogeneous  Gas  Reactions,  by 
('.  N.  HiNSUELwooD  and  C  R.  Prichard. 

A  Homogeneous  Oas  Reaction.  The 
Thermal  Decomposition  of  Chlorine  Mon- 
oxide. Part  I.,  by  C.  N.  Hins^elwood  and 
C  R.  Prichard. 

The  Direct  Union  of  Oxygen  and  Sul- 
phur,   by  R.  G.    W.    NoRRiSH    and    E.    K. 

RiDEAL. 

Note  on  Aqueous  Formaldehyde  Solu- 
tion, by  W.  R.  Ormandy  and  E.  C.  Craven. 

The  Interaction  of  Potassium  Tetroxide 
with  Ice  and  with  Dilute  Sulphuric  Aaid,  by 
H.  Hawley  and  H.  J.  S.  Sand. 


222 


%^ 


THE  CHEMICAL  NEWS. 


BRITISH   DYESTUFFS. 

An  imp<:)i*t.ant  letter  on  the  above  subject 
by  Prof.  W.  M.  Gardner  appeared  in  the 
Yorkshire  Post  on  September  12,  from 
which  the  following  is  taken:  — 

"  At  the  recent  general  meeting  in  Man- 
chester of  the  British  Dyestuffs  Corpora- 
tion (Limited),  the  Chainnan  indicated  that 
the  policy  of  the  directors  for  the  pi^sent 
would  be  not  to  strive  after  new  discoveries, 
but  to  develop  the  cheaper  manufacture  of 
known  products.  This  decision  has  led  to 
the  resignation  of  the  chief  research  chemi-st 
of  the  Corporation. 

It  must  be  recognised  that  the  direc- 
tors are  faced  with  enormous  difficulties. 
Their  caipital  charges  and  production  costs 
are  excessively  high  owing  largely  to  condi- 
tions beyond  their  control;  bad  trade  has 
greatly  reduced  the  demand  for  their  pro- 
ducts in  this  "country,  and  what  export 
trade  there  is  is  subject  to  the  competition 
of  Germany,  Switzerland,  and  the  United 
States.  Dye  users  are  strongly  urging  re- 
duction in  prices,  and  the  shareholders  in 
the  Corporation  have  hitherto  received  a 
very  meagre  return.  Under  these  condi- 
tions the  directors  are  bound  to  adopt  all 
possible  economies  which  do  not  militate 
against  ultimate  success,  and  having  spent 
£400,000  on  research  work  during  the  past 
four  years  they  propose  to  curtail  such 
work  in  the  future. 

Two  questions  arc  involved.  Is  this 
policy  the  correct  one;  and,  if  not,  what  is 
the  defect  in  the  organisation  which  has  led 
to  its  adoption? 

"  With  regard  to  the  first  point,  the  past 
history  of  the  industry  is  very  illuminating. 
It  originated  and  was  developed  here  for 
some  years,  but  soon  migrated  to  Germany, 
mainly  because  the  large  profits  made  were 
used  here  as  dividends,  but  in  Germany 
were  utilised  for  research  and  works  de- 
velopment. This  fact,  and  the  disastrous 
consequences  of  a  repetition  of  the  policy, 
have  been  pointed  out  again  and  again  by 
those  who  have  made  a  special  study  of  the 
question. 

"  The  declared  policy  of  the  Conpora- 
tion  seems  to  be  a  repetition  of  the  policy  of 
the  early  sixties,  which  led  to  the  ship- 
wreck of  the  British  dye  industry  in  the 
early  days.  It  is  diametrically  opposed  to 
the  policy  which  had  led  to  success  else- 
where. And,  in  expending  £400,000  in  four 
years  on  research,  the  Corporation  has  only 
been  fulfilling  an  essential   condition,       In 


OCTOBER  6,  1928. 


the  successful  manufacture  of  dyes  research 
is  as  essential  as  raw  material  and  special 
maohiner},  and,  appositely  enough,  the 
Board  of  Trade  Journal  of  August  30  (p. 
216)  gives  the  ofiicial  figure  of  21  million 
dollars  as  having  been  expended  on  dye  re- 
search in  the  United  States  during  the  past 
five  years.  It  is  well  known,  also,  that 
one  of  the  large  German  colour  works,  the 
Dadische  Co.,  expended  upwards  of  £900,000 
on  research  on  the  synthetic  production  of 
indigo  alone.  Research  is  the  lifeblood  of 
colour  manufacture,  and  the  only  wise 
policy  in  bad  times  is  to  intensify  the  work, 
which  will  lead  to  the  introduction  of  new 
and  valuable  products  from  which  a  rich 
harbest  will  be  reaped.  To  curtail  research 
is  to  admit  defeat  by  Continental  and 
American  competition.     .     .     ." 


GENERAL   NOTES. 


GERMANY'S    POTASH    INDUSTRY. 

The  Commercial  Secretary  at  Berlin  (Mr. 
H.  N.  Sturrock)  has  forwaided  to  the  De- 
partment of  Overseas  Trade  a  report  from 
the  Industrie  und  Handels  Zeitung  of  Sep- 
tember 5,  which  states  that  the  year  1922 
was  a  record  one  for  the  potash  industry, 
the  sales  of  pure  potash  increasing  from 
460,591  tons  in  1921  to  647,722  tons  in  1922, 
or  40  per  cent.  From  a  report  on  industry, 
by  the  Commerz  und  Privatbank,  it  is  clear 
that  the  enormous  increase  of  potash  sales 
in  1922  was  in  part  due  to  a  covering  in  ad- 
vance, having  regard  to  the  currency  depre- 
ciation and  to  anticipation  by  customers  of 
a  further  nominal  increase  of  potash  prices. 
During  the  first  months  of  1923,  customers 
showed  a  certain  reserve — a  natural  re- 
action after  large  purchases,  and  partly  due 
to  the  anticipated  stabilisation  of  the  mark. 
When  it  became  clear  that  this  could  not  be 
maintained,  the  demand  of  German  agricul- 
ture set  in  on  such  a  scale  that  in  June  the 
highest  monthly  sales  so  far  recorded  by  the 
potash  industry  were  effected,  viz.,  90,000 
tons  KoD.  In  spite  of  these  large  sales,  the 
level  of  the  previous  year  has  not  yet  been 
reached,  but  it  is  assumed  that  the  differ- 
ence will  be  made  good  during  the  follow- 
ing months,  provided  no  unforeseen  circum- 
stances arise.  Foreign  coimtries,  in  parti- 
cular, should  contribute  thereto,  as  foreign 
sales  in  1923  have  so  far  been  satisfactory. 
The  fact  must  not,  however,  be  lost  sight  of 
that  diflRculties  of  sale  in  the  potash  indus- 


OCTOBER  5,  1923. 


THE  CHEMICAL  NEWS. 


223 


try  would  arise  immediately  if  the  costs  of 
prwluction  were  rapidly  adjusted  to  the 
gold  parity,  but  foreigu  exchanges  were  to 
show  a  sinking  tendency.  In  such  case, 
the  potash  industry  would  doubtless  feel 
the  competition  of  the  Alsatian  works  on 
the  world's  market  seriously.  As  before, 
the  American  and  Dutch  markets  are  the 
most  important  customers  for  Gemian 
potash. 

The  income  of  the  industry,  measured  by 
distributed  profits,  is,  of  course,  as  in  the 
case  of  the  whole  of  German  industry,  ex- 
tremely meagre,  particularly  in  proportion 
to  the  gold  capital  invested  in  it.    • 

The  present  policy  of  concentration  has 
proved  exceedingly  successful,  and  has  re- 
sulted in  a  considerable  reduction  of  the 
costs  of  production.  Only  thus  has  it  been 
possible  to  keep  the  inland  prices  of  potash 
comparatively  low,  so  that  the  increase  ms 
connpared  with  pre-war  times  is  consider- 
ably less  than  in  the  case  of  other  compar- 
nble  y>roducts  of  German  industry. 


PITCH  FOR  BRIQUETTES. 

Mr.  R.  Ij.  Nosworthy,  H.M.  Consul  at 
Turin,  reports  that  a  local  railway  company 
is  in  the  market  for  a  oonsirlerable  amount 
of  pitch  for  use  in  the  manufacture  of  bri- 
quettes (^mattonelle   carbone). 

U.K.  hriiis  desirous  of  n'ceiving  furtlier 
particulars  regarding  this  matter  should 
apply  to  the  Department  of  Overseas  Trade, 
35,  Old  Queen  Street,  London,  S.W.I, 
quoting  reference  20579/ F.W./M.C.2. 


INTERVIEWS  WITH  THE  COMMER- 
CIAL SECRETARY  AT  BELGRADE. 
Capt.  E.  Murray  Harvey,  O.B.E.,  Com- 
mercial Secretary  at  Belgrade,  will  be  in  at 
tendance  at  the  Department  of  Overseas 
Trade  on  October  1,  2  and  3,  for  the  ipur- 
post!  of  int<'rviewing  manufacturers  and 
merchants  interested  in  trade  with  the 
Serb-Croat-Slovene  Kingdom. 

Such  intt^rviews  will  only  !»<  given  by  ap- 
pointment, and  applications  sihould  bo  ad- 
dressed to  the  Comptroller-General,  De- 
partment of  Overseas  Tra<le,  35,  Old  Queen 
Street,  London,  S.W.I.  In  all  cases  the 
reference  4937/T.G.  should  be  quoted. 


BRITISH    FLOUR    MILLERS' 

RESEARCH    ASSOCIATION. 

The    Secretary     of    the    Department     of 

Scientific  and  Industrial  Research  begs    to 

announce  that  a  licence,    imder  Section  20 

f>f  tlu"  Companies'  (Consolidation)  Act,  1008, 


has  been  issued  by  the  Board  of  Trade  to 
the  Research  Association  of  British  Flour 
Millei^,  which  has  been  approved  by  the 
Department  as  complying  with  the  condi- 
tions laid  down  in  the  Government  scheme 
for  the  encouragement  of  industrial  re- 
search. 

The  Secretary  of  this  Association  is  Mr. 
G.  H.  Ball,  LL.B.,  40,  Trinity  Square, 
E.G. 


NOTICES  OF  BOOKS. 

Practical  Chemistry  for  High  Schools, 
by  H.  B.  DcNNiCLiFF,  M.A.,  B.Sc, 
A.I.C.  Pp.  IX.  +  279.  London:  Mac- 
Millan  &  Co.,  Ltd.,  St.  Martin  Street, 
W.C.2.     1923.    5s. 

There  are  now  so  many  reliable  text- 
books on  practical  chemistry  that  a  new 
publication  should  possess  some  outstand- 
ing feature  to  justify  its  appearance. 

In  the  case  of  the  present  volume,  which 
is  presumably  intended  for  young  students 
who  have  not  previously  studied  chemistry, 
it  is  difficult  to  find  anything  strikingly  ori- 
ginal in  the  matter  or  the  presentation  of 
the  subject. 

Indeed,  certain  passages  might  well  have 
been  improved  upon  from  the  teaching 
standpoint,  and  the  book  leaves  the  impres- 
sion of  having  been  hastily  compiled. 

Certain  of  the  experiments  are  headed 
Demonstrations,  and  are  apparently  to  be 
performed  by  a  demonstrator  at  the  end  of 
the  ordinary  practical  work.  It  will  come 
as  a  surprise  to  most  chemists  to  find  that 
the  first  exiperiment  for  the  beginner  is  the 
ignition  of  CSj  I 

On  page  25,  in  the  section  on  the  use  of 
pipette  and  burette,  quite  complicated 
mathematics  (involving  the  volume  ot  a 
sphere)  is  introduced.  The  reviewer's  ex- 
perience is  that  even  the  simplest  chemical 
calculations  require  careful  presentation  to 
young  pupils. 

Most  of  the  illustrations  are  good,  others, 
e.g.,  the  dLstillation  apparatus  shown  on 
page  17,  could  be  clearer. 

The  old  method  of  folding  a  filter  paper  is 
shown  on  page  32,  but  there  is  no  mention 
of  the  modern  practice. 

On  page  67  the  author  gives  several  defi- 
nitions of  an  acid  which  he  terms  inconect. 
They  are  really  incomplete,  and  it  would 
have  been  better  to  have  explained  this  to 
the  student.  In  the  same  chapter  the  Ionic 
Theory  is  dismissed  in  a  few  linos,  and  there 
is  no  further  reference  to  ions  in  the  rest  of 


224 


THE  CHEMICAL  NEWS. 


OCTOBER  5,  1923. 


the  book,  and  not  one  ionic  equation  is 
given. 

For  some  reason,  the  Qualitative  Analysis 
Tables  for  identifying  metals  are  duplicated, 
and  this  part  of  the  book  seems  over-bur- 
dened with  tests  and  re-actions. 

These  points,  in  the  reviewer's  opinion, 
detract  from  the  value  of  a  volume  which  is 
intended  for  use  in  schools.  J.G.F.D. 

Field  Crops  in  South  Africa,  by  H.  D. 
Leppan,  B.ScA.,  and  G.  J.  Bosman, 
B.Sc.A.  Pp.  IX.  +  358.  Johannes- 
burg: Central  News  Agency,  Ltd.,  South 
Africa.  1923.  21s.  net. 
The  time  is  rapidly  aipproaching  when 
the  food  production  of  the  world  will  be- 
come a  matter  of  urgent  importance. 

In  his  volume,  The  Wheat  Problem,  pub- 
lished in  1898,  the  late  Sir  William  Crookes 
drew  attention  to  the  wasteful  methods  of 
cultivation  and  the  risks  this  entailed. 
Other  authorities  have  also  emphasised  the 
need  for  scientific  methods  in  agricultural 
practice. 

There  is,  fortunately,  increasing  evidence 
of  the  successful  application  of  scientific 
methods  to  crop  production,  and  this  is  not 
restricted  to  Great  Britain.  The  present 
volume  by  Messrs.  Leppan  and  Bosman  in- 
dicates that  considerable  progress  is  being 
made  in  the  Union  of  South  Africa. 

The  subject  of  agronomy  is  treated  in  its 
various  branches  in  as  comprehensive  a 
manner  as  possible.  The  authors  have 
taken  into  consideration  the  chemistry, 
physics  and  biology  of  the  soil  in  relation 
to  plant  culture.  They  also  indicate  the 
effect  of  changes  in  temperature,  humidity, 
air  currents,  and  light  upon  growth,  and 
deyote  due  attention  to  the  questions  of 
adaptation,  breeding,  and  control  of  pests. 
Reference  is  made  to  the  advances  in  these 
various  branches  of  the  subject  which  have 
been  made  by  the  Experimental  Stations  in 
South  Africa. 

The  principal  summer  crops  include 
maize,  sorghums,  potatoes,  lucerne,  vari- 
ous legumes,  cotton,  and  sugar-cane.  Win- 
ter crops  include  cereals  and  roots. 

By  reason  of  its  extremely  diversified 
climatic  conditions  and  peculiar  economic 
factors,  agriculture  in  South  Africa  pre- 
sents a  great  variety  of  problems.  Doubt- 
less considerable  progress  will  continue  to 
be  made  in  the  cultivation  of  those  crops 
most  suited  to  the  country. 

Those  interested  in  the  subject  and  wish- 
ing to  consult  this  important  volume  can 
procure  it  from  the  English  agents,  Messrs. 


Gordon    &  Gcftch,    15, 
E.C.4. 


St.    Bride    Street, 


Alloys  Resistant  to  Corrosion — A  General 
Discussion.  1923.  The  Faraday  Societv, 
10,  Essex  Street,  W.C.2.     Price  5s.  6d. 

Recent  Developments  in  Atomic  Theory, 
by  Leo  Graetz  (Professor  of  Physics  in  the 
University  of  Munich.  Pp.  XI.  +  174. 
1923.  Messrs.  Methuen  &  Co.,  Ltd.,  36, 
Essex  Street,  W.C.2.     9s.  net. 


iHis  lisL  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chanoery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Specifications   Published  this   Week, 
203013— Thwaite,  A.  H.,  and     Pease     &    Partners, 
Ltd.— Apparatus  for  drying,  grinding,  and 
neutralising  sulphate   of  ammonia   in   one 
operation. 
20801.'>-Saltriok,   W.   R.— Extracting  and    refining 

metals  and  alloys. 
203051— Soc.     of  Chemical     Industry     in     Basle.— 
Manufacture    of       2 :3-diamino-anthraqui- 
none. 
203059— Murdoch,  D.  G.,     and  Galbraith,  W.  L.— 
Reduction   of  organic     compounds,    particu- 
larly of  nitro  and  azo-derivatives. 
203124— Petroff,   G.— Production     of     phenol     alde- 
hyde condensation  products. 
181014— Pollak,   Dr.  T.— Manufacture  of  condensa- 
tion products  from  urea  or  its  derivative,"! 
nnd   formaldehyde. 
202678— Cocksedge,  H.  E.— Process     and    manufac- 
ture of    a    sodium    compound  and    a  new 
composition  containing  the  same. 
Abstract  Published  this  Week. 
200760— Alkali     thiosulpliates.— Koppers       Co.,     of 
800.     Union  Arcade     Building,     Pittsburg, 
U.S.A. 

Abstract  Published  this  Week. 
201302 — Synthetic  drugs.— Farbwerke  vorm.  Meis- 
ter,  Lucius,  &  Bruning,  Hoechst-on-Main, 
Germany. 
4-Amino'-a-  argentomercaptol>6nzene-l-carboxylic 
acid  is  obtained  by  reacting  upon  4-amino-2-mer- 
oaptobenzeiie-l-carlx)xylio  acid  witli  a  silver  salt. 
The  product,  in  the  form  of  its  alkali  salts,  is 
effacious  in  the  treatment  of  diseases  caused  by 
bacteria;  it  forms  an  N-methyl-w-sul phonic  acid 
with  formaldehyde  and  bisulphite,  and  can  be  di- 
azotized  and  coupled  with  R-salt.  In  an  example 
the  reaction  is  effected  with  silver  acetate  in  aque- 
ous acetone  containing  ammonia;  the  solution  is 
poured  into  a  mixture  of  acetone  and  spirit  and 
the  product  filtered,  dissolved  in  diluted  ammonia 
ryid  the  free  silver  compound  precipitated  by 
acid;  ammoniacal  silver  chloride,  silver  fluoride, 
or  silver  nitrate  may  be  used  in  place  of  the 
acetate. 

4-amini-2-meroaptobenzone-l-carboxylio  acid  is 
obtained  by  diazotizing  4-nitro-2-amino-benzene- 
1-carboxylic  acid,  treating  with  potassium  and 
cuprous  sulphocyanides,  and  reducing  the  nitro- 
sulphocyanobenzene  oarboxylio  acid. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  le.  6d. 
each. 


OCTOBER  12,  1923. 


THE  CHEMICAL  NEWS. 


225 


THE   CHEMICAL  NEWS, 

VOL.  GXXVII.       No.  3313. 

IS  THERE  AN  ELEMENT  OF  ZERO 

ATOMIC  NUMBER? 

Part  IV. 

By  F.  H.  LoRiNG. 

In  continuation  of  the  above  subject — 
The  Chemical  News,  1923,  CXXVI.,  pp. 
307,  325,  369 — attention  maj  be  drawn  to 
another  line  of  study,  but  before  iprocecdinj^ 
with  this  development,  it  is  considered 
necessary  to  refer  to  an  abstract  of  the  first 
two  papers,  which  appeared  in  Science 
Abstracts  for  September,  page  618,  as  fol- 
lows: — "  It  is  suggested  that  a  single  elec- 
tron might  be  regarde<l  as  r{'i)re8enting  an 
atom  with  atomic  number  zero,  since  tlic 
atomic  number  represents  the  number  of 
protons  in  the  atom,  and  a  single  electron 
of  course  contains  no  protons."  The  italics 
are  the  present  writer's.  Continuin<:j  the 
quotation  in  order  to  refresh  the  mind  (.f  tiic 
readier  as  to  the  general  scheme  of  arrange- 
ment involved  in  the  argument — "  If  the 
I'xistence  of  an  active  element  with  atoruic 
niimlx>r  zero  is  assumed,  and  if  the  number 
of  active  elements  below  each  of  the  inert 
ga.s«'s  is  subtracted  from  its  atomic  number, 
the  series  0,  1,  2,  3,  4,  5  is  obtained,  <tc." 

Now  it  was  not  the  writers  intention  to 
convey  the  idea  that  the  atomic  number 
was  exactly  represented  by  the  number  of 
protons  in  the  atom,  as  obviously  the  exist- 
ence of  isotopes  on  first  tbougiit  renders 
such  an  idea  impossible ;  in  fact  it  was  ex- 
plicitly stat^^d  that  the  electrons  in  the 
nucleus  of  the  atom  conditioned  it  in  terms 
of  atomic  number — see  bottom  of  page  32r) 
rt  seq.  (See  also  Aston's  "  Isotopes," 
pages  106,  107.) 

It  is  evident,  however,  that  the  existence 
of  sub-atoms  of  zero  atomic  number  of 
mass  1  might  bring  about  such  a  state  of 
affairs,  and  no  doubt  the  abstracter  gathered 
this  idea  from  the  argument  as  presented. 
This  vitnv  becomes  an  interesting  possibil- 
ity, but  it  will  suffice  merely  to  call  particu- 
lar attention  to  it  here. 

In  The  Chemical  News  of  July  26,  1012. 
vol.  CVI.,  ip.  37,  the  present  writer  showed 
that  the  periodic  table  could  be  partitioned 
into  a  series  of  5  natural  groups,  as  follows  : 
Inert  gase«;  Gronp  VIIT. ;  Group  Vv  to  Lu ; 


The 


re- 


Grouping  Cu,  Ag,  Au,  to  Br,  I, 
maining  elements. 

The  numbers  of  elements  in  these  respec- 
tive groups  and  groupings  were  given  as  8, 
9,  13,  20  or  21,  43,  the  sum  being  92.83  by  a 
formula  given  fot-  calculating  them.  This 
was  in  1912,  before  the  atomic  numbers 
were  known.  Had  the  atomic  numbers  been 
known  at  the  time,  the  radio-elements 
would  have  been  fully  included  in  the 
scheme.  The  term  element  is  now^  used  in 
the  atomic-number  sense  in  discussions  of 
this  kind. 

If  now  an  element  of  zero  atomic  number 
is  introduced  at  the  head  of  the  inert  gases, 
it  could,  of  course,  be  the  electron  as  an  ele- 
ment in  one  sense,  for,  like  the  inert  gases, 
its  atoms  do  not  appear  to  combine  with 
themselves,  since  they  (the  electrons)  rctpel 
each  other :  but  they  are  in  other  ways 
active. 

Another  view  is,  however,  possible,  and 
that  is  to  consider  an  element  of  neutral 
|)roperty  as  if  an  electron  had  combined 
closely  with  a  proton.  This  was  discussed 
in  Part  HI.  (p.  369)  of  this  series  of  papers. 
This  will  be  referred  to  again  below. 

It  will  be  seen  from  the  foregoing  that 
there  should  be  7  inert  gases;  9  elements  of 
Group  VIII.;  13  elements  of  Group  III. 
after  cerium,  generally  referred  to  as  the 
rare-earth  series  (extended  series  to  be  more 
precise);  21  elements,  of  which  Cu,  Ag,  Au, 
are  the  left-hand  members;  and  finally,  13 
elements,  the  left-hand  members  of  which 
arc  the  alkali  elements  and  including  hydro- 
gen and  those  of  atomic  numbers  72,  73,  74, 
75,  87,  88,  89,  90.  91,  92. 

Of  course,  some  of  the  elements  now  re- 
presented by  gaps  may  exist  in  very  small 
relative  quantities,  as  already  discussed  in 
these  pages — see  The  Chemical  Ncwa,  1922, 
vol.  CXXV.,  pp.  309,  386;  1923,  vol. 
CXXVI.,  p.  1. 

Considering  another  cognate  matter, 
coronium  is  known  in  the  sun,  but  it  is  not 
knov^Ti  on  the  earth,  so  that  it  is  in  the 
nature  of  events  to  expect  future  discovery 
in  this  connectign  to  throw  some  light  upon 
the  problems  here  discussed. 

To  show  the  trend  of  mrdern  thought, 
the  following,  from  page  157  of  a  new  book 
just  published.  Recent  Developments  in 
Atomic  Theory,  by  Tj.  Graetz,  translated 
from  the  Gemian  by  G.  Barr,  is  of  interest 
in  relation  to  these  matters.  In  this  expo- 
sition, Rutherford  [see  the  writer's  Atomic 
Theories,  pp.  48,  49]  remarks  that  it  is  pos- 
sible that  two    hydrogen    nuclei     [protons] 


226 


THE  CHEMICAL  NEWS. 


OCTOBER  12,  1923. 


with  one  electron  might  form  the  nucleus 
of  another  atom,  which  would  then  have  a 
mass  2  and  a  nuclear  charge  1,  so  that  it 
would  be  an  isotope  of  hydrogen.  But 
there  might  also  be  a  structure,  consisting 
of  a  hydrogen  nucleus  and  a  negative  elec- 
tron, in  which  the  electron  was  not,_  as  in 
the  'hydrogen  atom,  at  a  great  distance 
from  the  nucleus  but  directly  adjacent  to  it. 
Such  a  structure  would  be  electrically  neu- 
tral except  in  its  immediate  neighbourhood. 
At  the  same  time  it  would  have  a  certain 
linear  shape,  and  would  orient  itself  in  a  de- 
finite direction  in  a  magnetic  or  electric 
field.  The  possibility  is  not  remote  that 
what  we  call  gether—which  is,  as  is  well 
known,  a  very  bugbear  in  physics— might 
perhaps  consist  of  such  a  doublet.  _  The 
linear  extension  of  this  structure  [lines  of 
force?]  would  in  particular  afford  an  ex- 
planation of  the  fact  that  aether  propagates 
electric  and  magnetic  disturbances  in  the 
form  of  transverse  vibrations.  It  would 
then  also  be  conceivable,  according  to  an 
idea  of  Nernst's,  that  under  certain  circum- 
stances hydrogen  atoms  might  be  generated 
out  of  the  aether,  or,  conversely,  hydrogen 
atoms  might  be  absorbed  into  the  aether. 
Lodge  (Nature,  Aug.  4,  1923)  has  sug- 
gested that  electrons  are  generated  and  ab- 
sorbed in  a  similar  way,  involving  the  trans- 
formation of  the  energy  of  radiation.  This 
is,  of  course,  speculation,  but  there  are 
many  phenomena  known  to-day  which  make 
such  ideas  worth  serious  study. 

The  following  points  may  be  noted  m 
connection  with  this  study  :  — 

1. — 5  main  groupings  represented  by  the 
number  of  elements  in  each  one. 

2. —There  mav  be  7  inert  gases  or 
members  of  the  "first  group  of  this  series, 
thus  : 

Rn,  Tn,  An  (emanations)  At.  No.  86  (1) 
Xenon  „        ,,     54  (2) 

Krypton 

Argon  , , 

Neon  ) . 

Helium  ,, 

Zero  Element?  ,, 

3.— The  other  numbers,  9,  13,  21, 
together  with  those  above  (7),  in  additive 
agreement  with  the  atomic-number  series; 
and  they  all  stand  in  the  right  order  as  re- 
gards average  chemical  activity. 

4.— The  probable  fact  that  there  will  be 
some  gaps  in  the  periodic  table  which  will 
never  be  properly  filled  is  in  agreement 
with  the  "place  principle"  involved  in  the 
Boh^-Butherford  atom  theory;  and  in  con- 
formity therewith  the  groups  and  groupings 


,,     36 

(3) 

,,     18 

(4) 

,,     10 

(6) 

,,       2 

(6) 

,,       0 

(7) 

1,  43,  . 

ire, 

as  herein  evaluated  include  such  gaips  No- 
thini?  is  in  conflict,  however,  _  with  the 
atomic-number-series  classification  of  the 
elements  in  any  of  these  studies. 

5. The  three  inert  radio-active  gases  are 

isotopic,  but  each  one  being  inactive  chemi- 
cally this  isotopic  character  rests  only  on 
atomic  number,  so  one  is  tempted  to^  raise 
the  figure  to  8  or  9,  according  as  the  "zero 
element"  is  included  or  not,  but  the  balance 
of  the  evidence  seems  to  favour  the  lesser 
number,  7. 

6.— The  question  whether  the  zero  mem- 
ber can  be  an  atom  of  aether,  or  the  elec- 
tron, or  a  close  combination  of  a  proton 
with  an  electron,  or  perhaps  the_  element 
coronium,  makes  the  subject  an  intensely 
interesting  one. 


[British  Science  Guild  Publioit'* 

Service. — Pamphlet  No.  2.] 

THERMIONIC    VALVES.* 

By  Dr.  J.  A.  Fleming,  F.R.S. 

{Continued  from  Page  221.) 

The  Thermionic  Oscillation  Generator. 
The  thermionic  valve  in  its  two  and  three- 
electrode  formsi  iposisesses  the  power  not 
only  of  rectifying  and  detecting  electric  os- 
cillations, but  also  of  creating  so-called 
continuous  or  undamped  oscillations.  This 
discovery  at  once  rendered  possible  radio- 
telephony  on  a  large  practical  scale,  where- 
as it  had  previously  only  been  an  occasional 
feat  of  experts.  The  proper  coupling 
through  a  transformer  of  the  grid  and  plate 
circuits  results  in  the  production  in  these 
circuits  of  self-sustained  oscillations  by 
energy  drawn  from  the  plate  circuit. 

During  and  since  the  war,  improveniv^nts 
have  continually  been  made  in  the  ion- 
struction.of  large  generating  valves.  Begin- 
ning originally  vnth  very  small  powers  oi  n 
few  watts  in  valves  with  bulbs  like  incan- 
descent lamps,  very  large  valves  in  ^la?s 
bulbs  the  size  and  shape  of  Rugby  footballs, 
yielding  an  output  of  6  or  7  kilowatts,  are 
iaoM^  made.    Valves  of  10—20  kilowatts    m- 

*  Readers  of  "The  Chemical  News"  will 
no  douht  be  interested  in  one  of  the  practi- 
cal applications  of  electrons  as  apart  from 
their  functions  in  chemical  processes.  We 
have  pleasure  in  here  publishing  "in  toto' 
Pamphlet  No.  2,  issued  by  the  British 
Science  Guild,  being  "  Thermionic  Valves 
and  Their  Uses,"  by  Prof.  J.  A.  Fleming, 
F.R.S. 


^OCTOBER  12,  1923. 


THE  CHEMICAL  NEWS. 


227 


put  or  more  have  been  made  with  bulbs  of 
siJica.  The  most  recent  advance  in  this  di- 
rection has  come  to  us  jErom  the  United 
States.  A  method  of  making  high  power 
valves  with  pulb»  paitly  of  glass  and  partly 
of  copper  has  been  developed  by  the  West- 
ern Electric  Company  of  Amerien.  based 
rm  the  fact  that  a  copper  tube  with  a  sharp 
•  dge  can  be  welded  to  a  glass  tube.  In 
large  valves  a  source  of  trouble  is  the  heat- 
mg  of  the  metal  cylinder  by  the  bombard- 
ment of  the  electrons.  In  the  metal  bulb 
valves  the  copper  part  forms  also  the  anode 
cylinder,  and  it  can  be  kept  cool  by  immer- 
sion in  water.  Large  generating  Valves  of 
10  tf>  100  kilowatts  have  been  made  in  this 
manner,  and  the  General  Electric  Company 
of  America  are  sjiid  to  be  preparing  a  ther- 
mionic generating  valve  of  the  two  elec- 
trode or  Fleming  type  with  an  output  of 
l/KX)  kilowatts,  or  1,300  horse  power.  If 
this  can  be  done,  large  thermionic  valves 
will  replace  high  frequency  alternators  en- 
tirely in  long  distance  wireless  stations. 
Already  Marconi's  Wireless  Telegraph 
Coinpany  have  a  Valve  Panel  of  56  larj^i' 
glass  valves  in  their  Carnarvon  Radio  Sta- 
tion with  which  communication  is  made 
direct  to  Australia.  The  present  public 
Wireless  Telephone  broadcasting  stations  in 
Great  Britain  employ  large  valve  generators 
in  their  transmission  plant. 

Modern  Wireless  Telephone  and 
Telegraph  Valve  Receivers. 

The  improvements  made  in  the  construc- 
tif>n  of  the  thermionic  valve  and  the  clothe 
study  of  its  action  imposed  by  the  neces 
sity  for  developing  wireless  telegiaphy  and 
telephone  during  the  great  European  War 
have  given  us  an  extraordinarily  sensitive 
and  easily  managed  detector  of  electric 
waves,  and  the  advent  of  wireless  telephone 
broadcasting  has  created  a  novel  trade  in 
the  manufacture  of  these  valves  for  generat- 
ing, amplifying  and  detecting  electric 
waves. 

In  the  receiving  valve  most  commonly 
use<l,  a  straight  filament  of  tungsten,  or 
thoriated  tungsten,  or  else  platinum- 
indium,  coated  with  oxides  of  barium  and 
strontium,  is  used.  This  is  surrounded  by 
a  spiral  wire  forming  the  grid  and  by  a 
nickel  or  lYiolybdenum  cylinder  forming  the 
plate.  The  ends  of  the  filament,  grid,  and 
iplate  are  connected  to  pins  on  a  cap  so  that 
the  valve  can  fit  into  a  socket  like  an  elec- 
tric lamp. 


In  modem  wireless  telegraph  receivers, 
one  or  more  valves  are  used  to  amplify  the 
oscillations;  one  to  detect,  and- one  or  more 
to  amplify  the  rectiled  currents. 

Valves  of  this  type  were  made  to  the 
number  of  three  or  four  million  during  the 
war  (1914—1918),  and  are  manufactured 
now  by  the  hundred  thousand  per  annum 
for  wireless  broadcasting  purposes.  Large 
factories  employing  hundreds  of  workers 
are  devoted  to  their  manufacture. 

The  Thermionic  Telephone  Repeater. 

An  additional  great  service  the  ther- 
nnonic  valve  renders  is  as  a  perfect  tele- 
phone relay  or  repeater.  Telephone  elec- 
tric speech  currents  are  enfeebled  by  flow- 
ing along  a  telephone  wire,  and  for  long  dis- 
tance working  very  thick  and  therefore 
costly  wires  were  required.  Thermionic 
amphfyers  can,  however,  be  inserted  in  the 
run  of  line  to  re-enforce  the  currents  so  that 
they  start  on  a  further  journey  with  fresh 
strength.  By  the  use  of  these  repeaters, 
telephonic  speech  is  now  transmitted  right 
across  the  Continent  of  America  (4,000 
miles),  and  they  are  being  now  much  used 
by  the  British  Post  Office.  For  shorter  dis- 
tances a  great  economy  in  copper  can  be 
obtained  by  their  use.  '  It  would  be  feasible 
to  speak  from  London  to  Delhi  if  it  were 
worth  whUo  to  erect  the  line  and  repeater 
stations.  In  short,  the  thermionic  valve 
has  effected  a  revolution  in  ordinary  tele- 
phony just  as  it  has  made  possible  wireless 
telephony. 

Conclusion. 
It  will  be  seen,  therefore,  that  out  of 
purely  scientific  researches  and  discoveries 
by  Edison,  Fleming,  J.  J.  Thomson,  Irv- 
ing Langmuir,  Lee  de  Forest,  the  invention 
of  the  two-eleetrode  thermionic  valve  by 
the  author  in  1904  and  the  subsequent  de- 
velopment of  these  discoveries  by  the  ex- 
pert investigators  of  great  commercial  or- 
ganisations such  as  the  Western  Electric, 
The  General  Electric,  The  Marconi  Wireless 
Telegraph,  The  Osram  Lamp  and  Edison 
Swan  Electric  Lamp  Companies,  an  im- 
mense industry  has  been  built  up,  which, 
starting  from  very  small  beginnings  when 
the  first  Fleming  valves  were  made  at  the 
Edison  and  Swan  Electric  Lamp  Works  in 
1904,  and  the  Steam  Electric  Lamp  Works, 
England,  in  1907,  has  attained  now  (1923"; 
enormous  proportions  and  created  an  in- 
dustry which  has  yet  a  great  future  before 
it. 


228 


THE  CHEMICAL  NEWS. 


OCTOBER  12,  1923. 


A  RELIABLE  APPARATUS  FOR  THE 
RAPID  ANALYSIS  AND  REGULATION 
OF  HIGHLY    VISCOUS  SUBSTANCES. 

By  Db.  Gustav  F.  Dierfeld. 

Hitherto  there  has  been  a  considerable 
lack  of  apparatus  for  quickly  analysing  and 
regulating  the  application  of  highly  viscous 
substances  like  varnishes  for  graphic  pur- 
poses, lacquers,  tar  products,  varnishes 
composed  of  pitches  and  oils,  glue  gelatines, 
collotions,  etc.  Analyses  of  this  kind 
were  generally  performed  by  feeling  or 
touch,  whereby  many  mistakes  took  place, 
and  a  required  correction  could  not  be 
effected  in  a  quick  and  reliable  manner  rest- 
ing on  calculation,  and  very  troublesome 
difficulties  and  loss  of  time  and  money  could 
be  incurred  in  the  course  of  further  working. 
Dr.  Robert  Fischer,  jointly  with  the  Franz 
Hugershoff- works  in  Leipzig  (Germany), 
has  now  designed  a  very  cheap,  easily 
heated  apparatus,  making  possible  a 
thoroughly  reliable   and    exact  analysis     of 


highly  viscous  transparent  and  opaque  sub- 
stances within  the  shortest  time  and  under 
variable  conditions. 

This  apparatus  consists  of  an  external 
glasis  tube,  a  cooling  apparatus  containing  a 
thermometer,  has  a  plumb-line  on  one  side, 
and  is  supported  by  a  stand  (see  the  figure). 

Within  tne  outer  glass  tube  a  narrower 
one  is  arranged,  open  at  its  upper  end  and 
provided  at  its  lower  end  with  a  cock  and  at 
its  right  side  with  a  short  glass  tube  shaped 
like  an  elbow,  that  contains  another  ther- 
mometer and  leads  through  the  surrounding 
external  glass  tube.  A  contact  device  ar- 
ranged in  the  inner  tube  a  little  above  the 
cock  may  be  connected  with  an  incandes- 
cent lamp  or  electric  bell,  jointed  with  an 
electric  lead.  For  testing  a  viscous  sub- 
stance, the  apparatus  is  at  first  adjusted  by 
means  of  the  plumb-line  and  the  adjustinj^ 
screws  of  the  stand,  so  that  it  has  an  exactly 
vertical  position.  Then  the  exter-nal  tiibe 
is  filled  up  with  water  at  70°  S.  (158°  Fahr.) 
that  is  cooled  down  to  62°  C.  (143.6°  Fahr.). 
The  temperature  of  this  heating  liquid  is 
observed  by  means  of  the  thermometer,  ar- 
ranged in  the  external  tube  or  cooling  ap- 
paratus, which  makes  a  uniform  heating  of 
the  apparatus  possible  by  means  of  a  con- 
stant supply  of  warm  water.  Meanwhile, 
about  100  grams  of  the  substance  to  bo 
tested  {e.g.,  glycerine)  are  warmed  up  to 
70°  C,  and  a  sufficient  quantity  of  this 
liquid  is  poured  into  the  inner  tube  from 
above  up  to  the  destined  stroke,  and  is 
cooled  down  to  58°  C,  as  indicated  by  the 
aid  of  the  thermometer  in  the  elbow-like 
short  glass  tube.  As  stated,  the  difference 
of  temperature  of  4°  C,  and  the  tempera- 
ture of  the  liquid  to  be  tested  of  58°  C,  is 
always  the  same.  A  small  ball  of  alu- 
minium or  brass  is  then  let  fall  through  the 
upper  open  end  of  the  inner  tube ;  this  tube 
is  enlarged  at  the  sipot  of  its  wall,  opposite 
to  the  elbow-like  glass  tube,  so  that  this 
ball  is  not  turned  from  its  proper  way.  By 
means  of  a  stop-watch  the  time  of  falling  of 
the  ball  in  the  liquid  up  to  the  lying  on  the 
contact  device  is  determined.  This  time 
amounts  to  4  seconds  with  glycerine  of  a 
known  quality  used  generally  as  gauging 
liquid  for  gaining  a  decided  footing.  This 
value.  4.,  is  the  unit  for  the  temperatures 
62°-58°  C. 

Another  substance,  showing  at  the  same 
difference  of  temperature  with  a  time  of 
falling  of  16  seconds  for  the  same  ball,  has 
a  viscosity  of  4,  compared  with  the  above, 
t.e.,  its  viscosity  is  four  times  greater. 


OCTOBER  12,  1923. 


tHE  CHEMICAL  NEWS. 


229 


falling  ball  touches  tlie  contact  (k'vice,  the 
lamp  lights  up  or  the  bell  rings,  and  at  this 
moment  the  stop-watch  should  be  read.  In 
very  thin  or  diluted  liquids  the  time  of  fall- 
ing of  the  noiTnal  ball  may  be  so  little  that 
mistakes  of  observation  may  occur,  and 
may  cause  a  considerable  error.  To  avoid 
this  and  to  increase  the  time  of  falling  by  a 
multiple,  Dr.  Fischer  utilised  small  balls  of 
different  size,  three  of  aluminum  and  three 
of  brass — according  to  the  less  or  greater 
viscosity  of  the  substances  to  bo  tested. 
Of  course,  in  such  cases,  the  apparatus  is 
to  be  specially  gauged  for  each  of  the  balls. 

Whilst  a  bright,  transparent  liquid  is 
tested  in  such  a  manner  whereby  the  falling 
(>f  the  ball  is  distinctly  visible  for  examin- 
ing dark-coloured,  opaque  substances,  the 
apparatus  is  connected  with  the  incandes- 
cent laniip    or  electric  bell;    as  soon  as   the 

From  this  work  it  is  possible  to  compile 
tables,  containing  the  numbers  for  different 
mixtures,  for  the  adjusting  of  lacquers, 
varnishes,  etc.  A  single  number  is  then 
sufficient  for  showing  full  particulars  of  the 
viscosity  of  each  substance.  This  pro- 
ccedure  is  more  reliable  than  the  usual  one 
fw  samtples  of  different  substances,  which 
frequently  transform  or  deteriorate  in  the 
course  of  time.  As  admitted  by  experts, 
this  apparatus  of  Fischer's  has  been  used 
with  success  for  the  most  varied  industries. 


ORGANIC  MERCURY    COMPOUNDS. 

Part  III. 
By  R.  F.  Hunter,  F.C.S. 

{Continued  frofii  Page  217.) 

-  We  have  now  to  consider    the  derivatives 
of  phenols  and  related  con)ipounds,  deriva- 
tives of  aromatic  ketones  and  terpenes,  de 
rivatives  of  aromatic  acids,   and  lastly,  the 
derivatives  of  heterocyclic  compounds. 

The  first  to  be  considered  are  the  phenol, 
naphthol  derivatives,  etc. 

o  Chloromercuri  phenol. — The  first  typi- 
cal compound  is  usually  prepared  along 
with  the  m  and  ip  compounds  by  the  action 
of  mercuric  acetate  on  phenol.  It  reacts 
with  nitrous  acid  to  yield  p  nitroso  chloro- 
mercuri phenol.  Other  phenol  derivatives 
are : 

p  Acetoxy  mercuri  phenol ; 

p  Chloromercuri  phenol; 

p  Hydroxy  mercuri  phenol ; 

Di  acetoxy  mercuri  phenol ; 


p  Benzeneazo  o  acetoxy  mercuri  phenol  o 
and  p  dichloromercuri  phenol; 
Mercuri  bis  o  phenol; 
Mercuri  bis  o  phenylacetate; 
Mercuri  bis  p  phenylacetate. 
Phenol  ethers  readily  react  with  mercuric 
acetate,    for  instance,    anisole    has  deriva- 
tives, such  as : 

o  Mercury  Dianisyl; 
o  Acetoxy  mercuri  anisole ; 
p  Mercury  dianisyl. 

With  mercuric  acetate  anisole  yields  such 
compounds  as  p  acetoxymercuri  anisole. 

o  Mercury  diphenetyl,  o  acetoxy  mercuri 
phenetole,  p  mercury  diphenetyl  are  deri- 
vatives of  phenetole. 

Phenetole  heated  with  mercuric  acetate 
yields  p  acetoxy  mercuri  phenetole. 

As  examples    of  mercury    derivatives    of 
substituted  phenols  we  have  : 
ip  Ilydroxymercuri  o  chlorophenol ; 
o  Hydroxymercuri  p  chlorophenol ; 
4  Hydroxy  mercuri  2  nitro  phenol ; 
4  4'  Mercuri  bis  2  nitro  phenol ; 
2  Hydroxy  mercuri  4  nitrophenol ; 
2  Aceto.xy  mercuri  4  nitrophenol ; 
2  Chloromercuri  4  nitro  phenol; 
Hydroxy  mercuri  picric  acid; 
Chloromercuri  picric  acid, 
p  Chloromercuri  o  aminoiphenol ; 
6  6'  Mercuri  bis  1  hydroxy  2  methyl  ben- 
zene; 
4  arsenic  acid; 
o  Acetoxy  mercuri  p  cresol ; 
o  lodomercuri  p  cresol; 
Diacetoxy  mercuri  p  cresol ; 

0  Chloromercuri  p  cresol  methyl  ether. 
As  derivatives  of  the  naphthols  we  have 

4  acetoxy  mercuri  a  naphthol  prepared  from 
the  action  of  naphthol  in  mercuric  acetate 
in  acetic  acid  solution; 

2,  4  Diacetoxy  mercuri  a  naiphthol; 

1  Acetoxy  mercuri  ft  naphthol; 

2  Acetoxy  mercuri  1  naphthol  4  sulphonic 
{icid  and  its  sodium  salt. 

Derivatives  of  resorcinol  have  been  pre- 
pared, for  instance: 

Chloro  mercuri  resorcinol; 

Dichloro  mercuri  resorcinol; 

6  Acetoxy  mercuri  2  nitro  resorcin. 

The  first  mercury  derivatives  of  the  aro- 
matic acids  to  be  considered  are  those  of 
benzoic  acid  and  the  anhydride  of  o  hy- 
droxy mercuri.  Benzoic  acid  is  typical, 
and  is  prepared  by  fusing  mercuric  acetate 
and  benzoic  acid  until  the  reaction  is  com- 
plete. 

Derivatives  of  benzoic  ester  are : 

o  Chloro  mercuri  benzoic  methyl  ester; 


2ao 


THE  CHEMICAL  NEWS. 


OCTOBER  12,  1923. 


and  o  Chloromercuri  benzoyl  chloride. 

As  derivatives  of  substituted  benzoic 
acid  we  have : 

N  -  iso  di  acetoxy  mercuri  anthranilic 
methyl  ester; 

Ac  0  Hg  CeHg  (CO2  Me)  N  H  Hg  0  Ac 

H,  O; 

Acetoxy  mercuri  anthranilic  methyl  ester ; 

lodo  mercuri  anthranilic  acid; 

5,  5'  Mercuri  bis  2  amino  benzoic  methyl 
ester ; 

6,  6'  Mercuri  bis  2  amino  benzoic  acid; 
Chloromercuri    methyl  anthranilic   methyl 

ester ; 

lodomercuri  methyl  anthranilic  acid; 

Acetoxy  mercuri  p  amino  benzoic  ethyl 
ester. 

The  derivatives  of  cinnamic  and  salycilic 
acid  deserve  mention.  Examiples  of  the 
former  are : 

a  Acetoxy  mercuri  ^  methoxy  hydrocinna- 
mic  methyl  ester; 

a  Mercuri  di  ^  phenyl  anhydrohydracry- 
lio  acid; 

a  Acetoxy  mercuri  /3  ethoxy  hydrocinna- 
mic  methyl  ester; 

a  Acetoxy  mercuri  ^  isopropopy  hydro- 
cinnamic  methyl  ester; 

and  of  the  latter  case  : 

3  Halide  mercuri  2  hydroxy  benzoic  acid; 

Chloromercuri  salicylic  methyl  ester; 

Acetoxy  mercuri  salicylic  methyl  es'ter ; 

Mercuri  bis  salicylic  ethyl  ester; 

3  Acetoxy  mercuri  5  nitro  salicylic  acid; 

5  Amino  salicylic  acid 
are  examples. 

The  derivatives  of  ketones  and  terpenes 
are  not  of  great  importance.  We  might 
mention : 

Phenacyl  mercuri  chloride; 

Phenyl  o  chloromercuri  phenyl  ethyl  car- 
binol ; 

2  Hydroxy  mercuri  indandione  as  ketone 
derivatives. 

2  Chloro  mercuri  cineol  is  an  example  of 
a  terpinecol  derivative.  As  camiphor  deri- 
vatives vi^e  have  : 

a  a  Di  iodomercuri  camphor; 

a  Acetoxy  mercuri"  camphor;  and 

a  Halide  mercuri  camphor. 

We  have  now  to  consider  o,ur  last  group 
of  compounds,  viz.,  the  mercury  deriva- 
tives of  heterocyclic  compounds. 

Thiophene  in  acid  solution  reacts  with 
the  sulphate  of  mercury,  giving  a  series  of 
compounds. 

Chloromercuri  thiophene  is  obtained 
from  thiophene  in  alcohol,  saturated  mer- 
curic   chloride     and    concentrated    sodium 


acetate  solution.      It  reacts  with  halogens, 
acid  halides,  inorganic  iodides,  etc. 

Other  thiophene  derivatives  are  : 

a  lodo  and  bromo  mercuri  thiophene; 

a  Mercury  di  thienyl. 

As  derivatives  of  substituted  thiphenes 
we  might  mention : 

5  Chloro  mercuri  2  methyl  thiophene ; 

5,  5'  Mercuri  bis  2  chloro  thiophene; 

5,  5'  Mercuri  bis  2  iodothiophene ; 

3  Chloromercuri  2,  5  dimethyl  thiophene ; 

2,  5  Diohloromercuri  3  methyl  thiophene; 

2,  2'  Mercuri  bis  3,  4  dimethyl  thiophene. 

Among  the  compounds  of  this  group 
which  have  been  prepared,  we  have  deriva- 
tives of  indole,  pyrapolones,  for  instance  : 

3  Methyl,  3,  4  diacetoxy  mercuri  4  meth- 
oxy 1  a<jetoxy  mercuri  phenol  3,  4  dihydro 
5  pyrazolone  is  a  pyrazolone  derivative. 
Cyclomercuri  polymethylenes  are  said  to 
have  been  prepared. 

llie  mercury  compounds  have  been  re- 
viewed. Anything  like  a  full  review  is  im- 
possible in  an  article  such  as  this.  The 
field  is  a  very  big  one,  to  say  the  least  of  it. 
No  attempt  has  been  made  to  describe  the 
preparations.  These  can  be  found  in  Whit- 
more  s  excellent  work  and  in  the  original 
papers.  As  with  arsenic,  compounds  of 
lesser  importance  have  sometimes  been 
mentioned  where  more  deserving  ones  have 
been  omitted.  This  is  inevitable  in  an 
article  of  this  kind,  but  nevertheless,  if  the 
article  has  brought  the  subject  to  the  notice 
of  many  chemists  who  have  not  previously 
had  to  deal  with  the  subject,  I  shall  feel 
satisfied.  Again,  as  I  said  before,  the 
article  is  a  review,  not  a  thesis,  and  a  re- 
view, like  charity,  can  be  made  to  "  hide  a 
multitude  of  sins,"  and  this  being  so  I  do 
not  feel  called  upon  to  apologise  for  its  in- 
completeness, and  in  many  places,  lack  of 
experimental  detail. 


PRELIMINARY  REPORT  OF  THE 

MINERAL  PRODUCTION    OF  CANADA 

DURING    THE  SIX  MONTHS    ENDING 

JUNE  30,  1923. 

The  present  report  Is  issued  in  continu- 
ance of  the  policy  of  the  Dominion  Bureai 
of  Statistics  of  preparing  preliminary  esti- 
mates regarding  the  production  of  the  prin- 
cipal mineral  products  from  Canadian  de- 
posits. Data  are  given  showing  the  quan- 
tity and  value  of  each  metal  produced  and 
of      each     non-metallic     mineral    shipped. 


OCTOBER  12,  1923. 


THE  CHEMICAL  NEWS. 


231 


Comparative  figures  are  given  for  the  cor- 
responding period  of  the  previous  year  and 
revised  statistics  for  the  calendar  year  1922 
have  been  included. 

Measured  in  terms  of  the  metallic  and 
non-metallio  mineral  output  and  excluding 
structural  materials  and  clay  products,  the 
mineral  production  of  Canada  during  the  six 
months  ending  June,  1923,  was  valued  at 
$87,152,248,  as  compared  with  $60,361,109, 
the  value  of  the  corresponding  production 
in  the  first  six  months  of  1922.  The  output 
of  these  commodities  during  the  ^twelve 
months  of  the  calendar  year  1922  was 
valued  at  $144,762,501,  so  the  records  for 
the  present  year  show  that  an  appreciable 
advance  has  been  made  both  in  relation  to 
the  output  in  the  first  six  months  of  1922 , 
and  also  to  the  entire  calendar  year. 

The  outstanding  feature  of  the  metal  in- 
dustry was  the  recovery  in  the  producticHi 
of  nickel  and  copper.  The  re-opening  of 
the  smelters  and  refineries  operated  by  the 
International  Nickel  Compauy  and  the 
British  America  Nickel  Corixwation  re- 
sulted in  a  production  of  nickel  during  the 
first  six  months  of  the  year  which  was 
nearly  seven  times  graeter  than  the  produc- 
tion in  the  first  half  of  last  year,  and  the 
output  of  copper  was  more  than  double  the 
quantity  produced  in  the  corresponding 
period  last  year.  The  copper  output  during 
the  half-year  was  greater  than  the  total 
production  during  the  calendar  year  1922 ; 
the  nickel  output  was  also  nearly  60  per 
cent,  greater  than  the  entire  (juantity  made 
during  the  twelve  months  ending  Decem- 
ber, 1922. 

The  production  of  gold  and  silver  was 
maintained  at  about  the  same  levels  as  in 
the  corresponding  period  in  1922,  while  the 
outputs  of  asbestos,  coal,  lead  and  zinc 
were  higher  than  in  the  first  half  of  1922. 
Shipments  of  gypsum,  while  less  in  amount 
were  greater  in  value,  and  while  the  output 
•of  salt  declined  the  quantity  sold  was 
greater  than  in  the  half-vear  ending  June, 
1922. 

Power  shortage  was  again  exiporienced  in 
Northern  Ontario  during  the  spring  months, 
and  it  was  not  until  the  latter  part  of  April 
and  the  beginning  of  May  that  enough 
power  was  obtained  to  permit  capacity 
operation  of  the  Porcupine  mines.  The 
three  leading  producers  were  reported  early 


m  May  as  being  in  a  position  to  treat  aip- 
proximately  7,000  tons  of  ore,  the  Hollinger 
treating  about  5,000,  the  Dome  1,200,  and 
the  Mclntyre  1,000.  The  operation  of  th- 
enlarged  Mclntyre  plant  was  also  made 
possible  by  the  additional  power  obtained 
about  the  beginning  of  May. 

Power  developments  ui  Northern  On- 
tario have  been  watched  with  considerable 
interest  by  the  mining  industry.  Sturgeon 
Fails  power  is  now  available;  Metachewan 
is  expected  to  be  operating  by  fall,  and  the 
developments  on  the  Quinze  River  and  by 
the  Hollinger  on  the  Abitibi  River  are  being 
carried  forward  with  a  view  to  the  elimina- 
tion of  the  recurring  sipring  power  shortage 
that  has  handicapped  these  properties  up 
to  the  present  time. 


GENERAL  NOTE&. 


METAL  FOR  SYNTHETIC  AMMONIA  • 

TUBES. 
The  tubes  which  contain  the  catalyst 
for  synthesis  of  ammonia  must  support  the 
action  of  compressed  gases  at  temperature 
of  600  to  700"  C.  They  have  been  made  with 
alloys  poor  in  carbon  and  containing  nickel, 
chromium,  tungsten  or  similar  metals.  The 
percentage  of  nickel  may  be  60  per  oe6t. 
and  more.  According  to  a  l">ench  invention 
by  the  Soci^t^  Chimique  do  la  Grande 
Paroisse  a  very  soft  iron,  poor  in  carbon, 
can  be  utilised  for  hyper-pressure  treat- 
ment. The  composition  of  the  iron  is  simi- 
lar to  that  of  dynamo  and  transformer 
plates.  A  metal  employed  for  the  purpose 
contained :  Si,  0.018  per  cent. ;  S,  0.09  per 
cent. ;  C,  0.098  per  cent. ;  Mn,  0.93  per 
cent. 

Thin  round  plates  of  this  metal  were  sub- 
jected for  hundreds  of  hours  to  the  action  of 
a  mixture  of  N,  H  and  NH3,  at  a  pressure 
of  1,000  atmospheres  and  temperatures 
varying  from  700°  to  800°  C,  without  dis- 
playmg  any  sign  of  fragility.  Such  a  metal 
can  be  employed  for  catalyser  tubes,  pro- 
vided that  suitable  measures  are  taken  to 
provide  for  the  considerate  decrease  in  ten- 
sile strength  and  the  appearance  of  viscidity 
at  temperatures  above  500°  C. — (Tj' Industrie 
Chimique,  August,  1928.) 


232 


THE  CHEMICAL  T^BWs. 


OCTOBER  12,  192^. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  CHEMICAL  SOCIETY. 

The  following  papers  were  read  at  the 
Ordinary  Scientific  Meeting,  Oct.  4 : 

Note  on  Aqueous  Funnaldehyde  SuJiition, 
by  W.  E.  Ormandy  and  E.  C.  Craven. 

Discrepancies  in  the  published  values  for 
the  densities  of  aqueous  formaldehyde  solu- 
tions iprobably  arise  from  the  presence  of 
methyl  alcohol.  The  densities  of  solutions 
prepared  by  refluxing  with  water  are  now. 
found  to  agree  excellently  with  the  results 
of  Auerbach  and  Barschall,  who  prepared 
solutions  by  volatilising  paraform  in  a  cur- 
rent of  nitrogen  and  absorbing  the  gaseous 
formaldehyde  in  water.  The  density  and 
the  refractive  index  of  a  formaldehyde 
solution  appear  to  be  linear  functions  of  the 
formaldehyde  concentrations. 

The  specific  refractivity  of  the  formalde- 
hyde in  the  dilute  aqueous  solution  appears 
to  be  0.205,  which  agrees  well  with  the  as- 
sumption that  methylene  glycol  is  formed, 
and  this  is  also  borne  out  by  density 
measurem  ents . 

The  interactio7i  of  potassiuvi  tetroxide 
with  Ice,  and  with  dilute  Sulphuric  Acid, 
by  H.  Hawley  and  H.  J.  S.  Sand. 

It  was  shown  that  only  hydrogen  dioxide 
results  from  the  interaction  of  potassium 
tetroxide  with  ice  or  with  dilute  sulphuric 
acid. 

The  Direct  Union  of  Oxygen  and  Sulphur, 
by  E.  G.  W.  NoRRiSH  and  E.  K.  Eideal. 

The  reaction  of  oxygen  and  sulphur  has 
been  studied  bv  a  dynamic  flow  method,  be- 
tween 235°  and  385°.  Below  305°  it  pro- 
ceeds with  a  temjperature  coefficient  of  1.63; 
above  305°  this  falls  off  rapidly,  due  to  the 
secondary  formation  of  sulphur  trioxide. 
The  reaction  is  limited  to  the  surface  of  the 
sulphur  and  the  walls  of  the  vessel,  and 
proceeds  equally  well  on  both,  pointing  to  a 
liquid  film  covering  the  whole  surface  of 
the  vessel. 

A  table  of  seven  different  reactions  of  sul- 
phur was  given,  which  shows  that  their  cri- 
tical increments  are  simple  multiples  of  a 
constant  quantity,  which  is  considered  to  be 
the  half  value  of  the  work  required  to  create 
one  free  sulphur  bond. 

Prof.  J.  F.  Thorpe  also  read  two  papers 
dealing  with  the  work  of  himself  and  his 
collaborators  in  the  field  of  Isomerism  and 
Tautomerism, 


THE    INSTITUTE  OF  METALS. 
Programme  for  1923-24. 

The  Institute  of  Metals  has  just  issued 
its  programme  of  meetings  and  lectures  for 
the  session  1923-24.  There  are  over  thirty 
lectures  and  addresses  to  be  given  before  the 
Institute's  local  sections  in  Birmingham, 
Glasgow,  London,  Newcastle-on-Tyne,  Shef- 
field, and  Swansea,  as  well  as  at  meetings 
of  the  parent  Institute,  one  of  the  latter, 
including  a  lecture  by  Dr.  F.  W.  Aston, 
F.E.S.,  which  is  to  form  part  of  the  pro- 
ceedings of  next  year's  Empire  Congress  of 
Mining  and  Metallurgy. 

The  subjects  of  the  lectures  are  of  a 
character  to  interest  engineers  and  metal 
workers,  and  include  "  Extrusion  Prob- 
lems, "  Nickel  Brasses,"  "  Some  Im- 
pressions of  American  Non-Ferrous  Metal- 
lurgy," "  Metals  for  Lamp  Manufacture," 
"  X-Bays  and  Metallurgy,"  "  General 
Scientific  Brass  Foundry  Work,"  "Alloys 
for  use  with  Super-heated  Steam,"  "  The 
Density  of  Alloys,"  "  The  Annealing  of 
Non-Ferrous  Metals,"  "  The  Action  of 
Molten  Bras®  on  Nickel  Steel,"  "  Prqpel-, 
ler  Brass,"  "  Large  Metallic  Crystals  and 
Some  of  their  Properties,"  "  The  Cold 
Working  of  Metals,"  "  Electric  Eesistance 
Furnaces,"  "  Substitutes  for  Platinum," 
"  The  Metallurgical  Microscope,"  and 
"  Influence  of  Casting  Temperature  on 
the  Physical  Properties  of  Metals." 

A  ballot  for  the  election  of  members  of 
the  Institute  (whose  membership  covers 
that  of  the  local  .sections),  is  due  to  take 
place  shortly,  and  full  particulars  can  be 
obtained  from  the  Secretary  of  the  Institute, 
Mr.  G.  Shaw  Scott,  M.Sc,  36,  Victoria 
Street,  London,  S.W.I. 


THE  INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

Recent  Researches  Bearing  upon  the 
Origin  of  Petroleum,  by  E.  H.  Cunningham- 
Craig,  B.A.,  F.E.S.E.,  F.G.S.  (Member). 

Read  at  the  Royal  Society  of  Arts,  on 
Tuesday,  October  9. 

The  author  dealt  with  some  of  the  re- 
searches which  have  been  undertaken,  hav- 
ing a  distinct  bearing  upon  the  origin  of 
petroleum. 

The  genesis  of  petroleum  has  been  vari- 
ously attributed  to: — A.   Inorganic  Origin: 

(1)  Hypogene  causes;  (2)  Vulcanicity.     B. 
Organic  Origin :     (1)  From  animal  matter ; 

(2)  From  vegetable  matter. 


OCTOBER  12,  1923. 


THE  CHEMICAL  NEWS. 


233 


Of  the  inorganic  origin  there  is  little  to  be 
said. 

This  leaves  the  organic  theories  as  rivals, 
that  of  animal  origin  being  chiefly  sup- 
ported by  chemists,  while  the  vegetable  ori- 
gin theory  is  largely  held  by  geologists,  and 
has  gained  much  ground  in  recent  years. 

There  is  a  tendency  to  iuvestigate  the 
relations  of  coals  ^nd  lignites  to  petroleum. 
Every  country  that  contains  either  coal  or 
petroleum,  or  both,  can  furnish  some  evi- 
dence, and  it  is  becoming  obvious  that  tlie 
two  fuels  have  definite  relations  to  each 
other. 

The  three  main  oil-bearing  bmizons  in 
Trinidad  have  each  a  carbonaceous  iphase  in 
sonxe  other  district,  and  ttie  two 
phases,  petroliferous  and  curl)onaceous,  ap- 
proach each  other  very  closely  in  some 
localities. 

Similar  evidence  has  beeh  forthcoming 
from  many  countries,  e.<j.,  Venezuela, 
Jiurrna,  Assam,  Hungary,,  and  Roumania. 

Much  pertinent  evidence  from  Great 
Britain  was  ako  brought  to  light  by  the 
work  of  the  Petroleum  Research  Depart- 
ment during  the  war,  but  unpublished,  and 
the  relations  of  oil  to  coal  and  to  oil-shale 
have  been  made  clearer.  Perhaps  the  most 
striking  evidence  is  that  afforded  by  the 
boring  at  D'.Vrcy,  near  Kalkiith.  This  well 
was  drilled  on  tne  theory  that  oil-shale  de- 
notes petroleum  that  is  dead  and  buried, 
but  that  beneath  an  oil-shale  series  some 
free  petroleum  may  still  exist. 

By  treating  any  ooal  containing  a  fair  per- 
centage of  volatile  matter  with  hydrogen 
under  very  high  pressure  and  at  tempera- 
tures up  to  8riO°  F.,  a  remaikable  exother- 
mic action  is  induced  and  a  iporti<Mi  of  the 
solid  fuel  becomes  liquefied,  giving  as  a  re- 
sult a  product  indistinguishable  from 
heavy  crude  petroleum.  Similar  effects 
can  be  obtained  by  hydrogenating  heavy 
crude  oils,  lighter  oils  being  formed.  The 
work  of  Dr.  Bergius,  thougii  perhaps  hardly 
yet  successful  as  a  commercial  proposition 
when  coal  is  treated,  or,  as  it  is  stated, 
"  liquefied,"  has  certainly  opened  up  a 
vista  of  great  possibilities.  It  appears  that 
the  percentages  of  volatile  matter  in  the 
coal  is  one  of  the  determining  factors  con- 
trolling the  reaction,  another  being  the 
pressiu-e.  Pressures  as  high  as  3,0(X)  and 
even  5,000  lbs.  per  square  inch  have  been 
used,  but  ivction  may  conn m  nee  with  a  pres- 
sure of  no  more  than  600  lbs.  Tempera- 
tures need  not  apparently  bo  very  high,  hut 
as  the  action  is  exothermic  there  is  difficulty 


in  keeping  it  from  rising  too  ihigh.  The  re- 
acton  takes  place  in  an  autocuive. 

The  value  and  importance  of  these  re- 
j  searches  lie  in  their  siinilarity  to  the  con- 
ditions of  the  formation  of  oil.  It  has  long 
been  recognised  that  coal  is  a  finished  pro- 
duct, and  that  oils  cannot  be  fonned  from 
it  except  by  distillation. 

The  fact  that  the  reaction  is  exothermic 
must  not  be  lost  sight  of.  External  heat- 
ing of  the  autoclave  will  retard  the  action, 
and  the  heat  engendered  by  the  action  may 
l)e  sufficient  to  check  it  and  bring  about  an 
equilibrium.  But  in  Nature,  working 
slowly  through  countless  (periods  of  time, 
the  rapid  heating  up  of  the  material  by  an 
exothermic  reaction  will  be  obviated  by 
conduction. 

Prof.  Flynn  recently  separated  gels  from 
the  matrix  by  crushing  a  Nova  Scotia  tor- 
banite  and  floating  the  gels  in  brine,  so  that 
they  can  be  examined  and  analysed  apart. 
The  gels  are  tough  rather  than  liard,  and  so 
resist  crushing  successfully;  they  are  of 
large  size  and  rough  exterior,  and  are  fresh 
a"nd  free  from  signs  of  inspissation.  They 
contain  from  16  to  20  per  cent,  of  inorganic 
matter  in  a  fine  colloidal  state.  The  in- 
organic content  is  quite  conclusive  proof 
that  these  gels  are  not  vegetable  fossils. 
This  confirms  the  views  advanced  by  the 
writer,  and  if  oil  shale  denotes  petroleum 
petroleum    "  still-born," 


THE  OPTICAL  SOCIETY. 

An  Ordinary  Meeting  of  the  Society  was 
held  at  the  Imperial  College  of  Science  and 
Technolog}',  Imperial  Institute  Road,  on 
Thursday,  October  11.  The  following 
papers  were  read  and  discussed :  — 

Notes  on  the  Elementary  Algcbruic  The- 
ory of  a  Class  of  Fhotographic  Objectives, 
by  E.  T.  Hanson,  B.A. 

A  General  Survey  of  the  Thin  Double 
Lens,  by  T.  Smith,  M.A.,  F.Inst. P. 

New  Types  of  Levelling  Instruments  us- 
ing Reversible  Bubbles,  by  T.  F.  Connolly, 
M.Sc. 

Journal  of  Scientific  Instruments. 
The  first  regular  monthly  numbor  of  the 
Journal  of  ScientifiG  Instruments  prwlueed 
by  tlu^  Institute  of  Physics  with  the  co- 
operation of  the  National  Physical  Labora- 
tory, will  appear  on  October  15. 


234 


THE  CHEMICAL  NEWS. 


OCTOBER  12,  1923. 


SOCIETY  OF  PUBLIC  ANALYSTS  AND 
OTHER  ANALYTICAL  CHEMISTS. 

Ordinary  Meeting. 

Held  at  the  Chemical  Society's  Rooms, 
on  October  3. 

Mr.  P.  A.  Ellis  Richards,  President,  in 
the  chair. 

Certificates  were  read  for  the  first  time  in 
favour  of :  — 

Messrs.  Laurence  Eversley  Campbell, 
M.Sc,  (Lond.),  F.I.C. ;  John  Troubridge 
Hannon,  B.A.  (Cantab),  A.R.C.Sc,  A.I.C. ; 
Cyril  Langley  Hinton,  F.I.C. ;  Douglas 
William  Kent-Jones,  B.Sc.  (Lond.),  F.I.C; 
Thomas  William  Alan  Shaw,  M.So.  (Liv.); 
William  Hall  Simmons,  A.I.C. ;  Kenneth 
Edward  Nethercoate  Williams;  Percy  Noel 
Williams,  M.Sc.  (Liv.),  A.I.C. 

The  following  was  elected  a  member :  Mr. 
Robert  C.  Grimwood,  A.C.G.F.C,  D.I.C., 
A.I.C. 

The  following  papers  were  read  :  — 

The  Sampling  of  Coal :  the  General  Prob- 
lem and  some  Experiments,  by  J.  H.  Coste, 
F.I.C,  E.  R.  Andrews,  F.I.C,  and  W.  E. 
F.  POWNEY,  F.I.C. 

Attention  was  drawn  to  difficulties  en- 
countered in  sampling  coal  which  is  often  a 
heterogeneous  mixture,  and  in  consequence 
of  which  the  v.'wiations  in  composition  of 
different  "patches"  are  extremely  wide. 
These  variations  are  likely  to  be  more  ex- 
treme in  those  cases  where  the  bulk  is  large 
and  where  it  is  impossible  to  sample 
throughout  the  dump. 

General  considerations  that  should  govern 
the  sampling  were  suggested,  and  stress 
was  laid  upon  the  point  that  if,  as  often 
happens,  different  workers  obtain  different 
results  from  samples  taken  from  the  same 
bulk,  the  discrepancies  are  not  due  to  mis- 
takes in  working,  but  were  indicative  of  the 
variability  in  composition  of  the  coal.  Ex- 
periments were  described  in  which  (1)  it  was 
shown  how  difficult  it  is  to  obtain  a  homo- 
geneous set  of  samples'  from  so  small  a 
quantity  of  coal  as  70-80  lbs.,  and  (2)  the 
variation  in  composition  of  samples  taken 
progressively  from  a  bulk  of  about  400  lbs. 

Neiv  Test  for  Distingiiishinq  Castor  Oil 
from  other  Oils  and  determiyiing  its  Purity. 
by  H._  B.  Stocks,  F.I.C. 

Ordinary  soap    solutions  are    alkaline  to 


phenol-phthalein.  On  titration  with  "stan- 
dard acid  solution  a  point  is  reached  at 
which  a  state  of  equilibrium  exists  and  the 
pink  colour  disappears.  The  amount  of 
acid  required  increases  with  the  dilution  up 
to  about  1  part  in  150  or  higher,  at  which 
point  it  becomes  practically  constant.  With 
soaps  of  oleic,  palmitic,  and  stearic  acids, 
and  soaps  from  oils  composed  of  these  acids, 
the  figures  are  equivalent  to  approxinuitely 
half  the  total  combined  alkali.  With  castor 
oil  soap  it  is  only  3  to  11  per  cent,  of  the 
total.  5  grams  of  the  oil  to  be  examined 
are  saponified  with  alcoholic  potassium 
hydroxide,  neutralised,  evaporated  to  re- 
move alcohol,  made  up  to  100  ccs.,  10  ccs. 
being  diluted  with  250  ccs.  of  neutral  dis- 
tilled water  and  titrated  with  hydrochloric 
acid  in  presence  of  phenol-phthalein.  Cas- 
tor oil  gave  figijpes  varying  between  4,8  and 
7.9,  and  figures  are  given  in  the  paper  for  a 
number  of  fats  and  oils  and  rosin,  in  each 
"case  very  much  higher  than  for  castor  oil. 

The  Voliimetris  Estimation  of  Vanadium 
in  Steel,  by  A,  T.  Etueridge,  B.Sc, 
F.I.C,  M.B.E. 

The  estimation  is  carritnl  out  in  the  same 
solution  in  which  the  chromium  has  already 
been  estimated  by  treating  the  iiquious 
solution  of  the  sulphates  of  the  metals  with 
permanganate,  filtering,  removing  any 
colour  due  to  iron,  treating  with  standard 
ferrous  sulphate  solution  and  titrating  with 
permanganate.  This  gives  the  chromium 
figure.  The  solution  is  then  adjusted  so  that 
it  contains  about  10  per  cent,  by  volume  of 
sulphuric  acid,  excess  of  ferrous  sulphate  is 
added,  and  the  solution  titrated  with  potas- 
sium bichromate,  using  as  indicator  5  cc. 
of  diphenyl  carbazide  prepared  by  dissolv- 
ing 0.5  grams  in  1-2  cc.  glacial  acetic  acid, 
and  diluting. to'  500  cc,  and  adding  to  each 
5  cc,  3  drops  of  25  per  cent,  sulphuric  acid, 
and  1  drop  of  potassium  bichromate  solu- 
tion, resulting  in  the  formation  of  a  deep 
purple  colouration.  About  half  the  indica- 
tor solution  is  then  added  and  the  end  point 
occurs  within  1  or  2  drops,  with  the  forma- 
tion of  an  apple  green  tint.  It  is  necessary 
to  have  (1)  a  small  amount  of  ferrous  solu- 
tion present  at  the  time  the  incucator  is 
added,  (2)  10  per  cent,  sulphuric  acid,  (3) 
absence  of  nitric  acid  (except  in  traces). 

The  lodimctric  Deterwinaiion  of  Sugars, 
by  C.  L.  Hinton,  F.I.C,  and  T.  Macara, 
F.I.C. 

The  aldoses,  e.g.,    dextrose    and  lactose, 


OCTOBER  12,  1923. 


THE  CHEMICAL  NEWS. 


235 


are  quantitatively  converted  to  the  corres- 
ponding monobasic  acids  by  iodine  in  alka- 
line solution  at  ordinary  temtperature.  pro- 
vided the  proportions  of  alkali  and  iodine  to 
sugar  are  suitably  controlled.  The  slight 
oxidation  of  sucrose  and  levulose  found  by 
other  observers  is  confirnied,  and  the  extent 
of  this  action  is  shown  to  depend  consider- 
ably on  time  and  temperature  of  reaction  as 
well  as  on  the  proportions  of  iodine  and  al- 
kali used.  Using  standard  conditions  it  is 
possible  to  determine  sucrose  accurately  in 
mixtures  by  titration  before  and  after  inver- 
sion, but  the  determination  of  other  sugars 
is  liable  to  be  affected  by  non-sugar  reduc- 
ing substances.  The  mtthod  is  so  conveni- 
ent, however,  that  it  rocomniende  itself 
technically  for  approximate  determinaticais 
of  invert  sugars. 


CANADIAN  ASBESTOS  PRODUCTION. 

According  to  the  preliminary  report  on 
the  mineral  production  of  Canada,  compiled 
by  the  Dominion  Bureau  of  Statistics,  the 
total  asbestos  mined  during  the  first  six 
months  of  1923  amounted  to  1,482,102  tons, 
of  which  1,297,243  tons,  or  87.5  per  cent., 
was  milled.  Sales  tKlvanced  to  a  total  of 
99,042  tons,  valued  at  8,574,762  dols.,  a*; 
compared  with  sales  of  r)4,846  tons,  valued 
at  1,894,232  dols.  in  the  cwresponding 
period  of  1922. — Board  of  Trade  Journal, 
October  4. 


BRITISH    INDUSTRIES    FAIR. 

In  connection  with  notices  recently  pub- 
lished in  certain  daily  papers,  the  Depart- 
ment of  Overseas  Trade,  states  that  the 
voluntary  liquidation  of  the  British  Indus- 
tries Fair  (Birmingham)  Incorporated,  in 
no  way  affects  the  I/ondon  British  Indus- 
tries Fair,  organised  by  that  Department. 
Nor  will  the  liquidation  of  this  Association 
and  the  transfer  of  the  i-esponsibility  for  the 
management  of  the  British  Industries  Fair 
(Binningham)  to  the  Birmingham  Cham- 
ber of  Commerce  prevent  the  holding  of  the 
1024  British  Indnstrios  Fair  at  Tyondon  and 
Birmingham  as  usual.  The  London  section 
will  be  open  at  the  White  City  from  April 
28  to  May  9,  and  the  Birmingham  section 
follows  on  May  12  to  28. 


INTERVIEWS  WITH  H.M.  SENIOR 
TRADE  COMMISSIONER  IN  INDIA. 
Mr.  T.  M.  Ainscough,  O.B.E.,  Senior 
Trade  Commissioner  in  India,  is  at  present 
in  this  country  on  an  official  visit,  and  will 
be  in  attendance  at  the  Department  of 
Overseas  Trade  during  October  for  the  pur- 
pose of  interviewing  manufacturers  and 
merchants  interested  in  trade  with  India. 
Such  interviews  will  only  be  given  by  ap- 
pointment, and  all  applications,  quoting  the 
reference  4814  T.G.,  should  be  addressed  to 
the  ComptroUer-Gk'neral,  Department  of 
Overseas  Trade,  35,  Old  Queen  Street, 
Westminster,  S.W.l. 

CAST  IRON  RESEARCH. 
The  Monthly  Circular  of  the  British  Cast 
Iron  Research  Association  contains  valu- 
able data  on  malleable  iron,  together  with 
micros  obtained  from  the  research  work  in 
hand.  This  preliminary  information 
should  show  the  malleable  industry  how 
very  essential  it  is  to  push  forward  a  wide 
scheme  of  resefirch.  This  early  information 
will  be  supplemented  in  subsequent  bulle- 
tins. Members  only  are  privileged  to  ob- 
tain this  information.  Researches  to  dis- 
cover a  cast  iron  to  resist  corrosion  are 
being  carried  out.  Interesting  data  has  been 
sent  in  by  members,  from  which  it  is  evi- 
dent that  the  purposes  for  which  cast  iron 
was  ivquired  to  resist  corrosion  are  fairly 
large. 


THE  EVOLUTION  OF  CHEMICAL 
TERMINOLOGY.* 

By  James  F.  Couch. 

Cunuiic  cc  8ont  les  mots  qui  conservent 

•    lets  idccs  d-  qui  les  transmetient,    il  en  re- 

suite  qu'il    seroit    inrpoasible    de    perfec- 

iioner  la  science,  si  on  n'en  perfcctionoit 

le  langage .—Jjkyoi^vs.u. 

The  lack  of  ambiguity  in  thi-  practical 
use  of  the  term  hydroxide  may  well  occa- 
sion surprise  that  a  consideration  of  this 
term  has  been  included  in  this  series  of 
papers  upon  chemical  tcrminolog}-.  There 
are  few  chemical  terms  more  often  used 
and  certainly  there  i«  none  which  is  used  by 


*  [Reprinted  from  "The  American  Jour- 
nal of  Pharmacy,  Philadelphia,  Pa.,  July, 
1293.] 


^36 


tSE  CHEMICAL  NEWS. 


OCTOBER  12,  1923. 


the  chemist  with  more  specific  meaning. 
It  is  one  of  the  first  items  of  information 
that  he  receives  in  his  elementary  course  in 
chemistry.  It  stares  at  him  from  his  little 
shelf  of  reagents  in  the  laboratory,  and  it 
would  not  be  exaggeration  to  say  that  the 
first  example  of  applied  chemistry  he  learns 
is  the  broad  principle  that  hydroxides  neu- 
tralise acids  and  may,  therefore,  remedy 
accidents  to  fabrics.  His  most  indispens- 
able reagents  are  sulphuric  acid  and  sodium 
hydroxide,  and  he  comes  to  know  these 
substances  as  a  painter  knows  brushes  and 
a  sculptor  knows  marbles.  The  chemist 
grows  up  in  science  with  the  concept  hy- 
droxide; it  is  always  with  him;  it  is  ever  in 
use;  it  finally  becomes  immanent  in  his 
very  nature.  Why,  then,  should  he  not  be 
completely  famihar  with  it?  Where  is 
there  possibility  of  ambiguity  or  misconcep- 
tion in  the  use  of  this  term  ? 

From  the  foregoing  it  is  easy  to  believe 
that  I  have  never  inet  the  chemist  who 
does  not  cherish  a  conviction  that  he  knows 
what  a  hydroxide  is.  It  requires  more 
courage,  however,  to  supplement  that  as- 
sertion with  the  statement  that  I  have  not 
yet  met  a  chemist  who  really  does  know 
what  a  hydroxide  is,  and,  furthermore,  it 
is  not  at  all  difficult  to  convince  any  rea- 
sonable chemist  that  his  knowledge  in  this 
resipect  is  incomplete.  If  he  doubts  this  a 
very  few  adroit  questions  will  serve  to  bring 
him  to  an  impasse  and  demonstrate  the 
fact. 

Some  months  ago  I  set  out  to  investigate 
this  term  hydroxide.  The  examination  of 
available  facts  led  to  the  astonishing  con- 
clusion that  there  is  no  general  agreement 
in  the  definition  of  the  term,  so  that, 
strictly  speaking,  unless  one  specifically 
m'odifies  the  word  when  he  uses  it,  he  says 
next  to  nothing  definitely  when  he  employs 
the  term  hydroxide.  In  other  words,  we 
have  here  a  most  flagrant  example  of  inde- 
finiteness.  Here  is  a  concept  which  is  in 
daily  use,  which  enters  into  a  large  portion 
of  all  chemical  thought,  which  underlies 
and  conditions  many  important  chemical 
theories;  and  it  lacks  the  sine  qua  non  of 
scientific  terms,  precise  meaning ! 

This  fact  immediately  becomes  apparent 
upon  consultation  of  the  dictionaries  and 
the  textbooks  of  chemistry.  Wc  find  a 
diversity  of  opinion  among  authorities 
when,  as  is  not  always  the  case,  they  ven- 
ture to  define  the  term.  Many  writers  of 
inorganic  chemistries  present  no  definition 
of  hydroxide,  but  content  themselves  with 


refeiTing  to  the  formation  of  basic  hy- 
droxide, but  content  themselves  with  re- 
ferring to  the  formation  of  basic  hydroxides 
through  the  interaction  of  water  and  alka- 
line oxides  or  by  the  reaction  between  so- 
dium hydroxide  and  certain  metallic  salts. 
The  various  expressed  views  of  the  term 
hydroxide  may  be  classified  under  four  chief 
concepts :  there  is  the  view  that  these  sub- 
stances are  compounds  of  water  with 
oxides;  fundamentally  opposing  this  is  the 
view  that  hydroxides  are  hydroxyl  com- 
pounds and  of  this  conception  there  are  three 
main  divisi  iis :  first,  the  idea  that  any  hy- 
droxyl compound  is  an  hydroxide,  second, 
the  common  notion  which  may  briefly  be 
stated  thus,  hydroxides  are  hydroxyl  com- 
pounds of  basic  radicals,  and  third,  a  com- 
promise between  these  extremes  which  al- 
lows the  class  hydroxide  to  embrace  all  hy- 
droxyl compounds  but  prefers  its  applica- 
tion to  basic  substances. 

The  first  view  has  few  proponents  to-day. 
It  was,  however,  held  by  most  of  the  early 
chemists  and  has  been  supported  by  very 
capable  men.  D'Aubuisson^  in  1810  wrote: 
"  Mineralogists  and  chemists  have  too 
little  fixed  their  attention  on  M^ater  con- 
sidered as  a  constituent  of  minerals  with 
the  exception  of  those  salts  in  which  this 
substance  has  been  remarked  under  the 
narne  water  of  crystallisation.  Mean- 
while the  rocTis  of  which  it  forms  an 
essential  constituent  part  are  in  great 
number;  withviut  mentioning  those  which 
cpmpose  the  numerous  family  of  the  zeo- 
liths  I  will  cite  the  wavelite  recognised  by 
Davy  and  Klaproth  as  a  true  hydrate  o^f 
alumina,  composed  of  water  and"  alumina 
in  constant  pr(;i)ortion.  Diaspore  .  .  . 
seems  to  be  nothing  but  a  hvdrate  of  the 
same  earth.  The  opal  is  probably  only  ^ 
hydrate  of  silica." 

This  quotation  is  interesting  through  the 
knowledge  it  gives  us  concerning  conditions 
m  chemistry  a  century  ago.  It  appears 
that  only  a  very  few  chemists  had  any  real 
conception  of  the  importance  of  water  as  a 
constituent  in  compounds  and  consequentlv 
it  was  too  often  overlooked.  Berzelius,'^^ 
however,  grasped  the  significance  of  com- 
bmed  water,  and  in  1812  developed  an  hy- 
pothesis to  explaio  it  which  influenced 
chemical  thought  for  several  decades.  This 
was  his  notion  of  acid  and  basic  water : 

"  Hydrate,  oder  Verbindungen  des 
Wassers:  Erstens :  mit  Sauren.  Indie- 
sen  spielt  das  Wasser  ganz  die  Rolle  einer 
Basis;  die  Saure  nimmt  davon  zur  Satti- 


OCTOBEK  12,  1923. 


THE  CHEMICAL  NEWS. 


237 


gung  eine  Menge  auf,  welohe  genau  so  viel 
Sauerstoff    als    eine    Salz-basis    enthalt, 
von  der  diese  Mange  Saure  gesattigt  wiixi. 
"  Zweitens :   niit  Salxbasen.  Das  Was- 
ser  spielt  hier    in  so  fern   die  Eolle    eine 
Sawre,  uls  es  ihre  Stxlle  vertritt,  enthalt 
aber  nur  gleiche  Theile  Sauerstoff  mit  dor 
Basis,  oder  ist  zuwxilen  ein  submultiplum 
vom  Sauerstoff  der  Basis." 
He  uses  the  term  hydrate  freely,    speak- 
ing of  "Hydrate  der  Thoncrde"  and  "Eisen 
Hydrate."     Vauquelin**  in  1813,  repeating 
an    analysis    pubHshod    by  Prof.    Bruce  of 
New  York,  confirmed    the  findings    of  the 
American : 

"  It  apipears  from  this  analysis  that 
the  mineral  which  formed  the  subject  of 
it  is  simply  a  combination  of  magnesia 
and  water  (hydrate  of  magnesia)." 
Vogel,^'  writing  in  1818  "  Sur  l€«  Hy- 
drates," defined  them  thus: 

"  When  water  unites  with  a  solid  body 
and  preserves  with  it  the  solfd  state,  it  is 
in  this  case,  only,    that  one  gives    to  the 
combination  the  name  of  hydrate." 
He  reftjrs  to  soda  and  potash  as  hydrate  a. 
and  mentions  the  hydrate  of  lead.     None  of 
these  authors  used  the  term  hydroxide,  for. 
at  this  time,  it  had  not  been    generally  ac- 
cepted.    Grnham,""  considering  water  ns  n 
constituent  of  salts,    does    not  employ    the 
tenn  hydroxide,  but  he  had  the  concept,  foi* 
he  distinguishes  carefully  between  the  water 
combined  in  acids  and  that  in  bases  follow- 
ing   the    hvpathesis    of    Berzelius    already 
quoted.     Thus  Graham  : 

"  In  the  hydrates  of  the  caustic  alka- 
lies and  of  the  earths,  water  is  retained  by 
a  strong  affinity,  and  is  generally  sup- 
posed to  be  imited,  like  an  acid,  to  the 
alkali  or  earth.  In  such  hydrates  wat^r 
dis(^harges  an  add  function." 

"  In  the  case  of  hydrates  of  the  acids.* 
the  portion  of  water  which  is  found  to  be 
insciparable  by  heat,  or  to  be  very  strongly 
retained,  has  generally  been  presumed  to 
be  in  the  place  of  a  base  to  the  acid,  al- 
though little  attention  has  been  paid  to 
the  subject.  The  most  highly  concen- 
trated sulphuric  acid  retains  one  atom  of 
water,  ancl  is  supposed  to  be  a  sulphate  of 
water." 

*  //  is  hardly  necesnary  fo  remwd  fhr 
reader  that  at  this  era  the  oxy-acids  irerr 
not  regarded  as  hydrogen  eompomuh,  hvf 
vhat  we  noir  term  the  add  auhydridrs.  or 
acidic  oxides,  were  terwed^  adds  and  ihr 
covihinations  of  these  oxides  vHh  watrr 
were  called  hydrates  of  the  adds. 


In  the    "Hand-Book    of    Chemistry"    of 
Leopold  Gmelin,^"    published  in  1849,     we 
begin    to  got    a  more    definite     statement 
about  wuter-oompounds ;  he  defines  oxides: 
The    act    of    combination    of  oxygen 
with  other  bodies    is    called    oxygenation 
(combustion);     also    acidification,     when 
the    resulting    comjpound    is    of  an    acid 
nature;    oxidation  in    the  contrary    case. 
The  oxygen  is  the  oxygenizing  body  (sup- 
porter of  combustion);    also,  according  to 
circumstances,    the  acidifying  or  the  oxi- 
dizing body."     V.  2,  p.  38. 

"  Oxygen    forms  about   136    inorganic 
compounds;  they  are  as  follows:  — 

1.  Of  acid  nature  .     . 

a.  Non-metallic  oxygen  acids  .     . 

b.  Metallic  oxygen  acids    .     .     . 

2.  Compounds    not  of  acid    nature : 
Oxides."     V.  2,  p.  38. 

Gmelin  dc^s  not  use  the  term  hydroxide, 
which,  indeed,  was  not  common  in  Ger- 
many, the  word  hydrate  being  there  used. 
It  is  clear,  however,  that  his  idea  of  hy- 
drates was  that  of  the  modern  concept  of 
basic  hydroxides,  and  there  can  be  no  doubt 
that,  had  the  question  been  raised,  he  would 
not  have  extended  the  term  hydroxide  to 
include  the  oxy-acids.  Silliman**  is  not  so 
definite : 

"   .     .  it  combines  with  many  sub- 

stances, forming  a  large  class  of  hy- 
drates: hyflrate  of  lime  and  potash  are 
examples.  It  is  also,  as  we  have  seen, 
essential  to  the  acid  properties  of  com- 
mon suliphuric,  phosphoric,  and  nitric 
acids,  acting  here  the  part  of  a  much 
more  energetic  base  than  in  the  hy- 
drates."    p.  249. 

He  seems,  nevertheless,  inclined  to  limit 
hydrates  to  basic  compounds.  Newth" 
unequivocally  asumes  this  position: 

"Binary  compounds  that  are  formed  by 
the  union  of  elements  with  oxygen  are 
called  the  oxides  of  these  elements.  Cer- 
tain of  these  oxides  are  capable  of  enter- 
ing into  combination  with  water,  giving 
rise  to  substances  known  as  acids;  such 
acids  are  distinguished  as  acid-forming 
oxides,  or  acidic  oxides.  'nie.y  are  also 
sometimes  termed  anhydrides.  All  the 
nrm-metallic  elements,  except  hydrogen, 
form  oxides  of  this  order,  and  the  acids 
derived  from  them  are  known  as  the  oxy 
acids. 

"  Certain  other  oxides  also  unite  with 
water,  but  give  rise  to  compoimds  known 
as  hydroxides.  When  such  oxides,  which 
are  all    derived    from    the    metallic    ele- 


238 


THE  CHEMICAL  NEWS.    ' 


•  OCTOBER  12,  1923. 


iiionts,    are    brought    into    contact    with 
acids,  chemical  union  takes  place,  and  a 
compound  termed  a  salt  is  formed.   Such 
oxides  are    distinguished  as    salt-forming 
or  basic  oxides.      There    are  also    oxides 
which  are  neither  acidic  nor  basic."  ip.  17. 
These  quotations  serve  to  present  a  clear 
picture  of  the    notion  that    hydroxides    are 
water  compounds    and    they  show    in  addi- 
tion the  diversity  of  opinion    in  respect    to 
the  hmits  of  application    of  the  tei-m.       It 
will  be  obserevd  that,    while    the  term    hy- 
drate is  used  throughout  in  most  of  the  cita- 
tions, the  writers  clearly  had  in  mind  those 
compounds  which    to-day  would  be  termed 
hydroxides.     We  turn  then  to  the  consider- 
ation of  the  view    that  hydroixides    are  hy- 
droxyl  compounds,     and  first    examine  the 
broadest  application  of  this  view. 

This  conceiption  is  not  of  very  great  age. 
It  appears  only  a  short  time  before  the  pub- 
lication of  the  theory  of  ionisation. 
Fownes,^"  in  1885,  and  this  is  the  earliest 
reference  to  this  specific  concept  that  I 
have  found,  says: 

"Water  acts  on  many  oxides,  both  acid 
and  basic,  with  great  energy  and  con- 
siderable evolution  of  heat,  producing 
compounds  called  hydroxides."  p.  159. 
Under  "  hydrates,"  the  1880  edition  of 
Watt's  "  Dictionary  of  Chemistry,"  we 
read  the  following: 

"Another  way  of  stating  the  theoretical 
difference  between  hydrates  and  hydrox- 
ides is  to  say  that  hydrates  contain  water 
as  such,  and  that  hydroxides  contain  the 
elements  of  water."    p.  703,  v.  2. 

"The  term  hydroxide  is  sometimes 
used  in  a  narrower  sense  than  explained 
above;  by  some  chemists  it  is  applied 
only  to  compounds  whose  reactions  are 
best  explained  by  supposing  them  to  con- 
tain the  group  or  radicle  OH."  p.  704. 
Remsen*^  in  1899  supported  this  view : 

"   .     .     .     the  hydroxides  form  two  of 
the  most  important  classes  of  compounds, 
known  asi  acids  and  bases."    ip.  61. 
Goodchild  and    Tweney-^    define    an    hy- 
droxide thus: 

"A  compound  containing  the  hydroxy  1 
group  OH.       Hydroxides  may  be-  acid  or 
alkaline  in  character.",     p  298. 
"Funk  and  Wagnall's  Dictionary"'^  pre- 
sents this  definition : 

"A  compound  containing  the  group  hy- 
droxyl,  and  formed  by  the  imion  of  the 
moelcules  of  water,  so  that  a  rearrange- 
ment of  the  atoms  takes  place,  yielding 
hydroxy]."     p.  880. 


The  "Handworterbuch  der  Naturwissen- 
schaften,"  Jena.  1914,  is  in  accord  with 
this  view. 

"Hydroxyde  kennt  man  Verbindungen 

welche  die  einwertige  'Hydroxy I'   giuppe 

— OH  enthalten.     .     .     ."     v.  5,  p.  844. 

The  definition    given    by    " Webster's "'*- 

is : 

"A  compound  of  an  elemejit  or  radical 
with  hydrogen  and  oxygen,  not  regarded 
as  containing  water.  .  .  The  term  is 
usually  applied,  and  by  man^^'  chemists 
restricted,  to  compounds  containing  the 
group  OH,  or  hydroxyl.  Hydroxides  may- 
be basic,  neutral,    or  acid,    according  to 

Bibliography. 

^  d'Auhuisson:  Ann.  de  Chim.,  75,  225 
(1810). 

2  Berzelius:  Gilbert's  Ann.  der  Physik, 
40,  235-380  (1812). 

"*  Vauquelin,  Jj..N.:  Annal.  de  Chim.,  7, 
32  (1817). 

"  Vogel,  M.  :  J.  de  Pharm.,  4  (1818),  No. 
11. 

•  23  Graham,  T. :  Phil.  Mag.  and  J.  of  Set., 
3d.  Ser.,  6,  327-334,  417-424  (1835).  Trans. 
Roy.  Soc.  Edin.,  13,  Part  I. 

2"  Gmelin,  L.  :  "Hand-Booh  of  Chemis- 
try," Trans.  H.  Watts.     London. 

'"  Neivth,  G:  S.:  "  A  Textbook  of  Inor- 
ganic Chentistry,  1896. 

•''•'  Watts,  H.  :  "  Fownes  Manual  of 
Chemistry,"  ISS."). 

^^  Eemscn,  I.:  "Inorganic  Chemistry," 
Ed.  5,  1899. 

2^  Goodchild  and  Tweeny:  "A  Techno- 
logical and  Scientific  Dictionary,"  1906. 

'^  "New  Standard  Dictionary  of  the  Eng- 
lish Language,"  1909,  880. 

{To  be  Continued.) 


NOTICES  OF  BOOKS. 
The  Chemistry  Tangle    Unravelled,   bv 

F.  W.  Gray,  M.A.,  D.Sc      Pp.  VIII.  + 

148.  London:  Longmans,  Green  &  Co., 
39,  Paternoster  Row,  E.C.4.     1923.     Price 

6s.  net. 

Before  opening  this  little  volume,  the  re- 
viewer called  to  mind  the  vast  mass  of  ex- 
perimental work  that  had  given  rise  to  mul- 
titudes of  inorganic,  as  well  as  organic, 
compounds.  On  the  other  hand,  there  are 
the  countless  theories  dealing  with  compre- 
hensive, limited,  or  even  trivial  sets  of  ex- 
perimental facts  and  fancies. 


OCTOBEK  12,  1923. 


THE  CHEMICAL  NEWS. 


239 


Dr.  Gray's  book  is  evidently  an  earnest 
endeavour  of  an  ardent  teacher  to  place  be- 
fore the  student  and  drive  home  the  essen- 
tial fundamentals  upon  which  the  facts  of 
Inorganic  Chemistry  are  based. 

At  the  present  time  there  is  urgent  need 
for  such  a  text-book,  and  in  the  main  the 
author's  attempt  at  unravelling  the  tangle 
has  been  successful.  In  doing  so  he  ha'; 
not  hesitated  to  make  use  of  the  latest  ex- 
perimental results  and  theoretical  deduc- 
tions. He  commences  with  the  brief  essen- 
tials of  the  historical  development  of  the 
periodic  classification  of  the  elements,  and 
including  the  subject  matter  and  tlie  latest 
information.  Until  recently,  the  iperio<licitv 
of  the  elements  was  usually  and  most  suit- 
ably represented  by  Mendel^ef's  Table. 
There  are  now  other  schemes  (e.g.,  Loring's 
Wedge  Table.  The  Chemical  News,  1022. 
CXXV.,  387),  and  tHe  author  has  incorpor- 
ated a  pyramidal  scheme  which  he  states 
is  based  on  Ijangmuir's  conceptions  of 
atomic  structure. 

There  are  several  minor  points  in  which 
the  reviewer  feels  that  the  volume  might  be 
improved  to  increase  its  general  utility  to 
students.  It  sometimes  seems  rather  an 
account  of  the  tangle  than  its  unravelling. 
Thus,  whilst  avoiding  a  catalogue  of  facts. 
the  author  has  gone  to  the  extreme  of  as- 
suming that  the  student  already  has  a  gfxxl 
general  knowledge  of  them  in  his  posses- 
sion, even  though  they  be  in  a  tangle. 

In  the  chapter  entitled  Multiplex  .ininnn 
and  Multiplex  Cations,  reference  oould  be 
made  to  a  number  of  bodies  of  very  minor 
significance,  and  there  is  a  tendency  to  coin 
exipressions.  Most  of  the  information  in 
the  chapter  on  the  Formation  of  Complex- 
ions is  valuable  and  important,  but  the 
author  is  wrong  in  stating  (p.  92)  that  map- 
nesium  chloride  Ls  the  only  chloride  of  group 
11.  A  which  forms  double  chlorides.  In  the 
same  chapter,  the  presence  of  water  in  cer- 
tain double  salt*  is  disregarded. 

Except  at  the  end,  there  are  no  diagrams, 
which  is  a  disadvantage,  since  these  are 
very  helpful  in  visualising  various  matters. 

The  author  ha.s  undoubtedly  prorhicod  n 
book  which  should  stimulnto  a  true  interest 
in  science  in  the  students'  mind,  and  those 
who  take  wstudents  through  the  labyrinths 
of  advanced  Inorgnnic  Chemistry  would 
probably  profit  bv  a  perusal  of  this  work. 

J.G.F.D. 


Alloys  Resistant  to  Corrosion,  a  General 
Discussion  held  jointly  by  the  Faraday  So- 
ciety and  the  Sheffield  Section  of  the  Insti- 
tute of  Metals,  April  1923.     Price  5s.  6d. 

From  time  to  time  the  Faraday  Society 
arranges  meetings  for  discussions  on 
Physico-Chemical  subjects  of  importance 
and  interest.  At  these  meetings  papers  are 
read  and  discussed  by  the  eminent  scien- 
tists who  are  invited  and  attracted. 

Thus,  in  April  last,  there  was  a  general 
discussion  on  Alloys  Kesistant  to  Corrosion, 
held  jointly  by  the  Faraday  Society  with 
the  Sheffield  section  of  the  Institute  of 
Metals,  and  the  Manchester  Metallurgical 
Scxjiety  (an  account  of  which  appeared  in 
The  Chemical  News,  April  20,  pp.  246-9). 
The  contributions  were  subsequently  pub- 
lished in  the  Society's  Transactions,  but  in 
order  to  reach  a  wider  public,  are  now  re- 
printed in  book  fc«-m. 

No  definite  theory  of  corrosion  emanated 
from  the  discussion,  but  much  valuable  in- 
formation was  gathered  together  concern- 
ing the  methods  of  prevention,  etc. 

The  reprint  is  not  only  of  interest  to 
academic  physicist^s  and  chemists,  but  also 
to  engineers  aiid  technicians. 


i'h(')iii.Hlry,  Inorganic  and  Organic,  by 
Charlks  Loudon  Bloxam.  Eleventh  edi- 
tion, revised  bv  Arthur  G.  Bloxam, 
F.I.C.,  and  S.  Judd  Lewis,  D.Sc,  F.I.C. 
Pp.  IX.  +  832.  London:  J.  &  A. 
Churchill,  7,  Great  Marlborough  Street. 
1923.     Price  36s. 

In  Bloxam 's  chemistry,  both  the  Inor- 
ganic and  the  Organic  Sections  of  the 
science  are  considered  in  adequate  detail 
and  in  one  volume.  This  arrangement  cer- 
tainly has  obvious  advantages,  especially 
from  the  point  of  view  of  the  student  who 
needs  a  general  knowledge  of  the  whole 
science.  It  is  evident  that  the  present 
authors  had  this  in  mind,  since  there  is  a 
long  section  on  the  general  principles  of 
Physical  Chemistry  which  has  been  inserted 
following  the  treatment  of  the  non-metals 
and  preceding  the  chemistry  of  the  metals. 
The  early  chapters  deal  with  water  and 
its  elements;  the  Air  and  its  constituents 
and  the  general  properties  of  Gases ;  hydro- 
gen, occlusion,  reduction,  oxidation;  the 
halogens;  the  suliph\ir,  phosphorus,  carbon 
and  boron,  and  argon  groups. 

The    treatment    of  the    metals  as    based 
upon  the  Periodic  Classification. 

The  chapters  on  organic  chemistry  follow 
the  usual  plan  of  arrangement,  except  that 


240 


THE  CHEMICAL  NElVS. 


OCTOBER  12,  1923. 


aliphatic  and  aromatic  substances  are  de- 
scribed together  in  the  same  chapter. 

By  incorporating  both  branches  of  the 
subject  in  one  volume,  the  authors  have 
been  able  to  describe  such  organic  metallic 
derivatives  as  the  cyanides,  simple  and  com- 
plex, in  a  chapter  in  the  organic  portion  of 
the  book.  They  have,  however,  given  an 
account  of  acetylene,  ethylene  and  methane 
in  the  inorganic  section. 

The  section  on  physical  chemistry  gives  a 
good  account  of  the  present  position  in  that 
subject  and,  as  might  be  expected,  the 
chapter  on  spectroscopy  is  particularly  good. 

Whilst  such  a  comprehensive  volume  as 
this  lends  itself  to  criticism  on  the  grounds 
that  some  sections  must  receive  better  treat- 
ment than  others,  it  mus't  be  admitted  that 
this  edition  fully  maintains  the  traditions  of 
the  previous  ones. 

BOOKS  RECEIVED. 

From  Determinant  to  Tensor,  by  W.  F. 
Sheppard,  Sc.D.,  L.L.M.  Pp.  VIII.  + 
127.  1923.  The  Clarendon  Press,  Amen 
Comer,  Paternoster  Row,  E.C.4.  8s.  6d. 
net. 

Radio- Activity,  by  K.  Fajans,  Professor 
of  Physical  Chemistry  in  the  University  of 
Munich.  Pp.  XII.  +  138.  1923.  Messrs. 
Methuen  &  Co.,  Ltd.,  36,  Essex  Street, 
W.C.2.     8s.  6d.  net. 

Kolloide  in  der  Technik,  von  Dr.  Raphael 
Ed.  Liesegang.  Pp.  157.  1923.  Herr 
Theodor  Steinkotpff,  Residenzstrasse  12b, 
Dresden  &  Leipzig. 


We  have  received  a  coipy  of  the  Year 
Book  of  the  Michigan  College  of  Mines, 
1922-23,  which  also  contains  announce- 
ments of  the  courses  of  instruction  for  the 
session  1923-24. 


We  have  received  a  copy  of  the  Prospec- 
tus of  University  courses  in  the  Municipal 
College  of  Technology.  It  gives  particulars 
concerning  the  College  and  its  courses  and 
examinations. 


PAMPHLETS  ISSUED  BY  THE  UNION 

OF  SOUTH  AFRICA,  DEPARTMENT 
OF  AGRICULTURE. 

Notes  on  the  Chemical  Control  of  Cattle- 
Dipping  Tanks,  by  C.  0.  Williams,  B.Sc. 
Pp.  137  +  141. 

The  Estimation  of  Fineness  in  Basic 
Slaq,  by  Dr.  Chas.  F.  Juritz.     Pp.  5. 

Some  Analytical  Methods,  by  H.  F.  L. 
Bischoff  and  B.  de  C.  Marciiand,  B.A., 
D.Sc.     Pp.  8. 


Some  Observations  on  the  Sulphate- 
Molydate  Method  of  Determining  Phos- 
phoric Oxide,  by  V.  A.  Beckley  and  A. 
Marais.    Pp.  5. 

Investigation  of  Different  Methods  of 
Testing  Babcock  Milk  Bottles,  by  C.  0. 
Williams,  B.Sc,  A.R.C.S.  Pp.  132  + 

Representative  Transvaal  Soils. 
High  Veld  Sandy  Soil,  by  B.  de  C 
CHANT,  B.A.,  D.Sc.    Pp.  6. 

The  Composition  of  Some  Indigenous 
Grasses,  by  Alexander  J.  Taylor,  B.A. 
Pp.  218  +  232. 


136. 
The 

Mar- 


ims  list  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent  Applications. 
23557— Casale,  L. — Production  of  catalysts  for  syn- 
thesis of  ammonia.    Sept.  20. 
23570— Casale,   L. — Apparatus     for     catalytic     pro- 
duction of  synthetic  ammonia.    Sept.  20. 
23424— Dreyfus,     H.— Manufacture       of     aliphatic 

compounds.    Sept.  10. 
23565— Fraymouth,   W.   A.— Recovery     of     calcium 

oxalate,  &c.,  from  trees.    Sept.  20. 
23231— Badische   Anilin   &   Soda-Fabrik.— Manufac- 
ture of  €Tctive  carbon.    Sept.  17. 
23.348— Badische    Anilin     &    Soda-Fabrik.— Produc- 
tion of  vat  colouring-matters.     Sept.   18. 
203533— Badisclio  Anilin  and    Soda-Fabrik— Manu- 
facture    and  production     of  dyestuffs  and 
intermediate  products  therefor. 
203551— Hovey,  R.  B.,  and  Hovel,     F.  L.— Nitrate 
of  lime. 

Specifications   Puldished  this    Week. 
203352— Weizmann,   C,  and  Blumenfeld,     J.— Pro- 
duction of  titanic  acid. 
203383— Perkins,  W.  G.,  and  Beasley,  W.  H.— Pro- 
duction    of  refined     copper     from     copper 
oxide. 
186329— Parodi,   P.    Distilling  apparatus   for    con- 
tinuous operation. 

Abstract  Published  this  Week. 
201786-Dyes.— Kalle  &  Co.,  Akt  Ges.,  23,  Rhein- 
strasse,  Biebrich-on-Rhine,  Germany. 
Perylene  dcriiiatives.—By  treating  perylene- 
3 :4 :9 :10-tetracarboxylic  acid,  or  a  substitution 
product  thereof,  with  ammonia  or  primary  aro- 
matic or  aliphatic  amines,  it  is  converted  into 
difficultly  soluble  imides  which  dye  animal  and 
vegetable  fibre  in  fast  red  to  blue-violet  shades 
from  the  vat.  In  examples  the  acid  or  its  ammo- 
nium salt  is  lieated  with  ammonium  carbonate, 
methylamiue  liydrochloride,  or  aniline;  cthor 
suitable  amines  are  p-chloraniline,a  -  or  ^  -naph- 
thylamine,  a  -  or  ^-amino-anthraciuinone,  also 
diamines  such  as  o-,  m-,  and  p-plienylene-diamines, 
1  :  8-naphthylenediamine,  and  benzidine.  The 
perylene  3 :4 :9 :10-tetracarboxylic  acid  may  be 
prepared  by  oxidizing  with  hypochlorite,  chromic 
acid  or  other  oxidizing  agent,  the  vat  dyes  made 
Ijy  alkali  fu-^ion  of  perinaphthindanone  or  peri- 
naphthindancfione. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  onlr, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each. 


OCTOBER  19,  1923. 


THE  CHEMICAL  NEWS. 


241 


I 


THE   CHEMICAL  NEWS, 

VOL.  CXXVIL      No.  3314. 

AN  EXPLANATION  OF  THE  THEORY 

OF  THE  ROTATION  OF  THE  ATOMIC 

NUCLEUS. 

Part  IV. 

By  Herbert  Henstock. 

Oxides  (eontimiefl). 
Group  V. 

Before  discussing  the  oxidos  of  this  g[roiip 
and  esipecially  those  of  nitrogen,  it  will  be 
necessarj-  to  examine  the  very  interesting 
ease  of  the  nitrogen  nioleeulf  itself.  Pre- 
sumably the  two  nitrogen  atoms  are  linked 
by  a  treble  bond,  and  in  that  case  both 
atoms  will  have  distorted  octets,  whieh 
would  most  probably  take  the  forms  de- 
scribed below. 

If  we  take  the  positive  nitrogen  atom  and 
distort  it,  as  shown  in  Fig.  1  A.  the  dotted 
Hues  indicating  the  parts  of  the  cube  wliioh 
will  vanish,  we  should  then  have  a  figure  as 
slio^n  In  Fig,  1  B. 


ri')J 


2 


If  the  whole  of  Fig.  IB.  he  now  tuined 
through  an  angle  of  90°  so  that  the  side  a-  // 
of  the  triangle  x  y  z  comes  uppermost,  it 
will  be  seen  as  in  Fig.  2  A.  In  order  to  form 
a  treble  bond  the  negative  atoui  would  be 
as  shown  in  Fig.  2  B.,  and  if' this  wer<« 
taken  up,  turned  over,  and  applied  to  the 
positive  atom  so  that  x  y  and  z  in  each  atom 
coincided,  then  the  bond  would  be  complete 
and  the  molecule  of  nitrogen  would  he 
formed. 


On  viewing  this  arrangement,  several  in- 
teresting points  will  he  noticed. 

(1)  The  two  atoms  exhibit  no  free  valen- 
cies. 

(2)  Both  cubes  are  distorted  to  the  ut- 
most, which  the  number  of  electrons  will 
permit,  in  a  similar  way  to  carbon  as  re- 
presented by  the  tetrahedron. 

(3)  No  cube  face  is  opened  up  in  either 
atom  in  order  to  form  the  bond,  such  as 
occurs  in  the  case  of  carbon-monoxide. 
Therefore  the  nitrogen  molecule  will  be  very 
stable,  since  a  partial  opening  up  encour- 
ages further  opening  up,  so  that  the  nitro- 
gen molecule  should  be  more  stable  than 
tliat  of  CO,  which  is,  of  course,  the  case. 

(4)  The  positive  atom,  if  viewed  as  in 
Fig.  1  B.,  is  seen  to  be  identical  in  shape 
with  that  which  the  carbon  atom  has  in 
carbon-monoxide.  (See  Part  III.,  The 
ihcmical  News,  1923,  CXXVIL,  18.) 

(5)  There  are  the  same  number  of  elec- 
trons in  the  combined  octets  of  the  nitrogen 
molecule  as  in  those  of  CO. 

In  a  paper  by  Bone,  Hewitt  and  Towns- 
(nd,  read  before  the  ICoval  Societv  ^ April 
27,  1923),  Professor  Bone  stated  that,  "  In 
the  combustion  of  mixtures  of  2C0  +  Oj 
with  nitrogen  as  a  diluent,  the  nitrogen 
exerts  a  peculiar  energy  absorbing  influence, 
far  beyond  that  of  other  di  atomic  diluents, 
and  also  that  this  energy  absorbed  is  slowly 
liberated  again  as  the  system  cools  down." 
This  absorption  of  energy  may  be  due  to  the 
opening  up  of  the  octet  of  the  positive  nitro- 
gen atom,  which  might  go  as  far  as  the  rup- 
ture of  the  treble  bond  with  formation  of  a 
single  bond  or  even  the  complete  separation 
of  the  atoms,  which  would  permit  of  the 
opening  up  of  the  full  octets  of  both  atoms, 
and  thus  leave  them  with  three  free  and 
active    valencies    apiece,    permitting    their 


242 


THE  CHEMICAL  NEWS. 


OCTOBER  19,  1P23. 


union  with  other  atoms  such  as  oxygen.  The 
same  thing  probably  occurs  when  a  high 
tension  electric  current  is  passed  through 
air;  in  this  case,  considerable  energy  is  re- 
quired to  produce  this  efiect,  and  it  is  there- 
fore more  than  probable  that  both  these  ab- 
sorptionsi  of  energy  are  due  to  the  same 
cause.  The  converse  of  this  opening  up  pro- 
cess would  occur  on  cooling,  with  conse- 
quent re-emission  of  energy.  This  also 
agrees  with  their  further  statement  that 
"  The  nitrogen  becomes  activated  and  will 
combine  with  oxygen  when  in  this  state  ' ' ; 
the  activated  condition  is  that  in  which  the 
octets  are  reformed  ready  for  union  with 
other  atoms,  in  fact  the  converse  of  the  pro- 
cess sihown  in  Fig.  1. 

Again,  they  state    that    "  If   nitrogen    is 
used  as  a  diluent  in  exploding    mixtures  of 
hydrogen    and  oxygen,    no  such    activation 
occurs,  and  that  a  small  percentage  of  hy- 
drogen introduced  into  a  carbon  monoxide- 
air    mixture    is   sufficient    to    prevent    it." 
They  deduce  from  this  that    "  The    peculiar 
influence  of  nitrogen  in  2C0  +  0^  explosions 
is  due  to  its  ability  to  absorb  the  particular 
quality  of  radiation  emitted    when  CO  and 
oxygen  (but  not  when  CO,  oxygen  and  hy- 
drogen) react;    such  radiation  is  known    to 
be  of  a    different    wave    length    from    that 
emitted  during  the  flame  combustion  of  hy- 
drogen.    In  other  words,  there  seems  to  be 
some    constitutional      correspondence      be- 
tween CO  and  Nj  molecules  whereby  the  vi- 
brational energy  emitted  when    the  one  re- 
acts with  oxygen  is  of  a  quality  readily  ab- 
sorbed by  the  other,  the  two  acting  in  reson- 
ance."    Now,  if    observation    No.    4    (see 
above)  be  considered  in  connexion  with  this, 
it  seems  highly    probable    that    the    exact 
similarity  in  configuration    of    the    carbon 
and  positive    nitrogen    atoms    in    the    two 
gases,  combined  with  the    fact    that    each 
molecule  contains  the  same  number  of  ex- 
ternal as  well  as  internal  electrons  (observa- 
tion 5),  may  account  for  the  two  vibrating 
concurrently,   i.e.,   the  similarity    in  struc- 
ture accounts  for  the  similarity  in  resonance 
effects.     The  hydrogen  molecule,  having  an 
entirely  different  configuration  from  that  of 
CO  or  nitrogen,  would  inhibit  such    concur- 
rent vibration. 

Referring  to  their  statement  that  "  This 
energy  absorbing  effect  in  nitrogen  is  far 
beyond  that  of  all  other  di-atomic  gases  "; 
if  the  structm-es  be  worked  out  on  the  lines 
given  above,  no  other  di-atomic  gas,  with 
the  possible  exception  of  cyanogen,  will  be 
found  to  have  a  configuration  anything  like 


that  of  either  CO^pr  nitrogen,  and  ev^n  cy- 
anogen, the  nearest  to  tliem,  has  9  electrons 
in  the  combined  octets  of  its  molecule, 
whereas  CO  and  nitrogen  have  10  each. 

This  arrangement  of  the  nitrogen  mole- 
cule is  the  nearest  approach  to  a  sphere 
which  can  be  obtained  with  the  octets  of  the 
two  atoms,  which  agrees  with  the  calcula- 
tions of  Rankine  {Proc.  Roy.  Soc,  1921,  A. 
98,  360,  369,  331)  of  the  atomic  and  mole- 
cular diameters,  obtained  from  the  viscosi- 
ties. 

The  oxides  of  nitrogen  will  be  represented 
as  follows: — Nitrous  oxide,  N^N  =  0  in 
Fisr.  3. 


oiavJnx 
-vxrrx.cC 


This  foi-mula  gives  a  better  explanation 
than  any  other  of  the  ready  formation  of  the 
nitrogen  molecule  when  oxygen  is  ab- 
stracted from  N2O;  all  that  will  happen 
after  the  oxygen  has  left  the  molecule  is 
that  the  electron  from  (a)  will  travel  to  (fe), 
and  the  cube  corner  at  (a)  will  vanish,  leav- 
ing a  triangle  and  thus  reforming  the  nitro- 
gen molecule. 

A  further  argument  in  its  favour  is  that 
N2O,  which  might  be  looked  upon  as  the  an- 
hydride of  hyponitrous  acid,  docs  not  unite 
with  water  to  form  that  acid,  since  water  is 
not  a  strong  enough  reagent  to  rupture  the 
treble  bond  and  op  eh  up  the  nitrogen  octets, 
whereas  in  the  decomposition  of  hypo^ 
nitrous  acid 


H- 


-h       T 


o 


o 
{ 

H 


■¥ 


OCTOBER  19,  1923. 


THE  CHEMICAL  NEWS 


243 


to  N2O  and  water,  the  treble  l)i>nd  might  be 
easily  reformed  from  the  double  bond. 

It  is  also  in  agreement  with  Rankine's 
calculations  {loc.  cit.),  in  which  he  finds 
that  COg  and  N^O  molecules  are  similar  in 
size  and  shape,  which  can  be  seen  by  com- 
paring this  formula  with  that  given  for  CO2 
in  Part  III.  It  will  also  be  noticed  that 
the  two  gases  have  the  same  number  of  ex- 
ternal electrons  in  their  molecules. 

It  presents  no  free  valencies  in  the  nitro- 
gen atoms  which  precludes  the  easy  addi- 
tion of  oxygen  U>  form  higher  oxides.  As 
thus  constituted,  there  are  two  weaknesses 
in  the  NjO  molecule. 

(1)  In  the  pentavalent  nitrc^en  atom, 
both  positive  and  negative  bonds  come  into 
play  (rule  2). 

(2)  The  corner  at  x  (fig.  3),  which  is 
shared  bv  all  three  atoms,  will  be  oocu^jied 
by  two  electrons  (rule  6). 

The  oxygen  atom  is,  for  these  reasons, 
easily  detached  from  the  rest  of  the  mole- 
cule. 

Nitric  oxide  N  =  0  in  Fig.  4. 


{To  he  continued.) 


80ME  RECENT  RESE.\ROHES  IN 
ORGANIC  CHEMISTRY. 

By  R.  F.  Hunter,  F.C.S. 

Researches  in  the  field  of  Organic 
Chemistry,  have  increased  during  the  last 
few  vears  in  such  number  and  magnitude 
that  a  mention  of  a  few  of  the  problems, 
and  it  can  b<'  little  more  than  a  mention 
whicii  our  leading  researchers  and  pupils 
iiave  been  attacking,  would  not  seem  out 
of  place.  Since  those  of  us  who  are  aca- 
demic researchers  and  whose  duty  it  is, 
Ih.'nfore,  t-o  keep  pace    with  the  enonnous 


w<M-k  whicli  is  being  done,  are  finding  it  in- 
creasingly difiicult  to  keep  pace  with  new 
developments,  we  fear  that  the  industrial 
chemists  amongst  vis  must,  in  the  main, 
have  given  uip  (save  w^here  their  own  special- 
ised branches  are  touched  on)  as  a  hopeless 
task  the  attempt  to  keep  pace  with  the  re- 
searches carried  out  in  the  laboratories  of 
our  Universities.  This  being  so,  a  series  of 
articles  on  the  subject  should  not  be  out  of 
place.  One  point  necessary  to  mention  is 
this — the  brilliant  work  which  has  been 
carried  out  in  the  laboratories  of  the  Royal 
College  of  Science  during  the  last  ten  years 
or  so  under  the  guidance  of  Prof.  J.  F. 
Thorpe  and  Dr.  C.  K.  Ingold  on  Dynamic 
Tautomerism,  Stability  of  Spiro  Com- 
pounds, etc.,  has  not  been  included,  for  the 
reason  that  it  will  be  dealt  with  much  more 
fully  at  a  later  date.  The  researches  with 
which  we  propose  to  deal  are  those  which 
have  taken  iplace  during  the  last  three  years 
or  so,  that  is  to  say.  we  do  not  propose  to 
go  further  back  than  1920,  and  further  to 
confine  attention  on  the  work  done  in  this 
country. 

The  greatest  difficulty  is  obviously  to 
s<^parate  the  most  vital  considerations  from 
the  hosts  of  other  important  considerations, 
and  in  the  present  state  of  knowledge  and 
the  extreme  recent  date  of  the  work  this  be- 
comes difficult.  This  bein^  so,  it  will  not 
\yo  thought  necessary  if  less  miportant  prob- 
lems, sinc<^  they  will  only  be  shown  to  be 
of  lesser  importance  at  a  later  date,  are 
given  more  consideration  than  more  vital 
problems.  In  composing  this  piece  of  work, 
tlie  mat^'rial  has,  largely,  been  based  uipon 
the  accounts  given  in  the  Chemical  Society's 
■Jonrnal,  where  full  experimental  details 
and  foreign  references  can  be  found. 

An  interesting  preparation,  that  of  chlor- 
picrin  from  picric  acid  and  tri  nitro  toluenes, 
was  investigated  by  Orton  and  McKie. 
They  prepared  chlorpicrin  by  dissolving 
picric  acid  in  sodium  carbonate  to  give  the 
scxlium  salt,  obtained  a  paste,  and  acted  on 
this  with  chlorine  at  5°  C.  They  examined 
the  solubility  of  chlorpicrin  in  water,  and 
also  investigated  the  action  of  a  hypochlor- 
it«>  solution  on 

o  &  p  Nitro  phenol, 
2:4  Dinitrophenol, 

and  Trinitro  toluene  and  tri  nitro  tolu- 
ene residues. 

The  research    was  communicated    to  the 
Chemical  SfKjiety  in  November,  1920. 
The  same"   month,    Chattaway    and    Ray 


244 


THE  CHEMICAL  NEWS. 


OCTOBER  19,  1923. 


studied  the  old  familiar  problem    of  the  de- 
composition of  tartaric  acid  by  heat. 

Tri  thio  eai'bonate  and  per-thiocarbonates 
were  investigated  by  Yeoman  at  this  time. 
Among  the  problems  studied  were  the 
method  of  analysis,  the  compound  sodium 
tri  thio  carbonate  and  the  corresponding 
potassium,  calcium,  barium,  strontium  and 
ammonium  salts.  About  this  time  the  first 
part  of  Henstock's  work  on  the  bromine 
compounds  of  phenanthrene  appeared. 
Briefly  we  can  say  that  he  prepared  com- 
pounds which  appear  to  be,  and  which  he 
headed  as 

2  (?)  Bromophenanthrene  Dibromide, 
2  (?)  10  Dibromophenanthrone, 
2  (?)  10  Dibromophenanthrone, 
2  (?)  10  Dibrom  9  nitro  phenanthrone, 
2  (?)  10  Dibromo  9  amino  phenanthrone, 
10  Bromo  2  ethoxy  phenanthrone,  and 
9:10  Dinitro  2  ethoxy  iphenan throne. 
In  the  next  month,    Mclvenzie    and  Bar- 
row published  a  paper  on  |S  amino,  jS  phenyl- 
propic  phenone,  this  being  the  result  of  the 
fact  that  for  another  research  it  was  desired 
to  obtain  a  /3  amino  ketone    containing    an 
asymmetric  carbon  atom. 

In  the  experimental  work,  we  have  the 
preparation  of  ft  amino  ft  phenyl  propionic 
acid  from  cinnamic  acid  and  hydroxylamine 
and  the  study  of  the  action  of  ft  formyl- 
amino  ft  phenyl  propionyl  chloride  on  ben- 
zene in  the  presence  of  aluminium  chloride, 
the  action  of  cinnamoyl  chloride  on  ben- 
zene under  the  same  conditions.  Also  the 
preparations  of 

ft  Benzoylamino  ft  phenyl  prqpiophenone, 
ft  Phthalimino  ft  phenylpropionic  acid, 
ft  Phthalimino  ft  phenyl  propiophenone, 
ft  Benzoyl  and  phenyl  ethyl    phthalamic 
acid,  and 

ft  Amino  ft  phenyl  propiophenone. 
About  this  time  a  communication  of  Cof- 
fey's appeared  on  the  action  of  sulphur 
chlorides  on  substituted  ethylenes,  the 
action  of  propylene  on  sulphur  mono- 
chloride  and  the  synthethis  of  ft  ft'  "Dichlor- 
ide  n  propyl  sulphide,  one  of  the  many  re- 
searches entailed  by  the  production  of  mus- 
tard gas  ft  ft'  "dichlorethyl  sulphide  for  war 
purposes.  It  was  considered  that  propylene 
would  react  similarly  to  ethylene, 

2C2H,  +  S^Cl,  =  (Ch^  CICH,),  S  +  S. 
A  small  quantity  of  ft  ft"  'dichloridi  n  propyl 
disulphide  was  isolated. 

ftft"  'dichloride  di  n  propyl    sulphide  was 
prepared  according  to  the  scheme 
CH3  CH  (OH)  CH.Cl 

(CH3CH  (OH)  CHJa  S 

(CH3  CH  CI  CH,),  S. 


The  oxidation  of  ftft'  dichlorodi  n  propyl 
sulphide  by  nitric  acid  was  also  investigated. 
Brady  and  Gibson  connnunicated  from 
Woolwich  Arsenal  the  results  of  a  research 
upon 

2:4:6  Tri  nitro  totyl  methyl  nitro- 
amine. 

The  preparation  of  a  number  of  related 
compounds  were  incidentally  discussed. 

Ai-ylazoglyoxaline  carboxylic  acids  were 
studied  by  Fargher  about  this  time,  the 
work  mainly  experimental,  and  among  the 
preiparations  were  4-p-Bromohenzeneazo  2- 
phenyl  giyoxaline-5-carboxyIic  acid  4-p- 
Bromobenzeneazo  2-methylglyoxaline-5-car- 
boxylic  acid  2-p-Bromobenzeneazoglyoxa- 
line  4   :  5-dicarboxylic  acid. 

Meanwhile  Nierenstein  published  the 
third  part  of  the  research  on  the  constitu- 
tion of  cateohin  and  the  synthesis  of  aca- 
catechin.  The  communication  contained 
the  synthesis  of  2  :  4  :  6  :  3'  ;  4'-penta- 
hydroxy-3-phenylohroman.  This  was  ob- 
tained by  the  following  i^iethod  : — 3  :  4  : 
2'  :  4'  :  6'-penta-methoxy-diphenylmethyl- 
chloromethyl  ketone  was  converted  into 
4  :  6  :  3'  :  4'  tetramethoxy-3-phenylchro- 
man-2-one,  this  reduced  to  2-hydroxy-4  :  6 
:  3'  :  4'-tetra-methoxy-3-phenylchroman, 
and  this,  on  demethylation,  gave  the  re- 
quired 2:4:6:3':  4'-penta-Eydroxy-3-ipheny  1- 
chroman. 

Morgan  and  Vining  studied  in  some  detail 
the  subject  of  Dihydroxy  naphthaldehydes. 
Among  the  general  preparations  were  those 
of  Dihydroxy  naphthaldehydes  and  their  p 
Bromo  phenylhydrazones,  CgH^Br  NHN  : 
CH  Ci„  H5  (0H)2,  Dihydroxy  naphthylide- 
neanUines,  CgH^N   :  CH  C.^H^  (OH)^. 

A  paper  of  Morgan  and  Jones  appeared 
on  ortho  Chlorodinitro  toluenes,  and  among 
the  questions  studied  were  : 

Nitration  of  2  Chloro  6  nitro  toluene ; 
Action  of  diazonium  salts  on  6  Chloro ; 
2   :  4  tolylenediamines. 
The  action  of  primary    amines  on    4    :  5 
and  5   :  6  dinitro  o  chlorotoluenes. 

In  January,  1921,  a  number  of  papers  on 
organic  research  were  communicated  to  the 
J.C.S.,  these  were  briefly  as  follows:  — 

The  constitution  of  Disacharides,  Pt.  V., 
Cellobiose,  by  Haworth  &  Hirst,  which  con- 
sisted essentially  of  the  preparation  of  cel- 
lobiose, octa  acetate,  the  methyl ation  of 
cellobiose,  isolation  of  heptamethyl  methyl 
cellobiose,  the  hydrolysis  of  heptamethyl 
methyl  cellobiose,  and  the  conversion  of 
crystalline  tri  methyl  glucose  into  tetra- 
methyl  glucose. 

Derivatives  of    Gallic  Acid,    Pt.    II.,    by 


OCTOBER  19,  1923. 


fflE  CflSMlCAL  KfiWs. 


245 


Meldrum,  appeared,  in  which  condensations 
of  gallic  acid  were  examined.  In  the  ex- 
perimental work  there  appeared 

3:4:  5-Tri-hydroxy-2-tri-chloromethyl 
phthalide. 

The  lactone  of  7  :  8  dih}  di-oxy  2  :  4  bis 
tri-ohloro-methyl-6-i8-trichloro  -  a-hydroxy- 
ethyl  1    :  3-benzdioxine-5-carboxyiio  acid. 

The  lactone  of  7  :  8  i8/i/3-trichloroethyli- 
dene  dioxy  2  :  4  bis  tri  chloro  methyl  6 
fiftft-iri-chloro  a  hydroxy ethy  1-1  :  3-benzdi- 
oxine-5-carboxylic  acid.  6-MethyI-2  :  4-bis- 
tri-chloromethyl-1  :  3-benzdioxine  -  8  -  car- 
boxylic  acid.  4  Hydroxy  5  fift  dichlor- 
niethyl-m-toluic  acid.  6  Hydroxy  5  car- 
boxy-m-tolylacetic  acid,  and  /?/?^-trichloro 
4  :  4'  dihydroxy  a  a  di-m-tolyetliane-5  :  5'- 
dicarboxylic  acid. 

A  short  paper  by  Singh  and  Lai  appeared 
on  substituted  Quaternary  Azonium  com- 
pounds, which  contain  an  asymmetric  car- 
bon atom. 

The  work  of  Barrow  and  Griffiths  on  the; 
condensation  of  p-nitro-benzyl-chloride  with 
nitroso  compounds,  which  contained  a  new 
mode  of  formation  of  N  Oximino  ethers, 
appeared,  the  experimental  part  of  which 
contained  the  study  of  p-nitro-ben- 
zaldoxime-N-phenyl-ether. 

NO,  .  G,H,  .  CH  :  N  .  Ce  H,  :  0. 
Perkins  and  Tucker's  research  on  the  oxi- 
dation of  carbazole  appeared  about  this 
time.  In  the  experimental  portion,  we 
have  the  oxidation  of  carbazole  by  perman- 
ganate of  potash  in  acetone  solution.  From 
the  reaction  two  isomeric  dicarbazyls  wen- 
isolated,  both  of  formula  Cj^HjaNj,  a  third 
amorphous  product  of  oxidation  was  iso- 
lated. All  three  substances  were  found  lo 
be  capable  of  nitration,  bromination,  and  to 
react  under  certain  conditions  with  acetic 
j'nhydride. 

Towards  the  end  of  December,  1920,  Hep 
worth  commimicated    an    investigation    on 
the  action  of    Grignard  reagent    on    nitro 
esters. 

The  scheme  of  reactions  was  of  the  form 
RON  0,-^R0.  N  R,'  (OHg  X)  ,-^H  0  N  R  ' 
(O  Hg.)  Hg  X->.RO  NH  (OH)  R,> 

R  O  H  +  NR'  R'  OH. 
Among  the  preparations  were : 
Dimethyl    hydroxylamine     hydrochloride 
and  oxalate,  and  the  reactions  studied  wt-n' 
those  of 

Mg  Mel  on  ethyl  nitrate,  Mg  Et  Br  on 
ethyl  nitrate,  Mg  Br  Et  on  ethylene  glycol 
dinitrate.  Mg  Mel  and  Mg  Br  Et  on  nitro- 
glycerin'and  pentnei-ythrit^l  tetranitrate. 

Grossley  and  Renvuf  contributed  a  papor 
on  1    :   1  dimethyl    cyclohexane    from  hep- 


tenone,  the  research  was  mainly  on  Kelin- 
sky's  previous  work.  At  the  same  time 
there  appeared  another  paper  by  Nierenstein 
on  Gallotannin.  The  work  was  mainly 
quantitative,  and  essentially  consisted  of 
quantitative  observations  on  production  of 
Ellagic  acid  from  gaUotannin  and  several 
gallotannin  residues  were  studied. 

(To  be  continued.) 


THE    BRITISH  EMPIRE  EXHIBITION 

(1924). 

The  Editors  of  the  various  technical 
journals  met  Mr.  Woolcock,  the  General 
Manager  of  the  Association  of  British 
Chemical  Manufacturers,  at  the  offices  of 
the  Association  in  Piccadilly,  to  discuss 
with  him  the  progress  which  has  been  made 
with  the  preparation  of  the  Chemical  Sec- 
tion. In  the  course  of  the  conversation, 
Mr.  Woolcock  said:  — 

"The    Chemical    Section  which    is  being 
organised  by  the  Association,  and  occupies 
nearly  40,000  square  feet    in  the  Palace  of 
Industry,  will  be  built  in  such  a  way  as  to 
form  a  hall  within  the  palace.      About  one 
hundred  thousand    pounds  will  be  spent  in 
presenting  to  the  public  a  picture  of  the  pre- 
sent   state  of  British    Chemical    Industry. 
No  inuportant  firm  in  the  industry  will  be 
unrepresented,    and  the  whole  of  the  indi- 
vidual exhibits,  numbering  about  one  hun- 
dred, will,  by  reason   of  their  position    and 
character,  combine  to  form    a  magnificent 
illustration  of  the  industry.     The  treatment 
of  the  individual    stands    is  being    done  on 
lines  which  have  never  before  been  attemp- 
ted,   and    the  old    and  somewhat     hideous 
structures  which  have  disfigured  exhibitions 
in  the  past  will  not  appear.       Considerable 
attention  has  been  paid  to  the  lay-out  and 
to    the  decoration    of  the    Chemical    Hall. 
There  will,  for  example,  be  about    two  hun- 
dred yards  of  a  specially  painted  frieze,  il- 
lustrating various    operations    in   chemical 
manufacture,   and    as  the  majority    of  the 
stands  are  being  designed  by  the  same  archi- 
tect, the  treatment  of  each    stand  is  likely, 
while  nuiintaining  the  individuality    of  the 
occupier,  to  present  a  very  pleasing  picture 
of  the  hall  as  a  whole.       It  has  not,  how- 
ever,   been    considered    sufficient    that  we 
should  merely  show  visitors  examples  of  the 
products  of  tne  industry.     The  best  possible 
exhibition    of    this    kind    would    leave    one 
question  unanswou'd.     The  visitor  may   be 
satisfied  that  he  is  witnessing  a  demonstra- 


246 


TfiB  CHEMICAL  NEWS. 


OCTOBEK  i9,  192^. 


tion  of  the  position  to  whioh  the  industry 
has  attained,  but  what  the  critical  person 
who  examines  the  exhibit  requires  to  know 
is  whether  there  is  behind  tliis  example  of 
what  has  been  achieved  a  scientific  basis 
which  will  ensure  the  continuance  of  this 
progress.  For  this  reason,  in  the  centre  of 
the  Chemical  Hall,  there  is  to  be  illustrated 
the  progi'ess  which  has  been  made  in  pure 
chemistry  during  the  past  twenty  or  thirty 
years,  with  a  view  to  showing  that  the 
stream  of  scientific,  invention  in  this  coun- 
try is  still  flowing  steadily  onwards." 

Mr.  Woolcock  then  proceeded  to  outline 
the  scheme  of  classification  which  has  been 
adopted  for  the  Scientific  Section,  and 
enumerated  a  number  of  names  of  those 
scientists  who  have  already  promised  theii- 
assistance,  and  very  few  of  the  outstanding 
scientific  men  of  the  day  were  absent  from 
the  list.      Continuing,  Mr.  Woolcock  said : 

The  Scientific  Section  is  being  organised 
by  a  Committee  consisting  of  representa- 
tives of  the  following  bodies:  — 

The  Chemical  Society. 

The  Institute  of  Chemistry. 

T*he  Society  of  Chemical  Industry. 

The  Society  of  Dyers  &  Colourists. 

The  Pharmaceutical  Society. 

The  Institution    of  Petroleum  Technolo- 
gists. 

The  Institution  of  Chemical  Engineers. 
The  Committee  is  working  in  close  co- 
operation with  the  Koyal  Society.  Sir  Her- 
bert' Jackson  acts  as  the  representative  of 
the  Royal  Society  on  the  Committee,  and 
myself  in  a  similar  capacity  on  the  Royal 
Society  Committee.  In  this  way  we  shall 
prevent  any  overlapping.  In  order  that  both 
the  general  public  and  scientific  persons 
may  have  a  record  of  the  exhibit,  it  is  pro- 
posed to  publish  a  number  of  pamphlets 
(specially  written  for  the  purpose)  dealing 
in  popular  language  with  the  various  classes 
of  exhibits  in  the  Scientific  Section.  In 
addition  to  this  it  is  proposed  to  publish  in 
more  technical  language  a  work,  which  will 
not  only  explain  the  scientific  exhibits,  but 
which  will  put  on  record  in  a  very  complete 
form  the  state  of  our  knowledge  in  chemi- 
cal matters  at  the  date  of  the  Exhibition. 
It  is  anticipated  that  there  will  be  a  very 
large  demand  for  this  valuable  record,  and 
that  it  is  likely  to  find  a  place  on  the  book- 
shelf of  every  scientist.  The  various  chap- 
ters will  be  written  by  the  acknowledged 
experts  in  their  subjects,  and  I  anticipate 
that  the  contents  of  this  book  will  be  very 
valuable  matter  for  reference." 

Mr.  Woolcock   invited    the  assistance    of 


the  Editors  in  making  widely  known  what 
was  being  prepared  for  the  Exhibition  next 
year,  and  the  following  resolution  was 
unanimously  passed:  — 

"  That  our  best  thanks  be  extended  to 
Mr.  Woolcock  for  his  courtesy  in  inviting 
the  Editors  of  the  trade  and  technical 
press  to  meet  him,  and  that  we  under- 
take to  give  him  any  assistance  in  our 
power  in  organising  the  publicity  service 
of  the  Chemistry  Section." 


ANHYDROUS  ALUMINUM 
CHLORIDE. 

[Abstracted  from  Technical  Paper  321, 
By  Oliver  C.  Ralston,  issued  by  the 
U.S.  Dept.  of  the  Interior,  Bureau  of 
Mines.] 

Anhydrous  aluminum  chloride  is  a  pure 
white  microcrystalline  solid  which  is  usually 
yellow  to  brown,  or  bluish  to  greenish,  due 
to  the  presence  of  impurities,  especially 
iron.  When  heated,  it  sublimes  with  only 
a  hint  of  fusion  and  the  temperature  of  sub- 
limation— between  181°  and  195°  C. — is 
somewhat  difficult  to  measure.  Under  a 
pressure  of  about  2.5  atmospheres,  it  can  be 
melted  at  194°  C.  Its  boiling  point  at  at- 
mospheric pressure  is  thought  to  be  about 
179°  C.  When  condensed,  the  ruling  tem- 
perature in  the  condenser  is  about  181°  C. 

Aluminum  chloride  is  extremely  hygro- 
scopic, absorbing  moisture  from  the  air  to 
form  aluminium  oxide  (AI2O3)  and  hydrogen 
cholride  (HCl) ;  the  smell  of  the  latter  is  al- 
ways noticeable  whenever  a  container  of 
aluminium  chloride  is  opened.  This  re- 
action between  moisture  and  aluminum 
chloride  often  does  not  take  place  at  once, 
but  the  hydrochloric  acid  is  given  off  slowly 
on  standing.  If  the  surface  of  a  mass  of  an- 
hydrous aluminum  chloride  is  allowed  to 
"glaze"  with  a  coating  of  aluminum  chlor- 
ide hydrate  (AICI3.6H2O)  and  the  mass  is 
then  sealed  in  a  tight  container,  the  water 
of  the  hydrate  solwly  diffuses  to  the  re- 
maining anhydrous  material  and  reacts  to 
form  aluminum  oxide  and  hydrochloric  acid 
gas.  As  the  reaction  proceeds  the  pressure 
of  the  gas  finally  becomes  strong  enough  to 
burst  the  container.  A  glass  bottle  filled 
with  aluminum  chloride  which  has  been  ex- 
posed to  the  open  air  for  a  few  ininutes  be- 
fore being  placed  in  the  bottle  may  blow  its 
stopper  in  this  way.  Large  drums  filled 
with    the    commercial    product    have    been 


OGTOBEk  19,  1923. 


l-HE  CHEMICAL  NEWS. 


^1 


known  to  "  explode,"  probably  from  this 
cause. 

This  chloride  is  compeltely  soluble  in  a 
large  excess  of  water,  with  no  visible  hydro- 
lysis; it  dissolves  with  a  hiss  and  with  the 
generation  of  heat.  Aluminum  chloride  is 
also  easily  soluble  in  alcohol,  ether,  and 
liquid  chlorine,  and  dissolevs  quickly  in  dry 
petroleum  products,  producing  a  brown  to 
black  colouration.  SarrTple  bbttleg  contain- 
ing anhydrous  aluminum  chloride  shouiil 
not  be  sealed  with  paraffin,  as  the  salt  will 
turn  it  black.  The  solution  of  aluminum 
chloride  in  a  petroleum  product  may  segio- 
gate  into  two  layers  on  standing,  with  the 
aluminum  chloride  dissolved  in  the  highly 
coloured  lower  layer.  On  heating,  this 
layer  mixes  with  the  one  above.  No  teste 
have  been  made  to  see  if  a  small  amount  of 
aluminum  chloride  is  also  contained  in  the 
upper  layer.  Aluminum  chloride  ia  much 
more  soluble  in  warm  than  in  cold  oils;  in 
fact,  at  the  petroelum  refineries  it  is  dis- 
solved in  warm  oil  and  piped  to  the  stills, 
where  it  is  used  as  a  catalyzer. 

In  the  fused  condition  anhydrous  alu- 
minum chloride  mixes  with  sodium  chloride 
in  all  proportions.  The  double  compound, 
AlClj-NaCl,  is  supposed  to  exist  and  to 
have  a  melting  point  of  185°  C .  It  has  been 
obtained  by  volatilising  a  mixture  of  salt, 
alumina,  and  carbon  by  treatment  witii 
chlorine.  The  writer  has  not  made  a  quan- 
titative study  of  the  system  NaCl-AIClj, 
but  has  prepared  mixtures  of  the  two  which 
were  completely  fluid  at  a  temperature  as 
low  as  136°  C.  A  cutectic  between  the 
double  compound  and  aluminum  chloride 
probably  melts  at  about  this  temperature. 
The  double  compound  formed  the  basis  of 
the  early  aluminum  industry ;  it  was  the 
bath  from  which  aluminum  was  deposited 
by  metallic  sodium,  until  the  present  cryo- 
lite-alumina electrolytic  bath  displaced  it. 

The  first  large-scale  use  of  aluminum 
chloride  was  in  the  preparation  of  alu- 
minum metal  by  the  reaction  of  sodium 
metal  on  the  fused  double  aluminum- 
sodium  chloride.  At  first,  pure  anhydrous 
alundnum  chloride  was  made  and  added  to 
the  bath  as  the  latter  became  depleted  in 
aluminum ;  later,  it  was  found  much  more 
conevnient  to  prepare  the  double  compound, 
which  was  more  stable  in  air,  not  so  hygro- 
scopic, and  could  be  melted  find  cast  into 
blocks  or  rods  ready  to  drop  into  the  hath. 

Anhydrous  alumimmi  chloride  is  also 
used  on  a  large  scale  in  carrying  out  Fri»>del- 
Crafts  organic  reactions.       The    alimiinum 


chloride  acts  as  a  catalyst,  causing  the 
combination  of  two  materials  that  would 
otherwise  be  indifferent  to  each  other.  In 
the  manufacture  of  many  dyes,  perfumes, 
drugs,  and  pharmaceuticals  a  catalyzer  is 
used  at  some  point  in  the  process.  Alu- 
minum chloride  is  classed  more  or  less  with 
zinc  chloride  as  a  "condensing  agent"  for 
organic  chemical  work. 

Aluminum  chloride  is  also  being  con- 
sidered for  the  bleaohing  of  brick,  as  red 
briok  can  be  bleached  to  buff  if  iron  is  re- 
placed by  aluminum.  Some  steel  com- 
panies have  claimed,  moreover,  that  the 
chloride  could  be  used  in  removing  certain 
impurities  from  molten  metal.  Any  of  the 
uses  mentioned  might  develop  on  a  larger 
scael  if  a  cheap  product  could  be  produced. 
The  refining  of  petroleum,  however,  uses 
the  largest  amount  of  aluminum  chloride  at 
present,  and  seems  likely  to  demand  addi- 
tional supplies  of  the  chloride  in  the  future. 
This  salt  seems  to  fulfil  several  major  func- 
tions in  the  treatment  of  petroleum  pro- 
ducts. 

First,  it  converts  all  unsaturated  com- 
pounds. Frequently  this  conversion  is 
made  by  throwing  out  the  excess  of  carbon 
over  hydrogen  in  the  hydrocarbon,  where- 
upon the  carbon  blackens  the  aluminum 
chloride  and  forms  a  coke;  gases  need  not 
be  liberated.  The  most  astonishing  conse- 
quence of  this  saturating  action  is  that  un- 
stable gasoline  and  lubricating  oils  made 
from  asphalt-ba!=o  petroleum  yield  excellent 
stable  products  of  good  colour  and  odour;  in 
fact,  they  are  almost  paraffin-base  pro- 
ducts. 

The  second  main  effect  obtained  by  boil- 
ing petroleum  products  in  the  presence  of 
aluminum  chloride  is  a  cracking  action. 
High-boiling  hydrocarbons  can  be  con- 
verted into  low-boiling  hydrocarbons,  with 
the  formation  of  some  coke  and  some  fixed 
gases  as  by-prcxlucts.  A  topped  oil,  a  gas 
oil,  or  a  fuel  oil  can  be  treated  with  alu- 
minuTn  chloride  catalyzer  in  a  simple  boil- 
ing still  at  atmospheric  pressure  with  a 
yield  of  60  to  85  per  cent,  of  low-boiling  oil 
containing  fractions  of  petroleum  ether, 
gasoline,  and  kerosene.  The  residue  is 
coke  containing  the  aluminum  chloride,  and 
can  be  used  over  several  times  before  it  be- 
comes exhausted  by  the  aluminum  chloride 
losing  its  activity.  Possibly  the  aluminum 
chloride  is  buried  in  the  carbon  or  combines 
with  it.  The  distillates  arc  all  saturated 
sweet-smelling  products. 

If  desired,    the  distillation    need    not    be 


248 


tfiE  CHEMiCAL  T^feWS. 


OGTOBEK  19,  192^. 


carried  compeltely  to  ooke,  bul  can  be 
stopped,  and  some  excellent  lubricants  will 
be  found  in  the  heavier  fractions  remaining. 
Because  of  the  volatility  of  aluminum 
chloride,  a  reflux  must  be  used  to  catch  its 
vaipours  and  return  them  to  the  still  with 
any  condensed  hydrocarbons.  This  means 
that  nothing  heavier  than  kerosene  can  get 
past  the  reflux.  If  desired,  the  reflux  can 
hav  its  temperature  so  adjusted  that  no- 
thing but  gasoline  and  lower  boiling  hydro- 
carbons can  get  past  it  into  the  condenser. 
If  the  boiling  is  continued,  everything  in 
the  still  is  cracked  into  gasoline,  gas,  and 
coke.  The  amount  of  coke  remaining  in  the 
still  is  a  fraction  of  the  percentage  of  carbon 
originally  present  in  the  raw  hydrocarbons 
treated. 

A  third  function  of  aluminum  chloride  in 
petroleum  refining  is  to  remove  sulphur 
from  the  oil.  Part  of  the  sulphur  is  con- 
verted into  hydrogen  sulphide  gas  and  pos- 
sibly aluminum  sulphide  is  formed.  At 
any  rate,  aluminum  chloride  is  a  very  efli- 
cient  desuliphurizer.  The  desulphurizing 
uses  up  aluminum  chloride,  and  for  high- 
sulphur  oils  a  correspondingly  larger 
amount  of  aluminum  chloride  is  needed. 
Consequently,  to  make  the  process  com- 
mercialy  feasible,  only  a  very  cheap  product 
can  be  used  for  removing  sulphur,  and 
enough  of  an  excess  must  be  added  so  that 
there  will  be  free  aluminum  cJiloride  to  act 
as  catalyzer  for  the  saturating  and  cracking. 

Methods  of  Producing  Anhydrous 
Aluminum  Chloride. 
Oersted,  who  first  prepared  aluminum 
chloride,  passed  a  current  of  dry  chlorine 
over  a  heated  mixture  of  carbon  and  alu- 
mina. This  method  was  afterwards  used 
by  Wohler  (1827),  Leibig  (1830),  Bunsen 
(1854),  and  Deville  (1849).  Deville  was  one 
of  the  fathers  of  commercia  laluminum 
metal,  and  used  aluminum  chloride  as  the 
raw  material  from  which  to  extract  it.  The 
following  methods  of  producing  aluminum 
chloride  are  not  grouiped  chronologically, 
but  rather  by  relative  importance  in  pre- 
sent manufacture.  Those  near  the  end  of 
the  list  are  largely  processes  collated  from 
patent  literature  or  elsewhere. 

1.  Dry  chlorine  gas  acting  on    aluminum 
metal. 

2.  Dry  hydrochloric  acid  gas  acting  on 
aluminum  metal. 

3.  Chlorine  gas  acting  on  mixtures  of  alu- 
miniferousand  carbonaceous  materials. 

4.  Chlorine  gas  or  hydrogen  chloride  act- 
ing on  aluminum  carbide. 


5.  Chlorine  gas  acting  on  aluminum  ni- 
tride. 

6.  Chlorine  gas  and  carbon  disulphide 
vapour  acting  on  alumiuiferous  materials. 

7.  Chlorine  compounds  of  carbon  acting 
on  aluminierous  materials. 

8.  Chlorine  compounds  of  sulphur  or 
arsenic  acting  on  aluminiferous  materials. 

9.  Dry  load  chloride  reacting  with  alu- 
minum metal  or  with  aluminum  carbide, 

10.  Anhydrous  calcium  chloride  reacting 
with  aluminiferous  materials. 

11.  Aluminum  chloride  solutions  pre- 
pared by  any  wet  method,  then  evEnporated 
and  the  crystals  dehydrated. 

All  of  these  methods,  with  the  exception 
of  method  11,  are  performed  at  high  tem- 
peratures, usually  high  enough  to  sublime 
any  aluminum  cnloride  formed.  In  fact, 
the  great  volatility  of  aluminum  chloride  is 
frequently  the  main  inducement  to  reaction 
and  many  of  the  above  processes  are  endo- 
thcrmic.  Details  of  each  of  these  groups  of 
methods  ai-e  discussed  on  the  following 
pages. 


THE  EVOLUTION  OF  CHEMICAL 
TEEMINOLOGY.* 

By  James  F.  Couch, 

(Continued  from  Page  238.) 
"A  coirnpound  of  an  element  or  radical 
with  hydrogen  and  oxygen,    not  reg^u'ded 
as  containing  water.     .     .       The  term  is 
usually  applied,    and  by  manj' '  chemists 
restricted,    to  compounds  containing  the 
group  OH,  or  hydroxy  1.    Hydroxides  may 
be  basic,  neutral,    or  acid,    according  to 
the  nature  of  the  combining  atom  or  radi- 
cal.      Most     hydroxides,     commonly     so 
called,  however,  are  basic."     p.  1055. 
On  April  20  of    this  year    Science*    pub- 
lished a  list  of  rules  adopted  by  the  Nomen- 
clature Committee  of  the  American  Chemi- 
cal Society  and  that  of  the  London  Chemi- 
cal Society,  in  which  the  following  appears  : 
"The  word  hydroxide    should    be    used 
for  a  compound  with  OH  and  hydrate  for 
a  oomipound  with  H^O.       Thus,     barium 
hydroxide,    Ba  (0H)2;    chlorine  hydrate, 
Cla  lOH^O." 
Murray^*  defines  hydroxide  as : 


*  Science,  N.S.  57,  474  (1923). 

*  [Reprinted  from  "The  American  Jour- 
nal of  Pharmacy,  Philadelphia,  Pa.,  July, 
1923.] 


OCTOBER  19,  1923. 


THE  CHEMICAL  NEWS. 


249 


"A  compound  of  an  element  or  radical 
\vith  oxygen  and  hydrogen,  not  with 
water;  by  some  chemists  restricted  to 
cornpounds  whose  reactions  indicate  the 
presence  of  the  group  hvdroxyl  (OH)." 
p.  491,  V.  5. 

Mellor'*  "  extends  the  term  to  all  hy- 
droxyl  compounds  but  recognises  that  it  is 
used  in  the  narrower  sense  where  it  applies 
only  to  basic  compounds.  In  this  modified 
view  he  is  in  accord  with  Silliman.**  He 
says : " 

"From  this  point  of  view  water  can  be 
regarded  as  hydrogen  hydroxide,  H-OH, 
analogous  with  K-OH,  potassium  hy- 
droxide, and  Na-OH,  sodium  hydroxide. 
Excluding  certain  cari)on  compounds, 
the  hydroxides  of  the  non-metallic  i-le- 
ments  are  usually  acids,  and  the  hydrox- 
ides of  the  metals  are  usually  bases.  The 
term  'hydroxide'  is  generally  reserved  for 
compounds  of  the  basic  oxides  with 
water;  and  the  term  'anhydride'  is  usu- 
ally reserved  for  the  acid  anhydrides." 
p.  146. 

The  same  idea  is  repeated  in  his  great 
"Comprehensive  Treatise, "•"'■'  and  here  he 
insists  upon  the  broadest  extension  of  the 
term  in  theory : 

"Every  element,  excepting  fluorine  and 
the  argon  family,  appears  to  fwm  one  or 
more  hydroxides,  direct! v  or  indirectly." 
V.  1,  p.  395. 

Sharply  contrasted  with  these  views  is 
that  <M>ncept  of  the  term  hydroxide  whicii 
to-day  is  held  by  the  gn  it  majority  ,f 
chemists,  the  limitation  <>t  the  term  to 
those  hydroxy!  compounds  which  exhibit 
basic  properties.  As  I  shall  show,  this  view 
is  the  original  idra  exi)ressod  by  the  tcnii, 
and  has  l)een  held  continuously,  aItho'i-.7Vi 
obscured  and  distorted  by  changing  notion ■■■ 
of  chemical  theorj',  during  the  past  tweivj 
decades.     Williamson''  in  is.ll  wrote: 

"The  experiments  of  M.  Chanrol. 
agreeing  in  result  with  my  own,  h.ive 
clearly  proved  that  the  numerous  family 
designated  as  hydrated  oxides  arc  \ 
formed  by  the  juxtaposition  of  an  atooi 
of  water  with  un  atom  of  metallic  oxidr, 
e.g.,  KjO  +  H/),  but  that  the  cquivaK-nt 
of  the  molecule  is  half  that  quautitv. 
H  ^ 

namely  —  0 ;  they  are  not  compounds  of 

K 
water  but  products  of  substitution  in 
water  .  .  .  alcohols,  which  are  truly 
hydrated  oxides,  must  be  considered  as 
products  of  substitution  of  the  com- 
pound radicals,  ...  for  half  the 
hydrogen  of  water." 


At  that  time  the  comjpound  radicals,  or, 
as  we  should  to-day  term  them,  the  alkyl 
radicals,  and  the  alcohols  as  well,  were  con- 
sidered basic  in  nature.  This  work  of  Wil- 
liamson first  brings  out  clearly  the  idea  of 
hydroxy!  compounds. 

Roscoe^*  in  1873  definitely  Hmits  the  ap- 
plication of  the  term : 

"Viele  basische  Oxide  verbinden  sich 
mit  Wasser  zu  einem  Hydroxide."  p.  153. 
"Die  im  Wasser  loslichen  Hydroxide 
haben,  wie  schon  friiher  erwahnt,  eine 
alkalische  Reaction."  p.  154. 
Kolbe'"  concurs  in  this  view : 

The     name     hydrate     includes    two 
classes  of  bodies;   the  acid  hydrates    (the 
oxy-  or  sulpho-acids)    and  the  basic    hy- 
drates (the  hydrates  proper)."     p.  56. 
Nuttall'*  is  atlmiiably  definite  : 

"Hydroxide,  a  metallic  hydrate."      p. 
185. 

Rich  tor"  meets  the  issue  squarely  also: 
"Some  of  the  elements  yield  acids  by 
their  unicHi  with  oxygen,  or  more  correct- 
ly oxides,  whicli  form  acids  with  water. 
Most  of  these  are  the  metalloids.  .  .  . 
With  oxygen  the  metals  usually  yield 
oxides,  which  form  hydroxides  (hydrates) 
or  bases  with  water."  p.  84. 
The  "Century  Dictionary"*  supports  this 
view : 

"A  metallic  or  basic  radical  combined 
with  one  or  more  hydroxy!  groups,  as 
potassium  hydroxide,  KOH ;  ethyl  hy- 
droxide, CjHjOH.  Hydroxides  may  be 
regarded  as  formed  from  water  (HOH) 
by  the  substitution  for  one  of  its  hydro- 
gen atoms  of  a  metal  or  basic  radical.  An 
acid  radical  combined  with  hydroxyl  is 
calletl  an  acid,  the  term  hydroxide  being 
n^sorved  for  basic  compounds."  v.  5,  p. 
2940. 

The  following  quotations  are  taken  from 
the  fourth  edition  of  Roeooe  and  Schorlem- 
mer's  "Treatise  on  Chemistry"  :*5 

"  The  acid-forming  oxides  combine 
with  water  to  form  hydrates  which  are 
term(>d  acids."    ip.  261,  v.  1. 

"  The    basic    oxides     .  .     form    in 

combination  with  water    a  class  of  com- 
pounds termed    hydroxides  or    hydrated 
oxides.     .     .     ."    P-  260,  v.  1. 
These  quotations    show    that    since    the 
middle  of  the  last    century  there  have  been 
extant  and    co-existent    three    well-defined 
and  distinct  concepts  of  the  term  hydroxide 
and  <hnt  these  three  views  persist  to  the  pre- 
sent time,  particularly    in    textbooks.       In 
order  to  reach    a  decision    as    to    which    of 
these  three  definitions  we  should  accept  and 
which  discard,  let  us  consider  the  historical 


250 


THE  CHEMICAL  NEWS. 


m 


OOTOBEIi  19,  1923. 


development  of  the  term.  In  the  course  of 
this  investigation  we  shall  find  it  necessary 
to  go  back  to  the  very  beginning  of  modern 
chemical  nomenclature  and  to  examine  the 
works  of  those  men  who  laid  the  founda- 
tions of  our  science. 

The  word  oxide  was  coined  by  a  French 
chemist,  de  Morveau,^^  in  1787.  This  man 
of  genius  and  insight  formulated  the  first 
scientific  system  of  chemical  nomenclature 
with  Lavoisier,  Bertholet,  and  de  Fourcroy. 
He  was  specific  in  His  definition  of  the  word 
oxide,  and  the  meaning  he  gave  it  was 
generally  accepted  until  the  downfall  of 
BerzeUus'  electro-chemical  theory,  when 
chemical  th©oi*y  was  thrown  into  a  state  of 
flux,  and  the  term  oxide  was  extended  to 
incldue  the  oxygen  compounds  of  the  non- 
metals.     De  Morveau  says : 

"  Nous  avons  done  du  chercher  une  ex- 
pression nouvelle,  &  pour  la  rendre  con- 
sequent a  nos  principes,  nous  avons  forme 
le  mot  oxide,  qui  d'une  part  rapelle  la 
substance  avec  laquelle  le  metal  est  uni, 
qui  d 'autre  part  annonce  suffisamment 
que  cette  combinaison  de  I'oxig^ne  ne 
doit  pas  etre  oonfondu  avec  la  combinai- 
son acide,  quoiqu'elle  s'en  raproche  a 
plusiers  ^gards."     p.  56. 

"  Apr^s  avoir  ^tabli    la  distinction  des 
acides  &  des  oxides  metalliques,    c'est-a- 
dire  des    metaux    oxigene  &  des    metaux 
simplement  oxides.     .     ."     ip.  58. 
The  acids    are  not    oxides,    according    to 
this  statement,  but  are  compounds    of  oxy- 
gen    with     acid-forming     elements.       This 
curious  distinction  is  based    upon  a  differ- 
ence in  function  of  the  resulting  compounds 
and  shows  clearly  the  insight  of  the  man  in 
not  confounding  a  similarity    in  process  of 
preparation  with  a  systematic  likeness. 

The  next  event  of  interest  in  development 
of  the  word  hydroxide  occurred  twelve 
years  after  the  coining  of  the  term  oxide.  In 
1800  Joseph  Louis  Proust*  devised  the  word 
hydrate  and  applied  it  to  the  hydroxides  of 
CQpper. 

"  Le  second  est  une  combinaison  par- 

ticuliere    de  I'oxide    et  d'une  quantite    fixe 

d'eau  concrete,  d'ou  depend  sa    couleur, 

et  que  j'ai  cru  devoir  nommer  hydrate  de 

cuivre."     p.  41. 

Proust's  concept  of  hydrates  is  identical 
with  the  most  limited  modern  view  of  hy- 
droxides. Contemporaneous  chemists  ac- 
cepted the  term  and  used  it  in  this  sense  ex- 


*  "Recherches    sur  le  cuivre,"    Ann.    de 
Chim.,  1800,  32,  26-54. 


clusively.  The  use  of  hydrate  in  place  of 
hydroxide  still  persists  at  the  present  time, 
particularly  in  England,  where  the  term  was 
readily  accepted.  Proust  had  definite  ideas 
about  the  hydrates;  he  felt  that  they  were 
true  compounds  and,  in  defending  this 
view,  entered  into  that  brilliant  controversy 
with  Bertholet  which  eventually  firmly  es- 
tablished the  law  of  definite  proportions. 
Proust  says : 

"  100  parties  d 'hydrate  distillers  don- 
uent  24  parties  d'eau,  75  d 'oxide  noir  (of 
coppei),  et  la  valuer  d'un  grain  d 'acide 
carbonique,  etranger  a  cette  combinaison, 
et  qui  s'y  trouve  par  des  causes  que  nous 
eclaircirons  tout  a  I'heure."     p.  43. 

"  Dans  1 'hydrate  de  cuivre  recent,  il  no 
peut  exister  aucun  soupQon  d'acide."  p. 
43. 

He  subsequently  developed  the  idea,  and 
applied  the  term  to  other  metallic  hydrox- 
ides.*" *^  In  1804,  in  answer  to  objections, 
he  retorts  that  in  the  hydrates  the  water 
acts  the  part  of  an  acid  (p.  348),  thus  anti- 
cipating, by  eight  years,  Berzelius,  who  is 
generally  considered  the  father  of  that  idea. 
His  notions  are  well  displayed  in  the  follow- 
ing statements : 

L 'hydrate  est,  oomme  jel'ai  fait  voir 
anterieurement,  la  combinaison  d'un 
oxide  avec  I'eau."  "  .  .  .  je  n'hesi- 
terai  point  k  assurer  qu'il  y  a  non-seule- 
ment  des  hydrates  metalliques,  mais 
meme  aussi  dee  hydrates  alkalines  et  ter- 
reux." 

On  ne  peut  nier  aujourd'hui  que  la 
chaux  ne  se  combine  avec  I'eau."  p. 
347. 

Smithson,*^  reporting  the  analysis  of 
some  calamines,  uses  the  term  hydrate  in 
accordance  with  the  ideas  of  Proust : 

"...  it  seems  to  consist  of  two 
matters;  carbonate  of  zinc,  and  a  pecu- 
liar compound  of  zinc  and  water,  which 
may  be  named  hydrate  of  zinc."  p.  22. 
Klaproth  and  Wolff=^«  in  1810  reflect  the 
definite  concept  of  the  term : 

"Proust  first  gave  the  name  of  hydrate 

to  the  combinations    of    metallic    oxides 

with  water."    v.  2,  p.  518. 

John  Davyi*  in  1811    refers  to  "hidrate" 

of  potash,  and  Vogel*"  uses  hydrate,  both 

of  them  in  the  limited    sense  that    Proust 

imposed  upon  the  word.  Humphry  Davy^^  '^ 

did  not  accept  the  term,  apparently,  for  he 

makes  no  use  of  it. 

The  first  use  of  the  term  hydroxide  eluded 
our  search  for  months.  It  is  evident  that 
it  could  not  have  preceded    the  coining    of 


OCTOBElR  19,  1923. 


THE  CMBMlCAL  NEWS. 


261 


the  word  oxide,  which  occuiTed  in  1787,  so 
vyith  that  as  a  lower  limit  a  search  of  the 
literature  was  initiated  which  involved  the 
scrutiny  of  every  publication  which  might 
conceivably  include  the  word.  Cutbush" 
defined  the  term  in  1821,  and  it  was  used  by 
Henry"  in  1823.  Then  it  totally  disap- 
pears from  the  literature'  until  1851,  when 
it  reappears  in  the  "Catalogue  of  the  Great 
Exhibition."^  It  is  not  used  by  Kels,", 
Chaptal,^  Davy,"  '=>  Dalton,i"  Sillmian," 
Cutbush  in  1814,*  Hare,=*  Gay  Lussac,"  '» 
d'Aubuis&on,^  Vogel,**  or  Berzelius.*  These 
papers  cover  a  period  of  forty-two  years, 
from  1791  to  1833,  and,  had  the  term  been 
in  wide  lise,  would  undoubtedly  have  in- 
cluded it. 

,The  word  hydroxide  was  coined  in  1802 
by  Richard  Chenevix,*  who  propoeed  it  as  a 
better  form  than  Proust's  hydrate,  against 
which  Ghenevix  urged  some  objections.  He 
saya  : 

"  Hydro-oxide  had  been  a  much  more 
proper  appellation,  as  it  would  express 
the  coiiibination  not  of  Hydrogen,  but  of 
water;  which  is  the  truth."    p.  34. 

"  I    have    stated    before    that    Hydro- 
oxide,  or  Hydroxide,  would  be  the  proper 
term    for    all    combinations    of    metallic 
oxides  with  water;  for  such  combinatioub 
as  Copper,  Cobalt,  Nickel,  and  Uraniunt 
are  cntpable  of  nffonling."     p.  77. 
A  word  concerning  this  man,  now  almost 
forgotten    in  science,  who  coined   so  widely 
used  a  term,  may  not  be  out  of  place  here. 
Chencvix  was  born    in  Dublin,    Ireland,    in 
1774,    and  died    in  Paris    in    1830.      When 
twenty-four  years  of    age  he  published    his 
first  paper  on  a  chemical  subject,    and    for 
ten  years  was  active  in  chemistry,  j>ublish- 
ing  twenty-four    papers    in  all    until    1808, 
when  he  suddenly  disappears  from    scienti- 
fic literature.     In  the  latter  part  of  his    life 
he  was  n  successful  dramatist  and  novelist. 
He    evidently    did    not  possess    sufficient 
personal  influence  to  supplant  Proust's  hy- 
drate with  his  term,  for  to  the  prestige  of 
the  professor  at  Madrid  alone  can  we  attri- 
bute the  long  survival    of  the  former  term. 
It  was    not  until    a  great    development    in 
chemical  theory  and  a  fundamental  change 
in  point  of  view  demanded  a  revision  of  our 
notions  of  the    mechanism    of    water-com- 
binations   that     the     term    hydroxide     \\as 
firmly  established  in  chemical  terminology 
Watts,'  in  1864,  and  his  third  supplement, 
published  as  lat<>  as  1881,    rlo  not  mention 
the  term.     From  the  start,  however,  nn  ex- 
emplary definiteness    of  meaning    was    at 
tached  to  the  term.     Witness  Cutbush:* 


"Hydro-oxydates.  Oxydes  combined 
with  water."    p.  31. 

"Hydro-oxydes.  Oxydes  combined 
with  water."    p   31. 

"Hydrate.  A  chemical  combination  of 
a  body  with  water."     p.  29. 

"Oxydes.        Combinations     of     oxygen 

with     different     bases,      not    possessing, 

strictly  speaking,  acid  properties."  p.  49. 

"Sulphuric  acid.     .     .       A    compound 

of  sulphur  and  oxygen."    p.  73. 

and  Henry :  -^ 

"The  compounds  of  (metallic)  oxides 
and  water  in  which  the  latter  exists  in  a 
condensed  state,  are  termed  hydrates,  or 
hydro-oxides,  or  hydroxures."  v.  2,  p.  42. 
In  1851,'  after  a  disappearance  of  nearly 
thirty  years  from  the  literature,  it  still  is 
'       used  only  for  basic  compounds : 

"The  whole  coast  of  Andalusia  is  rich 
in  galenas ;  the  province  of  Malaga  yields 
this  product  mixed  with  pyritic  iron  and 
hydroxidated  iron,  at  Mijar."  p.  1326. 
"13.  Hydroxide  of  iron,  from  San  Clau- 
dio."  p.  1327.  "...  enveloping 
the  bunches  of  hydroxide  of  iron."  p. 
1328. 

These  quotations  make  it  clear  that,  in 
their  original  meaning,  both  of  the  terms, 
hydroxide  and  hydrate,  connoted  com- 
pounds of  basic  oxides  with  water  or  what 
we  should  to-day  refer  to  as  basic  hydrox- 
ides. .  The  original  meaning  of  the  word 
acid  i8  clear,  the  oxygen  compound  which 
(dissolved  in  water)  possesses  acid  proper- 
ties. An  acid  is  not  an  oxide,  de  Mour- 
veau,"  Cutbush,"  and  Hare.^"^  The  latter 
says: 

"All  the  binary  combinations  of  oxy- 
gen have  been  called  oxides,  when  not 
acid."     p.  209. 

The  correlative  term  base  is  equally  clear. 
Cutbu&h  defines  it : 

"Base  A  term  used  to  express  the 
earth,  alkali,  or  metal,  which  forms  a 
salt  with  an  acid."  p.  12. 
The  work  of  Williamson'^  made  neces- 
sary some  stated  distinction  between 
classes  of  compounds  in  which  water 
exists  as  such  and  in  which  it  exists  in  a  re- 
arranged form.  The  term  hydrate  was  con- 
venient and,  although  it  had  been  applied 
l)v  Proust  and  his  contemporaries  specific- 
ally to  what  we  now  term  hydroxides,  it 
hatl  gradually  been  extended  to  include  all 
compounds  of  water.  Substances  which 
contain  water  of  crystallisation,  hydrated 
compounds  in  which  the  water  is  patently 
present  in  something  more  than  physical 
union,  and  even  masses  which  were  merely 


262 


THE  CHEMICAL  NEWS. 


OCTOBER  19,  1923. 


moistened  with  hygroscopic  water,  were  all 
sub-summed  in  the  category  hydrate.  This 
state  of  affairs  was  not  so  serious  while  the 
BerzeUan  notions  of  chemical  theory  held 
the  field,  but,  when  the  electro-chemical 
hypothesis  was  overthrown,  the  newer  ideas 
demanded  more  definite  conceptions  of  the 
character  of  water  of  hydration;  more  spe- 
cific explanation  of  the  way  in  which  water 
is  combined,  and  some  way  of  distinguish- 
ing between  compounds  whose  water  may 
be  readily  driven  off  by  heating  and  those 
which  are  unaltered  by  any  heat  or  only  by 
very  high  heat. 

The  hypotheses  of  acid  water  and  basic 
water  no  longer  were  satisfactory;  it  was 
also  evident  that  a  great  difference  exists 
between  water  as  combined  in  the  alkaline 
hydroxides  and  as  united  in  crystalline  so- 
dium sulphate.  The  term  hydroxide  began 
to  be  used  again,  but  with  rather  indistinct 
meaning  as  denoting  something  in  which 
water  is  combined  more  firmly  than  in  the 
hydrates\  Clarke^  and  Perkin^*  attempted 
to  apply  physico-chemical  tests  to  com- 
pounds to  establish  a  definite  distinction  be- 
tween hydrates  and  hydroxides.  The  for- 
mer determined  the  specific  volumes  of  a 
large  number  of  water-compounds,  includ- 
iii'^  hydrated  salts  and  alkaline  hydroxides. 
He  found  that  the  effect  of  combined  water 
in  the  hydrated  salts  was  nearly  regular; 
that  the  mean  value  for  the  molecular  vol- 
ume of  each  molecule  of  water  of  crystalli- 
sation is  13.76,  but  that  there  is  no  such  re- 
gularity observed  in  compounds  in  which, 
as  we  would  now  say,  the  hydroxyl  group 
occurs.  Perkin  measured  the  magnetic  ro- 
tatory power  of  many  compounds  and  their 
hydrates,  and  came  to  the  conclusion  that  if 
hydration  increased  the  rotatory  power  by 
about  unity  the  new  compound  is  a  hydrate. 

The  distinction  between  the  two  classes 
of  compounds  is,  however,  difficult  to  draw 
from  such  data  and  considerations.  It  is 
far  simpler  and  more  satisfactory  to  decide 
the  question  by  analysis  of  the  chemical  re- 
lationships of  the  substance.  Muir  was  led 
into  the  absurdity  of  deciding  that  cupric 
hydroxide  is  a  hydrate,  whereas  arsenic  acid 
(H3ASO4)  is  an  hydroxide^^  by  failure  to 
observe  this  principle. 

This  mass  of  evidence  may  be  summar- 
ised thus  :  The  terms  hydrate  and  hydroxide 
were  originally  synonymous  and  were  spe- 
cifically applied  to  basic  hydroxides.  The 
acids  were  not  classed  as  oxides  and  the 
chemistry  of  the  alcohols,  phenols,  nnd  car- 
bohydrates had  not  been  developed,  so  that 
there  could  be  no    inclusion  of  these    com- 


pounds in  the  .concepts.  Tlie  term  acid 
was  confined  to  those  oxygen-compounds 
which  united  with  bases  to  form  salts,  and 
this  statement  also  defined  bases  as  those 
substances  whose  combination  with  acids 
produced  salts. 

The  original  conceptions  of  hydrates  and 
hydroxides  persisted  until  well  past  the 
middle  of  the  last  century;  the  term  hy- 
drate being  gradually  used  in  a  more  inclu- 
sive sense  until,  finally,  the  necessity  of  dis- 
crimination among  the  compounds  of  water 
forced  actio:',  and  the  result  was  a  nmddling 
of  both  notions  which  has  come  down  to  us 
at  the  present  day  and  constitutes  the  prob- 
lem of  this  paper. 

I  think  that  there  will  be  general  agree- 
ment to-day  that  hydroxides  are  not  to  be 
regarded  as  water  compounds ;  that  type  of 
substances  may  be  characterised  by  the 
term  hydrate.  The  characteristic  of  an  hy- 
droxide, then,  must  be  content  of  hy- 
droxyl, and  our  definition  of  the  term  will 
depend  upon  the  modifications  and  limita- 
tions which  we  impose  upon  this  concept. 

BiBLIOGRAPnY. 

^  "Catalogue  of  the  Great  ExhihUion," 
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^  Ghaptal,  M.  J.  A.  :  "Chimie  Applique 
aux  Arts."     Paris,  1807. 

®  Chcnevij'.  JR.:  "Reviarks  upon  Chetiii- 
cal  Nomenclature."     London,  1802. 

'  Cuthush,  J.:  Am.  Min.  J.,  1,  88-93 
(1814). 

"  Cutbush,  J. :  "Synopsis  of  Chemistry," 
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1"  Dalton,  J.  :  "A  New  System  of  Chemi- 
cal Philosophif,"  1810. 

'^  Dalton,  J.:  Nicholson's  J.,  29,  129 
(1811). 

1-  Davy,  H.:  Phil.  Trans.,  98,  1-44,  330- 
370  (1808);  99,  39-104,  450  (1809);  100,  16- 
74  (1810).    . 

''  Davy,  H.:  Nicholson's  J.,  29,  112-127 
(1811). 

^^  Davy,  J.:  Nicholson's  J.,  29,  35-37 
(1811). 

^^  Gay-Lussac  and  Thenard :  Ann.  de 
Chim.,  75,  90  (1810). 

^^  Gay-Lussac  and  Thenard :  Nichol- 
son's J.,  29,  38  (1811). 

-^  Hare,  R.:  Am.  Jour.  Pharm.,  4,  209 
(1833). 

^^  Henry,  Wm.  :  "The  Elements  of  Ex- 
perimental Chemistry,"  2nd  Am.  Ed.  Phil., 
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^'  Kels,  H.  W.  :  "Onomatologia  Chymfca 
Practica."     Vim,  1791. 


OCTOBER  19,  1923. 


THE  CHEMICAL  NEWS. 


253 


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(1814). 

"  Smiihson,  J.  :  Phil.  Trans.,  98,  12-28 
(1803). 

"'^  "New  International  Dictionary  of  the 
English  Language,"  1919. 

{To  be  continued.) 


GENERAL   NOTES. 


BOARD  OF  TRADE  ANNOUNCEMENT. 

Dyestuffs  (Import  Regulation)  Act. 
1920. 

Applications  for  Licences  in  September. 

The  following  statement  relating  to  appli 
cations  for  licences  under  the  Dyostuff< 
(Import  Regulation)  Act,  1020,  made  dur- 
ing September,  has  been  furnished  to  the 
Board  of  Trade  by  the  Dyestuffs  Advisory 
liicensing  Committee. 

The  total  number  of  applications  received 
during  the  month  was  457,  of  which  311 
were  from  merchants  or  importers.  To 
these  should  be  added  the  34  cases  out- 
standing on  the  1st  September,  making  a 
total  for  the  month  of  401.  These  were 
dealt  with  as  follows:  — 

Granted — 341  (of  which  300  were  denit 

with  within  7  days  of  receipt). 

Referred  to  British  makers    of  similar 

products — 79    (of    which    65    were    dealt 

with  within  7  days  of  receipt). 

Referred  to  Reparation  supplies    avail- 
able— 30  (all  dealt  with  within  2  days  of 

receipt). 

Outstanding  on  30th  September,  1923 

— 40  (all  dealt    with  at    meeting  of    the 

Committee  held  on  the  5th  October). 

Of  the  total  of  491  applications  received. 
395  (or  80  per  cent.)  were  dealt  with  within 
7  days  of  receipt. 


Dyestuffs  Industry  Development 

Committee. 

The  Board  of  Trade  announce  that  they 
have  appointed  Dr.  A.  T.  de  Mouilpied,  of 
the  British  Dyestuffs  Corporation,  Ltd.,  to 
be  a  member  of  the  Dyestufis  Industry  De- 
velopment Committee  set  up  under  Sub- 
section 2  (6)  of  the  Dyestuffs  (Import  Re- 
gulation) Act,  1920,  in  the  place  of  Dr.  Her- 
bert Levinstein,  F.I.C.,  resigned. 


REPORT  OF  OXYGEN  RESEARCH 
COMMITTEE. 

This  Report*  describes  certain  aspects  of 
the  work  of  the  Oxygen  Research  Commit- 
tee since  its  appointment  in  1919.  It  deals 
chiefly  with  the  technical  difficulties  which 
have  hitherto  restricted  the  commercial 
utilisation  of  liquid  oxygen  and  liquid  air, 
and  describes  in  particular  recent  improve- 
ments in  the  methods  of  handling  the  lique- 
fied gases  on  a  practical  commercial  scale. 
The  work  of  the  Committee  has  been  carried 
out  principally  in  the  Heriot  Watt  College, 
Edinburgh,  and  the  Air  Ministry  Oxygen 
Laboratory. 

♦  Published  for  the  Department  of  Scien- 
tific and  Industrial  Research,  by  H.M.  Sta- 
fionrnj  Office.     Price  8s.  6rf.  net. 


WIRELESS  STATIONS  IN  RUSSIA. 

A  translation  of  a  Decree  of  the  Council 
of  Peoples'  Commissaries  of  the  Union  of 
Soviet  Socialist  Republics,  dated  July  4, 
and  published  in  the  "  Izvestra  "  of  Sep- 
tember 12,  regarding  the  installation  of 
wireless  stations  by  State,  Trade  Union, 
and  Communist  Party  organisations  in 
Russia,  has  been  received  by  the  Depart- 
ment of  Overseas  Trade  from  the  British 
Commercial  Mission,  Moscow. 

The  Decree  lays  down  the  fundamental 
rules  to  be  observed  in  connection  with  the 
construction  and  exploitation  of  wireless 
stations  for  special  purposes  which  are 
stated  to  be  industrial  and  commercial 
wireless  stations,  wireless  stations  for  edu- 
cational and  scientific  purposes,  and  ama- 
teur wireless  stations. 

The  translation  of  the  Decree  may  bo 
seen  by  United  Kingdom  firms  on  applica- 
tion to  the  Department  of  Overseas  Trade 
(Room  53),  35,  Old  Queen  Street,  London, 
S.W.I.     (Ref.  8092/F.R./C.P.) 


254 


THE  CHEMICAL  NEWS. 


OCTOBER  19,  1923. 


ALGERIA :  MINING  CONCESSIONS 
FOB    SALE. 

H.M.  Cousul-General  at  Algiers  has  re. 
ceived  an  enquiry  for  the  names  and  ad- 
dresses of  British  firms  interested  in  the 
purchase  and  exploitation  of  mines  in 
Algeria. 

The  enquiry  indicates  the  existence  of  a 
calamine  deposit  with  exploratory  work- 
ings, in  addition  to  deposits  of  lead,  radio- 
active mineral,  silver  and  phosphate  con- 
taining 60  per  cent,  of  phosphate  of  lime. 

A  geographical  and  descriptive  Report 
(in  French),  with  analysis,  can  be  seen  by 
interested  British  firms  on  application  to 
the  Department  of  Overseas  Trade,  35,  Old 
Queen  Street,  London,  S.W.I.  (Ref. 
D.O.T.  11620  F.E.) 


FORMOSAN  SUGAR  CROP. 

H.M.  Consul  at  Tamsui  has  forwarded 
details  of  the  first  official  estimate  of  the 
sugar  production  in  Formosa  for  the  season 
1923-24,  which  allow  for  6,031,951  piculs 
centrifugals  and  153,578  piculs  of  brown 
sugar.  The  total  estimate  of  6,185,529 
piculs  would  be  equivalent  to  365,255  tons. 
The  area  under  cane  is  returned  at  287,122 
acres. 

These  figures,  both  for  crop  and  area 
under  cane,  are  below  those  put  forward  in 
the  preliminary  estimate.  In  the  event  of 
the  present  estimate  being  realised,  the 
1922-23  season's  output  will  be  exceeded  by 
230,731  piculs  centrifugals  and  47,519 
piculs  browns,  or  278,250  piculs  in  all,  and 
the  forUicoming  season  will  be  second  only 
in  the  results  attained  in  the  "  record 
year  1907,  when  the  total  production 
amounted  to  7,634,903  piculs  (450,841 
tons). — (From  the  Board  of  Trade  Jurnal, 
Octber  11,  1923.) 


PHOTOMICROGRAPHY. 

Photomicrography  as  an  applied  science 
is  rapidly  increasing  in  importance,  and  a 
knowledge  of  its  technique  has  often  proved 
of  great  value  to  works'  chemists. 

It  is  perhaips  not  sufficiently  widely 
known  that  there  exists  in  London  a  young 
and  vigorous  society  devoted  to  the  study 
and  advancement  of  photomicrography. 

The  Photomicrographic  Society  holds  its 
meetings  at  King's  College,  Strand,  W.C, 
at  7  p.m.  ■  The  programme  for  this  session 
includes  the  following :  — 

Nov.    14:     "High    Power    Photomicro- 


graphy," J.  E.  Barnard,'  FJnst.P., 
F.R.M.S. 

Dec.  12:  "General  MethcKls  in  Photo- 
micrography," E.  Cuzner,  F.R.M.S. 

Jan.  9 :  "  The  Practical  Use  of  Filters  in 
Photomicrography,"  J.  H,  Pledge, 
F.R.M.S. 

Feb.  13:  "  The  Etching  and  Structures 
of  Metals  and  Alloys,"  F.  A.  Ruddock, 
A.I.C. 

Mar.  12:  "  Low  Power  Photomioro- 
graphv,"  W.  H.  S.  Cheavin,  F.C.S., 
F.E.S".,  F.R.M.S. 

April  9 :  "  Photomicrogra(phy  applied  to 
Geology,"  Pfof.  W.  T.  Gordon,  M.A. 

May  15 :  Annual  General  Meeting  and 
Exhibition. 

In  addition,  informal  meetings  for  discus- 
sion and  demonstrations  on  photomicro- 
graphic matters  are  held  at  interval®. 

A  medal  and  a  certificate  are  awarded  an- 
nually, also  a  sum  of  money  is  awarded  for 
the  best  advance  in  photomicrographic 
technique. 

Although  no  definite  instruction  in  photo- 
microgi-aphy  is  given  by  the  Society,  it 
possesses  to  the  full  the  "  club  spirit," 
and  its  members  are  anxious  and  willing  at 
all  times  to  help  the  novice. 

Visitors  are  welcomed  at  the  ordinary 
meetings,  and  cards  of  invitation  and  fur- 
ther information  about  the  Society  will 
gladly  be  given  on  application  to  the  Hon. 
Sec,  1,  Plogarth  Hill.  Finchley  Road, 
Hondon,  N.W.ll.  E.  H.  Ellis. 


MACHINE  OIL  FOR  SOUTH  AFRICA. 

Mr.  W.  G.  Wickham,  His  Majesty's 
Senior  Trade  Commissioner  in  South  Africa, 
reports  that  the  South  African  Railways 
and  Harbours  Administration  are  calling  for 
tenders  to  be  presented  by  the  5th  Novem- 

j       ber,   1923, ,  for  the  supply    of  maohne    oil. 

j;       (Tender  No.  477). 

United  Kingdom  firms  desirous  of  re- 
ceiving further  information  regarding  this 
tender  should  apply  to  the  Department  of 
Overseas  Trade,  35,  Old  Queen  Street, 
London,  S.W.I,  quoting  reference  12290/ 
E.D.C.C./2.(B). 

Mr.  W.  G.  Wickham,  H.M.  Senior  Trade 
Commissioner  in  South  Africa,  roiports  that 
the  same  authority  are  calling  for  tenders, 
to  be  presented  by  the  5th  November,  1923, 
for  the  slipply  of  antifriction  grease.  (Ten- 
der No.  478).  .  : 
Reference,  12290/E.D./C.C./2.(C). 


OCTOBER  19,  1923. 


THE  CHEMICAL  NEWS. 


255 


LINSEED  OIL  FOR  SOUTH  AFRICA. 
The  Tender  Board  of  the  South  African 
Railway  Headquarter  Ofiices  at  JohanncK- 
burg  are  calling  for  tenders  for  the  supply 
and  delivery  "ex.  ship"  of  raw  and  double 
l)oiled  linseed  oil  for  the  six  months  ending 
80th  June,  1924.     (Tender  No.  476). 

A  copy  of  the  specification,  general  con- 
ditions of  tender,  etc.,  may  be  seen  at  the 
Department  of  Overseas  Trade. 


CHEMICAL  INDUSTRY  CLUB. 

The  Annual  Dinner  of  the  Chemical  In- 
dustry Club  will  take  place  at  the  Con- 
naught  Rooms,  on  Friday,  November  23. 

Several  men  prominent  in  the  chemical 
world  will  be  present — names  will  be  an- 
nounced later. 

Tickets,  15s.  each,  may  be  obtained  from 
members,  or  from  the  secretary,  2,  White- 
hall Court,  London,  S.W.I. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  CHEMICAL  SOCIETY. 

Ordinary  Scirntific  Meeting,    Thursday. 

October    18. 

The  following  paper  was  read:  — 

Studies  of  Electrovalency.      Part    III.— 

The  Catalytic  Activation  of  Molecules  and 

the  Reaction  of  Ethylene  and  Bromine,  by 

R,  G.  W.   NORRISH. 


SOCIETY  OF  GLASS  TECHNOLOGY. 

The  first  meeting  of  the  Society  for  the 
session  1923-24  was  held  at  SheflBeKI  on 
Wednesday,  October  17. 

The  Vice-Chancellor  of  the  University  of 
Sheflfield,  Sir  W.  H.  Hadow.  M.A.,  D.Mus.. 
made  the  presentation  of  the  "  Frank 
Wood  "  Medal  to  the  successful  candi- 
dates, A.  R.  Sheen,  B.Sc.Tech.,  and  F. 
Winks,  B.Sc.Tech. 

The  following  papers  were  received  and 
discussed :  — 

The  Effect  of  Titania  on  the  Properties  of 
Glass,  by  A.  R.  Sheen,  B.Sc.Tech.,  and 
Prof.  W.  E.  S.  Turner,  D.Sc. 

The  Estimation  of  Selenium  in  Qlass,  by 
A.  CousEN,  B.Sc,  A.R.C.Sc. 


ROYAL  MICROSCOPICAL  SOCIETY. 

A  Conversazione  was  hold  at  the  Exami- 
nation Hall,  8-11,  Quocn  Square,  Blooms- 
bury,  on  Thursday  evening,  October  11. 


There  were  two  Lantern  Demonstrations  : 

Some  Adaptations  of  Marine  Organisms, 
by  H.  G.  Cannon,  M.A.,.F.Z.S.,  F.R.M.S. 

The  Material  Basis  of  Heredity,  by  Prof. 
R.  RuGGLEs  Gates,  M.A.,  Ph.D.,  F.L.S., 
F.R.M.S. 

General  Exhibits. 

E.  W.  Bowell,  M.A.,  M.R.C.S., 
L.R.C.P.,  F.R.M.S.:  (a)  Photomicro- 
graphs of  Sections,  (b)  An  improvement  to 
the  Automatic  Microtome. 

L.  S.  Day :  Circulation  in  Newt. 

E.  H.  Ellis,  F.R.M.S.:  Capsule  of  Qrim- 
mia  pulvinata.  Slides  of  Moss  mounted  in 
Glycerine  Jelly. 

George  H.  Gabb,  F.C.S. :  Eggs  of  the 
Powder  Pest  Beetle  (Lyctus  brunneus). 
(Exhibited  for  the  first  time.) 

R.  Ruggles  Gates,  M.A.,  Ph.D.,  F.L.S., 
F.R.M.S.:  Comparison  of  Crossing  Over- 
stages  in  Lactuca  and  (Enothera. 

F.  B.  Gibbard :  Arrenhurvs  caudatus. 

L.  G.  Gilpin-Brown :  Legs  of  Syrphid 
Trophidia  scita. 

H.  Goullee :  Entomological  Specimens. 

J.  T.  Holder,  F.R.M.S.,  and  Miss  Hol- 
der: Eyes  of  Spider. 

J.  R.  Leeson,  M.D.,  F.L.S.,  F.R.M.S. : 
•  The  Fall  of  the  Leaf." 

R.  J.  Ludford,  Ph.D.,  B.Sc,  F.R.M.S.  : 
Keratin  Formation  (Gornification)  in  Can- 
cerous Growth  of  Mouse. 

J.A.Murray,  M.D.,  F.R.M.S.:  Iron- 
Alum  Hsematoxylin  Preparations  (27  years 
old). 

J.  C.  Myles:  Diatoms. 

H.  W.  R.  Room.  F.R.M.S.  :  Marine  Hy- 
drozoa  (Obelia  geniciilata),  showing  De- 
velopment and  Liberation  of  Sexual  Gooids. 

J,  Smiles  and  F.  Welch :  The  Elements 
of  Dark-ground  Illumination. 

C.  Tiemey,  D.So.,  F.L.S.,  F.R.M.S.: 
"  The  Hormrs  of  War." 

E.  E.  Warr:  Living  Diatoms. 
Trade    Exhibits. 

R.  &  J.  Beck,  Ltd.  :  New  form  Museum 
Microscope.  New  form  Dissecting  Micro- 
scope, with  and  without  Greenhough  Bino- 
cular. New  Apertometer.  Aplanatic  Ring 
Illuminator.  Focussing  Dark-ground  Illu- 
minator. Aquarium  Microscope.  Various 
forms  of  Microscopes  and  Apparatus. 

The  British  Drug  Houses,  Ltfl.  :  Micro- 
scopic Dry  Stains  and  Solutions.  Mount- 
ing Media.  Indicators  and  Buffer  Solutions. 
Comparator  Case.  Microscope.  Slide? 
stained  with  B.D.H.  Standard  Stains. 

Chapman  &  Alldridge,  Ltd.  :  A  Non- 
Achromatic     Microscope     Sub-stage      Con- 


256 


THE  CHEMICAL  NEWS. 


OCTOBER  19,  1928. 


denser  rendered  aplanatic  by  the  use  of  a 
prolate  spheroidal  surface.  A  device  'for 
centring  Microscope  Sub-stage  Condensers 
whose  iris  diaphragms  are  situated  between 
their  principal  focus  and  the  condenser.  A 
combined  Microscope  Objective  and  Dark- 
ground  Illuminator  for  metallurgical  work. 
A  Vertical  Thin  Glass  Illuminator  for  simi- 
lar work.  Specimens  kindly  prepared  by 
Dr.  Walter  Rosenhain,  and  lent  by  the 
National  Physical  Laboratory.  A  new 
Microscope  Focussing  and  Centring  Sub- 
stage.  New  "  Non-Flex  "  Microscope 
Stands. 

The  Edison-Swan  Electrie  Co.,  Ltd. : 
Pointolite  and  Fullolite  Lamps. 

Flatters  &  Gamett,  Ltd.  :  New  Series  of 
Slides,  mounted  in  Euparal.  British-made 
Stains  in  Tablet  Form. 

A.  Gallenkamp  &  Co.,  Ltd.  :  Microscopes 
and  Apparatus. 

Kawksley  &  Sons  i  Microscopes  and  Ap- 
paratus. 

Kelvin,  Bottomley  &  Baird,  Ltd.  : 
Microscope  Illuminant.  Microscope.  Op- 
tical Work  in  Quartz. 

R.  W.  Munro,  Ltd.  :  The  Denne  Photo- 
mjicrographie  Camera  and  Microscope. 

Ogilvy  &  Co.  :  Mono-Binocular  TVEicro- 
scopes,  having  Interchangeable  Bodies. 
High-power  Binocular  Attachment  for 
Monocular  Stands.  Low-power  Binocular 
Dissecting  Magnifier,  having  a  large  field 
of  view.  Ogilvy 's  Ejectric  Microscope 
Lamps. 

Rudolph  &  Beesley  :  "  Reichert  "  New 
Darkfield  Condenser.  "Reichert"  Change- 
able Condenser  for  Transmitted  and  Dark- 
ground  Illumination.  New  "  Reichert 
Opaque  Illuminator.  "  Reichert  "  Stereo- 
Inset.  "  Reichert  "  Microscopes  and 
Accessories. 

James  Swift  &  Son,  Ltd.:  Medical, 
Mineralogical  and  Metallurgical  Micro- 
scopes. High-power  Binocukfr,  Micro- 
meter Microscopes,  Gonimeters,  Diohroi- 
scopes,  Photomicrographic  Apparatus,  etc. 

W.  Watson  &  Sons,  Ltd.  :  Microscopes 
and  Accessories.  A  new  Immersion  Dark- 
ground  Condenser.  New  Condenser  Mount, 
incorporating  Centring  Arrangement.  A 
New  Greenhough  Binocular  for  Petrological 
Purposes.  A  New  Microscope  with  Inter- 
changeable Monocular  and  High-power 
Binocular  Bodies. 

THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 
The  first  Ordinary    Meeting  will    be  held 
on  Otoober  18,  at  6  p.m.,  when  Dr.  A.  Rus- 


sell, M.A.,  D.Sc,    President,    will    deliver 
his  inaugural  address. 

A  good  programme  of  Ordinary  Meetings 
and  Informal  Meetings  has  been  arranged 
for  the  coming  session. 


BOOKS  RECEIVED. 

Organische  Chemie,  von  Dr.  Rudolf 
PuMMERER.  Pp.  XI.  +  209.  1923.  Verlag 
von  Theodor  Steinkopff,  Residenzstr.  12b. 
Dresden  und  Leipzig. 

Molekulargrossen  von  Elektrolyten,  von 
Dr.  Phil  u.  Chem.  Paul  Walden.  Pp.  XI. 
+  350.  1923.  Verlag  von  Theodor  Stein- 
kopff,  Residenzstr.  12b,  Dresden  und  Leip- 
zig. 


1H18  lisi  is  specially  compiled  for  The  Chemical 
News,  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5.  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  frratuitously. 
Latest  Patent  Applications. 
^4023— Metallbank-und     Metallursische     Ges.— Sul- 

pliur  fiunace.    Sept.  26. 
24166 — Williams,  J.  G. — Manufacture  of  acid  phos- 
phate salts  soluble  in  water.     Sept.  28. 
Specifications   Published   this    Week. 
181395— Lilienfeld,  Dr.   L.— Manufacture    of  cellu- 
lose etliers. 
203812— Badische  Anilin     &  Soda  Fabrik.-Proeess 

for  producing  formic  acid  derivatives. 
203975 — Guillemin,  J.— Appliances     for   the  reduc- 
tion of  scoliosis  and  other   bone   deforma- 
tions. 

Abstract  Published  this  Week. 
202157— Dyeing    cellulose     acetate.— British       Dye- 
stuffs     Corporation,     Ltd.,     of  10,     Spring 
Gardens,     Braddiley,  J.,     and  Hill,  J.,   of 
Crumpshall   Vale  Chemical  Works,   Black- 
ley,  both  in  Manchester,  and  Anderson,  E. 
B.,   Mill   Heys,   Hemyock,     near   Tiverton, 
Devon. 
Acid  wool  and    substantive  dyes,     dyeing  with; 
azo  dyes,  forming  on  the  material. — Cellulose  ace- 
tate silk  is  dyed  by  means  of  aminonzo  dyes  con- 
taining    one  or  more  carboxylic  groups     but  not 
sulphonic  group,  the  amino  group  being  diazotiz- 
able.       The  dyes  may    be  diazotized  on  the  fibre, 
and     developed  with     the  usual   components.       A 
table    is  given,     showing  the     direct  shades     and 
those  deevloped  with      -naphthol,      -oxynaphthoio 
acid,     and  p-aminodiphenylamine  of  the  dyes  ob- 
tained from  the  following  comi^onents  :   m-amino- 
l>enzoic  acid  and  o-anisidine,  anthranilic  acid,  m- 
toluidine,       -naphthylamine,      4-nitro-2-anisidine, 
or  1 :2-aminonaphthol  ether;  anthranilic  acid  and 
o-anisidine;  p-aminobenzoic  acid  and  aminoliydro- 
quinone     dimethyl   ether;     p-aminosalicylic     acid 
and        -naphthylamine ;   -  5-acetylamino-2-amino-4- 
methoxytoluene     and       -oxynaphthoic     acid,     the 
product  being  hydrolyzed;     m-aminobenzoic  acid, 
p-xylidine,   and   m-phenylenediamine     or       -naph- 
thylamine.   The  fibre  is  dyed  in    an  aqueous  dye- 
bath,  with  or  without  the  addition  of  weak  acids 
or  salts. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  la.  6d. 
each. 


OCTOBER  26,  1923. 


THE  CHEMICAL  NEWS. 


257 


THE   CHEMICAL  NEWS. 


VOL  CXXVII.      No.  3315. 


ARE  THE  NATURAL  GROUPINGS  OF 

THE  ELEMENTS  AND  THE  SPECTRAL 

LINES  OF  HYDROGEN  RELATED? 

Part  I. 

By  F.  H.  Loring. 

It  seems  probable  from  Bohr's  theory  of 
the  atom  that  there  is  a  place  principle  in- 
volved, for  the  electrons  autornatically  take 
up  definite  orbits  when  they  are  displaced 
outwardly,  Jmd  on  returning  to  their  proper 
orbits  definite  wave  lengths  are  revealed 
in  the  line  spectrum  then  emitted,  thus 
involving  eijually  definite  orbits.  This  is  a 
very  extraordinary  phenomenon,  and  Bohr's 
formulation  of  the  action  by  the  use  of 
Planck's  quantum  energy  relatiMi  stands 
out  as  one  of  the  great  achievements  of 
science. 

It  is  very  curious  that  the  orbits  should 
occur  in  definite  places  as  due  to  definite 
quantised  energy  emissions,  iicnce  the  term 
"place  principle"  stated  above.  There  are, 
however,  other  phenomena  involving  a  simi- 


Nome  of  L 

ine. 

W 

'ave  Length 

Ha 

0563.04 

H^ 

48G1.40 

Hy 

4340.06 

HS 

4101.90 

He 

3970.25 

lar  place  principle  as  the  present  writer  has 
touched  upon  in  his  book,  "  The  Chemical 
Elements,"  published  by  Messrs.  Methuen, 
and  which  is  due  to  appear  shortly.  Men- 
tion may  be  made  of  several  relative  papers 
by  the  present  writer,  which  appeared  in 
this  Journal  under  the  title  : — "  Is  there  an 
element  of  zero  atomic  number?"  In  par- 
ticular see  this  Journal,  1923,  CXXVII.,  p. 
225,  and  the  references  therein  should  be 
consulted. 

The  foregoing  studies  do  not,  however, 
bring  out  clearly  the  "principle"  in  ques- 
tion, but  they  do  lead  up  to  it.  If  it  is  now 
assumed  that  the  wave-lengths  of  the  five 
main  lines  of  hydrogen  give  expression  to 
five  orbital  places  round  the  nucleus  of  the 
atom,  in  conformity  with  Bohr's  work,  then 
it  may  only  be  a  step  to  regard  the  periodic 
table  as  made  up  of  natural  groups  and 
groupings,  as  already  discussed  in  these 
pages — see  citations  above — and  that  these 
groups  represent  similar  places.  An  at- 
tempt is  here  made  to  show  an  exact  con- 
nection between  these  two  "place"  ideas, 
but  before  doing  so  a  brief  elementary  state- 
ment of  the  characteristic  feature  of  the 
hydrogen  emission  lines  will  be  given. 

Balmer,  in  1885,  showed  that  these  lines 
could  be  closely  formulated,  which  leads  to 
the  following  well-known  calculation:  — 

Formula  and  Calc.  Wave  Length. 
3646.13  X  3V(3?— 2=^)  =  6563 
3646.13  X  4»/(4=— 2=)  =  4861 
8646.13  X  5^(5=^—2=')  =  4340 
3646.1*^  X  6V(6='— 2^)  =  4102 
3646.13    X    r{{r—2^)   =  3970    . 


Referring  to  The  Chemical  News,  1923, 
CXXVII.,  p.  225,  the  five  natural  groups 
and  groupings  were  given  as  7,  9,  13,  21,  43. 

The  recent  discovery  of  hafnium  (=  cel- 
tium,  atomic  number  No.  72 — there  is  a 
dispute  as  to  priority  of  discovery  of  this 
element,  so  that  one  is  facetiously  inclined 
to  think  of  it  as  "celtafniuin")  as  an  cle- 
ment closely  allied  to  zirconium,  by  Coster 
and  Hevesy  {Nature,  Jan.  20,  1923)  makes 
it  necessary  to  raise  the  "18  level"  in  tlio 
wedge  table  originally  given  in  The  Chemi- 
cal New8,  1922,  CXXV.,  p.  386. 

It  will  be  seen  that  "17"  then  becomes  a 
limiting  number  in  the  wedge  system,  so 
that  hafnium  may  bear  a  seeondary  number 
4  in  order  to  complete  the  scries  to  which  it 
belongs  to  the  limit  17.  This  will  be  made 
eivdent  by  referring  to  the  (able. 


One  is  therefore  driven  to  the  supposition 
that  there  should  be  4  elements  imme- 
diately before  hafnium,  bearing  secondary 
numbers  0,  1,  2,  3.  This  would  raise  the 
total  number  of  elements  in  the  large  group- 
ing to  47 ;  but  since  the  last  wedge  is  incom- 
iplete  from  the  view  of  limiting  numbers,  a 
blank  should  follow  the  place  occupied  by 
uranium  of  atomic  number  92.  This  would 
then  raise  the  number  to  48.  The  necessity 
of  a  lacuna  of  atomic  number  93  was  shown 
in  a  paper  by  the  present  writer  in  The 
Chemical  News,  1922,  CXXV.,  p.  309. 

Now,  plotting  the  numbers  7,  9,  13,  21,  48 
against  wave  lengths  of  the  a  to  e  lines  of 
hydrogen,  taken  as  the  main  lines,  gives  a 
straight-line  curve  as  depicted  in  the  accom- 
panying diagram,  which  is,  by  the  way, 
carefully  drawn,  showing  that  the  intersec- 


258 


THE  CHEMICAL  NEWS. 


OCTOBER  26,  1923. 


tions  are  practically  perfect.  The  wave 
length  values,  in  Angstrom  units,  are 
selected  from  Sommerf eld's  "Atomic  Struc- 
ture and  Sipectral  Lines." 

It  will  be  seen  that  by  raising  the  total 
number  of  elements  in  the  large  grouping, 
i.e.,  from  44  to  48,  introduces  4  extra  ele- 
ments not  determined  by  the  atomic  num- 
bers. At  the  same  time  the  limiting  num- 
bers throughout  the  wedge  table  necessitate 
4  additional  elements  preceding  hafnium. 
The  wedge  table  is  so  complete  in  every  pos- 
sible way,  in  that  it  does  not  violate  the 
chemical  ideas  in  connection  with  the  ele- 
ments whilst  giving  scope  for  the  proper  ex- 
pansion of  the  rare-earth  elements  from  Pr 
to  Lu,  that  there  must  be  something  here 
worth  careful  study.     If  a  suggestion  may 


be  made,  it  seems  possible  that  the  4  extra 
elements  have  amalgamated  with  others  of 
the  series  involved,  for  they  would  probably 
have  prqperties  already  established  earlier 
in  the  series;  that  is  to  say,  in  the  first  series 
starting  with  xenon. 

The  reader  should  not  come  to  a  hasty 
conclusion  in  these  matters,  as  a  very  care- 
ful study  of  the  elements  at- the  places  indi- 
cated is  necessary.  In  counting  the  ele- 
ments in  the  large  grouping,  it  should  be 
noted  that  cerium  belongs  to  this  grouping, 
and  therefore  it  does  not  form  one  of  the 
rare-earth  13.  Cs,  Ba,  La,  Hf,  Ta,  W,  75 
and  H  belong  also  to  this  grouping.  If  the 
reader  will  refer  to  pages  14,  24,  28,  34,  in 
the  writer's  book,  "  The  Chemical  Ele- 
ments,"  this  grouping  will  be  made  clearer. 


e563-OA  RED 


4861-49  GREEN 


4340-6G  BLUE 


■4101 -90  VIOLET 


3970-25  VIOLET 


WAVE  LENGTH   ^ 


Note  on  Hydrogen. 

Inasniuch  as  the  wedge  table  is  made  use 
of  in  this  study,  attention  may  be  drawn  to 
the  group  classification  above  given  in  con- 
nection with  hydrogen  as  placed  in  the 
table.  Hydrogen  may  be  supposed  to  stand 
at  the  end  of  a  very  small  steep  wedge,  so 
that  its  level  will,  in  conformity  with  the 
other  extreme  levels  of  the  respective 
wedges,  approximate  to  that  of  fluorine,  and 
thereby  give  it  some  characteristics  that 
parallel  well  with  those  of  the  halogen  ele- 
ments. At  the  same  time,  hydrogen  being 
over  lithium,    its  electropositive  character, 


due  to  the  readiness    with  which    it    parts 
with  its  single  electron,  is  accounted  for. 

Now  this  short  high  wedge  should  con- 
tain, besides  hydrogen,  an  element  coming 
into  the  inert  group,  but  perhaps  on  a 
shghtly  higher  level,  owing  to  the  steepness 
of  the  wedge.  Since  this  extra  element,  re- 
garded as  the  zero-atomic-number  member, 
was  discussed  in  the  previous  papers  cited 
(see  this  Journal,  CXXVIL,  p.  225),  no  fur- 
ther argument  is  called  for  here.  This  note, 
however,  shows  that  the  wedge  scheme  is 
satisfactory,  and  therefore  the  significance 
of  the  "limiting  numbers"    made  use  of  in 


OCTOBER  26,  1923. 


THE  CHEMICAL  NEWS. 


259 


this  study  should  be  taken  into  account  in 
probing  the  more  obscure  phase  of  the  argu- 
ment. 

Summary. 

Plotting  the  values  7,  9,  13,  21,  48,  at 
right-angles  to  the  wave  lengths  of  5  main 
hydrogen  lines  gives  a  straight-line  curve 
which  suggests  that  the  "place  principle" 
of  the  main  hydrogen  orbits  is  fundamen- 
tally the  same  as  the  places  in  the  periodic 
table  as  represented  by  natural  groups  and 
grouipings  containing  respectively  these 
numbers  of  elements  in  each  ;  but  a  peculiar- 
ity develops  at  hafnium,  which  is  discussed, 
^t  is  shown  that  the  wedge  table  throws 
some  light  on  the  problem  involved  in  this 
study;  and  that  hydrogen  can  be  so  placed, 
in  conformity  with  the  other  elements  and 
in  no  way  an  exception,  that  its  two-fol(T 
property,  so  to  speak,  is  accounted  for. 
This  gives  the  wedge  table  a  greater  useful- 
ness and  reliability  in  developing  the  argu- 
ment that  four  extra  elements  may  be 
merged  or  amalgamated  with  others  so  that 
they  will  have  lost  their  separate  identities. 


AN  EXPLANATION  OF  THE  THEORY 

OF  THE  ROTATION  OF  THE  ATOMIC 

NUCLEUS. 

Part    IV. 

By  Hrrhert  Hk\ stock. 

Oxides  (confiimrd). 

(Continued  from  Page  243.) 

The  nitrogen  octet  is  distorted,  thus  ex- 
hibiting no  free  valencies,  but  it  may  be 
easily  opened  up  in  the  direction  of  the 
dottexi  lines,  when  bonds  would  be  formed 
permitting  other  atoms  to  join  the  mole- 
cule, which  explains  the  case  with  which 
this  compound  unites  with  oxygen. 

It  is  often  stated  that  nitric  oxide  is  the 
most  stable  of  the  oxides  of  nitrc^en,  and 
with  respect  to  the  effects  of  heat  this  may 
be  the  case ;  but  in  its  behaviour  to  the 
action  of  other  atoms  it  is  the  weakest  of 
the  nitrogen  oxides,  as  witness  its  spontane- 
ous union  with  oxygen. 

The  halogens  will  unite  with  the  positive 
edge  (a-d),  see  Fig.  4,  cnippounds  of  this 
nature  being  unstable  (rule  2) :  oxygen  will 
tmite  with  the  face  a-h-c-d  to  form  a  double 
bond  in  NO^,  but  there  will  then  be  two 
electrons  at  (c),    which  mnkcs    the    bond  a 


weak  one  (rule  6),    with    the    consequence 
that  the  oxygen  is  easily  detached. 

Nitrogen  tetroxide,   in  Fig.  5,   the  cubes 
representing  nitrogen  atoms. 


-0 

±0 

4 

{\ 

X 

J 

\-  1 

f 

M 

K^ 

M 

\t 

A-/ 

"Am/^^ 

^     \J 

■f 

:o 

P 

LO.S 

The  oxygen  is  united  by  double  bonds  as 
represented  in  Fig.  4. 

There  will  be  two  electrons  at  x  and  two 
at  y  (Fig.  5],  the  single  bond  will  therefore 
be  weak  (rule  6). 

When  this  gas  is  dissolved  in  water,  a 
mixture  of  nitrous  and  nitric  acids  is 
formed.  If  the  exiplanation  of  this  be  writ- 
ten with  the  correct  polarity  signs  included, 
the  mechanism  of  the  reaction  becomes 
plain. 


.4-  /V 


"*  /vt- 

^^ 

-     / 

"'.-) 

-f 

HO 

H 

^0 
^0 


The  OH  unites  with  positive  nitrogen  and 
the  hydrc^en  with  one  of  the  negative 
bonds  of  oxygen,  the  double  bond  between 
this  and  the  other  nitrogen  becoming  a 
single  bond,  a  negative  edge  of  the  oxygen 
linking  with  a  positive  edge  of  the  nitrogen. 
Nitrogen  tri  oxide  in  Fig.  6. 


7U. 


Trurnx/y^       ayyu/QJiAx 


±0 


260 


THE  CHEMICAL  NEWS. 


OCTOBER  26,  1923. 


Nitrogen  pentoxide  in  Pig.  7 

±0 


^'57 


«t 


It  will  be  seen  that  at  a  and  b  there  will 
be  two  electrons,  and  the  same  thing  applies 
to  c  and  d,  therefore  the  bonds  uniting  these 
two  hitrogen  atoms  to  the  middle  oxygen 
will  be  weak  enough  to  be  broken  by  water ; 
thus : 


oj  +!- 


o 


+  - 
HO 


+  ± 


o~  /\/ 


^ 


+ 
H 


0 

o 


Those  bonds  uniting  the  two  oxygen 
atoms  (marked  dark)  to  the  nitrogen  will  be 
weak,  from  the  same  cause,  and  these  oxy- 
gen atoms  are  therefore  the  nitrite  oxygen, 
which  splits  off  to  form  nitrite. 


+ 
H 


0 


0 


—      =  HNO,  +  0. 
0 

Phosphorus  tri  oxide  is  usually  written 
P2O3,  but  the  vapour  density  agrees  with 
the  formula  P^Og,  it  will  probably  be  con- 
stituted as  follows:  — 


±         +       -        +         ± 

O  =-T  -  o  -  T  =  <o 


-h 


n± 


-h 


-f 


That  is,  it  will  be  like  N2O3  given  above, 
but  the  molecule  is  doubled,  a  spare  double 
bond  being  free  in  each  nitrogen  atom  of 
N2O3,  and  this  would  apply  equally  to  P2O3. 


Phosphorus  pentoxide,  if  it  exists  as 
such,  will  be  like  N2O5,  see  Fig.  7,  but  the 
double  molecule,  Vfi^^,  will  be  probably 


o 

I 
0 

0 

I 

0 


\\_ 


-f 


o 


T 


+ 


o 

I 

o 


\ 


0 


which  can  be  easily  seen  on  drawing  out  the 
octets. 


The  oxides  of  arsenic,  antimony  and  bis- 
muth will  be  constituted  similarly  to  the 
oxides  of  nitrogen. 


Chemical  Research  Laboratory, 
School  Gardens, 

Shrewsbury. 


OCTOBER  26,  1923. 


THE  CHEMICAL  NEWS. 


261 


SOME  RECENT  RESEARCHES  IN 
ORGANIC  CHEMISTRY. 

By  R.  F.  Hunter,  F.C.S. 
(Continued  from  Page  245.) 

Skri  Krishna,  and  Pope,  the  first  of  these, 
condensation  of  m  dimethylamino  phenol 
with  benzaldehyde  included  the  prepara- 
tions of  4  dimethylamino  2  hydroxy  benz- 
h^drol  and  a  number  of  derivatives. 

The  second  paper  dealt  with  phenol  citra- 
conein,  and  included  the  preparation  of  K 
salt,  tetra  bromo  derivative,  and  the  diace- 
tyl  and  dizenzoyl  derivatives. 

Another  paper  appearing  about  this  time 
was  one  by  Fargher  and  l\ing  on  the  addi- 
tative  compounds  of  antihyrylamino  diace- 
tic  acid,  the  experimental  parf  of  which 
included  the  study  of  the  salts  of  anti- 
hyrylamino diacetic  acid,  the  additive  com- 
pounds of  anti-hyrylamino  diacetic  acid  with 
neutral  salts,  the  additiev  compounds  of  the 
salts  of  anti-hyrylamino  diacetic  acid  with 
neutral  salts,  and  the  preparation  of  the 
ethyl  ester  of  anti-hyrylaminodiacetic  acid. 

Meanwhile  the  quantitative  reduction 
by  hydriodic  acid  of  halogenated 
malonyl  derivatives  was  being  studied  by 
Whiteley  and  West,  the  first  part  which 
concerned  itself  with  the  amides  and  S  Di- 
alkyl  and  aryl  substituted  amides  of  Mono 
and  Di  bromo  malonic  acid,  appeared  about 
ths  time.  The  experimental  work  was  of 
consderable  magnitude.  Bromomal<Miide, 
CH  Br  (CONH  Me)2,  was  prepared  from 
malonamide,  bromomalon  dimethylamide, 
Ch  Br  (CONH  Me)2,  was  prepared  from 
Malondimethylamide,  bromo  malondiethyl- 
amide,  CH  Br  (CONH  Et),,  and  the  di- 
bromo  compound,  C  Bra  (CONH  Et),,  were 
obtained  from  Malondictliylamide.  The 
corresponding  compounds  from  malondi  n 
propylamide,  CH  Br  (CONH  Pr)^,  and 
C  Br  J  (CONH  Pr),,  the  bromo  compound, 
CH  Br  (CONH  C^H,)^,  from  maloni  n 
bulylamide,  the  iso  comjwund  from  malondi 
isobutylamide,  the  compounds,  CH  Br- 
(CONH  CHjPh)^  and  C  Br^  (CONH  CH,- 
Ph)2,  from  malondibenzvlamide,  bromo- 
malonyl  diurethane,  CIl'^Br  (CONH  CO^- 
Et)^,  from  malonylduirethane.  A  number 
of  other  bromo  compounds  were  also  pre- 
pared. 

The  reduction  of  ureides  of  mono  and  di- 
bromo  malonic  acids  by  HI.  and  of  bromo 
ketones  by  HI,  were  also  studied. 

From  the  same  college  (the  Royal  Col- 
lege of  Science)  a<ppeared  Naik's  paper  on 
the  formation  and  properties    of  dithio  ke- 


tones (RjC  :  S  :  S)  and  di  thio  ethers 
(RjS  :  S),  which  included  the  preparation 
of  di  thio  mesonanilide,  (NH  Cg  H^  CO)a- 
C  :  S  :  S,  its  nitration,  bromination,  hy- 
drolysis and  reduction. 

Other  disulphide  bodies  were  isolated. 

About  the  same  time.  Pope  and  Smith's 
paper  of  S^Clj,  on  substituted  ethylenes,  in 
which  P  fi '  Dichlorodipropyl  sulphide, 
(C  H  Me  CI  CHJ.S  and  ^8/5'  dichloro-di-sec- 
butyl  sulphide  rC  H  Me  CI  CH  Me)2S.  were 
described,  anotlier  paper  on  /3^'  dichlordi- 
ethyl  disulphide  appeared  by  Bennet,  in 
which  the  following  were  investigated : 

Oxidation  of  fi^'  dichlordiethyl  sulph- 
oxide  to  a  sulphonic  acid. 

The  preparation  of  monothio  ethylene  gly- 
col, SH  CHj  CHj  OH,  of  iSiS'  dichlorodi- 
ethyl  disulphide  and  the  oxidation  of  the  di- 
sulphide. 

Some  experiments  on  the  production  of 
compounds  containing  arsenic  as  a  centre 
of  optical  activity  were  described  by  Bar- 
row and  Turner,  which  necessitated  the 
study  of 

y  Phenyl  propyldimethylarsine ; 

Phenyl  y  phenylpropylmethylarsine; 

As  -  Methyl  tetra  hydro  arsinoline ; 

Phenyl  a  naphthylmethylarsine  and  its 
oxide. 

Hydroxy  phenyl  a  naphthylmethyl  arso- 
nium  d  a  bromo  camphor  II  sulphonate ; 

Methyl  ethylio  do  arsine ; 

Phenyl  a  naphthyl  methyl  ally!  arsonium 
bromide ; 

Phenyl  and  naphthyl  benzylmethyl  ar- 
sonium bromide. 

Three  papers  now  appeared  together : 
One  on  the  action  of  alkyl  nitrates  on  piper- 
idine,  by  Gibson  and  Macbeth,  in  which  the 
action  of  ethyl,  propyl  and  butyl  nitrate  on 
piperidine  was  studied.  The  second  was  on 
Friedel  Crafts  Reaction,  Migration  of  halo- 
gen atoms  in  the  benzene  nucleus,  by  Coisa- 
row.  The  third  was  by  Green  and  Price  on 
the  Chlorovinyl  chloroarsines.  Among  the 
compounds  investigated  in  this  research 
were  ft  Chlorovinyldichloroarsine,  CH  CI  :- 
CH  As  CI2,  ftft'  Dichlorodivinylchloro- 
arsine  (CH  Cl :  CH)2  As  CI,  and  fili'ft"  Tri- 
chlorotrivinylarsine  (CH  Cl :  CH)3  As. 

In  February,  1921,  Kenner  and  Stubbings 
communicated  to  the  Chemical  Society's 
Journal  a  paper  on  the  second  form  of  6  :  6' 
Dinitro  diphenic  acid  and  its  conversion 
into  new  cyclic  systems,  in  the  experimen- 
tal part  of  which  were  the  preparations  of 
2-Chloro-3-nitrobenzoic  acid. 


262 


T&lB  CHEMICAL  NfiWS. 


OCTOBER  26,  1923 


# 


y  6   :  6'-Dinitro-diphonic  acid; 

6  :  6'-Diammo-2  :  2'-ditolyl; 

y  6   :  6'-diacetylaminodiphonic  acid; 

the  di  lactamo  of  y  6  :  6'-diaminodiiphenic 
acid  and  1  :  lO-dimethyl-5  :  6-naphtha  iso- 
diazine. 

The  following  month  Morgan  and  Grist 
investigated  their  aryl  sulphonyl  naphthy- 
lene  diamines  and  -sulphonio  acids,  describ- 
ing a  variety  of  new  compounds. 

Meanwhile,  a  further  research  on  residual 
affinity  and  co-ordination,  reaction  of 
selenium  and  tellurium  acetyl  acetones,  ap- 
peared by  Morgan  and  Drew,  in  the  experi- 
mental part  of  which  we  have 

Tellurium-0-ethylacetylacetone  trichlor- 
ide, CH3  C  (0  C2  H3)  :C  H  C  0  CH2  Te  CI3, 
and  its  derivatives,  and  the  reactions  of 
selenium  acetyl  acetone. 

This  was  followed  by  another  paper  on 
the  action  of  S2CI2  on  ethylene,  in  which  we 
get  dichlorodiethyl  trisulphide, 

CH2  CI  CH2  S  S  S  CH2  CH2  01, 
Pseudo  solutions  of    S    in    ji3;S'-dichlorethyl 
sulphide,  and  the  study  of  the  absorption  of 
C^H^  by  S2CI2. 

In  March,  1921,  Scott  and  Cohen's  work 
on  the  carbamido  acids  and  their  hydantions 
appeared,  in  which  the  preparation  of  o- 
Acetyl-carbamidobenzoic  acid,  N  H  Ac- 
C  O  N  H  Cg  H^  CO2  H,  and  the  correspond- 
ing o-Benzoyl  carbamidobenzoic  acid  are 
described,  and  a  fairly  complete  study  of 
carbamidophthalic  acid  and  its  hydrantion 
is  given.  The  action  o'f  sodium  hypo 
chlorite,  methyl  sulphate,  etc.,  on  hydran- 
toin  are  described. 

Papers  have  appeared  on  the  Organic  De- 
rivatives of  Thallium,  by  Goddard,  in  which 
thallium  dimethyl  carbonate,  chromate,  ni- 
trate, thiocyamate,  thallium,  diethyl  chro- 
mate and  thallium  diethyl  trichloro  acetate 
are  described,  and  on  organic  derivatives  of 
tellurium,  the  action  of  ammonia  and  al- 
kalis on  and  dimethyl  telluronium  di  iodide, 
by  the  late  Richard  Henry  Vernon. 

One  of  the  series  of  papers  on  non- 
aromatic  diazonium  salts,  3  :  5-Dimethyl- 
iso-oxazole-4-diazonium  salts  and  deriva- 
tives, by  Morgan  and  Burgess,  appeared  at 
this  time.  ■  Among  the  preparations  we 
have  4-nitro-3  :  5-dimethyl  iso  oxazole  4- 
amino-3  :  5-dimethyl-iso-oxazole  and  its 
hydrochloride;  4-acetyl-amino-3  :  5-dim- 
ethyl-iso-oxazole, 

C,  H,  ON.  N  H  CO  CH3, 

4-Benzylideneamino-3  :  5-dimetbyl-iso- 
oxazole, 


5  -  dim- 


C«H,  CH 


N  Cj^  He  0  N. 

fa 


4-o-Nitro-benzylideneamino-3 
ethyl-iso-oxazole, 

NO2  CgH^  CH  :  N.  C,  He  On. 
3     :     5-Dimethyl-iso-oxazole-4-azoresorci- 
nol,  and  3   :  5-diniethyl-iso-oxazole-4-azo-/3- 
naphthylamine. 

A  paper  by  Fargher  and  Pyman  on  4  ^- 
methyl  amino  ethylglyoxaline  appeared  in 
May,  1921.  The  work  was  important,  since 
4  fi  aminoethyl  glyoxaline  is  isolated  from 
ergot,  and  is  an  intense  stimulant  of  plain 
muscle.  Among  the  experimental  prepara- 
tions were  : 

a-Chloro-/3-glyoxaline  4-proipionic  acid  d- 
1-a-methyl  amino  |8-glyoxaline-4-propionic 
acid,  4  /ii-methyl-amino  ethyl  glyoxaline  di- 
picrate  and  dihydrobromide. 

Cohen's  paper  on  hydrogenated  quino- 
lines  is  also  worthy  of  mention,  and  de- 
scribes the  preparation  and  properties  of  a 
number  of  interesting  substances. 

May,  1921,  saw  another  pamper  on  studies 
in  the  camphane  series,  amino  phenylamino 
camphor,  by  Forster  and  Saville. 

In  the  experimental  work  we  have  the  ni- 
tration of  phenylamino  camphor  and  the 
nitrosoderivative,  p-amino-phenyl-amino- 
camphor,  derivatives  of  p-benzeneazoipiienyl 
amino  camphor-p-sulphobenzeneazophenyl- 
amino  camphor  and  4-amino-l-naphthyl- 
amino  camphor. 

Two  papers  have  a^ppeared  by  Kipping 
and  Sands  on  the  organic  derivatives  of  sili- 
con, the  first  of  which  dealt  with  saturated 
and  unsaturated  silico  hydrocarbono,  Si^Phg. 
They  investigated  the  action  of  sodium  on 
diphenylsilicon  dichloride,  and  that  of  io- 
dine on  unsaturated  silico  hydrocarbon,  giv- 
ing octa  phenyl  di  iodosilicotetrane, 
Si^Phgla. 

The  actions  of  tetra  chloroethane  and  of 
boiling  CgHjNOj  on  the  unsaturated  silico- 
hydrocarbon  were  also  investigated. 

Their  second  paper  was  on  the  use  of 
piperidine  as  an  analytical  reagent. 

At  the  same  time  there  appeared  Davies* 
two  paipers  on  the  cumulative  effect  of 
chlorine  atom  and  methyl  and  sulphonyl 
chloride  groups  on  |ubstitution  in  benzene 
nucleus.  This  necessitated  some  important 
preparations. 

Davies  summarised  his  results  in  some- 
thing of  this  way  : 

The  nitration  of  2  chloro  p  toluene- 
sulphonyl  chloride  leads  to  2-chloro-5-nitro- 
p-toluenesulphonyl  chloride  and  2-chloro-6- 
nitro-p-toluenesuliphonyl  chlorides.  The 
proportion  of  these  isomerides  shows  orien- 
tation due  to  chlorine  atom  is  much  greater 


OCTOBER  26,  1923. 


THE  CHEMICAL  NEWS. 


263 


than  united  directive  effects  of  methyl  and 
sulphonyl  groups.  The  sulphonyl  group 
and  not  the  nitro  is  reactive  in  the  5-nitro, 
and  can  be  replaced  by  OH  by  boiling  with 
dilute  NaOH. 

Monochlorination  at  70°  of  chloro-p-tolu- 
ene  sulphonyl  chloride  leads  mainly  to  2  :  6- 
dichloro-p-toluene  sulphonyl  chloride. 

The  second  paper  contained  the  prepara- 
tion of  6-chloro-o-toluene  sulphonyl  chlor- 
ide, 6  chlorosaccharin,  tlu-  nitration  of  6- 
chloro-o-toluenesulphonyl  chloride  6-chloro- 
3-nitro-o-toluenesul phony  1  chloride  gave  6- 
chloro-4-nitro-o-toluenesulphnoyl  chloride. 

Monochlorination  "^f  o-toluenesulphonyl 
chloride  in  presence  of  HbClj  leads  to  forma- 
tion of  isomerides  6-chloro-o-toluenc8ul- 
phonyl  chloride  in  40  per  cent,  yield  nitra- 
tion at  25°  of  this  results  in  production  of  6- 
chloro-4-nitro-o-toluenesulplionyl  chloride 
and  the  3-nitro  compound  and  the  sulpho- 
nyl chloride  is  replaced  by  OH  by  boiling 
with  NaOH  solution. 

Field's  paper  on  mitragynine  and  mitra- 
versine,  two  new  alkaloids  from  species  of 
mitragine  is  worthy  of  note.  Published  in 
conjunction  with  it  was  Stedman's  New  De- 
gradation product  of  Physostigmine.  At 
the  same  time,  June,  1921,  there  appeared 
Brady  and  Bowman's  research  on  Dinitro 
tolyl  hydrazines,  (published  at  this  time, 
and  included  the  study  of  several  nitro- 
toluene  and  hydrazine  derivatives. 

The  first  of  Bamett's  studies  in  the  an- 
thracene series  appeared  at  this  time,  and 
included  some  unusual  prepiirations  such  as 
9  :  10-dhydro  anthraquinyldijpyridinium  di- 
bromide,  on  which  the  action  of  NaOII,  N 
Hj,  primary  and  secondary  aliphatic 
amines,  pyridine  and  quinoline,  and  prim- 
ary and  secondary  aromatic  amines  was 
studied. 

Published  at  the  same  time  was  a  paper 
by  Challenger  and  Alliprcss  on  organic  deri- 
vatives of  bismuth.  Among  some  of  the 
compounds  prepared  by  these  researchers 
were : 

Di  a  naphthyl  chlorobismuthine,  the  cor- 
responding bromo  compounds  and  naphthyl 
bismuthine  dibromide,  phenyldibromobis- 
muthine,  and  tri  m  tolyl  bismuthine  and 
the  action  of  Grignard  roaj^n^nts  on  various 
of  those  and  other  compounds  was  also  in- 
vestigated. 


THE  EVOLUTION  OF  CHEMICAL 
TERMINOLOGY.* 

By  James  F.  Couch. 

(Continued  from  Page  253.) 

The  most  inclusive  definition  of  the  term 
hydroxide  is  the  statement  that  it  denotes 
a  substance  which  contains  an  hydroxyl 
group. 

Defined  in  this  way  the  class  hydroxide 
will  contain  a  very  diverse  collection  of 
substances.  In  addition  to  the  metallic 
hydroxides  we  shall  include  the  oxy-acids, 
such  as  sulphuric  acid  and  phosphoric  acid 
and,  of  course,  we  naust  admit  the  acid 
salts,  such  as  sodium  bisuliphat6  NaO.SOj.- 
OH,  as  well  as  the  basic  salts.  Alcohols, 
phenols,  the  enol  forms  of  tautomeric  ke- 
tones must  also  be  admitted.  Resoroin, 
then,  may  be  termed  orthosalicyl  hydroxide. 
All  of  the  organic  acids,  both  the  carboxylic 
and  sulphonic  acids,  belong  in  this  class;  we 
shall  term  formic  and  oxalic  acids  hy- 
droxides. The  hydroxy-acids,  such  as  lac- 
tic acid,  have  a  double  claim  to  recognition 
as  hydroxides  owing  to  their  content  of  two 
hydroxyl  groups.  The  hydroxy-amines, 
hydroxy-pyridines,  hydroxy-quinolines,  and 
the  derived  alkaloids  amidst  the  intricacies 
of  whose  constitutional  formulas  nestles  an 
hydroxyl  group,  all  come  clamouring  for  in- 
clusion. Nm"  can  we  bar  out  that  great 
class  of  hydroxyl  compounds,  the  carbohy- 
drates from  glycollio  aldehyde,  the  simple 
bioee,  through  the  whole  class  to  the  com- 
plex cellulose,  f  >r  the^ carbohydrates  bristle 
with  hydroxyl  groups. 

There  are  certain  difficulties,  however, 
which  arise  as  a  result  of  so  wide  an  exten- 
sion of  the  meaning  of  the  term  hydroxide. 
H  all  these  substances  are  to  be  considered 
hydroxides,  it  follows  that  they  must  have 
names  in  conformance  with  this  aspect  of 
their  constitutions.  Systematic  classifica- 
tion requires  this.  But  an  effort  to  satisfy 
that  demand  would  lead  us  into  absurdity 
and  cause  us  to  coin  a  large  number  of  new 
names  which  would  be  of  no  other  service 
than  to  bolster  the  theory.  Sulphuric  acid 
must  become  sulphuryl  hydroxide;  sulphur- 
ous acid,  thionyl  hydroxide;  and  what  we 
should  name  thiosulphuric  acid  and  tetra- 
thionic  acid  is  not  very  clear.      Phosphoric 

♦  [Reprinted  from  "The  American  Jour- 
nal of  Pharmacy,  Philadelphia,  Pa.,  July, 
1928.] 


264 


THE  CHEMICAL  T^BWS. 


OCTOBER  26,  192b. 


acid  would  easily  become  phosphoryl  hy- 
droxide; but  what  should  we  name  hypo- 
phosphoric  acid?  With  the  alcohols  and 
phenols  there  would  be  no  more  than  ixioder- 
ate  difficulty;  the  organic  acids,  however, 
would  not  be  so  readily  disposed  of,  and  the 
carbohydrates  would  present  a  problem 
which  is  not  at  all  pleasant  to  contemplate. 

A  more  serious  objection  to  the  broad  de- 
finition arises  from  the  consequences  to 
chemical  theory.  If  we  apply  the  term  hy- 
droxide to  such  a  varying  and  heterogene- 
ous array  of  substances,  the  concept  hy- 
droxide loses  all  specificity  as  a  functional 
mark ;  it  converts  the  term  into  a  mere 
character  and  divests  it  of  all  practical 
value.  The  far  larger  portion  of  the  sub- 
stances enumerated  is  not  chiefly  character- 
ised by  the  content  of  hydroxyl  but  the 
chemical  properties  depend  upon  other 
atomic  complexes  and  the  presence  or  ab- 
sence of  hydroxyl  is  frequently  of  very 
minor  importance.  The  class  loses  most  of 
its  significance  and  its  members  no  longer 
possess  outstanding  common  properties. 

The  extension  of  the  class  to  include  all 
hydroxyl  compounds  serves  no  scientific  or 
practical  purpose.  If  the  class  cannot  be 
considered  a  homogeneous  unit,  and  it  cer- 
tainly cannot  be  so  considered  if  it  is  to  con- 
tain acids,  bases,  and  alcohols,  which  have 
their  own  specific  properties  as  classes,  the 
utility  of  the  term  for  either  purpose  is 
much  impaired.  If  the  members  of  the 
class  do  not  exhibit  certain  properties  which 
readily  identify  them  as  belonging  to  the 
category,  and  aH  of  these  various  classes 
enumerated  above  do  not  fulfil  this  require- 
ment, it  is  impossible  to  assign  definite 
characters  to  the  class,  and  consequently 
the  significance  of  the  class-term  is  de- 
stroyed. 

From  such  considerations  we  must  con- 
clude that  the  extension  of  the  term  hy- 
droxide to  include  all  hydroxyl-compourids 
could  have  but  one  consequence,  the  worth- 
lessness  of  the  term.  The  second  idea,  that 
of  allowing  the  term  to  embrace  all  hy- 
droxyl^  compounds  but  of  restricting  its  use 
to  basic  compounds,  does  not  avoid  the  ob- 
jections raised  against  the  other  inclusive 
idea  and  creates  its  own  ohjection  on  the 
ground  of  vagueness. 

There  remains,  then,  the  concept  that  an 
hydroxide  is  an  hydroxyl-compound  with 
basic  properties.  This  most  limited  defini- 
tion excludes  the  oxy-acids,  the  alcohols, 
the  phenols,  enol-ketones,  organic  acids, 
sulphonic  acids,  and  all  the  rest  of  that 
galaxy  admitted  by  the  broad  definition. 


The  first  point  in  favour  of  this  narrow 
view  is  the  fact  that  this  concept  is  the  one 
which  is  held  by  the  greater  number  of 
chemists  at  the  present  time.  This,  in  it- 
self, is  no  argiunent  for  the  correctness  of 
the  concept,  but  it  is  an  important  con- 
sideration in  a  case  like  the  present,  where 
the  preferableness  of  conflicting  notions  is 
being  studied.  It  would  be  easier  to  get 
general  agreement  to  this  definition  than  to 
any  other. 

Although  this  narrow  definition  is  suip- 
ported  by  the  historical  data,  an  argument 
based  upon  whose  facts  will  not  be  con- 
sidered of  first  importance.  We  cannot  con- 
sent to  bind  ourselves,  to  the  notions  of  a 
hundred  and  twenty  years  ago,  for  we  know 
that  those  ideas  of  chemical  relationships 
were  inaccurate  in  the  light  of  our  present 
knowledge.  We  can,  by  such  evidence, 
readily  demonstrate  that  the  term  acid  is 
misused  to-day,  and,  indeed,  that  term  has 
had  many  modifications  of  meaning  since 
Lavoisier's  time ;  but  such  an  effort  could 
not  result  in  any  real  benefit  to  chemical 
nomenclature.  Certainly,  no  general  term 
is  to-day  used  with  more  specificity  of 
meaning  than  is  the  word  acid.  Conse- 
quently the  historical  facts,  while  impor- 
tant, cannot  be  considered  final  reasons  for 
the  acceptance  of  this  narrow  view. 

A  more  important  argument  in  support  of 
this  limited  concept,  however,  is  based 
upon  functional  relationships.  Throughout 
chemical  nomenclature  the  idea  of  func- 
tional similarities  is  most  important  in  clas- 
sification. The  acid  function  is  the  only 
property  shared  in  common  by  all  the  mem- 
bers of  the  large,  perhaps  the  largest, 
chemical  classification  of  substances,  the 
acids.  Diverse  as  their  structure  may  be, 
various  as  their  components  are,  differing 
most  widely  in  physical  properties,  in  solu- 
bility, in  state  of  aggregation,  yet  all  pro- 
ducing hydrogen  ions  under  proper  circum- 
stances, whence  hydrogen  ion  concentra- 
tion comes  to  be  the  measure  of  acidity. 
The  possession  of  this  one  function  classifies 
the  substance  as  an  acid. 

Is  there  a  corresponding  function  which 
characterises  an  Hydroxide?  Unless  we 
limit  the  term  to  the  basic  hydroxides, 
those  which,  when  soluble,  ionise  to  radical 
and  hydroxyl  ions  in  solution,  it  will  be 
difficult  to  find  one  single  common  property 
among'  hydroxyl  compounds.  Reactions 
with  phosphorus  halides,  which  are  of 
broadest  application,  will  not  suffice  defi- 
nitely to  distinguish  them  in  every  case. 

It    appears     likely    that     the    confusion 


OCTOBER  26,  1923. 


THB  CHEMICAL  NEWS. 


265 


which  has  arisen  out  of  the  idea  that  oxy- 
acids  are  hydroxides  is  due  to  lack  of  just 
this  sort  of  consideration.  This  concept 
apparently  had  its  beginnings  at  the  time 
when  chemical  theory  decided  that  water  is 
necessary  for  the  acid  function  and  the 
natural  analogy  of  both  acidic  and  basic 
oxdos  combining  with  water  to  form  in  the 
one  case  acids  and  in  the  other  bases  was 
too  alluring  for  resistance.  This  ctmclusion 
was  brought  forward  a  few  years  before 
Ai-rhenius  published  its  nvolutionising 
theory;  it  is  quite  probable  that,  had  the 
theory  of  ionisation  been  accepted  first,  no 
acid  would  ever  have  been  termed  an  hy- 
droxide. Happening  in  the  other  way, 
however,  and  in  the  face  of  the  numerous 
new  ideas  consequent  upon  the  electrolytic 
hypothesis,  the  study  of  water  combination 
was  neglected,  and  such  in ) perfect  ideas  as 
had  been  formulated  were  allowed  to  stand 
unchallenged. 

From  no  functional  point  oi  view,  then, 
can  an  oxy-acid  be  considered  to  fall  into 
the  class  of  hydroxides.  On  the  c(Hitrary, 
the  very  opposite  properties  of  acids  and 
basic  hydroxides  indicates  fiuilaniental  dif- 
ferences in  the  nature  of  the  ct)mbined  hy- 
droxyl  groups.  In  the  one  ease  the  hy- 
droxyl  group  is  split  by  ionisation,  its  hy- 
drogen appears  as  hydrion,  and  its  oxygen 
occurs  in  the  anionic  portion  of  the  electro- 
lyte. In  the  basic  hydroxides  the  hydroxy! 
ionises  as  such. 

Another  fundamental  distincticm  will  le- 
come  apparent  if  the  mechanism  of  the  re- 
action between  ionised  water  and  an  acidic 
oxide  is  compared  with  tli.tt  of  ionised 
water  with  a  basic  oxide. 

The  same  argument  applies  when  we 
consider  the  alcohols  as  hydroxides.  These, 
when  they  ionise,  yield  hydro^'cn  ions  only, 
neevr  hydroxyl  ions.  For  theoretical  rea- 
sons they  are  sometimes  considered  as 
basic  hydroxides,  yet  this  concept  cannot 
justify  itself  in  the  face  of  critical  analysis. 
Many  of  the  ideas  we  hold  concerning  the 
alcohols  are  the  result  of  the  pedagogical 
practice  of  comparing  them  w  ith  the  alka- 
line hydroxides  for  the  sake  of  impressing 
the  facts  of  organic  chemistry  upon  our  stu- 
dent minds.  True,  we  have  a  series  of 
"salts"  of  the  alkyl  radicals  and  "can 
match  the  more  important  mineral  salts 
with  examples  from  the  organic  compounds. 
But  it  is  not  difficutl  to  see  that  there  is  a 
fundamental  difEerenoe  between  the  two 
classes  of  substances.  Methyl  chloride,  to 
consider  a  well-known  alkyl    "  salt,"  is  no 


chloride  in  the  sense  that  sodium  chloride 
is ;  it  does  not  ionise  to  form  chloride  ions 
until  it  has  first  been  hydrolysed.  It  is 
rather  chloromethane,  and  this  is  the  pre- 
ferred terminolc^;  the  other  name  is  re- 
tained for  historical  and  commercial  reasons. 

In  the  phenols  the  hydroxyl  group  also 
lacks  any  basic  function,  and  here,  when 
there  is  any  ionisation,  hydrion  and  not  hy- 
droxyl ion  is  formed.  The  replacement  of 
the  phenolic  hydroxyl  by  anions  does  not  re- 
sult in  true  salts.  This  is  recognised  in  their 
nomenclature;  we  speak  now  of  chloroben- 
zene,  not  of  phenyl  chloride,  and  of  chloro- 
phenol,  not  of  salieyl  chloride  (which  in- 
deed would  be  a  quite  different  substance). 

In  the  hydroxy  organic  acids  the  hy- 
droxyl has  no  basic  functions  whatever, 
and  the  consideration  of  these  compounds 
as  hydroxides  would  lead  to  such  a  cum- 
brous nomenclature  that  the  Geneva  system 
is  much  to  be  preferred.  Yet  these  sub- 
stances must  be  included  in  the  class  hy- 
droxide unless  we  are  to  define  it  narrowly. 

In  the  nitrogen  organic  compounds  the 
presence  of  hydroxyl  is  always  of  minor  im- 
portance. Where  the  hydroxyl  is  united 
with  the  ring  nitrogen  we  have  the  pyri- 
dinium,  quinolinium,  etc.,  bases,  which  are 
true  basic  hydroxides,  analogous  with  am- 
monium hydroxide.  Hydroxyl,  substituted 
in  the  ring,  however,  becomes  phenolic  and 
is  no  longer  basic.  The  same  situation 
occurs  with  those  alkaloids  which  add  water 
to  the  basic  nitrogen  atom  to  form  true  hy- 
droxides; the  hydroxyl  so  combined  func- 
tions as  an  anionic  group.  When  the  hy- 
droxyl is  combined  with  carbon  in  the  alka- 
loidul  molecule  it  functions  as  a  phenolic  or 
as  an  alcoholic  group. 

The  phenomenon  of  amphoteric  hydrox- 
ides appears,  at  first  glance,  to  present  dif- 
ficulties in  the  way  of  limiting  the  term  hy- 
droxide to  basic  compounds.  The  hy- 
droxides of  aluminium,  zinc,  chromium, 
lead,  etc.,  dissolve  in  acids  and  in  strong 
alkalies  to  fwm,  in  the  one  event,  salts  of 
the  metal,  and  in  the  other,  compounds 
which  have  been  considered  metallic  alu- 
minates,  zincates,  chromites,  plumbates, 
and  so  on.  Creighton*  has  just  reported  the 
formation  of  metallic  salts  of  cupric  acid  by 
the  solution  of  cupric  hydroxide  in  strong 
alkalies.  As  representative  of  this  class  of 
phencMnena,  with  the  possible  exception  of 


♦  J.  Am.  Chctn.  Soo.,  45,  1237  (1923). 


266 


THE  CHEMICAL  NEWS. 


OCTOBER  26,  1923. 


the  last  case,  let  us  consider  the  case  of  alu- 
minium hydroxide. 

From  the  evidence  it  might  be  argued 
that  aluminium  hydroxide  may  behave 
either  as  an  acid  or  as  a  base  and,  indeed, 
the  term  "amphoteric"  was  coined  to  de- 
scribe just  this  condition.  If  there  is  any 
validity  in  such  an  argument  we  miust  pos- 
tulate the  dissociation  of  aluminium  hy- 
droxide in  solution,  however  slight  the  con- 
centration may  be,  into  not  only  hydrogen 
and  hydroxide  ions,  but  into  aluminium  and 
aluminate  ions.  The  mere  statement  of  the 
logical  consequences  of  the  idea  at  once  de- 
monstrates that  it  is  preposterous.  No  one 
will  to-day  question  the  conditions  which 
follow  the  solution  of  aluminium  hydrox- 
ide in  strong  acid.  There  is  agreement  that 
this  process  is  analogous  to  the  solution  of 
any  metallic  hydroxide  in  a  strong  acid. 
This  settles  the  question  of  the  basic  be- 
haviour of  aluminium  hydroxide.  What, 
then,  shall  we  say  about  the  solution  of  this 
substance  in  strong  alkaJies?  If  it  develops 
an  acid  function  we  must  postulate  disso- 
ciation of  hydrogen;  if  we  wish  to  escape 
from  this  absurdity  we  are  forced  to  deny 
the  actual  formation  of  sodium  aluminate. 

This  is  not,  of  course,  the  impasse  that  it 
appears  to  be.  The  way  out  of  the  difficulty 
lies  in  a  criticism  of  our  use  of  the  word 
solution  in  this  connection,  and  when  we 
carefully  consider  this  point  we  see  at  once 
that  we  cannot  view  the  acid  and  alkaline 
"solutions"  of  aluminium  hydroxide  as 
qualitatively  similar.  There  need  be  no 
question  of  hydrogen  ion  formation  here  at 
all,  for  we  are  really  dealing  with  a  two- 
phase  system  in  which  micels  of  aluminium 
hydroxide  surrounded  with  an  envelope  of 
.  adsorbed  sodium  ions  form  the  dispersed 
phase.  In  other  words,  the  system  belongs 
to  colloid  chemistry,  and  considerations  of 
the  formation  of  a  sodium  salt  are  quite  be- 
side the  point.  Aluminium  hydroxide  is  a 
base,  a  weak  base,  to  be  sure,  but  a  base, 
nevertheless,  and  it  is  peptised  by  sodium 
hydroxide. 

The  same  reasoning  may  be  applied  to  the 
"amphoteric"  hydroxides  of  zinc,  chro- 
mium and  lead,  which  are  dispersed  in  alka- 
line solutions  and  which  the  older  chemistry 
considered  might  form  compounds  known 
as  zincates,  chromites,.  and  plumbates.  The 
case  of  cupric  acid  cannot,  according  to 
Creighton,  be  disposed  of  in  this  way,  yet 
he  makes  no  assumption  of  the  dissociation 
of  cupric  hydroxide  to  form  hydrogen  ions, 
assuming,  rather,  that  the  cuprate    ion  re- 


ceives its  two  negative  charges  from  nega- 
tive hydroxyl  ions.  This  view  cannot,  of 
course,  aft'ect  the  truly  basic  character  of 
cupric  hydroxide. 

But  if  we  are  to  limit  the  term  hydroxide 
to  basic  compounds,  what  term  shall  we  use 
to  designate  the  larger  class  included  in  the 
broader  definition  of  the  word  ?  If  we  must 
have  some  way  of  designating  all  substances 
which  contain  hydroxyl  groups,  they  may 
conveniently  be  referred  to  as  hydroxyl 
compounds.  This,  indeed,  describes  them 
much  better  than  the  term  hydroxide,  for 
the  first  phrase  refers  definitely  to  a  struc- 
tural similarity  just  as  the  phrases  carbon- 
compounds,  nitrogen-compounds,  or  sulpho- 
oomipounds,  do,  and  without  binding  us  to 
any  specific  statement  as  to  functional 
characteristics. 

On  the  contrary,  it  may  be  urged  that  the 
term  bases  is  sufficient  for  the  basic  hy- 
droxides, and  with  some  show  of  reason. 
The  term  base  may,  however,  include  sub- 
stances which  do  not  contain  hydroxyl 
groups  and  which  do  not  react  with  water  to 
form  them.  Witness  the  "onium"  bases, 
many  of  which  do  not  form  OH. 

From  all  these  considcratuins  it  appears 
that  the  greatest  practical  as  well  as  scien- 
tific utility  will  be  served  by  the  limited 
concept  of  the  term  hydroxide. 

Bibliography. 

*  "The  Cchtury  Dictionaiy  and  Cyclope- 
dia," Vol.  5,  p.  2940  (1911). 

'  Clarke,  F.  W. :  Am.  J.  Sci.,  (3),  8,  428. 

^^  Fourcroy  and  Vauquelin :  Tromms- 
iorff  J.  d.  Pharm.,  6,  259-271,  Stiilc  2 
\1799). 

"  Fremy,  E. :  Ann.  de  Chim.  et  dc  Phys., 
Ser.  3,  23,  385  (1848). 

="•  Kolbe,  H.:  "A  Short  Textbook  of  In- 
organic Chemistry."  Trans.  Humpidge,  T. 
S.     New  York,  1884. 

^^  Mellor,  J.  W.  :  "  Modern  Inorganic 
Chemistry,"  1914. 

^^  Mellor,  J.  W.  :  "A  Comprehensive 
Treatise  on  Inorganic  and  Theoretical 
Chemistry,"  London,  1922.  Vols.  1  and  2. 
^®  Murray,  James:  "A  New  English  Dic- 
tionary on  Historical  Principles,"  5,  491. 

^'  Nuttall,  P.  A.:  "'Dictionary  of  Scienti- 
fic Terms,"  1885. 

^^  Richter,  V.  von:  "Textbook  of  Inor- 
ganic Chemistry,"  Am.  Ed.  5.  Trans. 
Smith,  E.  F.     Philadelphia,  1900. 

**  Roscoe:  "Kiirzes  Lehrbvch  dcr 
Cheviic,"  1873,  Ed.  4. 


6CT0BBB  26,  1923. 


THE  CHEMICAL  NEWS. 


26? 


■■••''  Williamson,  A.  W.  :    Chcni.    Gaz.,    9, 

"  Gorham,  J.  :  "The  Elements  of  Chemi- 
cal Science."    Boston,  1819. 

2«  "Justus":  NichoLson',^  J.,  28,  67 
(1811). 

"  Kolbe,  H.:  J.  Chem.  Soc,  4,  41-79 
(1852). 

^^  Macquer,  P.  J.  :  "Dictionairc  do 
Chemie."    Paris,  1778. 

"  Muir,  M.  M.  P.:  In  Walt's  "Diction- 
ary of  Chemistry,"  Ed.  1880,  Vol.  2,  pp. 
703-706. 

="  Perkin,  W.  H.:  J.  Chen.  Soc,  777 
(1886). 

Watts,  H.  :  "Fownes  Manual  fJ,eS(x} 

**  Watts,  H. :  "Dictionary  of  Chemistry" 
(1864),  3rd  Supplement,  1881. 

"  Williamson,  A.  W.  :  J.  Chem.  Soc  .  17 
421  (1864). 


GENERAL  NOT  I  < 


GEH.MA.NY'S  TRADE  ANJ^  nSi^Ooiia 
IN  SEPTEMJ3ER. 

Tho  Commercial  Secretary  at  Berlin  (Mr. 
J.  W.  F.  Thelwall)  has  forwarded  to  the 
Department  of  Overseas  Trndf  a  review  of 
Germany's  trade  and  industry  during  Sef)- 
tember. 

The  devastating  effect  of  the  occupation 
and  separation  of  the  Khini  Imd  and  the 
Ruhr  district  may  now  Ix  seen  in  all 
branches  of  German  industry  The  heavy 
fall  of  the  murk  as  a  result  jnuinly  thereof 
caused  a  great  increase  in  tlic  prices  of  all 
materials  nnd  in  wages;  and  as,  owing  to 
the  too  substantial  and  rapi<l  currency  de- 
preciation, it  was  impossible  for  industry  to 
obtain  the  requisite  capital,  the  existing 
shortage  of  capital  and  credit  in  trade  and 
industry  was  greatly  accentuated  in  the 
month  under  review,  particularly  as  the 
Reichsbank  were  compelled  by  circum- 
stances to  restrict  the  granting,'  of  credit  still 
further.  Partly  for  these  reasons,  and  also 
owing  to  the  heavy  burden  of  taxation,  the 
world's  market  pnces  were  k  ached  or  ex- 
ceeded in  more  and  more  siplures  of  trade 
and  industry.  The  consequences  were  in- 
creased stagnation  in  sales  and  further  re- 
strictions of  work. 

The  reports  of  the  Chambers  of  Com- 
merce show  that,  although  further  largo 
portions  of  trade  and  industry  have  gone 
over  to  the  system  of  calculating  prices  in 
gold  marks,  no  final  solution  of  the  diffienl- 
ties  presented  by  the  cum  luy  depreciation 
has  been  arrived  at  so  long  as  a  stable  cur- 


rency depreciation  has  been  arrived  at  so 
long  as  a  stable  currency  has  not  been 
created,  enabling  all  branches  of  industry, 
including  the  retail  trade,  to  fix  prices  on  a 
stable  basis  and  to  ensure  the  counter-value 
for  deliveries  and  services. 
Mining. 

In  the  Central  German  brown  coal  dis- 
trict the  output  incri  ased  as  compared  with 
tho  preceding  month,  which  was  affected  by 
strikes.  The  demand  for  raw  coal  declined 
towards  the  end  of  the  month.  The  produc- 
tion of  wet  f)ress  bricks  came  to  a  standstill 
in  September.  The  call  for  briquettes  was 
greatly  restricted,  so  that  it  was  necessary, 
in  part,  to  produce  for  stock.  Coal  prices 
rose  in  the  period  from  the  1st  to  the  10th 
of  September  in  proportion  to  the  advance 
in  wages  suid  salaries  and,  in  virtue  of  the 
negotiations  in  the  Reich  Coal  Council, 
were  fixed  on  a  gold  mark  basis  as  from 
September  17.  In  fixing  wages,  arbitration 
was  twice  resorted  to. 

In  Upper  Silesia  the  pit  coal  production 
fell  off,  as  there  were  two  less  working  days 
in  September  as  compared  with  the  preced- 
ing month.  Strike  movements  in  various 
pits  also  interfered  with  production.  As  in 
the  other  coal  districts,  the  calculation  of 
coal  prices  in  gold  marks  was  introduced  in 
Upper  Silesia  as  from  September  17.  Cal- 
culati(m  in  gold  marks  was  urgently  neces- 
sary, as  the  heavy  losses  resulting  from  the 
former  paper  mark  prices,  owing  to  the 
rapid  currency  depreciation,  could  no  longer 
be  borne  by  the  pits.  In  consequence  of  an 
anticipated  substantial  rise  in  prices,  the 
demand  for  coal  increased  at  times,  but,  in 
general,  it  was  exceedingly  weak,  mainly  in 
view  of  the  lack  of  working  capital  in  in- 
dustry and  of  the  want  of  purchasing  power 
on  the  part  of  household  coal  consumers. 
Potash. 

In  the  potash  industry  there  were  fewer 
sales  than  in  the  previous  month.  Shifts 
ha<l,  in  cMisequence,  to  be  dropped,  and 
the  dismissal  of  workers  could  no  longer  be 
avoided.  Potash  prices  were  repeatedly  in- 
creased, but  in  no  way  kept  pace  with  the 
advance  in  prices  of  all  materials,  fuel,  and 
explosives,  and  with  the  rise  in  wages  and 
salaries.  Agriculture  held  back  with  orders 
on  account  of  lack  of  money.  Only  sul- 
phate of  potash  products  could  be  sold  to  a 
certain  extent  to  foreign  countries,  fre- 
quently, howeviT,  only  at  a  loss  in  con- 
sideration of  the  position  of  the  world's  mar- 
ket prices.  A  large  ipart  of  the  production 
had  to  be  taken  into  stock. 


268 


THE  CHJSMICAL  NEWS. 


OCTOBER  26,  1923. 


Petroleum. 

In  the  petroleum  industry  the  profits  of 
the  works  declined  in  consequence  of  the  in- 
crease in  wages  and  costs.  The  degree  of 
employment  continued,  however,  satisfac- 
tory. Owing  to  long-dated  contracts  for  de- 
livery, sales  are  ensured  for  some  time 
ahead. 

Metal  Industry. 

The  metal  market  was  adversely  affected 
by  the  general  situation.  .  German  metal 
prices  have,  in  part,  risen  above  the  world's 
market  level.  This  applies  specially  to  lead. 
The  metal  industry  continued  to  limit  its 
purchases  and  only  to  cover  absolutely  es- 
sential requirements,  with  the  result  that  a 
minimum  amoun,t  of  business  was  trans- 
acted in  the  month  under  review. 

Aluminium  Industry. 
In  the  aluminium  industry  in  Luden- 
scheid  and  neighbourhood,  employment  was 
poor.  Inland  and  foreign  sales  were  bad, 
as  the  purchasing  power  of  the  inlarid  popu- 
lation has  declined  still  further,  and  increas- 
ing foreign  competition  renders  export  more 
and  more  difficult.  The  Customs  policy  of 
foreign  countries  also  hampered  export. 
The  same  applies  to  other  products  of  the 
Ludenscheid  finished  metal  goods  industry. 

ELectrical  Industry. 
The  position  of  the  electrical  industry  be- 
came worse,  particularly  as  the  cutting  off 
of  the  occupied  territory  has  greatly  re- 
stricted the  market  for  its  products.  Cus- 
tomers could,  in  part,  no  longer  raise  the 
requisite  capital  for  new  orders.  Practi- 
cally no  extensions  of  industrial  plant  and 
overland  power  stations  are  being  carried 
out.  Prices  have  exceeded  those  of  the 
world's  market. 

Chemical   Industry. 

Foreign  sales  of  chemical  preparations 
have  declined  to  an  alarming  extent.  The 
existing  stock  of  orders  is  considerably 
below  that  which  is  normally  on  hand,  both 
as  regards  quantity  and  value.  In  the  in- 
terests of  the  workers,  restrictions  of  opera- 
tions have,  so  far,  not  been  introduced, 
though  this  will  be  difficult  to  avoid  in  the 
event  of  the  continuance  of  present  condi- 
tions. 

Glass  Industry. 

Employment  in  the  sheet  and  hollow 
glass_  industry  fell  o.ff.  The  shortage  of 
working  capital  and  the  exceptionally  high 
rate  of  interest  for  bank  credits  rendered 
production  very  much  more  difficult.  The 
industry  was  forced  to  go  over  to  calculation 
in  gold  marks.    Inland  and  foreign  sales,  in 


consequence,        were     quite     unimportant. 
Prices  obtainable    abroad  were  so  low  that 
th^  works  were,    in  part,,  not  even    able  to 
secure  half  the  absolutely  necessary  inland 
price. 

Paper  Industry. 

The  position  of  the  Berlin  envelope  in- 
dustry became  worse.  Still  fewer  orders 
were  received,  and  the  number  of  workers, 
who  had  latterlv  been  working  only  three 
days  a  week,  had,  therefore,  to  be.  again  cut 
down.  The  shortage  of  money  would  not 
permit  of  any  new  purchases  of  raw 
materials.  The  available  stocks,  so  long  as 
they  lasted,  were,  therefore,  worked  up. 
Wages  rose  very  considerably.  In  conse- 
quence, it  appeared  doubtful  whether  it 
would  be  possible  to  continue  work  for  even 
two  or  three  weeks  longer. 

The  entire  German  printing  industry 
found  itself  in  a  serious  position.  All  firms 
in  the  type-founding  industry  had  been 
working  short  time  since  September  1,  the 
majority  only  24  hours.  The  position  of 
the  newsipaper  printing  works  was  the  most 
difficult.  That  of  the  jobbing  and  book 
printers  was  similar;  it  was  only  with  the 
greatest  effort  that  they  were  able  to  raise 
sufficient  money  for  the  payment  of  wages, 
salaries,  and  for  the  purchase  of  printing 
paper.  Orders  from  abroad  came  in  spar- 
ingly, as  the  chief  markets,  Switzerland, 
Holland  and  Scandinavia,  owing  to  the 
general  dullness  of  business  prevailing  there 
also,  were  no  longer  very  capable  of  pur- 
chasing. There  is  no  prosipect  of  an  im- 
provement in  the  situation.  It  is  more 
likely  that  further  considerable  restrictions 
of  work  will  have  to  be  reckoned  with  in  the 
immediate  uture,  as,  in  view  of  the  difficult 
economic  conditions  generally,  firms  are  not 
in  a  position  to  work  for  stock.  Zinco- 
graphic  works  also  have  been  working  half- 
time  for  weeks.;  besides  the  curtailment  of 
hours,  dismissals  have  also  had  to  be  re- 
sorted to. 

Leather  Industry. 

The  prices  for  raw  hides  and  skins  ad- 
vanced 40-50  fold,  as  compared  with  the 
preceding  month,  in  proportion  to  the  cur- 
rency depreciation.  As  a  result  of  the  diffi- 
cult financial  conditions,  only  the  most 
necessary  requirements  were  covered.  There 
was  a  brisker  demand  solely  for  ox  and  cow 
hides  and  calf  skins.  On  the  leather  mar- 
ket business  was  stagnant  practically  the 
whole  of  the  month.  The  position  on  the 
boot  and  shoe  market  was  still  worse,  as, 
owing  to  the  rapidly  increasing  prices, 
buyers  were  almost  completely  absent. 


OCTOBER  26.  1923. 


THE  CHEMICAL  NEWS. 


269 


DISINFECTANT  FLUID  FOR  SOUTH 
AFRICA. 

Mr.  W.  G.  Wickhain,  H.M.  Senior  Tr a di' 
Comniissioner  in  South  Africa,  reports  that 
the  South  African  Railway  Adini^stration 
are  calling  for  tenders  for  the  supply  of  dis- 
infectant fluid  during  the  period  January  1, 
1924,  to  June  30,  1924.     (Tenrld-  No.  482.) 

A  copy  of  the  tender  form,  specification, 
ind  conditions  of  tender  is  available  for  in- 
pection  by  United  Kingdom  firms  at  the 
i)epartment  of  Overseas  Trade,  35,  Old 
Queen  Street,  London,  S.W.I.  (Ref.  No. 
12337  E.D./C.C.  (2). 

The  South  African  Rail\v;iy  and  Har- 
bours are  calling  for  tenders,  t(j  be  presented 
by  November  12,  1923,  for  the  supply  of  red 
oxide  paint  in  paste,  duriiii,'  the  jHjriod 
January  1  to  June  30,  1924.  (Tender  No. 
484.) 

A  complete  set  of  documents  comprising 
general  conditions  of  stores  contracts,  ten 
dor  form  and  specification  may  be  inspectcii 
at  the  Dept.  of  Overseas  Tracle. 


CHEMICALS  (COAGULANTS)  FOR 
SOUTH    AFRICA. 

The  Rand  Water  Board  are  calling  fo; 
tenders  (contract  No.  249)  for  the  suji' 
and  delivery  of  150  short  tons,  or  ait  i 
natively  300  short  tons,  aluminium  sulphate 
or  alumino- ferric,  on  or  before  noon  on  Fri- 
day, November  9,  1923.  Reference  No. 
12342/E.D./C.C./2. 


BRITISH  EMPIRE  CAXrFT? 
CAMPAIGN. 

PROQUESS  OF  THE  ApPK AL. 

By  consent  of  the  Ministry  of  Health  and 
the  Stationery  Office,  the  organisers  of  the 
British  Empire  Cancer  Campaign  have 
acquired  the  right  to  publish  the  reccntlv 
issued  report  of  the  Ministry  of  HealtK 
Committee  on  Cancer.  This  will  shortly  hr 
available,  and  to  be  obtained  fiio,  on  appli- 
cation to  the  Secretary.  British  Empire 
Cancer  Campaign,  19,  Berkeley  Street. 
W.l.  Other  literature  in  the  form  of  leaf- 
lets, pamphlets,  etc.,  is  also  available  for 
distribution,  and  applications  from  nil  who 
desire  information  on  the  objects  of  the 
campaign  will  be  readily  complied  with. 

Preparations  are  well  advanced  for  an  in- 
tensive campaign  throughout  the  country, 
which  will  be  conducted  through  the  local 
branches  of  the  Red  Cross,  and  will  culmi- 
nate in  a  "Cancer  Week"  to  be  held  early  in 
1924. 

An  interesting  feature    of  recent    collec- 


tions has  been  the  ready  response  to  aip- 
pcals  made  from  the  stage  by  popular  music 
hall  artistes.  The  Holborn  branch  of  the 
Red  Cross  has  organised  collections  at  the 
Holborn  Empire  and  other  music  halls  of 
the  Gulliver  circuit.  Miss  Marie  Kendall, 
Miss  Lucille  Benstead,  and  other  well- 
known  performers  have  addressed  their 
audiences  during  the  interval,  and  alto- 
gether about  i;l,000  has  been  collected  by 
these  means  in  the  past  few  weeks. 

Subscriptions  to  the  Campaign  Fund  con- 
tinue to  be  received  in  a  steady  stream  at 
the  offices  of  the  British  Red  Cross  Society. 
A  veiy  much  larger  sum,  however,  is  re- 
quired if  the  aims  of  the  Campaign  are  to  be 
carried  out  speedily.  Subscriptions  should 
be  sent  to  the  Hon.  Arthur  Stanley,  G.B.E., 
C.B'.,  M.V.O.,  British  Red  Cross  Society, 
19,  Berkeley  Street,  W.l,  or  to  any  of  the 
branches  of  Lloyd's  Bank. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


ROYAL  MICROSCOPICAL  SOCIETY. 
20,  Hanovrr  Sqitarb,  London,  W.l. 

PrcRidcnt :     Professor  Frederic  J-  Cheshire, 

C.B.E.,  F.Innt.P. 
Hon.    Secrefarieif.      Joseph      E.    Barnard, 
F.Inst. P.,  James  A.  Murray,  M.D. 

The  section  of  the  Society  which  has  been 
formed  to  deal  with  the  Industrial  Applica- 
tions of  the  Microscope, *and  to  assist  in  the 
•  lopment  of  Industrial  Research  in 
i-  ish  Industries,  held  a  meeting  on  Octo- 
ber 2\. 

Progr.vmme. 

7.0  p.m. — E.xhibits  and  Practical  Demon- 
strations of  new  and  improved  instruments 
and  apparatus  of  interest  to  those  engaged 
in  the  Industries  and  to  Microscopists  gener- 
ally. 

8.0  p.m. — Communications:  — 

Professor  F.  J.  Cheshire,  C.B.E., 
P.R.M.S.,  presided. 

Mr.  J.  E.  Barnard,  F.Inst.P.,  F.R.M.S., 
delivered  the  first  of  a  series  of  Lecture  De- 
monstrations, which  embodied  a  practical 
course  of  instruction  in  the  Manipulation  of 
the  Microscope.  Detailed  syllabus  of  these 
lecture  demonstrations  may  be  had  on  ap- 
plication. 

Lecture  1. — The  work-table  of  a  micro- 
scopist  who  requires  an  ever- ready  equip- 
ment. Illuminants  suitable  for  various 
classes  of  work. 


270 


THE  CHEMICAL  NEWS. 


t 


OCTOBER  26,  1923. 


Dr.  Marie  C.  Stopes,  D.Sc,  Ph.D., 
F.L.S. :  The  Microscopy  of  Recent  Coal  Re- 
search. 

Future  meetings  will  be  held  as  follows : 
November  28 :  Dr.  Sidney  H.  Browning, 
L.R.C.P.,  M.R.C.S.,  F.R.M.S.,  The  Appli- 
cation of  the  Microscope  to  Industrial  Dis- 
eases. 

January  23 :  Sir  Robert  A.  Hadfield, 
Bart.,  D.Sc,  F.R.S.,  F./nst.P.,  F.R.M.S., 

will  preside. 

Captain  J.  W.  Bamfylde,  Some  Failures 
in  Steel  as  revealed  hy  the  Microscope  and 
recorded  by  Photography. 

Mr.  H.  B.  Milner,  M.A.,  D.LC, 
F.G.S.,  A.M.I.P.T.,  The  Use  of  the  Micro- 
scope in  the  Petroleum  Industry. 


GEOGRAPHICAL  SOCIETY  OF 
LONDON. 

The  next  meeting  of  the  Society  will 
take  place  on  Wednesday,  November  7,  at 
5.30  p.m.,  when  the  following  communica- 
tions will  be  read:  — 

On  the  Skeleton  of  Iguanodon  atherfiel- 
DENSis  sp.  nov.,  from  the  Wealden  Shales  of 
Atherfield  {Isle  of  Wight),  by  the  late  Regi- 
nald Walter  Hooley,  F.G.S. 

[Dr.  A.  Smith  Woodward,  F.R.S.,.  has 
consented  to  read  this  paper,  and,  by  kind 
permission  of  Mrs.  Hooley,  the  skeleton  of 
I.  atherfieldensis  will  be  exhibited  in  the 
meeting  room.  Dr.  Smith  Woodward  will 
probably  contribute  some  general  remarks 
on  the  genus  Iguanodon.] 

The  Igneous  Rocks  of  the  Tortworth  In- 
lier,  by  Prof.  S.  H.  Reynolds,  M.A., 
Sc.D.,  F.G.S. 


THE  CHEMICAL  SOCIETY. 

Paipers  read  at  the  Ordinary  Scientific 
Meeting,  held  on  October  18:  — 

The  Chemistry  of  the  glutaconic  acids. 
Part  XV. :  Three-carbon  tautomerisryi  in  the 
cyclopropane  series.  Part  2.  By  F.  R. 
Goss,  C.  K.  Ingold,  and  J.  F.  Thorpe. 

Further  experimental  evidence  was 
brought  forward  that  the  tautomeric  rela- 
tionship of  the  three  isomeric  esters  of  cy- 
clic glutaconic  acid  is  such  that  after  the 
mobile  hydrogen  atom  has  passed  into  the 
carboxyl  group,  as  in  the  enol-ester,  it  can- 
not return  to  the  position  which  it  takes  up 
in  the  normal  ester  directly,  but  only  by 
way  of  its  position  in  the  labile  ester,  i.e., 
on  the  a-carbon  atom  of  the  system,    which 


forms  a  halting  place  in  the  two  stage  mi- 
gration. 

In  view  of  the  apparent  impossibility  of 
reducing  the  acid  to  a  saturated  cyclopro- 
pane acid,  the  converse  process  has  been 
studied.    The  acid 

.CHCO,H 

GHaCnr'^l 

^CHCOaH 

has  been  isolated  in  its  three  possible  stereo- 
isomeric  modifications,  and  a  double  bond 
has  been  introduced  into  each.  In  each  case 
the  product  is  a  cyclic  glutaconic  acid. 

Studies  of  Elcctrovalency.  Part  III.  : 
The  Catalytic  Activation  of  Molecules  and 
the  Reaction  of  Ethylene  and  Bromine,  by 
R.  G.  W.  NoRRisn. 

The  hypothesis  was  advanced  that  mole- 
cular activation  is  at  least  partly  a  catalytic 
process  consisting  in  the  polarising  of  the 
reactant  molecule  by  association  with  the 
molecule  of  a  polar  catalyst,  either  in  a 
gaseous,  surface,  or  liquid  phase.  Dowry's 
view  that  the  molecules  of  unsaturated  or- 
ganic compounds  which  are  unreaetive  in 
their  resting  form  may  become  reactive  by 
developing  an  electro-valance  in  the  double 
bond,  is  a  special  form  of  this  hypothesis  in 
which  the  complete  ionisation  of  the  bond  is 
postulated.  The  hypothesis  was  tested  by 
investigating  the  reaction  between  ethylene 
and  bromine.  The  dried  gases  practically 
ceased  to  react  when  enclosed  by  "non- 
polar"  walls  of  paraffin  wax,  but  reacted 
rapidly  when  enclosed  by  a  "polar"  surface 
of  glass,  stearic  acid  or  cetyl  alcohol.  The 
reactivity  of  the  gases  as  measured  by  the 
bimolecular  velocity  constant  varies  with 
the  chemical  nature  of  the  enclosing  sur- 
face, being  greatest  for  stearic  acid.  On 
passing  diy  "ethylene  and  bromine,  diluted 
with  air,  through  a  paraffined  tube,  and 
then  through  a  glass  tube,  no  ethylene  di- 
bromide  was  observed  in  the  paraffined 
tube,  while  about  0.3  gm.  collected  in  the 
glass  tube. 

Selenium,  Trioxide  and  Chlorselenic  Acid, 
by  R.  R.  Le  G.  Worsley  and  H.  B.  Baker. 

The  action  of  ozone  on  dry  selenium  had 
already  been  shown  to  produce  only  the  di- 
oxide, but  by  the  use  of  a  solvent  this  agent 
has  carried  the  oxidation  a  stage  further 
and  selenium  trioxide  has  been  isolated. 
The  solvent  used  was  selenium  oxychloride, 
which  when  alone  was  unaffected  by  ozone. 
The  solution  of  selenium  in  the  oxychloride 
showed  little  or  no  apparent  change  T)y 
treatment  with  7  per  cent,  ozone  for  30 
hours,  but  after  this  the  trioxide  separated 


OCTOBEK  26,  1923. 


THE  CHEMICAL  NEWS. 


271 


out  in  considerable  quantity.  Analysis 
showed  62.01  per  cent,  of  s.  i,-niuni,  SeOj 
requiring  62.26.  The  niolceniar  weight  by 
lowering  of  the  freezing  point  of  phosphorus 
oxychloride  was  found  to  be  136.  Selenium 
trioxide  is  a  very  pale  yellow  powder  of  den- 
sity 3.6.  It  decomposes  at  120°  without 
melting  or  subliming.  It  dissolves  in  water 
with  evolution  of  heat,  but  is  insoluble  in 
ether  and  other  common  solvt  nts.  It  com- 
bines directly  with  dry  hydrogen  chloridt, 
prfxlucing  chlorselenic  acid,  whi(^  is  very 
similar  to  chlorsulphonic  acid.  Analysis 
and  molecular  weight  determinations  con- 
firm the  existence  of  the  new  acid. 

The  Chemistry  of  Pohjcyrlic  SiructureH 
in  Relation  to  their  HoinocjirHc  Unsatura- 
ted Isomcrides.  Part  V.  :  Orirntatiun  in 
the  gem-dimethyl-dicyc\opent  ine  series,  by 
R.  C.  Grimwood,  C.  K.  Ingoi.i),  and  J.  F. 
Thorpe. 

The  proof  adduced  by  recent  experiments 
that  derivatives  of  dimethylr//r/6pt»nta(liene 
are  tautomeric  with  corresponding  deriva- 
tives of  dimethyldicj/c/oipenl«  lie,  and  that 
the  nucleus  of  each  substancr  of  the  series 
possesses  two  distinct  phases  \\  hich  together 
confer  on  the  compound  a  liial  chemical 
character,  raises  certain  problems  of  struc- 
ture, principally  relating  to  tin-  orientation 
of  attached  groups,  whioli  n  (juire  special 
methods  for  their  solution. 

^  CH  =  CH  CH— CH 

(I)    CMe,  \  I         CMr ,  ^  I  II 

OH  =  CH  ^CH— (H 

Thus  there  are  two  positions  in  which 
the  sodio-ester  might  methylate  on  carbon. 

It  was  shown  that  the  substance  has 
formula 

<C(C02Et)  CMeCO,Et 
I  I 

C(COjEt)00 


THYSICS  IN  THE  TEXTILE 
INDUSTRIES. 

The  fifth  of  the  series  of  public  lecture* 
on  "Physics  in  Industry"  being  given  under 
the  auspices  of  the  Institute  of  Physics  will 
deal  with  this  subject. 

The  lecture  was  delivered  by  Dr.  A.  E. 
Oxley,  Physicist  to  the  British  Cotton  In- 
dustries Research  Association,  at  the  Insti- 
tution of  Electrical  Engineers,  Victoria 
Embankment,  London,  on  Monday,  Octo- 
ber 22,  at  5.30  p.m. 

The  chair  was  taken  by  Sir  Charles 
Parsons,  K.C.B.,  F.R.S.,  who  has  just  suc- 
ceeded Sir  J.  J.  Thomson  as  President  of 
the  Institute. 


CORRESPONDENCE. 


DOES  CANADA  PREFER  FRANCE? 

(F^oM  Lt.-Co.m.  F.  W.  Astbury,  M.P.) 

To  the  Editors  of  The  Chemic.\l  News. 

Sirs, — Before  the  Overseas  Premiers  re- 
turn from  the  Imperial  Conference  to  their 
various  Dominicms,  it  would  be  useful  if  we 
could  all  come  to  a  clearer  understanding 
about  the  policy  underlying  the  Franco- 
Canadian  Convention,  which  came  into 
force  at  the  beginning  of  last  month.  The 
effect  of  certain  concessions  made  by 
Canada  in  that  agreement  to  France  has 
been  to  reduce  the  preference  on  British 
goods  as  compared  with  French,  a  trading 
advantage  which  at  the  moment  is  being 
very  considerably  emphasised  by  the  cheap- 
ness of  the  franc. 

The  first  result  of  the  situation  is  most 
interesting.  A  syndicate  of  French  manu- 
facturers have  already  set  up  in  Canada  a 
dye-house  where  grey  goods  imported  under 
the  Convention  may  be  coloured  in  the 
Dominion.  A  needless  blow,  that  is  to  say, 
is  being  delivered,  not  only  at  our  textile 
trades,  but  at  British  dyestufis  precisely 
when  this  young  industry  is  taking  the  road 
to  real  prosperity. 

The  frank  opinion  of  the  Imperial  Con- 
ference u{>on  the  whole  question  would  cer- 
tainly be  illuminating.  New  Zealand's 
views  would  in  particular  be  valuable,  for 
there  a  "depreciated  currency  duty"  has 
just  been  adopted  to  allow  Britons  a  reason- 
able chance  of  competing  for  business  in 
British  markets. — Yours,  Ac, 

Fred  W.  Astbury. 

14,  8t.  Peter's  Square,  Manchester. 
October  15,  1023. 


PROPORTIONALITY  AND  HEAT  OF 
FORMATION. 

To  the  Editors  of  The  Chemical  News. 

Sirs, — Last  year,  Mr.  Hawksworth  Col- 
lins had  a  paper  in  The  Chemical  Neus 
(CXXV.,  81  and  07).  dealing  with  some 
thermo  chemical  data.  In  conjunction  with, 
some  previous  communications  of  mine,  I 
would  like  to  point  out  that  the  law  he  indi- 
cates is  in  application  to  compounds  ob- 
tained as  gases.  Heat  of 

Formation. 

^    )  3  v   =  2  68,360 


H' 

H— O 

I 
H— O 


4  v   =  8 


45.300 


272 


THE  CHEMICAL  NEWS. 


OCTOBER  26,  1923. 


In  water,  the  change  of  volume  on  com- 
bining is  one-third,  the  gas  vokunes  are 
2  V  H  +  1  V  0,  and  in  hydrogen  peroxide 
2  V  H  +  2  V  0.  Before  combining,  a  gas 
volume  4  would  become  less  on  combina- 
tion should  hydrogen  peroxide  behave  simi- 
larly to  water,  as  its  heat  of  formation  indi- 
cates. Should  the  reduction  in  volume  be, 
say,  one-fourth,  from  the  similarity  of  struc- 
ture of  the  compounds  and  in  four  volumes, 
2  H  +  2  O  becoming  3  v  hydrogen  peroxide, 
the  product  of  molecular  weight  and  change 
of  volume  is  j  x  34  =  8.5;  in  water  it  is 
1-  X  18  =  6,  and  is  sufficiently  close  in  pro- 
portionality to  the  heats  of  these  compounds 
as  given  in  the  above  table. 

It  is  sufficient  to  lend  strong  confirmation 
to  the  views  expressed  by  Mr.  Collins  from 
the  information  in  his  table  as  applying  to 
these  compounds. — Yours,  &c.. 

J.  C.  Thomlinson,  B.Sc. 


NOTICES  OF  BOOKS. 
Radio -ActiviUj,  by  K.   Fajans,   Profes- 
sor of  Physical  Chemistry  in  the  Univer- 
sity   of    Munich,    translated    by    T.     S. 
Wheeler,    B.Sc,    A.R.C.Sc.I.,    A.I.C, 
and   W.    G.    King.       Pp.    XII.    +    138. 
Messrs.  Methuen  &  Co.,  Ltd.,  36,    Essex 
Street,  W.C.2.     1923.    8s.  6d.  net. 
The    subject    of    Radio-Activity  has    de- 
veloped,   and  is  still  developing  so  rapidly, 
that  the  treatises  which  gave  the  latest  in- 
formation on  this  Science  a  year  or.  two  ago 
are    already     incomplete.       Prof.     Fajans' 
volume,    now    translated    into    English    by 
Messrs.    Wheeler  and  King,    although  very 
complete  in  itself,    comes  as  a  kind  of  sup- 
plement   to  the    earlier    works    on    Eadio- 
Activity. 

The  book,  which  is  very  readable  and  can 
be  easily  understood  by  all  who  possess  an 
elementary  knowledge  of  chemistry  and 
physics,  surveys  the  whole  field  of  Eadio- 
Activity..  It  opens  with  a  study  and  classi- 
fication of  the  Elements  prior  to  the  dis- 
covery of  the  radio-active  transformations. 
Thef  three  radio-active  series  are  then 
described,  and  an  account  is  given  of  the 
chemical  properties  of  the  radio-elements. 

There  is  also  a  short  chapter  on  the  Dis- 
placement Laws  and  their  application.  The 
significance  of  the  isotopic  varieties  of  lead 
as  the  end  products  of  the  disintegrations  is 
emphasised.  Recent  important  work  on 
Isotopy  in  other  elements,  its  detection  by 
the  positive  ray  method,  attempts  to  separ- 
ate isotopes  and  their  general  properties 
are  all  disoussed. 


I  Prof.    Fajans    has    himself    made    many 

valuable  contributions  towards  the  elucida- 
tion of  the  phenomena  of  Radio-Activity, 
but  he  has  largely  confined  himself  to  an 
exposition  of  the  results  of  others,  and  his 
name  does  not  even  appear  in  the  index. 
The  importance  of  his  Monograph  may  be 
gathered  from  the  fact  that  it  has  gone 
through  four  editions  in  the  original  (the 
translation  is  based  on  the  fourth  German 
edition),  and  should  pass  through  several 
English  editions. 

The  translation  has  been  M-ell  done,  the 
illustrations  have  been  well  chosen,  and  the 
publishers  have  done  their  part  well. 

BOOKS  RECEIVED. 

Kelly's  Directory  of  the  Chemical  Indus- 
tries. Pp.  XXX.  +  903.  1923.  Kelly's 
Directories,  Ltd.,  186,  Strand,  W.C.2.  3bs. 

Treatise  on  General  and  Industrial  Or- 
ganic Chemistry,  by  Dr.  Ettore  Molinari. 
Pp.  VIII.  +  457  to  897.  Second  English 
Edition,  Part  II.  1923.  Messrs.  J.  &  A. 
Churchill,  7,  Great  Marlborough  Street, 
W.l.     308.  net. 

The  Electron  in  Chemistry,  by  Sir  J.  J, 
Thomson,  O.M.,  F.R.S.  Pp.  144.  1923. 
J.  B.  Lippinoott  Company,  Philadelphia. 

The  Expert  Witness,  by  C.  A.  Mitchell, 
M.A.,  F.I.C.  Pp.  XV.  +  188.  1923. 
Messrs.  Hefler  &  Sons,  Ltd.,  4,  Petty  Cuey, 
Cambridge.     Ts.  6d.  net. 


x'His  list  is  specially  compiled  for    The  Chemical 

News,  by  Messrs.  Eayner  &  Co.,  Registered  Patent 

Agents,  of  5.  Chancery  Lane,  London,  from  whom 

all  information  relating  to  Patents,  Trado  Marks, 

and  Designs  oan  be  obtained  gratuitonsiy. 

Latest  Patent  Applications. 

24495— Fa r1)onfabriken  vorm.     F.     Bayer     &  Co.— 
Manufacture  of  silicic  acid  gels.    Oct.  2. 

24367— King,   P.  H.— Method  of  retarding  oxidisa- 
tion in  gums  and  resins.    Oct.  1. 

24477— Monterumici,   R.— Preparation  of   magnesia 
hydrate.    Oct.  2. 
Specifications   Published   this    Week. 

204223— McDougall,  I.,  and  Howies,  P.- Process 
for  the  manufacture  of  lead  arsenate. 

192376— National  Aniline  &  Chemical  Co.,  Inc.— 
Alkylation  and  aralkylation  of  carbazol. 

197690— Soc.  d'Etudes  Chimiquos  Pour  Tlndustrie. 
Abstract  Published  this  Week.  ■ 
amide  of  manures     containing  soluble  or- 
ganic nitrogen. 

203709— Jouve,  A.  J.  B.,  Helbronner,  A.,  and  Soc. 
Hydro-Electrique  &  Metallurgique  du 
Palais.— Manufacture  of  chromates  and 
bichromates. 

—Process  for  the  manufacture  from  cyan- 
-Lignone  derivatives;  cellulose;  sulphurous 
acid.- Cross,  C.  F.,  of  3,  New  Court,  Lin- 
coln's Inn,  London,  and  Engelstad,  A.,  of 
Vardol,  Norway. 


202016- 


NOVEMBER  2,  1923. 


THE  CHEMICAL  NEWS. 


273 


THE   CHEMICAL  NEWS, 


VOL.  CXXVII.       No.  3316. 


ARE  THE  NATURAL  GROUPINGS  OF 

THE  ELEMENTS  AND  THE  SPECTRAL 

LINES  OF  HYDROGEN  P.ELATED? 

Part  II. 

By  F.  H.  Loring. 

In  this  Journal  of  October  20,  1923,  pages 
257-259,  the  subject  as  indicated  by  the 
iibove    title    was    tentatively  d,    it 

being  shown  that  the  a,  ft,  y,  <  lines 

of  hydrogen  were  directly  rehticd  to  certain 
natural  groups  and  grouping's  of  the  ele- 
ments represented  by  a  series  of  five  num- 
bers, so  that  from  these  emission  lines  the 
said  numbers  could  be  derived.  It  is  pro- 
posed to  designate  these  groups  and  group 
ings  by  the  above  Greek  letters,  as  shown  in 
the  seheme  at  the  conclusion  of  this  pari  of 
the  paper.  The  scheme  also  s<  rves  to  sum- 
iiiarise  the  main  features  involved  in  this 
study. 

The  subject  merits  wider  treatment,  as, 
indeed,  in  principle  it  is  a  v<  -  y  interesting 
problem.       Before,    however.  the 

matter  further,  the  following  may 

be  noted: — If  the  relationship  in  question 
holds,  then  one  could  say  with  some  truth 
that  the  law  of  the  part  in  the  law  of  the 
whole,  and  therefore  the  hydrogen  atom  in 
a  part  of  every  element  taken  in  the  atomic 
sense;  and  Prout's  hypothesis  is  true.  The 
word  is  in  this  statement  may  carry  an 
added  meaning,  such  as,  ta  convertible  into. 

Prof.  Eddington,  in  his  "  Mathematical 
Theory  of  Relativity,"  gives  expression  to 
a  significant  idea,  viz. :  "  This  suggests 
striving  for  an  ideal — to  show,  not  that  the 
laws  of  nature  come  from  a  special  con- 
struction of  the  ultimate  basis  of  every- 
thing, but  that  the  same  laws^  of  nature 
would  prevail  for  the  widest  possible  variety 
of  that  basis." 

This  statement  seems  to  be  very  signifi- 
cant, but  be  this  as  it  may,  the  relationship 
shown  clearly  indicates  that  if  it  is  true, 
then  it  should  be  the  means  of  finding  fur- 
ther interesting  relations  between  the  spec- 
trum of  hydrogen  and  the  elements  taken 
collectively.  This,  in  fact,  has  been  the 
case  in  a  general  way  quite  apart  from  this 
particular  relation,  as  is  instanced  in  the 
energy  levels  of  an  atom  which  become 
realised     in    other     atoms    by    bv>mbarding 


them  with  electrons.  It  must  be  remem- 
bered, too,  that  in  the  electron  orbits  of  the 
hydrogen  atom  the  major  axes  of  the  ellipses 
traced  out  in  space  are  related  to  each  other 
as  the  squares  of  numbers  1,  2,  3,  &c.,  are; 
and,  moreover,  the  X-ray  spectra  of  the 
elements  as  found  by  Moseley  stand  in  uni- 
form step-wise  relationship  if  the  frequen- 
cies of  the  lines  of  the  elements,  taken  con- 
secutively according  to  their  atomic  num- 
bers, are  re -proportioned  by  taking  respec- 
tively their  square  roots.  In  conformity 
with  these  relations  the  atomic  numbers 
grow  progressively  by-  steps  of  one  each 
time,  beginning  with  hydrogen,  and  "  the 
difference  between  the  atomic  weight  [indi- 
vidual mass  value]  and  the  atomic  number 
represents  the  number  of  electrons  there 
must  bo  in  the  nucleus  [of  the  atom]  in 
order  to  bring  its  net  charge  down  to  the 
atomic  number  " — to  quote  the  words  of  B. 
Russell  in  his    "  A. B.C.  of  Atoms." 

Furthermore,  the  Kosscl-SommerfeTd 
law,  which  shows  similar  inner  structures  of 
the  atom  to  be  common  to  consecutive  ele- 
ments, means  that  a  common  type  or  sys- 
tem of  atom  building  is  involved,  and  from 
the  foregoing  this  implies  that  hydrogen  is 
the  smallest  positive  unit  in  the  architec- 
tural structure  of  the  atom.  Sommerfeld, 
in  hfs  "  .\tomic  Structure  and  Spectral 
liines, "  page  373,  says:  "  We  next  assert 
that  the  itpnrk  spectrum  of  ench  rlcmrnt  is 
in  structure  the  same  as  the  arc  spectra  of 
the  element  that  precedes  it  in  the  periodic 
si/stem;  that  is,  that  it  consists  of  doublet, 
triplet,  or  so-called  non-series  lines,  accord- 
ing as  the  arc  spectrum  of  the  preceding 
element  is  composed  of  doublets  (like  the 
alkalis),  or  triplets  (like  the  alkaline  earths), 
or  of  lines  that  apparently  succeed  one  an- 
other without  regularity  (like  most  ele- 
ments at  the  right  of  the  periodic  system, 
in  particular  the  inert  gases).  Here  we  have 
emmeiated  the  [Spectral]  Latv  of  Displace- 
ment, which,  like  the  law  of  displacement 
of  radio-activity,  leads  from  one  element  of 
the  iporiodic  system  to  a  neighbouring  ele- 
ment. The  meaning  of  our  displacement 
law  as  applied  to  our  model  of  the  atom  is 
obvious.  Each  colunan  of  the  periodic 
system  is,  in  general  language,  character- 
ised by  a  certain  valency;  or,  in  our  mwlel, 
by  a  certain  number  of  external  electrons. 
On  the  other  hand,  we  know  that  the  line- 
structure  pf  the  speetra  is,  without  excep- 
tion, the  same  in  each  column  of  the  series. 
If,  now,  the  atom  loses  one  electron  by 
ionisation,  then  it  becomes  a  member  of  the 
pnH'cding  column  in  its  external  behaviour, 


274 


THE  CHEMICAL  NEWS. 


NOVEMBER  2,  1923. 


and  thus,  as  our  law  of  displacement  asserts, 
it  will  conform  in  the  structure  of  its  lines 
with  the  members  of  the  preceding  column ; 
numerically,  it  will  be  best  comparable  with 
the  element  that  immediately  precedes  it  in 
the  periodic  system." 

Enough  has  been  said  here  to  show  how 
intimately  the  elements  (atoms)  are  struc- 
turally connected;  and  whether  the  inert 
gases  are  allocated  to  the  right  or  to  the 
left  of  the  table  makes  no  real  difference, 
since  the  table  has  to  be  considered  as  de- 
veloped continuously.  This  continuity  is 
shown  by  the  radio- atoms  which,  in  their 
'  change  from  one  type  to  another,  pass  right 
across  the  table.  The  inert  gases  are,  how- 
ever, quite  distinctive,  as  may  be  judged 
from  the  above  quotation,  especially  when 
taking  other  factors  into  account.  The 
grouping  of  the  elements  is  a  natural  pro- 
cedure, and  it  seems  to  have  a  certain 
counterpart  in  the  line  spectrum  of  hydro- 
gen, as  already  indicated. 

Considering  the  hydrogen  lines,  it  is 
known  that  those  made  use  of  in  this  study 
are  not  in  one  sense  pure  lines,  but  that  they 
are  made  up  of  fine-line  companions.  For 
examiple,  the  Ha  line  appears  to  have  a  cer- 
tain complexity,  which  Sommerfeld  has 
attributed  to  a  relativity  effect,  since, 
according  to  this  theory,  the  elliptical 
orbits  rotate  in  their  own  planes,  the 
nucleus    occupying    one    foci — just    as    the 


planet  Meroury  describes  an  elliptical  orbit 
round  the  sun,  and  it  turns  slowly  in  its  own 
plane  round  this  luminary  as  the  pivot. 
The  ellipse  in  this  case  is  not  a  mathematic- 
ally closed  one,  but  it  becomes  a  sort  of 
elliptical  spiral.  The  calculated  wave 
lengths  for  the  above  line  when  reduced  to 
vacuum  figures  are  as  follows:  — 
Ha  Line. 
6564.501 

0.516 

0.563 

0.658 

0.674 

0.720 
Ajpart  from  this  ultra  refinement, 
Balmer  series  linos  made  use  of  ; 
study  stand  out  in  strong  contrast  to  the 
general  "  background,"  by  reason  of  their 
marked  intensities.  These  intensities  (P>) 
taken  advisedly  from  W.  M.  Watt's  "Studv 
of  Spectra  Analysis,"  1904, -p.  230.  do  not 
give  an  adequate  idea  of  their  development 
as  now  understood,  but  they  will  serve  a 
general  purpose  of  comparison  with  the 
corresponding  group  numbers  (.V),  thus:  — 


these 
this 


A 
48 
21 
13 

9 

7 


B 

20  a 

2013 
15  y 
10  8 


*-z 

o 
o 
o 
o 
o 

0 


lO- 


2  34567 

2  3456  7« 

2  3  4-  5  6  7  8  9  «  II   12  13  14  15  16  17 

2  3  4  5  6  7  8  9  lO  II  12  13  14  15  16  17 
2  3  4  5  6  7  8  9  10  1112  13  14  15  16  17*- 
" '8 (0KlK^3>4,  5  6  7  8  9  10  II  12  13  14  15  16  17 


2-1-4  = 
6  +  4  = 
10-1-4  = 
l4-t-4-  = 
18  +  4  = 


e 

lO 
14 
18 

22— LIMIT. 


14.- 


■22- 


\ 


At.  No. 72. 


0    I    2  3  4  56  7«-At.  No.93. 

GROUP  €  •=  3ero-atamic-number  element?  He  Ne  Ar  Kr  Xe  (86 

/-— 5Iir — N 
GROUP  S=  Fe  Co  Nl    . 
Ru   Rh  Pd    ' 
Os  Ir   Pt 


y- 


7\ 


/— JIE ^ 

G  ROUPif  =    Pr  Nd  61  So  Eu  Gd  Tb  Dy  Ho  Er  Tm  Yb  Lu 

_^  I     a    BL    E   3Z:    "21   50. 

GROUPp  =  Cu  Zn  Ga  Ge  As  Se   Br 

Ag  Cd  In  Sn  Sb  Te    I 

Au  HgTL  Pb  BL  Fb  85 


13 


1 

TT 

III   H 

Y 

YT 

w 

GROUPo<=  H 

Ll 

Be 

B    C 

N 

O 

r 

NaMq 

AL  51 

P 

S 

Cl, 

K 

Ca 

Sc  Tl 

V 

Gr 

Mn 

Rb 

Sr 

Yb  Zr 

Nb  Mo  43 

Cs 

\i,o 

La  Ce 

(see  above) 

lO)(i) 

(2)  (3)  72  Ta  W 

75 

87 

Ra  Ac  Th  Fb 

u 

93 

I  Row    ending  ^A/l^^1    I. 

3  Rows  ending  vviHi  7. 

4  Rows    ending  wihh  17. 

(    )=  Overla(j^ing  member's    probably 
mcr'ged     in   like    elemcnhs. 


21 


F 

ef 

n 

0 

V 

CD 

Ti 

>~ 

0) 

X 

CJ. 

F 

0 

,? 

L 

R 

o 

a) 

^ 

01      t 


-c  0 


X  £ 


Z  ^    J3 


48^ 


NOVEMBEE  2,  1923. 


THE  CHEMICAL  NEWS 


275 


Interesting  developmenis  in  connection 
with  the  hydrogen  lini's  scim  to  be  fovf- 
shadowed,  but  of  more  iiinicdiati'  interest 
njay  be  the  following  schema  which  gives  at 
a  glance  the  group  system  i\olved  by  reason 
of  this  study. 

Notes  Kbspkcting  thk  Scheme, 

Refemng  to  the  wedge  pt  riodic  table  (see 
The  Chemical  Neics,  1922,  CXXV.,  p.  387; 
or  the  writer's  "  Atomic  Theories,"  2nd 
Edition,  frontispiece;  or  tlii  writer's  "  The 
Chemical  Elements,"  pa^u  s  34,  107-110), 
which  conforms  with  the  ihove  lay-out  in 
every  respect,  Mn  is  on  a  lower  level  than  01 ; 
similarly,  Ce  is  on  a  low(  r  level  th;in  Zr. 
while  the  element  72  (ec  Itiura  or  h 
rises  to  the  level  of  Zr.  This  also  - 
that  the  overlapping  at  this  part  of  the 
table  is  to  be  expected.  The  overlapping 
extension,  moreover,  accounts  for  the  ten- 
dency of  a  zero-valency  member  to  appear 
in  this  ipart  of  the  table,  .t-;  has  been  the 
case  with  some  of  the  earlier  schemes.  Sir  J. 
J.  Thomson  claims  to  haw  found  an  inert 
gas  of  atomic  weight  168,  hut  this  is  doubt- 
ful, though  the  (0)  memlx  i-  falls  at  about 
167.  See  the  writer's  "  Th.  Chemical  Ele- 
ments,'' pages  149,  150.  Keferring  now  to 
H,  this  being  on  a  short  sttcp  wedge,  as  al- 
ready explained  in  Part  I.,  it  is  raised  to  the 
level  of  F.  Considering  the  "7"  and  "17" 
elements  at  the  highest  part  of  thr 
wedges,  th^  are  chemiially  alike,  as 
instanced  in  the  halogens  which 
occupy  these  extreme  plac<'s  as  far  as  filletl. 
93  represents  a  lacuna  nol  filled,  for  it  i- 
based  upon  a  minimum-prcnluction  limiting- 
series  (see  The  Chemical  News,  1022. 
CXXV.,  p.  309),  thus:  — 

At.  No.       Difi. 
98 

2 


Pa  =  91 
85 
75 
61 
43 

Sc  =   21 


—  6 

—  10 

—  14 

—  18 

—  22 


The  small  amount  of  Se  compared  with 
Ca  and  Ti  on  each  side  of  Sc  supports  this 
observation;  and  it  will  be  seen  that  thr 
series  becomes  a  Jimitincj  one  by  reason  of 
the  values  of  the  differences  shown.  There 
appears  to  be  comparatively  small  quanti- 


ties of  Pa,  and  UXj  which  is  an  isotope, 
when  considering  the  surrounding  olements. 
The  radio-isotopes,  of  course,  are  included 
in  the  atomic-number  places  characterised 
by  the  elements  Ra,  Ac,  Th,  &c. 


DI ACETYL  ACETONE  AND 
PSEUDO-CUMENE. 

By  J.  C.  Thomlinson,  B.Sc. 

-V  table  giving  all  the  proposed  formulae 
for  diacetyl  acetone  would  be  too  cumber- 
iiome  in  a  short  note  of  this  kind. 

The  following  ring  structure. 


CH,  •  C  H  O  •  CH.. 

I 
CH,  •  C  H  0  •  CH. 


> 


0 


is  advanced  for  this  substance,  since  it  may 
be  obtained  by  the  oxidation  of  pseudo- 
cumene  wilh  chromic  under  suitable  con- 
ditions:— 

C.H,  (CH,)  +  90  =  CeH.  A  +  3  CO,. 

This  oxidation  is  similar  to  that  which 
takes  place  when  alcohols  are  oxidised  by 
chromic  acid. 


THE    SALTS    OF   MALEIC,    FHMARIC 
AND    INACTIVE    MALIC   ACIDS. 

By  John  Morris  Weiss  and  Charles 
Raymond  Downs. 

(From  the  "Journal  of  the  American 
Chemical  Society,"  October,  1923.) 

In  various  investigations  which  had  for 
their  purpose  the  development  of  analytical 
methods  for  mixtures  of  maleic,  fumaric 
and  malic  acids,  a  number  of  salts  of  these 
three  acids  were  prepared  and  studied. 
The  results  are  admittedly  incomplete,  and 
in  cert.ain  instances  the  compounds  deserve 
further  study.  We  are  presenting  here  the 
results  obtained,  regretting  that  we  did  not 
have  the  time  to  study  all  the  compoimds 
thoroughly,  but  hoping  that  others  will  do 
so.  ^^'e  wish  to  express  our  thanks  to  Dr. 
G.  C.  Bailey,  Dr.  H.  E.  Williams,  and  Dr. 
Wolesensky,  for  the  careful  work  whi.'h 
they  carried  on  under  our  direction  in  ipre- 
paring  and  ddorrnining  the  formulae  and 
solubilities  of  a  number  of  the  compounds 
described,  and  to  Mr.  E.  C:  Buck  for  the 
very  careful  preliminary  search  of  the 
literature  which  he  made  in  this  connec- 
tion. 


276 


THE  CHEMICAL  NEWS. 


NOVEMBER  2,  1923. 


Ammonium  Salts. 
Analysis. — These  salts  were  analyzed  hy 
distilling  the  material  with  an  excess  of 
standard ,  sodium  Hydroxide  solution  and 
collecting  the  distillate  in  an  excess  of 
standard  sulphuric  acid.  The  distillate,  ti- 
trated back  with  methyl  orange  as  indicator, 
gave  the  ammonia  content;  and  the  flask 
residue,  titrated  back  with  phenolphthalein 
as  indicator,  gave  the  acid  radical  content. 

Ammonium  Fumarate.^  —  The  product 
was  best  prepared  by  treating  fumaric  acid 
suspended  in  water  with  coned,  ammonium 
hydroxide  in  slight  excess  of  the  calculated 
amount,  concentrating  in  a  vacuum  at  not 
over  60°,  adding  a  little  ammcnium  hydrox- 
ide to  make  up  for  losses  in  concentration 
and  allowing  the  substance  to  crystallize. 
The  crystals  were  filtered  and  washed  with 
alcohol. 

Analyses.  —  Calc.  for  (NHJ^C^HgO^ : 
NH3,  )2.67;  C^H^O,,  77.33.  Found:  NH3, 
22.55;  C^H^O,,  77.40. 

The  aqueous  solution  of  the  salt  is  stable 
at  60°,  but  when  boiled  it  loses  ammonia ; 
4.5506  g.  of  salt  was  dissolved  in  200  cc.  of 
water  and  the  solution  distilled,  the  distil- 
late being  collected  in  standard  acid.  In  50 
minutes  0.08148  g.  of  ammonia  distilled 
with  150  cc.  water,  reipresenting  7.9  per 
cent,  decomposition.  On  the  addition  and 
distillation  of  150  cc.  more  water,  0.03983  g. 
of  ammonia  was  volatilized  (3.8  per  cent.). 
The  final  limit  of  this  decomposition  or  the 
product  formed  was  not  determined. 

Ammonium  Acid  Fum^arate.^ — Fumaric 
acid  was  neutralized  by  two  molecules  of 
ammonium  hydroxide  with  litmus  as  indi- 
cator and  a  second  portion  ol  fumaric  acid 
equal  to  the  first  added.  The  mixture  was 
fractionally  crystalHzed  into  two  lots  cf 
crystals,  each  equivalent  to  slightly  more 
than  J  of  the  whole,  the  balance  in  the 
mother  liquor  being  discarded. 

Analyses.— C^\c.  for  NH^C.HgO^ :  NH,, 
12.78;  C.H^O,,  87.21.  Found:  Fraction  1: 
NH3,  11.70;  C,H,0„  87.70;  Fraction  2: 
NH3,  12.70;  C,H,0„  87.40. 

Ammonium  Maleate.^'  ' — We  were  not 
able  to  obtain  crystalline  material  by  the 
same  method  as  that  used  for  ammonium 
fumarate.  Under  ordinary  pressure,  the 
solution  does  not  lose  ammonia  by  evapora- 


^Keiser  and  McMaster,    Am.    Chem.    J., 
1913,  XLIX.,  84. 

^  Rieckher,  Ann.,  1844,  XLIX.,  31. 
»  Buechner,  Ann.,  1844,  XLIX.,  57. 


tion.  Only  a  thick  sirup  results  which  can- 
not be  crystallized.  When  the  solution  is 
evaporated  in  a  vacuum,  the  solid  obtained 
is  ammonium  acid  maleate.  This  salt  de- 
serves attention  by  future  investigators. 

Ammonium  Acid  Maleate.^ — This  salt 
was  obtained  by  the  same  method  as  de- 
scribed under  the  corresponding  fumarate. 
Analyses. — Calc.  for  NH^C^HgO^ :  NH,, 
12.78;  C^H^O^,  87.21.  Found  :  NH3,  17.72; 
C,H,0„  87.16. 

Sodium  Salts. 
The  sodium  acid  maleate^  *,  sodium 
maleate^  ',  sodium  acid  fumarate-^  and  so- 
dium fumarate*  ^  *  were  prepared  by  mix- 
ing the  acids  with  the  proper  amounts  of 
S'odium  hydi oxide  in  water  solution,  allow- 
ing the  salt  to  crystallize  and  drying  it  at 
room  temperature. 

The  data  on  water  of  crystallization  as 
given  in  the  literature  were  confinned  by 
ignition  to  sodium  carbonate.  In  the  case 
of  the  sodium  acid  fumarate,  where  there 
are  no  data,  we  found  the  crystalline 
material  to  be  anhyd roils. 

Barium  and  Strontium  Salts. 
Barium  acid  maleate,^  barium,  male- 
ate,-''  ^  ",  barium  fumarate'*  and  barium  i- 
malate,^  "  i'  have  been  described.  We  did 
not  isolate  these,  but  observed  that  a  heavy 
white  precipitate  of  slight  solubility  was 
obtained  when  a  10  per  cent,  solution  of 
barium  chloride  was  added  to  a  10  per  cent, 
solution  of  either  sodium  maleate  or  fumar- 
ate. With  sodium  i-malate  only  a  slight 
precipitate  was  formed. 

Strontium  acid  maleate  and  strontium 
maleate''  and  strontium  ?-inalate'^  have 
been  prepared. 

Strontium  fumarate^  has  been  described 
as  containing  three  molecules  of  water  of 
crystallization. 

We  prepared  this  salt  by  mixing  stron- 
tium nitrate  and  sodium  fumarate  in  water 


^  Bodewig,  Z.  Kryst.,  1881,  V.,  558. 

^  Chandler,  Sour.  Am.  Chevi.  Hoc,  1908, 
XXX.,  694. 

^  Kannonikov.,  J.  prald.  Chem.,  1885, 
[2],  XXXI.,  321.  * 

^  Kekule  and  Strecker,  Ann.,  1884, 
CCXXIII.,  170. 

«  Vorlaender,  Ann.,  1894,  CCLXXX.,  177. 

»  KekMle,  Ann.,  1861,  CXVII.,  120. 

'"  Bui  sine,  Compt.  rend.,  1888,  GVL, 
1426. 

'^  Dnboux  and  Cutiat,  Helvetica  Chim. 
Acta,  1921,  IV.,  735, 


NOVEMBER  2,  1923. 


THE  CHEMICAL  NEWS. 


277 


solution  in  equimolecular  prop«rtions,  fil- 
tering off  the  precipitate  and  drying  at  100° 
at  wnich  temperature  it  was  anhydrous. 

Analyses.  —  Calc.     for     SrC^HjO^ :     Sr, 
43.45;  H,  0.99.  Found:  Sr,  43.25;  H,  1.13. 
Calcium  Salts. 

The  compositions  were  determined  by 
igniting  the  salts  to  calcium  oxide. 

Calcium  Acid  Malcatc-*  was  prepared  and 
found  to  conespond  with  the  formula  as- 
given  for  5  molecules  of  watef  of  crystalli- 
zation. With  the  neutral  salt/*  the  same  co- 
incidence was  observed,  this  salt  containing 
one  molecule  of  water. 

Analysis. — Calc.  for  CaC^HjO^.HjO  :  Ca, 
23.25.     Found:  23.28. 

Calcium  Fumarate'^  ^  *-  w  as  prepared  by 
precipitating  a  sodium  fumarate  soluti-.n 
with  calcium  chloride,  and  filtering,  wash- 
ing and  air-drying  the  product.  Our 
material  corresponded  to  the  trihydrate  de- 
scribed in  the  literature. 

Analyses.  —  Calc.  for  CaC^Hj()^.3HjO : 
Ca,  19.23;  H,  3.84.  Found  :  Ca,  19.47;  H. 
4.01. 

Calcium  Acid  Fumarate  is  not  de8cribe«l 
in  the  literature.  When  a  solution  of  sodium 
acid  fumarate  was  mixed  with  a  molecular 
equivalent  of  calcium  chloride  and  evapor- 
ated, crystals  were  obtained  which  were 
separated  and  air-dried. 

Analysis.  —  Caic.  for  CaC,H,0,.2H,0  : 
Ca,  13.06.     Found:  13.22. 

■  Calcium  Acid  i-Malate^'^  is  stated  to  con- 
tain one  molecule  of  water  of  crystalli/.a-  ' 
tion.  Our  preparation  was  made  by  heat- 
ing 62.8  g.  of  i-malic  acid  with  20  g.  of  cal- 
cium carbonate,  filtering  the  solution,  nl- 
lowing  it  to  crystallize,  and  separating  and 
air-drying  the  crystals;  yiold,  64  g.  The 
substance  was  found  to  be  the  anhydrous 
salt. 

Analysis. — Calc.  f(H-  '"  ''Tr,„0,  .•  ('a. 
I'S.OiS.     Found:  12.85. 

Magnesium  Salts. 

Magnesium  acid  malente,  magneRiutii 
maleate,'  '*  magnesium  fvmiarate*  and 
magnesium  i-nialate"  have  been  described. 
These  salts  were  not  prei)are(l,  but  note  was 
made  that  none  of  the  thn  e  acids  is  pre- 
cipitated from  it«  sodium  salt  solutions  (10 
per  cent.)  by  soluble  magnesium  com- 
pounds.     In  an  attempt  to  produce   the    «"- 


"  Carius,  Ann.,  1867,  CXTJI.,  129. 
"  Brewer,  Ber.,  1875,  VITI..  863. 
»*  Wnlden,  Z.  rhysik.    Chrui.,    18^7.     I 
529. 


malate,  magnesium  oxide  was  dissolved  in 
i-malic  acid.  On  concentrating  the  filtered 
solution  a  syrup  was  obtained  which  did 
not  crystallize,  but  solidified  on  standing  to 
a  hard  white  mass. 

Cobalt  Salts. 
Cobalt  Maleate  is   not    described    in   the 
literature. 

Cobalt  was  precipitated  as  carbonate 
from  a  solution  of  its  nitrate  and  the  latter 
filtered,  washed  and  suspended  in  water. 
An  equivalent  quiuitit^  of  maleic  acid  was 
added  and  the  soluti<m  filtered  and  evapor- 
ated. 

.4m»Zi/»ia.— Calc.  for  CoC^H^O^.llHaO : 
Co,  15.90.     Found:"  16.80. 

Cobalt  Fumarate'^  is  stated  to  correspond 
to  the  formula  CoC4H,0^.3HjO;  this  we 
were  unable  to  confirm.  Using  concen- 
trated solutions  of  cobalt  nitrate  and  so- 
dium fumarate,  a  copious,  crystalline,  pink 
precipitate  was  obtained.  This  was  washed 
and  air-dried. 

Analyses— C&\e.  for  CoC^H,0,.4HjO  :  C, 
19.59;  H,  4.08;  Co,  24.07.  Found:  C, 
20.86;  H,  8.80;  Co,  23.93. 

When  the  pink  compound  was  dried  at 
100*  it  became  somewhat  bluish  frcwti  loss 
of  water. 

Analysii.  —  Calc.  for  CoC4Ha0..2H.O  : 
Co,  28.23.     Found:  28.62. 

Cobalt  i-Malate. — This  is  not  described  in 
the  literature.  It  was  prepared  by  treating 
cobalt  carbonate  suspended  in  water  with 
the  calculated  amount  of  i-malic  acid  and 
evaporating  the  mixture  to  dryness  at  100°. 
The  formula  seems  to  be  that  of  a  tri- 
hydrate. 

Analyses.  —  Calc.  for  CoC^H^Oj.SH.O : 
C.  4.08;  H,  24.07;  Co,  19.69.  Found:  C, 
1.15;  H.  23.40;  Co,  19.28. 

Nickel  Salts. 
The  nickel  was  determined  by  digesting  a 
sample  with  concentrated  ammonium  hy- 
dro.xide,  adding  water,  a  small  amount  of 
sodium  iodide  (0.02--0.05  g.),  a  few  drops 
of  standard  silver  nitrate  solution  and  an 
excess  of  standard  sodium  cyanide  sf>lution. 
The  excess  was  titrated  back  with  silver 
nitrate  to  a  slight  permanent  precipitate. 

Nickel  Fumarate^  is  stated  to  contain  4 
molecules  of  water  of  crystallization.  The 
salt  was  prepared  by  mixing  dilute  solutions 
of  nickel  nitrate  and  sodium  fumarate  and 
concentrating  until  a  green  crystalline  pre- 


'"'  (Johalt   was  determined    by  ignition    to 
cobaltoHs  cobaUic  oxide,  CojO^. 


27S 


TfiE  CHEMICAL  NEWS. 


NOVEMBER  2,  1923. 


cipitate  was  formed,  and  removing  soluble 
materials  by  repeated  bailing  with  water. 

Analyses. — Calc.  for  ISliC4H204.4H,0  : 
Ni,  24.08;  calc.  for  NiC.jH,0^.5H,0  :  22"43. 
Found:  23.42. 

If  the  precipitation  of  the  nickel  fumar- 
ate  is  carried  on  in  concentrated  solution,  a 
diiferent  product  seems  to  be  formed. 

Analyses.— Calc.  for  NiC^H^O^.yH^O  :  C, 
18.27;  H,  4.56;  Ni,  22.43.  Found:  C. 
18.44;  H,  4.06;  Ni,  22.30. 

Nickel  Maleate^  resembles  the  fumarate 
in  general  properties,  but  appears  to  bo 
more  soluble.  This  compound  was  not  ana- 
lyzed. 

Nickel  i-Malate  is  not  described  in  the 
literature.  It  is  extremely  soluble  in  water 
and,  therefore,  cannot  be  precipitated.  If 
nickel  carbonate  is  dissolved  in  malic  acid  a 
green  solution  is  obtained,  which,  on  con- 
centration, forms  a  jelly.  On  long  standing 
at  room  temperature,  the  sample  lost  water 
and  crystals  began  to  appear.  This  com- 
pound was  isolated  but  not  analyzed. 
Manganous    Salts." 

Manganous  Acid  Maleate. — This  com- 
pound has  not  been  previously  described; 
69.6  g.  of  maleic  acid  was  dissolved  in  the 
minimum  amount  of  water  at  30°,  and  to 
this  was  added  34.6  g.  of  manganese  car- 
bonate. A  solid  separated  which  was  dis- 
solved by  warming  it.  As  the  solution  was 
cooled  in  ice  water,  a  granular  pink  precipi- 
tate was  formed  which  was  filtered,  washed, 
reerystallized  from  water,  and  dried  at  room 
temperature;  yield,  32.5  g. 

Analyses. —Calc.  for  MnC8H.O„.4V^H.,0  : 
C,  25.60;  H,  4.20;  Mn,  15.02.  Found:  C, 
25.37;  H,  3.91;  Mn,  15.19. 

From  examination  of  the  crystals  micrc;- 
scopically,  it  appears  that  the  salt  is  stable 
m  the  air  and  in  a  vacuum  over  sulphuric 
acid. 

Manganous  Maleate  has  not  been  pre- 
viously described.  It  was  prepared  in  the 
same  manner  as  the  acid  salt,  except  that 
twice  as  much  manganese  carbonate  wa^ 
used.  It  appears  to  be  stable  at  100°.  In 
dil.  water  solution  it  decomposes  with  the 
formation  of  manganese  dioxide. 

Analyses.  ~  Calc.  for  MnC,H,0,.3H.,0  : 
C,  21.53;  H,  3.58;  Mn,  24.64.  Found  :^  C, 
21.01;  H,  3.31;  Mn,  24.48. 

Manganous  Fumarate^  has  been  stated  to 
have  the  formula  MnC,H„0,.3H,0.  Our 
results  did  not  confirm  this'.  To  11.55  g.  of 
manganese  carbonate  we  added  11.6  g.  of 
fumanc  acid.  -The  slight  excess  of  carbon- 
ate was  filtered    off  and    the    filtrate    eva- 


porated until  a  precipitate  appeared,  at  first 
flocculent  and  then  granular.  This  was 
filtered  off  and  dried  at  room  temperature. 

Analyses. — Calc.      for     MnC4H20^ :       C, 
28.41;    H,  1:18;    Mn.  32.54.      Found:     C, 
27.55;  H,  1.42;  Mn,  32.02. 
Zinc  Salts. 

Zinc  was  determined  by  ignition  to  zinc 
oxide. 

Zinc  Acid  Maleate^*^  was  not  prepared. 

Zinc  Mali'Mte^  was  made  by  quickly  mix- 
ing a  Saturated  maleic  acid  solution  with 
zinc  carbonate  as  a  paste  in  a  mortal-  and 
filtei'ing  before  the  zinc  maleate  separated. 
Zinc  maleate  formed  as  a  white,  granular 
precipitate  which  was  washed  and  dried  at 
room  temperature. 

Analyses.— Csiic.  for  ZnCJl.,0^.21ifi  :  C, 
22.80;  H,  2.78;  Zn,  30.42.  Found:  C, 
21.78;  H,  2.78;  Zn,  30.68. 

When  a  solution  of  zinc  maleate  is  heated, 
it  decomposes  giving  a  flocculent  precipi- 
tate. 

Zinc  Fumarate^  has  been  described  in  two 
modifications  with  3  and  4  molecules  of 
water,  respectively.  Our  product  was  made 
by  treating  a  suspension  of  fumaric  acid 
with  an  excess  of  zinc  carbonate  in  a  mor- 
tar, filtering  the  mixture  and  eva^porating 
the  filtrate  until  crystallization  began. 
Colourless  crystals  were  obtained  and  dried 
at  room  temperature. 

Analyses.— Ga\c.  for  ZnC^H^O^.SH^O  :  C, 
17.81;    H,  4.45;    Zn,  24.26.       Found:     C, 
17.24;  H,  4.25;  Zn,  24.42. 
Iron  Salts. 

Ferric  Maleate'*  has  been  described  as  an 
indeterminate  smear.  On  evaporation  of  a 
mixture  of  two  molecular  equivalents  of 
ferric  hydroxide  and  three  molecular  equi- 
valents of  maleic  acid  a  dark,  nearly  black, 
amorphous  mass  was  obtained  which  was 
dried  at  100°.  When  analyzed  this  showed 
approximately  the  composition  of  the  dihy- 
drate. 

Analyses.— Cah.  for  Fe,(C4H.,Oj3.2H,0  : 
C,  29.4;  H,  2.04;  Fe,  22^88.  'Found  :' C, 
27.34;  H,  2.59;  Fe,  22.90. 

In  solution  this  material  seems  to  be  able 
to  hold  an  excess  of  ferric  hydroxide. 

Ferric  Fumarate'-^  could  not  be  prepared 
from  ferric  hydroxide  and  fumaric  acid. 

Ferric  i-Malate^^  was  not  prepared,  but 
considerable  work  was  carried  on  with  ferric 


'"  Richter,  Z.  Chem.,  1868,  XL,  449. 
''  Pickering,  J.  Chem.  Sac,  1914.  CIII  . 
1358. 


NOVEMBEK  1,  1928. 


THE  CHEMICAL  NEWS. 


279 


ammonium  i-malatc.  One  molecular  equi- 
valent of  ferric  hydroxide  (pK  cipitated  cold 
because  when  precipitated  h  t  it  did  not 
dissolve  properly)  was  mixed  with  a  clear 
solution  of  2  molecular  equivalents  of 
malic  acid  and  the  mixture  \\  as  heated  to 
60".  One  molecular  equivah  nt  of  ammo- 
nium hydroxide  was  then  udl'  d,  and  the 
mixture  heated  rapidly  to  lioiling.  The 
work  was  carried  on  in  semi-darkness  as  the 
material  is  light  sensitive.  A  clear,  red- 
brown  solution  resulted  which  was  cooled 
rapidly  in  an  ice-bath,  t  sliowcd  no  ferrous 
iron  when  tested  with  foniryanide  solu- 
tion. The  solution  was  not  stable  even  in 
the  dark,  as  ferrous  iron  appeared  on  stand- 
ing and  gradually  increased.  When  a  thick 
solution  was  painted  on  glass  and  dried  in  a 
dark  closet  at  room  temperature  a  solid 
similar  to  ferric  ammonium  citrate  was 
produced  which  contained  no  ferrous  iron. 
When  it  was  dried  between  30°  and  40" 
some  reduction  took  place. 

To  compare  the  sensitivity  of  ferric  am- 
monium malate  and  citrate,  dilute  soiutioDS 
of  each,  free  from  ferrous  iron,  were  placed 
in  sunlight  and  tested  for  ferrous  iron.  After 
5  minutes  the  malate  showed  a  faint  test 
for  ferrous  iron  and  after  10  minutes  a  very 
positive  test,  while  the  citral<'  was  negative 
at  24  minutes  and  showed  a  positive  test 
only  after  39  minutes.  In  the  dark  at  100* 
after  /i  minutes  the  malate  showed  ferrous 
iron,  while  after  20  minutes  the  citrate  still 
tested  negatively. 

Attempts  to  produce  ferric  ammonium 
maleate  or  fumarate  in  the  same  way  were 
unsuccessful. 

CoppKR    Salts. 

Copper  was  estimated  volumetrically  in 
acetic  acid  solution  by  intans  of  sodium 
iodide  and  thiosulphate. 

Copper  Fumarate^  "  "  has  been  described 
both  as  a  dihydrate  and  trihydrat<\  We 
obtained  our  material  by  precipitating  fu- 
maric  acid  with  copper  sulphate.  The  pale 
blue  precipitate  was  washed  and  dried  at 
100^ 

Analyses.  —  Calc.  for  CuC.HjO,. 211,0 : 
C,  22.47;  H,  2.80;  Cu.  20.78.  Found:  C, 
21.70;  H,  3.06;  Cu,  20.45. 

Copper  Maleate'  "  was  prepared  by  pre- 
cipitating a  solution  of  equimolecular  equi- 
valents of  copper  sulphate  and  maleic  acid 
with  sodium  carbonate.      A  deep  blue  crys- 


^^   Virhrrlnn.  J.   Chem.   Soc. ,1012,     CT., 


174. 


talline  precipitate  formed  which,  as  stated 
by  the  previous  investigators,  is  the  mono- 
hydrate. 

Analyses.— C&h.  for  CuC^H^O^.H^O :  C, 
24.54;  H,  2.04;  Cu,  32.50.  Found:  C, 
24.05;  H,  2.39;  Cu,  32.22. 

Copper  i-Malate  has  not  been  described. 
When  equivalent  quantities  of  cQpper  car- 
bonate and  j-malic  acid  solutions  are  mixed 
and  the  mixture  is  evaporateii,  a  hard  vitre- 
ous blue  mass  is  formed,  which  aft4?r  seve- 
ral weeks  becomes  crystalline.  It  contains 
at  this  stage  25.02  per  cent,  of  copper, 
which  indicates  a  trihydrate  (25.49  per  cent. 
of  copper).  On  continued  exposure,  the 
mass  becomes  paler  blue  and  shows  the  pre- 
ponee  of  25.70  per  cent,  of  coipper. 

Analyses.  —  Calc.  for  CuC,H/),.2HjO  : 
C.  20.72:  H,  3.45;  Cu,  27.28.  Found:  C, 
20.80;  H,  3.16;  Cu,  25.70. 

This  formula  is  quite  doubtful  and  further 
work  is  indicated. 

Cadmium  Salts. 

Cadmium  salts  of  maleic  and  lumaric 
acids  have  not  bein  described  in  the  litera- 
ture. Cadmium  was  determined  by  ignit- 
ing the  salt  to  the  o.\ide,  CdO,  in  a  stream 
of  oxygen. 

Cadmium  Fumarate. — Prepared  by  pre- 
cipitating sodium  fumarate  with  cadmium 
chloride  in  concentrated  solutions  this 
forms  a  copious,  finely  divided,  white  pre- 
cipitate. It  was  filtered,  washed  and  dried 
at  100°. 

Analyses.  —  Csl\c.  for  CdCJl^O^:  C, 
21.20;  H,  0.88;  Cd,  49:57.  Found:  C, 
21.08;  H,  1.18;  Cd,  49.29. 

Cadmium  Maleate. — This  was  made  by 
mixing  equimolecular  proportions  of  cad- 
mium chloride  and  sodium  maleate  in  solu- 
tion and  evaporating  to  crystallization.  The 
salt  was  washed  repeatedly  with  hot  water 
and  dried  at  room  tennperature. 

Analyses.  —  Calc.  for  C(IC,Hj0^.2HjO : 
C.  18.29;  H,  2.28;  Cd,  42.75.  Found:  C, 
17.76;  H,  2.27;  Cd,  42.50! 

The  salt  retains  sodium  chloride  tena- 
ciously and  needs  exhaustive  washing  to 
purify  it. 

Anti.mony  Salts. 

No  literature  references  were  found  to 
these  salts,  and  all  attempts  to  fonn  the 
maleate,  fumarate  or  t-malate  by  dissolving 
antimony  trioxide  in  the  corresponding  acid 
were  unsuccessful.  In  the  case  of  t-malate, 
some  oxirle  is  di--i>lved  (never  jnoj-e  than  21 
per  cent,  of  that  calculated),  but  apparently 


280 


t&ie  CHEMICAL  KJSVVb. 


NOVEMBER  2,  192^. 


an  excess  of  acid  is  required  to  prevent  hy- 
drolysis so  that  the  salt  cannot  be  isolated.^' 
Sodium  Antimonyl  i-MaJate. — ^Attempts 
were  made  to  prepare  this  salt  by  heating 
40  g.  of  sodium  hydroxide,  144  g.  of  anti- 
mony trioxide  and  134  g.  of  i-malic  acid  in 
water  solution  under  a  reflux  condenser. 
After  15  hours,  82.8  g.  of  antimony  trioxide 
remained  undissolved.  This  was  removed, 
dissolved  in  potassium  acid  tartrate  and  re- 
ipreeipitated,  washed  and  added  again  to  the 
mixture.  In  this  way  all  but  31  g.  of  the 
original  quantity  was  finally  dissolved,  and 
all  attempts  to  increase  this  failed.  The 
final  solution  was  evaporated  to  a  thick 
syrup  which,  on  seeding,  solidified  to  a 
white,  hard  mass.  It  can  be  powdered,  and 
is  apparently  stable  and  very  soluble  in 
water.  The  problem  of  these  complex  salts 
is  interesting  and  deserves  further  work. 
Lead  Salts. 

Lead  was  determined  gravimetrically  as 
the  chromate  or  by  titrating  excess  of  di- 
chroinate  with  sodium  iodide  and  thiosul- 
phate. 

Lead  Fiiniaratc-  is  stated  to  occur  as  the 
dihydrate.  When  equimolar  quantities  of 
lead  nitrate  and  sodium  fumarate  were 
mixed  in  aqueous  solution,  fine  crystalline 
Jlakes  were  obtained  which  were  filtered  and 
dried  at  100°. 

Anahjscs.  —  Calc.  for  PbC,H.,0^ :  C. 
14.91;  H,  0.62:  Pb,  64.48.  Found:  C, 
14.48;  H.  0.88;  Pb,  64.22. 

Lead  Malcaie'^  -"  is  stated  to  occur  as  the 
trihydrate.  When  we  prepared  it  in  a  man- 
ner similar  to  that  used  for  the  fumarate, 
we  obtained  the  anhvdrous  salt. 

^na/v/ses.  —  Calc."  for  VhGJl.,0^:  C, 
14.91;  H,  0.62;  Pb,  64.47.  Found:  C, 
14.94:  H,  0.78;  Pb,  64.20. 

Lead  i-Malate^^  is  the  subject  of  varying 
opinion,  being  reported  as  anhydrous,  with 
1^  molecules  water  and  with  3  molecules 
water.^  This  salt  was  obtained  as  a  white 
precipitate  by  interaction  of  lead  nitrate  and 
sodium  i-malate  in  aqueous  solution.  When 
heated  to  100°  it  softens  to  a  dough-like 
mass.    Its  formula  is  doubtful  but  seems  to 


''  Henderson  and  Barr,  J.  Chem.  Soc, 
1806,  LXIX.,  1451.  Ucnderson  and  Pren- 
tice, ibid.,  1894,  LXVII.,  1030. 

="•  Pelouze,  Ann.,  1834,' XL,  263. 

^'^  Lloydl,  Ann.,  1878,  CXCIL,  80.  Ke- 
kule,  Ann.,  1864,  GXXX.,  1.  Pasteur, 
Ann.  chini.,  1852  [3]  XXX.,  49.  Werigo 
and  Tanatar,  Ann.;  1874,  CLXXIV.,  367." 


approach  the  composition  PbG4H^05.V2HL20' 

Analyses.— C&\c.  for  FbCJl^O^.'l  Jlfi  : 
C,  13.78;  H,  1.48;  Pb,  59.48.  Found:  C, 
11.91;  H,  1.46;  Pb,  59.42. 

Silver    Salts. 

Silver  was  determined  as  the  chloride. 

Silver  Maleate^  ''. — This  was  formed  by 
precipitating  '  silver  nitrate  solution  with 
sodium  nuileate  and  was  obtained  as  a 
white  precipitate  which  was  dried  at  100°. 

Analysis. — ^  Calc.  for  AgaC^HjO^  :  Ag, 
65.42.     Found:  65.44. 

The  compound  deflagrated  when  heated 
during  combustion  (leaving  metallic  silver) 
and  the  carbon  and  hydrogen  results  are 
considered  unreliable. 

Silver  Fumarate. — This  compound  has 
not  been  described.  It  was  prepared  in  the 
same  way  as  was  the  maleate,  and  behaved 
similarly.  Its  silver  content  was  64.90  per 
cent. 

Solubilities. 

A  number  of  the  salts  were  tested  for 
solubility  in  water.  Samples  were  placed 
in  60  cc.  bottles  with  distilled  water  and 
securely  stoj)pered.  They  were  then  held 
in  a  thermostat  at  the  required  tempera- 
ture for  24  hours,  25  cc.  portions  of  the 
clear  solutions  were  withdrawn  in  a  weigh- 
ing bottle  by  means  of  a  pipet  with  cotton 
filter,  weighed,  transferred  to  a  platinum 
dish,  evaporated  to  dryness  and  heated  to 
constant  weight  at  100°.  With  the  acid 
salts,  the  amount  of  solute  was  determined 
by  titration.  The  sampling  of  the  solutions 
saturated  at  60°  and  100°  was  done  entirely 
under  the  surface  of  the  water  in  the  ther- 
mostat with  an  apparatus  described  by 
Pawlewski.^^. 

The  solubility  results  are  given  in  Table  I. 
Summary. 

The  data  in  the  literature  regarding  the 
salts  of  maleic,  fumaric  and  i-malic  acids 
have  been  reviewed  and  the  water  of  cry- 
stallization of  a  number  of  these  salts  de- 
termined. In  some  cases  the  work  agrees 
with  that  of  past  observers,  but  in  others 
new  numbers  are  apparently  justified.  Some 
11  salts,  not  previously  described,  were  pre- 
pared and  the  water  of  crystallization  de- 
termined in  certain  cases  definitely. 

The  solubilities  in  water  of  22  salts  were 
determined  and  tabulated.  In  general,  fu- 
marates  are  less  soluble  than  the  corres- 
ponding inaleates. 

50,  East  41.st  Street,  New  Yorl-,  N.Y. 


Patdewski,  Ber.,  1899,  XXXII. ,  1040. 


NOVEMBEB  2,  1923. 


THE  CHEMICAL  NEWS. 


281 


Tablk  I. 


Compound. 


Solubilities  of  Fumarates,  Maleates  axd  Malaxes. 


F<Mmula. 


Cadmium  fumarate  ..  CdC^HjO^ 

Cadmium  maleate  ....  C(lC4H304.2HjO 

Calcium  acid  fumarat  (  i(C4H^OJj.2H20 

Calcium  fumarate  ....  C  aC^HjO^.SHjO 

Calcium  acid  maleate  (  ii(C^HjO^)j.oHjO 

Calcium  maleate  (   iC^HjO^.HjO 

Cobalt  fumarate  (   >C,H,0^.4HjO 

Coipper  fumarate  (  ii(\,H^()^.2H,0 

Copper  maleate  (  iiC\Hj(\.H,0 

Lead  fumarate  ri^CjH.O^ 

Lead  i-malate  ri.C,H,0,V,H,0 

Lead  maleate  i'  (",HjO^ 

Manganous  fumarat<  i<  \Hj()^ 

Nickel  fumarate  ImO^H.O^.^H^O 

Silver  fumarate KgCJlfi^ 

Silver  maleate V^C^HjO^ 

Sodium  acid  fumarate  NaC^HjO^ 

Sodium  fumarate  N.ijC^HjO, 

Sodium  acid  maleate  N.iC,Hj()^.3HJ^) 

Sodium  maleate  N.iX',H./J^.*/,HjO 

Strontium  fumarate  SrC^UjO^ 

Zinc  fumarate  ZnC^HjO^.SHjO 


Solubilities  in  g.  per  100  g.  of  water. 

60°  100 


l'4.78 


25° 

30° 

40° 

0.09 

0.6(3 

5.19 

1.56 

21.13 

41.89 

2.49 

0.88 

0.02 

0.12 

0.025 

0.21 

0.052 

0.14 

0.36 

0.013 

0.12 

2.88 

6.87 

10.74 

22.83 

6.73 

12.81 

96.06 

0.29 
1.96 

18.15 


31.3 


30.2 
288.0 


STREATFEILD  MEMORIAL  LECTURE. 

The  Stroatfeild  Memorial  Lecture  was  de- 
livered by  Mr.  E.  M.  Hawkins,  F.LC,  at 
the  Finsbury  Technical  College,  on  October 
25.  He  dealt  with  various  aspects  of  Ana- 
lytical Chemistry. 

After  reference  to  the  value  of  the  train- 
ing which  he  and  his  former  fellow  students 
had  received  at  the  college  under  Meldola, 
Streatfeild  and  Castell  Evans,  the  lecturer 
emphasised  the  importance  <>f  a  know!e<lge 
of  Physics,  Mathematics  iind  Physical 
Chemistry  to  the  present-day  Analyst  and 
Consultant.  He  advised  the  students  to 
qualify  as  soon  as  possible  aflvr  the  college 
course  for  membership  of  the  Institute  of 
Chemistry,  and  emphasised  the  importance 
of  the  Finsbury  course  in  iprimarily  training 
men  for  the  practice  of  Chemistry. 

First  among  the  qualifications  required  in 
the  analyst  the  lecturer  placed  accuracy 
and  reliability,  to  which  shf>uld  be  added 
the  ability  to  decide  to  what  degree  of  accu- 
racy his  results  attained.  He  should  also 
have  a  due  sense  of  his  responsibility  in 
carrying  out  his  work,  especially  when  ex- 
tensive repetition  gave  to  it  an  a[)pearance 
of  drudgery. 


Secondly,  there  was  the  need  for  rapidity 
to  be  associated  with  accuracy,  as  few  stu- 
dents realised  the  speed  of  manipulation 
which  would  be  required  of  them  when  they 
obtained  a  post  after  leaving  college. 

Thirdly,  it  was  of  great  imiportanoc  that 
the  students  should  cultivate  the  gift  of  ex- 
pressing his  results  suitably  in  a  report,  for 
much  good  experimental  work  was  marred 
bv  the  inability  of  the  chemist  to  write  up 
his  results  in  such  a  way  that  the  bearing  of 
the  Work  could  be  properly  appreciated  by 
those  who  read  the  report.  It  was  neces- 
sary that  the  chemist  should  not  be  easily 
moved  from  an  opinion  formed  after  care- 
ful cwisideration  of  results  which  were 
obtained  by  honest  work  and  patient  inves- 
tigaticm. 

In  conclusion,  the  lecturer  stated  that  of 
the  three  classes  of  men  ipractising  chemis- 
try— w<M-ks'  chemists,  public  analysts,  con- 
sultants— the  first  class  would  greatly  out- 
number the  public  analysts  when  trade  le- 
vived,  whilst  consulting  chemists  would  be 
men  of  wide  experience  and  high  attain- 
ments who  would  be  called  upon  by  manu- 
facturers to  solve  their  problems,  and 
should  be  highly  renumerated  for  such 
work. 


282 


THE  CHEMICAL  NEWS. 


NOVEMBER  2,  1923. 


PROCEEDINGS  AXD  NOTICES  OF 
SOCIETIES. 


PHYSICAL  SOCIETY  OF  LONDON. 

A  meeting  was  held  on  Friday,  October 
26,  at  the  Imperial  College  of  Science, 
South  Kensington,  S.W. 

The  following  papers  were  read:  — 

The  Fine  Siructure  of  Some  Sodiuin  Salts 
of  the  Fatty  Acids  in  Soap  Curds,  hy  S.  H. 
Piper,  D.S.O.,  B.Sc,  and  E.  N.  Grindley, 
B.Sc. 

X-Ray  Analysis  of  Solid  Solutions,  by  E. 
A.  Owen,  M.A.,  D.Sc,  and  G.  D.  Pres- 
ton, B.A. 

Cohesion,  by  Dr.  H.  Chatley. 

Proceedings  of  the  meeting  held  on  June 
22,  Alexander  Russell,  M.A.,  D.Sc,  in  the 
chair  :  — 

The  Excitation  and  Ionization  Potentials 
of  Gases  and  Vapours,  bv  Prof.  F.  Horton. 
M.A.,  D.Sc,  F.R.S.,  'Holloway  College, 
University  of  London. 

The  study  of  ionization  potentials  dates 
back  to  the  discovery  of  the  phenomenon  of 
the  ionization  of  gases  by  collision,  but  the 
theoretical  importance  of  a  knowledge  of  the 
least  difference  of  potential  through  which 
an  electron  must  fall  in  order  to  acquire 
sufficient  energy  to  ionize  a  gaseous  atom  or 
molecule  on  collision  with  it  has  greatly  in- 
creased since  the  propounding  by  Bohr  of 
his  theory  of  atomic  structure.  Bohr's 
theory  predicted  the  possibility  of  an  atom 
being  excited  to  emit  radiation  by  the  im- 
pact of  an  electron  having  energy  in  excess 
of  a  definite  minimum  amount— an  Amount 
corresponding  to  an  "excitation"  potential 
less  than  that  required  for  ionization.  This 
prediction  has  been  verified  experimentally 
for  a  large  number  of  different  atoms,  and 
the  study  of  excitation  and  ionization  poten- 
tials has  yielded  strong  support  for  the  fun- 
damental assumptions  o  the  theory. 

The  experimental  methods  of  investiga- 
tion may  be  divided  into  two  classes:  — 

(1)  Those  depending  on  the  detection  of 
the  loss  of  energy  by  the  colliding  electron. 

(2)  Those  depending  on  the  detection  of 
the  radiation  or  ionization  resulting  from 
the  collisions. 

An  account  was  given  of  several  investi- 
gations by  each  method,  and  the  results 
obtained  were  briefly  sumitiarised.  The 
case  of  helium  was  referred  to  in  greater  de- 
tail.    Bohr's    view  of  the    structure  of    the 


helium  atom  was  described,  and  the  way  in 
which  it  leads  to  the  prediction  of  a  meta- 
stable  state  of  this  atom  was  indicated.  Ex- 
perimental results  in  support  of  this  view 
were  quoted. 

Finally,  the  prediction  of  the  absorption 
by  a  normal  atom  of  radiation  emitted  by 
another  similar  atom  during  the  transition 
from  an  excited  to  the  normal  condition  was 
explained,  and  j^e  experiments  by  means  of 
which  the  prediction  has  been  verified  were 
described. 


THE  SOCIETY  OF  PUBLIC  ANALYSTS 
AND  OTHER  ANALYTICAL  CHEMISTS. 
The  next  meeting  of  the  Society  will  be 
held  on  Wednesday,  November  7,  at  the 
Chemical  Society's  Rooms,  Burlington 
House,  Piccadilly,  W.,  at  8  p.m.  The  fol- 
lowing papers  will  be  read:  — 

.4  Quantitative  Study  of  the  Limitations 
of  the  Reaction  between  Atnnionia  and  So- 
dium, by  DiNSHAW  Rattonji  Nanji  and 
William  Simpson  Shaw. 

The  Gold-Beaters'  Shin  Test  for  Tannins, 
by  Phyllis  H.  Price,  B.Sc. 

Deter)nination  of  Nitrogen  in  Coal,  by  W. 
Donovan,  M.So. 

The  Estimation  of  Lead  in  Water  and 
Urine,  by  J.  C.  Thresh,  D.Sc,  M.D., 
F.I.C. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 

Ordinary  Meeting,  November  1. 

Industrial  Research,  trith  Special  Refer- 
ence to  Electrical  Engineering  Develop- 
ment, by  W.  Wilson,  B.E.,  M.Sc,  Mem- 
ber. 

During  the  past  40  years,  radical  changes 
in  manufacturing  conditions  have  rendered 
industrial  research  essential  for  the  attain- 
ment of  reasonable  efficiency  and  progress. 

Industrial  research  is  divisible  into  two 
orders,  the  more  general  and  the  more  par- 
ticular, both  being  necessary  for  the  produc- 
tion of  a  new  article.  The  second  is  usually 
termed  "  Development,"  and  is  the  special 
subject  of  this  paper. 

While  British  men  of  science  and  applied 
science'  have  been  pre-eminent  for  general 
research,    little  attention    has  been    paid  to 


NOVEMBER  2,  1923. 


THE  CHEMICAL  NKWS. 


•283 


develoiprnent.  Hence  few  inventions  have, 
within  recent  years,  been  brought  to  their 
conclusion  in. this  country,  as  compared 
with  the  great  amount  of  original  scientific 
work  which  has  been  successfully  accom- 
plished. 

The  reasons  for  this  were  analysed,  and 
the  cause  is  traced  to  lack  of  the  co-opera- 
tion necessitated  by  modern  manufacture. 
This  want  is  filled  by  development  depart- 
ments. 

The  various  functions  of  the  latter  were 
dealt  with.  Their  outcome  is  the  removal 
of  all  non-standard  work  and  technical 
troubles  from  the  shops  and  drawing  offict's, 
and  the  provision  of  original  and  matured 
designs  of  new  and  improved  articles  for 
manufacture. 

The  negligible  value  of  ordinary  sources 
of  novel  suggestions  was  discussed,  and  the 
qualifications  of  a  development  man  are  de- 
duced. The  question  of  staflfing  the  depart- 
ment, and  the  educational  qualifications 
which  the  staff  should  posst  ss,  are  then 
treated. 

Practical  matters,  including  buildings 
and  equipment,  procedure  in  development, 
the  recording  and  filing  of  results  and  data, 
and  the  indexing  of  literature  and  informa- 
tion were  discussed. 

A  short  summary  was  given  of  the  prin- 
cipal industrial  research  organisations  in 
(^ireat  Britain,  with  a  brief  discussion  on  co- 
ordination. 


THE  SOCIETY  OF  GLASS 
TECHNOLOGY. 

The  first  mee-ting  of  the  Society  of  Glass 
Technology  for  the  session  11)23-24  was  held 
in  Sheffield  on  October  17,  the  President, 
Prof.  W.  E.  S.  Turner,  D.Se.,  in  the  chair. 

"Frank  Wood"  Medals  were  presented  to 
Mr.  A.  H.  Sheen,  B.Sc.Tech..  and  Mr.  F. 
Winks,  B.Sc.Tech.,  by  Sir  W.  H.  Hadow, 
C.B.E.,  M.A.,  D.Mus.  The  design  of  the 
medals  was  the  work  of  Mr.  Percy  Metcalfe, 
a  former  pupil  of  Prof.  W.  Rothenstein, 
Professor  of  Civic  Art  in  tlu'  University  of 
Sheffield.  Prof.  Rothenstein  pointed  out 
that  it  had  been  the  custom  during  the  last 
century,  when  new  medals  were  struck,  to 
go  to  France  for  them,  hut  whenever  an 
Englishman  got  his  chance,  he  showed  tha< 
he  could  do  this  work  inuch  better  than  any- 
(>ne  else.  People  would  not  realise  that  to 
have  faith  in  their  own  cont-emporaries  was 
one  of  the  first  duties  of  citizenship. 


A  paper,  illustrated  by  lantern  slides,  en- 
titled. The  Effect  of  Tiiania  on  the  Proper- 
ties of  Glass,  by  A.  R.  Sheen,  B.Sc.Tech., 
and  Prof.  W.  E.  S.  Tukkeu,  D.Sc,  was 
given  by  Mr.  Sheen.  Much  has  recently 
been  shown  in  the  production  of  heat  resist- 
ing glass.  Manufacturers,  esipecially  of 
scientific  glassware,  were  realising  the 
necessity  of  making  a  glass  which  had  a 
high  thermal  endurance,  and  which  was 
also  capable  of  resisting  the  attack  of  sub- 
stances with  which  the  glass  came  into  con- 
tact, whether  solid,  liquid,  or  gaseous. 
Modern  heat  resisting  glasses  contained  a 
high  percentage  of  silica  and  also  boric 
oxide  in  considerable  amount,  e.g.,  the  well 
known  glass,  Pyrex  (which  owed  its  high 
thermal  endurance  to  its  exceptionally  low 
coefficient  of  expansion,  0.0000032)  con- 
tained approximately  80  per  cent,  silica  and 
12  per  cent,  boric  oxide.  In  the  case  of  sili- 
ca the  difficulty  was  to  obtain  a  sufficiently 
high  melting  temperature.  Glasses  con- 
taining boric  oxide. were  very  readily  melted, 
but  here  the  objection  was  the  effect  of  the 
oxide  on  the  durability  of  the  glass.  Recent 
research  in  the  Department  of  Glass  Tech- 
nology of  Sheffield  University  has  shown 
that  as  the  BjO,  content  of  a  glass  was  in- 
creased, the  durability  towards  water  and 
acid  increased  to  a  maximum,  and  then,  as 
the  BjOj  content  was  further  increased,  the 
flurability  fell  off  rapidly.  Boric  oxide  con- 
taining glasses  (and  of  oourso  glasses  with 
high  silica  content),  on  account  of  their 
acidic  nature,  were  readily  attacked  by 
alkalis.  What  information  there  was  con- 
corning  the  use  of  titania  in  the  tproduction 
of  glass  .seemed  to  point  to  the  fact  that 
titania  glass<^s  were  heat  resisting,  but  no 
experimental  data  were  given.  It  was  with 
this  consideration  specially  in  mind  that 
this  piece  of  work  was  undertaken. 

At  the  outset,  preliminary  tests  were 
made  to  find  out  what  mixture  of  silica,  ti- 
tania and  soda  would  give  glasses  at  the 
hij,diest  temperature  obtained  in  glass  melt- 
ing practice,  e.g.,  temperature  of  1,400°  to 
l,4o()°  C.  It  was  found  impossible  to  ob- 
tain a  glass  from  silica  and  titania  alone  at 
this  temperature.  Batches  were  then  cal- 
culated out  on  the  basis  of  the  glass  form- 
ula : 

0  SiOj  X  Na^O  yTiO,,  where  x  +  y  =  2, 
and  it  was  found  that   the  first  six  members 
of  the  series  gave  glasses  quite  readily,  i.e., 
glasses  of  the  approx-mate  molecular  com- 
positions :  — 


284 


(1)  6  SiOa  l.QNa^O;  aiTiO^. 

(2)  6  SiOa,  1.8  Na^O,  0.2  TiO^, 

etc.  etc.  etc. 

(6)  6  SiO^,  1.4  Na^O,  0.6  TiO^. 
in  which  the  soda  was  gradually  replaced 
by  titania.  Above  1.8  mol.  Ti02,  i.e.,  13 
per  cent.  TiOa,  it  was  found  increasingly 
difficult  to  melt  the  glass,  and  higher  tem- 
peratures were  required. 

It  was  found  that  if  these  glasses  were 
melted  under  reducing  conditions,  their 
colour  varied  from  light  amber  to  dark 
brown.  Therefore,  part  of  the  soda  content 
was  added  as  nitrate,  and  the  melting 
operation  was  carried  out  in  crucibles  with 
well-fitting  lids.  By  this  means,  colourless 
glasses  were  obtained. 

There  were  indications  during  these  melt- 
ing operations  that  titania  glasses  were  heat 
resisting.  It  was  found  in  many  cases  that 
the  glass  could  be  removed  straight  from 
the  furnace  and  allowed  to  cool  down  in  the 
open  air  without  splintering  or  cracking  of 
the  mass  of  glass  occurring. 

After  considering  the  analyses  of  these 
six  glasses,  the  first  question  dealt  with  was 
the  durability  of  the  titania  glasses  towards 
water.  It  was  found  on  comparing  witli 
the  correstponding  lime  and  magnesia  glasses 
that  the  titania  glasses  were  less  attacked 
than  the  lime  glasses,  especially  in  the 
earlier  members  of  the  series.  The  dura- 
bilities of  the  titania  glasses  were  found  to 
be  practicaTTy  the  same  as  those  of  the  cor- 
responding magnesia  glasses. 

The  annealing  temperatures  were  found 
to  be  rather  less  than  those  of  the  corres- 
ponding lime  and  magnesia  glasses. 

Next,  the  important  question  of  thermal 
expansion  was  dealt  with.  It  was  originally 
intended  to  determine  this  optically  by  the 
Fizeau-Pulfrich  method,  but  after  discus- 
sion it  was  eventually  decided  to  repeat  the 
melts  on  a  large  scale  to  draw  tubing  and 
determine  the  expansion  by  the  ordinary 
dilatometer  method.  The  thermal  expan- 
sions of  these  titania  glasses  (only  the  first 
four  glasses  of  the  series  were  tested)  were 
only  slightly  less  than  those  of  the  corres- 
ponding lime  glasses.  Therefore,  if  titania 
glasses  are  heat  resisting,  it  is  certainly  not 
due  to  their  having  a  low  expansion,  as  is 
the  case  with  Pyrex  glass,  for  example,  but 
the  cause  must  be  sought  in  some  other  fac- 
tor, such  as  tensile  strength  or  elasticity. 

These  glasses  possessed  good  working 
properties,  their  viscosity  increasing  rs 
titania  replaced  soda.  Throughout  all  the 
glasses  melted  in  connection  with  this  work 
there  was  hardly  any  evidence  of  devitrifica- 


THB  CHEMICAL  NEWS. 


NOVEMBER  2,  1923. 


tion  occurring.  TJiis  bore  out  the  state- 
ment of  previous  workers  that  titania  hin- 
dered devitrification. 

Mr.  a.  Cousen,  B.Sc,  A.R.C.S.,  then 
gave  a  paper  entitled  The  Estimation  of 
Selenium  in  Glass.  Illustrating  his  re- 
marks with  experiments,  Mr.  Cousen  said 
that  dufing  researches  on  the  use  of 
selenium  as  a  decolourising  agent,  it  was 
found  desirable  to  obtain  a  process  for  the 
estimation  of  selenium  in  the  glasses  ob- 
tained. The  amount  of  selenium  actually 
added  to  the  batch  was,  in  general,  of  an 
order  sufficient  to  give  only  1  part  of  the 
element  per  42,000  pai'ts  of  glass,  or  0.0024 
per  cent.,  if  no  less  occurred.  Since,  how- 
ever, selenium  was  volatile  at  the  tempera- 
ture of  the  furnace  (the  boiling  point  at  1 
atmosphere  pressure  is  680°),  values  con- 
siderably less  than  the  above  were  likely  to 
be  found.  The  only  chemical  method  for 
estimating  selenium  in  glass  so  far  pub- 
lished was  that  of  Frankel,  and  described 
by  Witt  (Sprechsaal,  1914),  and  this  was 
not  quite  comparable,  since  it  dealt  with 
proportions  of  selenium  at  least  ten  times 
as  great  as  those  it  was  desired  to  estimate. 

The  following  modification  of  the  above 
process  M^ns  found  to  give  results  of  fair 
accuracy.  Twenty  grams  of  finely  pow- 
dered glass  were  dissolved  slowly  in  hydro- 
fluoric acid,  and  after  standing  in  the  cold, 
with  the  exception  of  selenium,  the  pro- 
ducts of  decomposition  were  dissolved  by 
pouring  into  excess  of  boiling  water.  The 
selenium  itself  was  filtered  off  on  a  filter 
pulp  pad  in  a  Gooch  crucible.  From  the 
pad  the  selenium  was  removed  by  treating 
with  a  dilute  chlorine  solution  (about  one 
three-hundredth  normal).  To  the  filtered 
solution  was  added  1  cc.  of  5  per  cent,  gum 
arable  and  5  cc.  of  half  per  cent,  phenyl  hy- 
drazine hydrochloride — the  whole  being 
made  up  to  50  cc.  Colloidal  selenium  was 
obtained,  a  yellow  colour  slowly  developing, 
which  was  after  half  an  "hour  matched 
against  a  standard  solution  of  sodium 
selenite  similarly  treated.  The  method  on 
testing  with  synthetic  mixtures,  gave  re- 
sults well  within  0.0002  per  cent,  of  the 
actual  values,  and  a  commercial  glass,  for 
which  selenium  had  been  used  sufficient  to 
give  theoretically  0.0025  per  cent.,  was 
found  to  contain  actually  only  0.0006  per 
cent,  of  the  element. 

To  the  discussion  that  followed  there  con- 
tributed the  President,  Messrs.  W.  J.  Eees, 
J.  H.  Davidson,  and  J.  R.  Clarke.  Mr. 
Cousen  replied. 


NOVEMBER  2,  1923. 


During  the  forenoon  a  party  df  members 
of  the  Society  had  an  opj)orlunity  of  visit- 
ing the  River  Don  Works,  Sheffield,  of 
Messrs.   Vickers,  Ltd. 

The  next  meeting  will  be  held  in  the  lec- 
ture room  of  the  Coal,  Gas  and  Fuel  Indus- 
trial Deipartment,  the  Univirsity,  Leeds,  on 
the  afternoon  of  Wednesday.  November  21. 


>VjTHB  CHEMICAL  NEWS. 


285 


THE  INSTITUTION  OF  ELECTIHCAL 
ENGINEERS. 

There  will  be  a  wireless  section  meeting  in 
the  lecture  theatre  of  the  Institution,  on 
Wednesday,  November  7.  An  inaugural 
address  will  be  delivered  by  the  Chairman, 
Mr.  E.  H.  Shaughnessy,  O.li.E. 


INSTITUTE  OF  METALS. 
Lecture  on  American  Mktalluroy. 
Dr.  W.  Rosenhain,  F.R.S.,  is   to  U'ctijre 
before    the     Institute     of    Metals,    Londnn 
Local     Section,    on    Some    ImpreHniotiH    of 
AmericMn      Non-Ferrous     MrtaUurgy, 
Thursday,  November  8. 


on 


THE  INSTITUTE  OF  PHYSICS. 
At  the  last  meeting  of  the  lioard  the  fol- 
lowing Corporate  Members  were  electefl:- 
Frllows:  G.  R.  Bolsover,  J.  A.  Jones,  ('. 
H.  Lander,  T.  Takamine,  A.  Warren;  Ahho- 
ciatcH-.  K.  R,  Brain,  A.  L.  Gregwm,  J.  S. 
Grew,  .1.  A.  Hughes,  E.  O.  Jfercus,  T.  .]. 
I/onsdale,  R.  D.  Thompson,  J  P.  Wood. 


GENERAL    NOTES. 


NETHERLANDS. 

Tenders  Invited  for  Various  Goons. 

Mr.  R.  V.  Laming,  O.B.E.,  the  Comm.r- 
cial  Secretary  at  The  Hague,  informs  tlir 
Department  of  Overseas  Trade  that  ih.- 
Colonial  Establishment,  Westerdoksdijk  2. 
Amsterdam,  is  calling  for  tenders  for  various 
goods,  tenders  to  reach  the  Director  of  thf 
Colonial  Establishment  (through  the  Dutch 
representatives  of  United  Kingdom  firms) 
by  1  p.m.  on  October  31.  1923. 

The  goods  required  include  white  writing 


paper,  cardboard,  packing,  copying  and 
miscellaneous  paper,  leather  hat  bands, 
hard  haberdashery  for  uniforms,  nails,  shoe 
rivets  and  hooks  and  eyelets,  ironmongery, 
zinc  sheets,  earthenware  pipes,  street 
cobbles,  fireproof  stone,  bookbinders'  glue, 
sealing  wax,  certain  chemicals  and  oils,  and 
soap  and  soap  powder. 

The  tenders  are  called  for  under  the 
usual  general  conditiMis,  but  the  Dcipart- 
ment  of  OversjBas  Trade  has  available  for 
inspection,  by  interested  British  firms, 
copies  of  the  specitications  (in  Dutch),  con- 
taining special  requirements  and  dates  of 
delivery.  These  may  be  seen  on  applica- 
tion to  the  Department  at  35,  Old  Queen 
Street,  S.W.I  (Room  84). 

It  will  be  noted  that  tenders  must  be  sub- 
mitted through  local  representatives.  The 
Department  will  be  pleased  to  place  U.K. 
finns  desirous  of  tendering  and  not  repre- 
sented in  Holland,  in  touch  with  firms  hav- 
ing branches  in  Holland  who  may  be  willing 
to  act  on  their  behalf  in  this  matter.  (Re- 
ference:  20890/F.W./G.P.). 


UNIFORMS    AND    GENERAL    STORES 

FOR  EGYPTIAN  POSTAL 

ADMINISTR.VnON. 

Mr.  E.  Homan  Mulock,  H.M.  Commer- 
cial Agent  for  Egypt,  reports  that  the  Pos- 
tal .\dministration  at  Alexandria  is  inviting 
tenders,  to  be  presented  in  Alexandria  by 
noon  on  November  15,  1923,  for  the  supply 
of  uniforms  and  general  stores  (including 
mail-bags,  boots,  calcium  carbide,  candles, 
furniture,  hardware,  lamps,  steel  stamps, 
etc.). 

Further  particulars  may  be  obtained  by 
interested  United  Kingdom  firms  on  appli- 
(ration  to  the  Department  of  Overseas 
Trade,  where  a  copy  of  the  specifications, 
ecmditions,  and  form  of  tender,  etc.,  is 
Mvailable  Ux  inspection  up  to  October  31. 
After  that  date  these  documents  will  be 
foi-warded  on  loan,  in  order  of  application, 
to  firms  in  the  provinces,  who  may  be  un- 
able to  arrange  for  their  inspection  by  a 
London  representative. 


The  Ministry  of  Agriculture  and  Fisheries 
has  re-issued  Leaflet  No.  80,  on  The  Use  of 
Artificial  Manures.  It  is  pointed  out  that 
there  are  two  mnin  classes  of  manures:  — 


286 


Tnr.  CHEMICAL  NEWS. 


NOVEMBER  2,  1923. 


(1)  Natural  (organic) — the  direct  product 

of  animals    or    plants,     such    as    farmyard        , 
manure,     seaweed,     green     manure,       fish 
waano,  &c. 

(2)  Artificial  (inorganic)— this  term  is 
used  quite  correctly  of  such  manures  as 
superphosphate,  nitrate  of  lime  and  others 
which  are  produced  by  processes  of  manu- 
facture; it  is  also  used,  not  quite  correctly, 
of  mineral  manures  such  as  mineral  phos- 
phate, potash  salts  and  nitrate  of  soda, 
which'  are,  strictly  speaking,  natural. 

There  are  three  forms  of  food  which 
plants  mainly  require  from  the  soil,  nitro- 
gen, potash  and  phosphates.  Artificial 
manures,  as  a  rule,  supply  only  one  of  these 
forms.  Each  class— nitrogenous,  potassic 
and  phosphatic — comprises  several  kinds  of 
manures  which  differ  in  their  action,  Thiis 
in  the  nitrogen  class,  nitrate  of  soda  is 
quicker  in  its  action  than  sulphate  of  am- 
monia, and  in  the  phosphate  class  super- 
phosphate is  quicker  than  raw  phosiphate. 
Or  one  kind  may  he  more  suitable  to  a  cer- 
tain crop  than  ^another,  as,  in  the  potash 
class,  sulphate  of  potasK  is  better  than  kain- 
it  for  potatoes,  and  in  the  phosphate  class 
basic  slag  is  usually  better  for  grassland. 

Guidance  is  given  as  to  the  average  quan- 
tities required  by  different  crops.  Three 
points  require  to  be  noted : 

1. — If  a  plant  is  stinted  in  one  of  its  re- 
quirements, even  though  other  requirenrients 
are  abundantly  provided,  the  result  will  be 
little  better  than  if  it  had  been  equally 
stinted  of  all. 

2. — It  is  equally  wasteful  to  use  too 
much  as  too  little  manure.  The  right 
amounts  will  lie  somewhere  in  the  neigh- 
bourhood of  what  is  here  given;  the  actu- 
ally correct  amounts  can  only  be  learned 
by  experience  and  by  trial. 

3. — Costs,  both  one's  own  and  those  given 
in  records  of  trials,  must  be  studied.  The 
dressing  which  produces  the  highest  yield 
is  not  always  the  most  economical. 

Of  hardly  less  importance  than  the  selec- 
tion of  manures  is  their  distribution.  What- 
ever amount  of  manure  is  employed,  care 
should  be  taken  to  spread  it  equally  over  the 
soil.  Artificial  manures  are  easier  to  spread 
evenly  when  they  are  fine  and  free  from 
lumps.  It  may  be  necessary  to  pass  the 
material  through  a  quarter-inch  riddle, 
breaking  all  the  lumps  that  fail  to  go 
thrr/Ugh.  Seme  manures  change  into  hard 
lumips  if  stored  for  some  months.  This  is 
one  reason  why  it  is  seldom  desirable  to 
store  manures    for  a  long  period.       If    this 


has  to  be  done,  the  addition  of  a  small  i)io- 
portion  ot  peat-litter  dust  or  sawdust  will 
help  to  keep  them  from  caking.  One  often 
sees  artificial  manure  being  sown  contain- 
ing lumps  as  large  as  peas,  and  sometimes 
as  large  as  walnuts.  Not  only  does  the  pre- 
sence of  lumps  prevent  much  of  the  crop 
getting  its  air  share  of  the  dressing,  but  the 
spots  on  which  the  lumps  fall  are  actually 
poisoned,  so  that  the  plants  are  weakened 
or  killed  outright. 

Where  possible,  manures,  especially  the 
slower  acting  manures,  should  be  thor- 
oughly mixed  with  the  soil.  For  instance, 
where  artifioials  are  being  applied  to  a  corn 
crop,  they  should  be  aipplied  at  seed  time, 
so  as  to  get  the  benefit  of  the  subsequent 
harrowing. 


*  NOTICES  OF  BOOKS. 

Practical  Physical  Chemistry,  by 
Alexander  Findlay,  M.A.,  D.Sc.  Pp. 
XVI.  +  298.  Fourth  Edition.  London: 
Messrs.  Longmans,  Green  &  Co.,  39, 
Paternoster  Row,  E.C.4.  1023.  7s.  6d. 
net. 

The  first  edition  of  Prof.  Findlay 's  indis- 
pensable Practical  Physical  Chemistry  ap- 
peared in  1906,  and  the  third  in  1914.  Since 
the  latter  date  the  demand  for  the  book  has 
been  met  by  the  printing  of  new  impres- 
sions. 

Nearly  a  decade  has  elapsed  since  the 
subject  matter  has  been  revised,  and  hence, 
in  the  latest  edition,  he  includes  many  al- 
terations and  extensive  additions,  yet  the 
general  character  of  the  book  as  a  student's 
laboratory  companion  remains  unaltered. 

New  matter  has  been  introduced,  dealing 
with  Cottrell's  Ebullioscopic  Method  for 
determining  Molecular  Weights,  and  ac- 
counts of  the  Abbe  Eefractometer  and  Hil- 
ger's  (constant  deviation)  Wave-length 
Spectrometer  are  also  included. 

Another  important  addition  is  a  chapter 
containing  .  a  very  suitable  set  of  experi- 
ments illustrating  some  of  the  more  striking 
properties  of  the  colloidal  state  of  matter. 

It  is  now  generally  recognised  that  prac- 
tical physical  chemistry  must  form  a  part 
of  a  gerieral  chemistry  curriculum,  and  the 
appearance  of  the  present  new  edition 
should  enable  Prof.  Findlay 's  volume  to  re- 
tain its  popularity  among  both  students  and 
lecturers. 


I 


NOVEMBER  2,  1923. 

Kelly's  Directory  of  ihc 
dustries.        Pp.    XXXI. 
Kelly's  Directories,    Ltd., 
W.C.2.    30s. 


THE  CHEMICAL  NEWS. 


287 


Chemical    In- 

903.      1923. 

186,    Strand, 


Information  is  given  concerning  chemical 
manufactuiers,  manufacturing  chemists, 
wholesale  dniggists,  drysa  Iters,  chemists 
and  drug  stores  (wholesaU-  and  retail).  Full 
lists  of  the  trades  comiprised  will  be  found 
in  this  book. 

The  sections  of  Kelly's  Directory  of  th»' 
Chemical  Industries,  1923,  include: — An 
aliphabetical  arrangement  of  the  names  in 
the  towns  and  villages  under  each  county, 
with  the  populations;  a  f^eneral  classifica- 
tion of  trades  for  London  and  its  suburbs, 
i.e.,  classified  lists  of  profission  and  trades 
with  the  names  arranged  alp'habetically  of 
tiiose  engaged  therein;,  a  similar  classifica- 
tion for  the  rest  of  England,  Scotland  and 
Wales;  the  names  for  the  principal  towns  of 
Ireland,  arranged  under  tow  ns  and  trades  ; 
and  the  names  of  the  Channel  Islands  and 
the  Isle  of  Man  arranged  under  town?. 

Another  feature  is  the  list  of  proprietar\ 
brands  and  articles  which  gives  the  makers' 
name  and  address  after  the  name  of  thr 
articles. 

It  is  very  apparent  that  many  alterations 
have  been  necessary,  and  it  need  hardly  be 
pointed  out  that  out-of-date  tlircctories  are 
often  the  cause  of  much  Inconvenience  and 
irritation.  This  ajpplies  to  thoge  for  the 
chemical  industries  as  well  as  others. 


Report  of  the  Oxygen  Research  Com- 
mittee. Pp.  VII.  +  177;  with  43  text 
figs,  and  6  plates.  8s.  Od.  net.  By  pot 
88.  9d.  Published  by  H,M.  Stationery 
Office  for  the  I3ept.  of  Scientific  and  In- 
dustrial Ilesearch. 

This  report  describes  certain  aspects  of 
the  work  of  the  Oxygen  IJc^carch  Commit- 
tee since  its  appointment  in  1919.  It  deals 
chiefly  with  the  technical*  difhculties  which 
have  hitherto  restricted  the  commercial 
utilisation  of  liquid  oxygen  and  liquid  air, 
and  describes  in  particular  recent  improw- 
ments  in  the  methods  of  handling  the  liqui- 
fied gases  on  a  practical  commercial  scale. 
The  work  of  the  Committee  has  been  car- 
ried out  principally  in  the  ITeriot  Watt  Col- 
lege, Edinburgh,  and  the  .\ir  Ministry  Oxy- 
gen T^aboratory. 

The  subject  matter  of  the  report  is  ar- 
ranged under  the  following  headings:  — 


Part  I. — The  Storage  of  Liquefied  (Juscs  : 
The  vacuum  vessel ;  the  physics  of  the 
vacuum  vessel;  exiperimeutal  analysis  of 
heat  entry;  adsorbents  and  adsorption. 

Part  II.— The  Manufachtrc  of  Metal 
Vacuum  Vessels  for  Liquefied  Gases:  De- 
fects of  containers  and  vaporisers;  improve- 
ments in  the  design  of  vaporiser  receptacles ; 
the  assembly  of  vacuum  vessels;  the  test- 
ing of  vacuum  vessels;  the  problem  of  eva- 
cuation; evacuating  plant. 

Part  III.— Vacuum  Vessels  in  Use  :  Glass 
vacuum  flasks;  the  transference  of  liquefied 
gases;  some  results  of  the  periodic  testing 
of  vaporisers;  decay  of  vacua  in  metal  flasks. 

Part  IW.— The  Transport  of  Liquefied 
Gases  attd  Compressed  Gases:  Protection 
and  suipport  of  containers  in  transit;  losses 
during  transport;  railway  regulations  for 
the  transport  of  liquid  air;  the  transport  of 
compressed  oxygen. 

•Appendix. — Physical  Data. 

Index. 

Copies  may  be  obtained  through  any 
book.^ollcr,  or  direct  from  H.M.  Stationery 
Office. 


BOOKS  RECEIVED. 

Van  Nostrand's  Chemical  Annual,  bv 
John  C.  Olsen,  A.M.,  Pn.D.  Pp.  XXII.  + 
900.  t^fth  issue,  1928.  Messrs.  Constable 
&  Co..  Ltd.,  10-12.  Orange  Street,  W.C.2. 
21s.  net. 

Smith's  General  Chemistry  for  Colleges, 
by  Jamks  Kenm.mx,  Pp.  XIII.  +  747. 
1923.  Messrs,  Hell,  York  House  P-rtn^'al 
Street,  W,C.2,     18s.  6d.  net. 

Recent  Developments  in  Atomic  Theory, 
by  Leo  Gbaetz,  Professor  of  Physics  in  the 
University  of  Munioh.  Pp.  XL  +  174. 
1923.  Messrs.  Methuen  &  Co.,  Ltd.,  30, 
Essex  Street,  W.C.2.     9s.  net. 

Chemical  Engineering  Catalog',    by  Tiik 

Chemical    Catalog    Company,    Inc.  Pp. 

1,050.     Eighth  Annual  Edition,  1923.  The 

Chemical  Catalog  Company,  Inc.,  19,  East 
24th  Street.  New  York,  U.S.A. 

The  Manufacture  of  Nitric  Acid  and  Ni- 
trates, by  Allin  Cottbell,  M.Sc,  F.I.C, 
M.I.Chem.E.  Pp.  XV.  +  554,  1923. 
Messrs.  Gurnev  i*^  Jackson,  33,  Paternoster 
Row,  E.C.4.     "Hlis.  net. 


288 


THE  CHBMICAI.  NEWS. 


NOVEMBER  2,  1923. 


Elementary  Chemical  Calculations,  by 
Martin  Meyer,  Ph.D.,  College  of  the  City 
of  New  York.  Pp.  VI.  +  131.  1923.  Ox- 
ford Book  Company,  175,  Fifth  Avenue, 
New  York,  U.S.A. 


PUBLICATIONS    RECEIVED. 

Bulletins  issued  by  the  U.S.  Department 
of  the  Interior,  Bureau  of  Mines:  — 

The  Electrothermic  Metallurgy  of  Zinc, 
by  B.  M.  O'Hara.    Pp.  VI.  +  106. 

Timbering  of  Metal  Mines,  by  E.  A.  Hol- 
BROOK,  Richard  V.  AcxEton,  and  Harry  E. 
TUFFT.     Pp.  VII.   +  72. 

Water-Gas  Tar  Emulsions,  by  W.  W. 
Odell.    Pp.  IV.  +  51. 

Leaching  Nonsulphide  Copper  Ores  with 
Sulphur  Dioxide,  by  Charles  E.  van  Bar- 
NEVELD  and  Edmund  S.  Leaver.  Pp.  V.  + 
91. 


I'His  list  is  specially  compiled  foT  The  Chemical 
News,  by  Messrs.  Rayner  4  Co.,  Registered  Patent 
Agents,  of  5.  Chanoe-y  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Mark.s, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent  Applications. 

25111— British  Cellulose  &  Chemical  Manufactur- 
ing Co.,  Ltd.— Treatment  of  cellulose  deri- 
vatives.   Oct.  9. 

25328— Crundall,  S.  F.  W.— Production  of  titanium 
compounds.    Oct.  11. 

25274i — Thorn,  I.— Process  of  hardening  products 
of  condensation  from  phenols  and  alde- 
hydes.   Oct.  10. 

25478— Hoffman  la  Roche  &  Co..  Akt-Ges.  F.— 
Manufacture  of  emulsions  of  bismuth  salts. 
Oct.  12. 


Specifications  Published  this   Week. 

18280*— Ges  Fur  Kohlentechnik.— Process  and  ap- 
paratus for  separating  ammonia  and  ben- 
zol hydrocarbons  from  coal  distillation 
gases, 


187593— Howard,  H.— Process     for  the     production 
of  hydrogen  sulphide. 

192703 — Soc.   d'Etudes  Chiniiques  pour  riiulustrie. 
Process  for   the     manufacture     of     urea 
from  cyanamide. 


Abstract  Published  this  Week. 


203743— Hypodermic  injections.— Kato,     J.,     of  33, 
Ekandocho,  Kamikyo-ky,  Kyoto,  Japan. 

Hypodermic  injections;  colloidal  sols. — A  re- 
medv  to  be  injected  into  hfemorrhoids  consists  of 
a  colloidal  suspension  of  metallic  magnesium  in  a 
harmless  and  chemically  inert  liquid  such  as  gly- 
cerine, olive  oil,  or  liquid  paraffin.  Tlie  colloidal 
suspension  is  prepared  by  finely  powdering  the 
magnesium,  suspending  it  in  the  glycerine,  &c.. 
and  passing  an  electric  current  of  2  amps  at  40 
volts  between  platinum  electrodes  for  a  period  of 
two  hours  with  continuous  stirring  and  cooling. 
The  preparation  is  stored  in  an  atmosphere  of 
hydrogen  or  nitrogen. 

Lignone  sulphonic  acid-t;  pulp,  preparation  of. 
—Wood  and  like  lignified  materials  are  resolved 
by  treatment  at  100-110°  C  with  a  strong  aqueofls 
solution  of  sulpliurous  acid  which  is  originally 
substantially  free  from  sulphuric  acid.  Prefer- 
ably the  process  is  carried  out  in  a  digester  lined 
witli  acid-resisting  cement,  and  the  materials 
under  treatment  are  rapidly  agitated.  In  an  ex- 
ample, wood  prepared  as  for  the  bisulphite  pro- 
cess is  treated  with  six  times  its  weight  of  a  seven 
per  cent,  solution  of  sulphurous  acid  purified 
from  sulphuric  acid.  The  mass  is  heated  with 
open  steam  for  six  hours;  then  steam  at  a  tem- 
perature of  105-110°  C.  is  employed  foi-  a  further 
ten  hours  to  complete  the  resolution.  The  liquor 
containing  the  lignone  derivatives  may  be  eva- 
porated to  dryness,  preferably  under  reduced 
pressure,  or  prepared  in  concentrated  form  for 
transport.  These  derivatives  are  stated  to  be 
different  from  those  contained  in  sulphite-cellu- 
lose liquor. 


Sulphurous  acid  for  use  in  the  process  is  ren- 
dered free  from  sulphuric  acid  by  treatment 
with  barium  sulphite  or,  according  to  one  Pro- 
visional Specification,  with  barium  acetate  or  bi- 
sulphite. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each. 


JOUKNALS    FOR    SALE. 

JOURNAL  OF  THE  CHEMICAL  SO- 
CIETY, 1915,  1920,  complete  with 
Indexes,  £1  each  year.  Journal  of  Indus- 
trial &  Engineering  Chemistry,  1919,  £1. 
Chemical  Neivs,  1921,  1922,  15s.  each  year. 
All  unbound,  but  in  excellent  condition. — 
H.E.,  c/o  The  Chemical  Neivs,  97,  Shce 
Lane,  London,  E.C.4. 


NOVEMBER  9,  1923. 


THE  CHEMICAL  NEWS. 


289 


THE    CHEMICAL  NEWS, 


VOL.  CXXVII.      No.  3317. 


BRITAIN  HER  OWN  CHEMIST. 
Progress  of  a  Vital  Industry. 

A  sum  of  £10(),()00  is  to  be  spent  on  the 
Chemical  Section  of  the  British  Empire 
Exhibition  at  Wembley  next  year.  It  is  to 
occupy  40,(XX)  squart-  feet  in  the  Palace  of 
Industry,  and  it  will  be  built  iu  such  a  way 
as  to  form  a  self-contained  Imil  within  the 
1 'a lace.  It  is  intended  to  j)r(sent  to  the 
public  a  complete  picture  of  the  present 
state  of  the  British  Chemical  Industry. 
No  important  firm  in  the  industry  will  \yo 
unrepresented,  and  their  exhibits  will  num- 
IxT  over  a  hundred. 

In  an  interview  last  week.  .Mr,  \V.  1.  I  . 
WoolecKrk,  C.B.E.,  General  Manager  of  the 
British  Association  of  Chen  ileal  Manufae 
turers,  said  that  the  chemical  hall,  in  which 
the  exhibits  will  be  grouiped,  would  Ik?  th»- 
most  comprehensive  exhibition  of  the  pro- 
duets  of  Tiritish  science  and  industry  ever 
brought  together.  It  would  certainly  he 
the  biggest  thing  British  chemical  industry 
has  yet  attempted,  and  there  will  be  every 
hope  of  impressing  the  Empire  both  witli 
their  present  position  and  their  prospects. 

They  were  not  going  to  be  content  with 
an  impressive  H.pectacle  of  past  achieve- 
ments; they  desirfd  to  illustrate  what  is 
behind  the  processes  of  production.  They 
hope,  also,  to  show  that  by  reason  of 
British  invcnticai  and  research  there  are 
guarantees  that  the  industry  will  never  be 
left  behind  again. 

A  group  of  the  best  scientific  minds  in 
this  country  are  co-operating  with  the  Afso- 
ciation  in  illustrating  the  advances  made  in 
the  last  20  years  in  every  branch  of  pure 
chemical  science.  The  impt^rtancc  of  the 
chemical  industry  in  the  daily  life  of  any 
nation  is  vital,  and  they  are  going  to  illus- 
trate it.  There  is  the  sulphuric  acid  indus- 
try, which  is  such  an  index  of  national 
prosperity  that  Disraeli  once  said:  "  The 
measure  of  a  country's  iprosperity  can  be 
gauged  by  the  amount  of  sulphuric    acid  it 


is  producing  per  head  of  population."  The 
alkali  industry  is  one  of  the  most  impor- 
tant of  the  chemical  industries,  boo,  and  its 
development  is  one  of  the  romances  of 
Britain. 

Then  there  are  all  those  industries  which 
have  arisen  out  of  the  distribution  of  coal, 
the  production  of  coal-tar  products,  and 
the  preparation  of  the  thousand  and  one 
substances  of  the  dyestufif  and  fine  chemi- 
cal industries.  The  discovery  of  the  first 
artificial  colouring  matter  was  made  in 
England;  its  development  was,  as  one 
might  expect,  left  to  the  Germans.  In 
1013,  80  per  cent,  of  the  dyestuflfs  used  in 
this  country  were  obtained  from  Germany 
and  Switzerland ;  to-day  we  produce  80  per 
cent,  of  what  we  require,  and  import  only 
20  per  cent. 

The  discoveries  of  British  chemists  in 
the  class  of  chemicals  called  antiseptics 
have  been  instnunental  in  saving  thousands 
of  valuable  lives,  and  such  discoveries  are 
only  the  beginning.  The  extraordinary  pro- 
gress made  in  recent  years  in  British  labora- 
tories has  helped  to  make  the  disease- 
lidden  lands  within  and  without  the  Em- 
pire safe  for  the  white  man.  Without  these 
remedies,  some  of  which  are  quite  new  to 
science  and  have  been  elaborated  during 
and  since  the  war,  British  colonization  and 
trade  in  the  tropics  and  sub-tropics  would 
be  seriously  handicapped. 

Chemistry  is  the  "  open  Sesame  "  of 
modem  industry.  The  constant  scientific 
control  of  the  manufacture  of  foodstuffs,  of 
the  means  of  locomotion,  of  the  supply  of 
gas  and  water,  is  essential  in  modern  life. 
The  establishment  of  a  complete  British 
chemical  industry  is  a  great  achievement. 
The  Association  considei^  it  vital  that  the 
Chemical  Section  at  the  British  Empire 
Exhibition  should  adequately  represent  the 
growing  importance  of  the  industry.  That 
is  why  the  Committee  is  taking  such  pains 
to  ensure  that  the  disiplay  they  are  arrang- 
ing shall  bo  fully  represented. 

We  certainly  think  that  whatever  dam- 
age the  war  may  have  done  to  the  industry, 
good  support  and  representation  in  the 
matter  will  again  put  it  on  a  substantial 
and  even  more  progressive  basis.        J.AL 

— (7?j/  courteHy  of  the  BriiiKh  F.wpirp 
ExhihifioH,  1924*  Inc.) 


9 


290 


THE  CHEJMICAL  NEWB. 


NOVEMBER  9,   1928. 


ARE    THE  NATURAL  GROUPINGS    OF 

THE  ELEMENTS  AND  THE  SPECTRAL 

LINES  OF  HYDROGEN  RELATED? 

Part  III. 
By  F.  H.  LoRiNG. 

In  continuation  of  the  above  subject — see 
The  Chemical  News,  1923,  Vol.  CXXVIL, 
pp.  273-275 — the  question  arises  as  to 
whether  the  argument  presented  can  be 
strengthened  by  taking  into  consideration 
certain  phenomena  that  may  be  in  some  un- 
known way  related  thereto. 

Since  the  atom  is  now  believed  to  be  a 
planetary  system  in  which  the  electron  re- 
presents the  planet  and    the  nucleus  of  the 


atom  the  sun,  a  consideration  of  our  solar 
system  iii  connection  with  these  studies  is 
of  interest.  It  is  possible  that  a  planetary 
system  such  as  our  solar  system  is  not  an 
ideal  one  to  comipare  with  the  so-called 
planetary  system  of  hydrogen.  Sir  O. 
Lodge  has  practically  raised  this  question, 
but  so  far  as  the  writer  is  aware,  no  direct 
or  indirect  relations  have  been  found  com- 
parable in  exactitude  with  Bode's  Law.  It 
will  be  seen  from  the  accompanying  table 
that  the  groups  a,  /3,  y,  8,  e  afford  direct 
values  which,  so  far  as  they  extend,  agree 
about  as  well  with  certain  planetary  dis- 
tances as  do  Bode's  figures,  especially  when 
the  comparison  is  made  in  the  manner  in- 
dicated in  the  table  referred  to. 


Semi-Major  Axis  of 

Oi 

^BIT. 

Bode's  Law. 

Earth  =  10. 

Diffs. Millions 

of  Miles  /lO. 

Gi'oups. 

Dif£b 

Mercury 

0  +  4  = 

4 

3.87 

+0.13 

3.6 

— 

— 

Venus 

3  +  4  = 

7 

7.23 

-0.23 

6.72. 

7 

+0.28 

Earth 

6  +  4  = 

10 

10.00 

0.00 

9.29 

9 

-0.29 

Mars 

12  +  4   = 

16 

15.23 

+0.77 

14.16 

13 

-1.16 

Asteroids 

24  +  ?  = 

28 

27* 

251 

21 

Jupiter 

48  +  4  = 

52 

52.02 

-0.02 

48.33 

48 

-0.33 

Saturn 

96  +  4  = 

100 

95.39 

+4.61 

88.62 

— , 

— 

Uranus 

192  +  4  = 

196 

191.90 

+4.1 

178.28 

— 

— 

Neptune 

384  +  4  = 

388 

300.70 

+88 

279.35 

— 

— 

*  This  is  a  mean  value,  the  extremes  being  below  25.5  to  above  28.5. 
f  This  is  a  mean  value,  the  extremes  being  below  23.7  to  above  26.5. 
Above  planetary  data  taken  from  Kaye  and  Laby's  "Tables  of  Phys.  and  Chem. 
Constants." 


Notes. 

In  the  column  giving  the  distances  from 
the  sun  in  millions  of  miles  divided  by  10,  it 
should  be  noted  that  the  figures  are  mean 
ones. 

With  regard  to  the  asteroids,  or  minor 
planets  as  they  are  often  termed,  there  may 
have  been  a  planet  of  moderate  size 
and  of  small  mass,  between  Mars 
and  Jupiter,  which  was  reduced  to 
comparatively  small  fragments  by  disrup- 
tion. There  are  over  800  minor  planets, 
the  largest  having  a  diameter  of  about  400 
miles. 

It  has  been  shown  mathematically  that  if 
such  a  catastrophe  had  occurred,  the  orbits 
of  the  small  bodies  should  at  some  time  in 
their  paths  pass  through  the  place  where 
the  disruption  took  place  in  space,  but  this 
coincidence  is  apparently  not  the  case. 
From  other  considerations,  such  as  a 
series  .of  catastrophies,  the  calculation 
may  require  revision,  so  that  the  whole 
problem  of  the  asteroids  is  one  that  should 
not    necessarily    carry  weight  in  the    argu- 


ment against  the  rules  made  evident  in  the 
above  table. 

It  is  to  be  noted  that  the  smallest  mean 
distance  for  the  minor  planet  Medusa  is 
198, 134, OCX)  miles;  so  that  in  a  remote 
sense  the  group  forms  a  kind  of  mass  band 
(their  planes  do  not  coincide),  one  edge  of 
which  corresponds  fairly  closely  with  the 
value  21. 

The  following  quoted  paragraph  from  the 
first  of  a  series  of  articles  on  the  atom  by 
Sir  0.  Lodge,  in  Bcama,  of  July,  August, 
September,  October,  1923  (continued),  is  of 
interest,  but  the  agreement  between  Bode's 
law  and  Bohr's  law  of  orbital  radii  in  re- 
sipect  a^  the  hydrogen  atom  is  not  as  close  as 

.  are  the  a,  ft,  y,  8,  e  group  values  in  the 
comparison  given  above  in  the  table.  Ijodgo 
says: — "  The  electric  case  is  simpler  than 
the  planetary,  for  the  planets  differ  in  mass 
as  well  as  in  distance,  whereas  the  elec- 
trons are  all  alike  and  differ  only  in  distance 
from  the  centre.  Every  orbit  will  have  its 
characteristic  moment  of  momentum,  and 
if  we  could  say  that  this  moment  of  momen- 
tum,    having    a    certain    value     1    for    an 


NOVEMBEK  9.  1923. 


J6 

^^B  CHEMICAL  NEWS 


291 


iiiueniio.st  orbit,  was  2  for  thf  next,  3  for 
the  next,  and  so  ou,  it  would  be  delightfully 
siiiipie.  In  othf'r  words,  if  tlu'  moment  of 
iiioiiienfcuin,  or  what  is  praclically  the  same 
thing,  the  rate  of  sweeping'  jtrcas,  is  not 
only  constant  for  each  orbit,  but  proceeds 
by  equal  steps  or  simple  imiltiples  from 
one  orbit  to  the  next,  how  much  simpler 
the  law  of  succession  would  be  than  the  at 
present  unknown  law  of  succession  of  the 
planets — the  discovery  of  which  was'  at- 
tempted bmg  ago  by  the  astronomer  Bfxle. 
Well,  strange  to  say,  this  Hint  pie  laic  doea 
appear  to  hold  rather  accuratrjy  for  the 
atomic  orhitn.  'J'his  was  discovered  not  by 
B<Kle,  but  by  Bohr.  Calling  the  unit  mo- 
ment of  momentum  a  lot  (which  is  a  con- 
venient name  employed  by  auctioneers  for 
an  indivisible  group  which  you  can  take  or 
leave  as  a  whole),  the  moments  of  momen- 
ta characteristic  of  successive  orbits  have 
to  be  1  lot,  2  lota,  3  lots,  etc.,  as  the  orbits 
increase  in  radii;  and  the  result  is  that  the 
radii  f>f  successive  orbits  jprf>ceed  as  the 
squares  of  the  natural  numb<rs,  provided 
the  law  of  attraction  is  as  the  inverse 
squari'  of  the  distance — as  for  electrical  at- 
traction we  know  it  is.  Because,  according 
to  Kepler's  Third  r^aw.  r'  varies  as  T'  (cube 
of  distance  proportional  to  square  of 
perioflic  time),  or.  what  is  the  same  thing, 
the  product  rv^  is  the  same  for  all  the  orbits. 
Hence  vr  proceeds  according  tn  the  natural 
numbers,  1,  2,  3,  4,  etc.,  in  arithmetical 
progression,  the  radii  r  must  preceed  ac- 
cording to  the  squares  of  these  numbers.  1, 
4,  9,  16,  etc.  This  is  algebraically  neces- 
sary. These  are  tlie  successive  Bohr  orbits, 
which  seem  to  be  the  only  stable  and  per- 
manent ones;  no  other  orbits  seem  pos- 
sible. .\  particle  [electron]  may  drop  from 
one  f>rbit  to  the  next,  but  it  cannot  rest  or 
revolve  in  any  intermediate  position.  The 
full  reason  of  this  has  still  to  be  discovered, 
but  the  fact  is  evidenced  by  many  con- 
siderations." 

An  interesting  view  in  connection  with 
Bodes  law  is  discussed  by  Miss  M.  A. 
Blagg  in  a  pap^'r  in  the  Uo\pd  Astronomical 
Sociclii  Monthly  Notes,  19*18,  vol.  73,  p. 
414. 

Referring  to  the  diagram  shown  on  page 
2o8,  this  is  reproduced  to  the  scale  of  about 
i  millimeter  per  unit,  but  the  values  were 
re- proportioned  to  bring  them  into  the 
range  of  the  plotting  selected.  In  the  case 
of  the  wave  lengths,  the  original  unit  was 
increased  by    dividing  them    by    30.       The 


group  values  were  raised  by  multiplying 
them  by  3. 

The  calculation,  quite  apart  from  the 
plotting,  is  obviously  a  simple  one,  viz.  :  — 
Wave  length  (A)  in  Angstrom  units  minus 
3540,  divided  by  61.5  =  the  group  values; 
that  is  to  say,  (A  -  3540)/61.5  =  a,  /8,  y,-&c. 

The  figures  given  on  page  274  of  Part  11. 
as  being  representative  of  the  fine  lines  of 
hydrogen  in  respect  of  the  Ha  line  resolu- 
tion, were  taken  from  Foote  and.  Mohler's 
book,  "  The  Origin  of  Spectra,"  1922;  but 
the  noughts  before  tlu?  decimal  places 
should  be  cancelled. 

Corrections.  —  On  page  258,  right-hand 
coluiim,  fifth  line  down,  "first"  should 
read  "prior."  On  page  274,  left-hand 
oolunm,  fourth  line  from  bottom,  "since" 
shfHiId  read  "moreover."  On  same  page, 
right-hand  column,  second  line  from  top, 
"and  by"  should  read  "which."  Piuther 
down,  paragraph  beginning  with  "Apart," 
first  line,  "these"  should  read  "the."  The 
large  table  of  figures,  etc.,  should  be  la- 
belled at  the  top  "Scheme."  (^n  page  275. 
right-hand  column,  second  line  from  top, 
•'when  considering"  should  read  "as  com- 
pared with." 

PiPlCENT  RESEARCHES    IN  OliGANIC 
CHEMISTRY. 

By  R.  F.  Hunter,  F.C.S. 
{Continued  from  page  263.) 

In  July,  1921,  a  short  paper  by  Fair- 
bourne  and  Toms  on  a  Monosodium  gly- 
ceroxide.  in  which  preparations  of  a  Mono- 
so<lium  (ilyceroxide,  CH,  (OH)  CH  (OH) 
CH,ONa,  (jivcerol  2:  4  Dinitro  phenyl 
ethJr.  C,H,(NO,),  O  (;H,(()n)  CH,  O  H 
2  :  4  Dinitro  phenyl  ally!  ether.  2  :  4  Dini- 
tro Hexvl  Dibromopropyl  ether,  C8H3(N()2)^ 

0  CH,  CH  Br  CHJ3r,  were  described. 
Th»'  third  part    of  Barton  and    Trinner's 

investigations  on  intluence  of  nitro  groups 
<Mi  reactivity  of  substituents  in  benzene 
nucleus,  partial  reduction  of  dinitro  tolu- 
enes by  Sn  Clj  and  H  CI,  in  which  the 
action  of  ammonia  on  3  :  4  dinitro  oxylene 
was  also  studied,  appeared.  The  fourth 
part,  communicated  at  the  same  time, 
dealt  with  the  condensation  of  ethyl  3  and  5 
nitro  2  chlor6benzo,ites  with  hydrazines, 
had  Kenner  and  Witheim  as  its  authors, 
and  the  experiment, il  part  gave  an  account 
of  the  action  of  hydrazine  hydrate  on  ethyl 
2  chloro  5  nitro    benzoate  and    derivatives. 

1  nitro    2    carbothoxy    phenyl     hydrazine. 


292 


THE  CHEMICAL  NEWS. 


NOVEMBER  9,  1923. 


NO2  CJl.iCO^Et)  N  H  N  H„  benzaldehyde 

4  nitro    2  carbethoxy  phenyl  hydrazone,    5 
nitro  3  keto  1    :  3  dehydroindazole, 

^O.GJl,  <;  ^  N  H 

5  amino  3  keto  1   :  3  dehydroindazole  were 
examined. 

The  action  of  phenylhydrazine  on  ethyl  2 
chloro  5  nitro  benzoate  was  studied,  and 
compounds  5  nitro  3  keto  2  phenyl  1  :  3  de- 
hydroindazole, 3  chloro  5  nitro  indazole,  3 
chloro  5  nitro  2  phenylindazole,  7  nitro  3 
keto  1    :   3  dehydroindazole  prepared. 

The.  action  of  the  same  reagent  on  ethyl 
2  chloro  3  nitro  benzoate  was  examined 
with  the  preparation  o  2  nitro  6  carbethoxy 
hy drazobenzene , 

N02CeH3(C02Et)  N  H  N  H  C^Hs, 
and  of  7  nitro  3  keto  2  phenyl  1    :  3  dehy- 
droindazole. 

In  July,  Morgan  and  Webster's  paper  on 
the  isomeric  diazonium  salts  of  dehydro- 
thio  toluidine  aippeared.  They  found  these 
to  exist  in  syn  and  anti  modifications  and 
prepared. 

1  Phenyl  5  methyl  benzothiazole  4'  azQ 
naphthol  syn  and  anti  1  phenyl  diazohydro- 
chlorides,  Potassium  syn  and  anti  1  phenyl 
5  methyl  benzothazine, 

4'  diazo  oxides, 

Sodium  syn  and  anti  phenyl  5  methyl 
benzothiazole, 

4'  diazosulphonates, 

Syn  and  anti  1  phenyl  6  methyl  benzo- 
thiazole, 

4'  diazo  cyanides, 

4'  Cyano  1  phenyl  5  methyl  benzothia- 
zole, 

Syn  1  phenyl  5  methyl  benzothiazole  4' 
diazo  salts,  such  as  acid  diazo  chromate, 
nitro  prusside,  forrieyanide,  diazo  carbon- 
ate, diazo  chlorate,  and  diazo  ortho  borate. 

A  paper  was  published  by  Mason  on  6 
Hydroxy  ^3:4  methylenedioxy  phenyl 
ethyl  amine  and  derivatives  at  this  time. 

/?  Hydroxy  /5  3  :  4  methylenedioxy 
phenyl  ethylamine  and  its  salts  and  deriva- 
tives were  prepared. 

Part  II.  of  Perkin  and  Titley's  work  on 
Epi-oamphor  appeared  also  at  this  time, 
and  among  the  substances  prepared  and 
examined  were  : 

Hydroxy  methylene  1  epieamiphor, 

Benzoyloxy  methylene  epieamphor, 

Hydroxy  methylene  epieamphor  semi 
carbazone, 

Anilinomethylene  epieamphor, 

ft  Naphthyl  aminomethylene  epieamphor. 


Aminomethylene  epieamiphor, 

1  and  d  epicanipholenonitrite, 

1  and  d  epicampholeiiic  acid, 

Dihydi'oepicampholenolactone,   and 

dl  campholenic  acid. 

Published  at  the  same  time  was  the  first 
part  of  King's  work  on  derivatives  of  sul- 
phur in  commercial  salvarsan  and  the  ex- 
perimental part  contains  an  account  of 
reduction  of  3  nitro  4  hjdroxy  phenyl- 
arsenic  acid  with  sodium  hyposulphite,  iso- 
lation of  3  amino  4  hydroxy  5  sulphino- 
phenylarsenic  acid  and  3:3'  Diamine  4  : 
4  '  dihydroxy  5  :  5'  disulphino  arsenoben- 
zene. 

Oxidation  of  3  amino  4  hydroxy  5  sul- 
phino  phenylarsenic  acid  to  3  amino  4  hy- 
droxy 5  sulphophenyl arsenic  acid  3  :  3  '  di- 
amino  4:4'  dihydroxy  5:5'  disulphino- 
arsenobenzene. 

3  :  3'  Diamine  4  :  4'  dihydroxy  5  sul- 
phino  arsinobenzene  hydrochloride. 

3  :  3'  Diamino  4  :  4'  dehydroxy  5  sul- 
pho  5'  sulphino  arsenobenzene. 

The  action  of  magnesium  phenyl  haloids 
on  diphenyl  chloracetyl  chloride,  and  the 
constitution  of  triphenylvinylalcohol  was 
studied  by  McKenzie  and  Boyle,  who  ex- 
amined the  constitution  of  the  alcohol,  the 
actions  of  Mg  Ph  Br  and  Mg  Ph  I  on  di- 
phenylchloracetyl  chloride,  and  that  of  Ph 
Mg  Br  on  triphenylvinyl   alcohol. 

Some  new  tri  cyclic  bases  by  Moore  and 
Doubleday  appeared  at  the  same  time, 
among  which  mention  may  be  made  of  the 
following: — 1  :  4  endo  methylene  6  methyl 
tetra  hydro  quinoxaline  and  1  :  4  endo 
ethylene  6  methyl  tetra  hydro  quinoxaline 
and  1  :  4  endo  tri  methylene  6  methyl 
tetra  hydroquinoxaline. 

Three  other  papers  also  appeared  by 
Atack  which  dealt  with  the  structural  iso- 
merism of  oximcs,  criticism  of  the  Hantzsch 
Werner  hypothesis,  and  a  n  >vv  theory  of 
constitution  of  isomeric  oximes.  The 
avithor  summarised  his  results  in  the  fol- 
lowing way :  — 

(1)  The  Hantzsch  Werner  hypothesis  of 
the  stereo  isomerism  of  oximes  is  criticised 
in  view  of  the  fact  that  it  fdls  to  explain 
characteristic  reactions  of  the  so-called  syn 
and  anti  oximes,  their  mode  of  intercon ver- 
sion, etc.,  and  further,  fails  to  interpret 
Beckmann  reaction  as  applied  to  the  ben- 
zildioximes. 

(2)  A  new  structural  theory  of  isomerism 
of  oximes  is  advanced,  which  explaing  satis- 
factorily the  number  of  isomerides  known 
to  exist,  the  differences  in  the  salt  fwrning 


NOVEMBER  9,  1923. 


THE  CHEMICAL  NEWS. 


293 


properties  of  the  oxime  groups  present  in 
isomeric  oximes  and  formation  of  0  and  N 
ethers. 

The  paper  on  the  structural  isomerism  of 
oximes,  Part  II.,  was  summarised  thus:  — 

(1)  A  fourth  isomeric  benzildioxime,  M  1* 
217°,  has  been  prepared,  differentiated  by 
colour  and  behaviour  of  nickel  compound, 
and  by  other  reactions  from  the  three 
known  benziloximes. 

(2)  The  Hontzsch  Werner  hypothesis 
only  admits  of  the  existence  of  3  isomeric 
benzildioxinies,  whereas  the  structural 
theory  admits  of  six. 

Heipworth  and  Clapham's  paper  on  the 
action  of  Grignard  reagents  on  organic  sul- 
phur compounds  contained  an  account  of 
the  action  of  magnesium  phenyl,  ethyl  bro- 
mide, and  of  magnesium  benzyl  chloride  on 
benzene  sulphonyl  chloride.  The  action  of 
magnesium  methyl  iodide  on  ethyl  niercap- 
tan  and  preparation  of  thio  esters  from  mag- 
nesium ethyl  thiol  bromide. 

The  action  on  ethyl  thiobenzoate  of  Mg 
Et  Pr  and  Mg  Ph  Pr,  and  on  di  isoamyl  sul- 
phoxide,  diphenyl  sulphoxide  phenyl  benzol 
suliphoxide  and  trimethylene  trisulphoxide. 

Action  of  Mg  Me  I  on  diphenylsulphone. 
phenyl  be nzylsul phone,  trimethylonetrisul- 
phone  and  ethyl  phenylsulphoneacetate. 

Watson  and  Dult's  paper,   from  Bengal, 
on  dye>i    derived    from    phenanthraquinone 
contained  preiparation  of  azinc    derivatives 
of     phennnthrene,     2    amino    phenanthra 
phonazine, 

N  H,  C,,H,  <^     ^    C.H,. 

4  Aminophenanthraphenazine, 

2   :  7  Diaminophenanthraphenazine, 

4    :  5  Diaminophenanthraphenazine, 

2  :  7  Diaminodihydrophenanthraiphen 
azine, 

2  :  "7  Dihydroxy  dihydro  phenanthra- 
phcnazine, 

2   :  7  :  11  Triaminophenanthraphenazine. 

2  :  7  DTamino  15  hydroxy  phenanthra- 
naphthazine  13  sulphonic  acid, 

2  :  7  Dinitro  15  hydroxy  phenanthra- 
naphthazine  13  sulphonic  acid, 

2  :  7  Dinitro  11  :  4'  dimethyl  flavindu- 
linp  chloride, 

Phenanthraquinone  2    :   7  bis  (2')  azo    7' 
amino      hydroxynaiphthalene    3'    sulphonic 
acid, 
C.JTc  0,  [N,  C...  H,  (NH,)  (OH)  S  0,  H^,. 

Phenanthraquinone  4  :  5  bis  (2')  azo  7' 
amino  1'  hydroxynaphthalene  3'  sulphonic 
acid. 


11  Aminophen  anthra  phenazine  2  :  1 
bis  (2')  azo  7'  amine  1'  hydroxy  naphthalene 
3'  sulphonic  acid, 

N  H,  C,„  H,N,   [N,C,„H,  (NH,  (OH) 
SO3H].. 
and 

2  :  7  Diaminophenanthraquinone  di- 
phenyl hydrazone  p  p'  disulphonic  acid. 

The  second  ipart  of  Naik's  paper  on  dithio 
ketones  and  ethers  was  communicated  in 
June  to  the  T.C.S.,  and  contained  in  the 
experimental  portion  references  to  the  pre- 
paration of  dithio  mesoxo  p  toluidide,  the  o 
compound,  dithio  mesoxo  a  and  (3  naphthyi- 
amine, 

Dithio  mesoxomone  p  toluidide, 
Dithio  mesoxomonophenylamide. 
Ethyl  dithiomesoxo  p  tolylamide, 
Ethyl  dithiomesoxo  o  tolylamide, 
Methyl  malono  p  toluidide  disulphide, 
Methyl  malono  o  toluidide  disulphide, 
Methyl  malono  o  toluidide  disulphide, 
Methyl     malono     dimethylamide      disul- 
phide. 

The  interaction  of  ethyl  so-diocyanoaoe- 
tate,  ethyl  sodiomalonate,  ethyl  cyanoace- 
tate,  and  of  ethyl  malonate  and  SjClj,  and 
also  of  1  :  1  dimethyl  cyclo  hexane  3  :  5 
dione  and  sulphur  monochloride,  3:5:3' 
:  5'  tetraketo  4  :  4'  bis  dithio  1:1:1': 
1'  tetra  methyl  di  cyclo  hexyl  2  :  2'  disul- 
phide was  carried  out. 

Interaction  of  cyclohexane  spiro  cyclo- 
hexane  3  :  5  dione  and  SaClj.  1  :  1'  di  cy- 
clo hexanespiro  3  :  5  3'  :  5'  tetra  keto  4t  : 
4'  bis  dithiodi  cyclo  hexyline  2  :  2'  :  6  :  6' 
bis  disulphide. 

Interaction  of  cyclopentanespiro  cyclo- 
hexane, 3  :  5  dione  and  SjClj,  cycloipen- 
tane  spiro  3  :  5  diketo  4  dithio  cyclohexane 
gave  a  y  disulphidoacetonide  carboxydiani- 
lide. 

Ethyl  y  phenylcarbamjl  a  y  bis  disul- 
phido  aceteacetate  a  y  disulphidoacetone  di- 
carboxydi  p  toluidide. 

Two  papers  by  Hepworth  are  worthy  of 
note.  The  first,  on  the  action  of  Grignard 
reagent  on  tervalent  organic  iodo  com- 
pounds, containing  an  account  of  the  action 
of  magnesium  powder  on  iodobenzene  di- 
chloride  and  ip  iodo  toluene  dichloride.  The 
second  paper  was  on  the  accelerated  forma- 
tion of  magnesium,  alkyl  and  aryl  haloids. 

Dudley's  paper,  entitled  Amino  acylcho- 
line  esters,  deserves  mention,  and  contains 
an  account  of  glycyclocholine  platino  and 
auri  chlorides,  N  Ue,  CI  C,H,0  CO  CH,- 
NH„  H  CI  Pt  CI,  H,.0,  and"  N  Me,  CI  C^- 
H,0  CO  CH,  N  H,  H  CI,  Au  CI,. 


294 


THE  CHEMICAL  NEWS. 


NOVEMBER  9,  1923. 


A  paper  on  the  aefion  of  sodium  on 
phenylacetate  Was  published  by  Perkin  and 
described : 

2  Methyl  benzo  y  pyrone,  dehydroacetic 
acid, 

1  Hydroxy  3  methylxanthone,  its  methyl 
ester,  and  2  4  nitro  1  hydroxy  3  methylxan- 
tlione. 

Mills,  Harris  and  Lambourne's  research 
on  the  Doebner-Miller  quinaldine  synthesis 
contained,  among  other  things,  the  synthe- 
sis of  6  Ethyl  quinaldine. 

Coffey  and  Ward's  paiper  on  allyl  com- 
pounds deserves  mention,  as  does  the  for- 
mer's paper  on  linoleic  and  hexabromo- 
stearic  acids,  publisheqf  at  the  same  time. 
At  this  time  a  further  piece  of  Goddard's 
work  appeared,  and  contained  an  account  of 
thallium  dimethyl  and  diethyl  o,  m  and  p 
nitro  phenoxides,  and  also  of  dinitro  and 
trinitro  phenoxides. 

Simonsen  and  Kerns'  synthesis  of  1  :  6 
di  hydroxy  2  methyl  anthraquinone  ap- 
peared about  this  time,  in  the  experimental 
part  of  which  reference  is  made  to  3  nitro  2 
methoxy  p  toluic  acid  and  3  nitro  2  methoxy 
p  toluidine. 

Two  papers  which  appeared  at  this  time 
and  deserving  mention,  are  those  on  the 
cupri  tartarate,  by  Packer  and  Wark,  and 
the  labile  nature  of  halogen  atoms  in  sub- 
stituted nitro  methanes,  by  Macbeth  and 
Pratt,  and  the  colorations  produced  by  sub- 
stituted' nitro  forms  by  Macbeth  and  Gra- 
ham. Two  tpapers  also  appeared  by  Mc- 
Bain  and  his  co-workers  on  the  hydration 
of  the  fibres  of  soap  curd. 

Two  papers  were  also  published  by  Perkin 
and  Robinson  and  Perkin  and  Scarborough. 
The  first  on  "Studies  of  Configuration  of  aa' 
Dibromodibasic  Acids,  Pt.  I.,  The  Dibromo- 
adipic  Acids  and  Synthesis  and  Resolution 
of  trans  cyclo  pentane  1:2:3  tri  car- 
boxylic  acid."  The  second  on  "Resolution 
of  dl  trans  cyclo  pentane  1  :  3  dicarboxylie 
acid,"  appeared  in  the  T.C.S.  for  July.  '  ; 
'  Coffey's  second  paper  on  oxidation  of  dry- 
ing oils  appeared  in  the  same  issue,  and  con- 
tained a  and  /3  Linf)lenic  acids  and  linolie 
acid. 

The  second  part  of  King's  work  on  Sal- 
varsan  contained  the  study  of  the  Monosul- 
phonation  of  p  nitro  phenol,  the  diamina- 
tion  of  6  nitro  4  amino  phenol  o  sulphonic 
acid,  6  nitro  phenol  o  sulphonic  acid,  and  an 
aeeoimt  of  6  amino  phenol  o  sulphonic  acid 
and  its  nitration  and  the  reduction  of  iso- 
meric nitro  amino  comipounds  to  the  same 
4   :  6  diamino  phenol  o  sulphonic  acid. 

Krishna's  paper  on  Phenol coumarin    and 


Resorcinolooumarin  deserves  mention,  pub- 
lished at  the  same  time  as  Cohen  and  Froe- 
licher's  research  on  the  nitro  and  amino  de- 
rivatives of  m  hydroxy  benzoic  acid.  This 
paper  contains  an  account  of  4  amino  in  hy- 
droxy benzoic  acid  and  its  derivatives. 

Hamer's  paper  on  isomeric  iso  cyanines 
contains  details  of  the  preparations  of 
■quinaldine  and  quinoline  derivatives  and 
methiodides,  such  as  nitro,  amino,  quinal- 
dines,  einnamaylamine,  quinaldine,  and 
quinolines. 

Short's  method  for  preparation  of  acyl 
phenyl  hydrazines  appeared  at  this  time 
with  Burrow's  and  Turner's  paper  on  addi- 
tiv^  compounds  from  arsines  which  de- 
scnbes  compounds  such  as  Ph  Me^  As,  P  I3 
and  Ph  Me2  As,  As  I3. 

They  also  published  an  account  of  the  al- 
kylation  of  nitroprussic  acid. 

Kenner  and  Witham's  paper  on  the  in- 
fluence of  steric  factors  on  intra  molecular 
condensation  was  communicated  in  August, 
1921,  to  the  Chemical  Society,  and  contains 
the  preparation  of  7  chloro  1  hydrindone 
and  5  chloro  1  hydrindone. 

Henstoek's  paper  on  9  :  10  dehydrophen- 
anthrene  is  worthy  of  note. 

The  third  part  of  McLeod  and  Robinson's 
researches  on  pseudo  bases,  dialkyl  amino- 
methyl  alkyl  ethers,  and  sulphides,  was  also 
published  at  this  time,  and  is  of  sorne  in- 
terest. An  interesting  and  characteristic 
property  of  pseudo  basic  carbinols  is  the  for- 
mation of  ethers  by  simple  treatment  with 
alcohols. 

Further  work  on  teripenes,  by  Henderson 
and  Marsh,  has  appeared  in  the  form  of  the 
study  of  action  of  hypochlorous  acid  on  pi- 
nene  and  the  preparation  of  pinene  dichlor- 
hydrins.  CioH^gO^Cla,  and  of  chlorohydrins, 

^iflHiyOaCl. 

Two  papers  by  Heilbron  and  Buck  were 
published  together,  on  the  reactivity  of 
double  conjugated  unsaturated  ketones"  the 
first  on  4'  dimethylamino  2  hydroxy  di 
styryl  ketone,  and  contains  a  description  of 
the  compound  and  various  analogous  and  ke- 
tonic  bodies,  such  as  OH  C^H^CH :  CH  CO 
CH:  CH  C,H,N  Me.C^H,  (N  Me,)  CHO. 

The  additive  compounds  of  4'  dimethyl- 
amino 2  hydroxy  distyryl  ketone,  4'  di- 
methylamino 2  methoxy  distyryl  ketone 
were  also  examined. 

The  second  paper  deals  with  the  action  of 
hydro'Xylamine  semicarbazide  and  phenylhy- 
drazine  on  4'  dimethylamino  2  hydroxy  dis- 
tyryl ketone  and  its  methyl  ester"  in  the  ex- 
perimentid  part  of  which  we  find  a  descrip- 
tion of  the  compound,  0  H  Ce.HCH   :  CH 


NOVEMBER  9,  1923. 


THE  CHEMICAL  NEWS. 


295 


CO  CH   :    CH    CgH^N    Me^N  H^OH,    am 
other  analogous  bodies. 

Papers  by  Morgan  and  Challenor  and 
Morgan  and  Burgess,  on  the  ortho  chloro  di- 
nitro  toluenes,  and  referring  to  bases  iroin  2 
ehloro  4  :  5  dinitro  toluene  and  non-aroma- 
tic diazwiium  salts,  have  appeared,  in  which 
the  condensation  of  G  chloro  3  :  4  tolylene 
diamine  with  diketones  and  ortho  quinones 
was  studied,  and  the  interaction  of  6  chloro 
3  :  4  tolylenediamine  and  foiiii aldehyde  (a) 
in  neutral  solution,  (b)  in  acid  solution. 

The  diazo  reaction  in  the  iso-oxazole 
series  was  also  investigated,  and  conqwunds 
such  as  3  :  o  dimethyl  is<>  o.xazole  4  azo 
acetyl  acetone  examined. 

The  paper  by  Fairbounu-  on  wtho  di- 
methyl anthraquinone  and  dirivatives  is  of 
interest.  Among  the  compounds  prepared 
were  2  :  3  and  1  :  2  dimethyl  anthraquinone 
and  1   :  2  dicarboxylic  acid. 

A  long  research  on  Harmine  and  Harma- 
line.  the  synthesis  of  norhannan,  by  Ker- 
mack,  Perkin  and  Kobi^j^son,  has  also  ap- 
peared. It  may  be  j)omted  out  that  the 
fused  pyridine-pyrolle  nucleus  type  of  or- 
ganic coniipound  has  receivetl  little,  if  any, 
attention.  Hannine  is  methyl  metho.xy  4 
carboline.  The  compounds  norharmine  and 
harman  are  obtained  by  elimination  of  the 
niethyl  and  methoxy  groups  from  harmine. 
The  relation  between  harman  and  trypto- 
phan wa.s  discusised  in  the  Journal  of  the 
Chemical  Society,  1919.  The  experimental 
work  included  the  following  preparations: 
Harman  from  tryptophan,  harmolic  Jicid. 
norharmoi,  norhannan.  3  carboxyindole  3 
acetic  fvcid,  etc.  It  also  included  the  con- 
densation of  indole  2  carboxylic  ohioridt^ 
with  alanhie  ester  and  so<iium  derivative  of 
ethyl  aeetoHcelate,  and  a  description  of  0 
methoxy  indole,  11  methoxy  5  keto  4  :  5  de- 
hydroindole  diazine,  and  the  synthesis  of 
norhannan  and  the  study  of  fi  methoxy  3 
methyl  indole  2  carboxylic  acid  and  of  (> 
methoxy  3  methyl  indole. 

The  paiper  by  Simonscm  on  the  essential 
oil  from  andropc^on  waraneusa  and  the  con- 
stitution of  piperitone  is  worthy  of  note. 

A  very  interesting  paper  by  Moir  has  ap- 
peared on  the  calculation  of  colour  in  cyclic 
substances,  and  a  method  of  calculating  the 
colour  of  dicyclic  substances  and  monocy- 
clic substances  is  detailed  in  the  papers. 

In  October,  two  more  pipers  were  com- 
municated by  Morgan  and  (Hover  and  Mor- 
gan and  Vining.  The  first  on  the  familiar 
subject  of  ortho  chlorodinitro  toluenes,  dealt 
with  2  chloro    3   :  4  dinitro    toluene.      The 


second  paper  was  on  dinaphtha  1:7:1':  7' 
diquinone,  and  described  the  oxidation  of 
dihydroxy  naphthalenes  with  metallic  per- 
oxides. Compounds  such  as  dinaphtha 
1 : 7  : 1' :  7'  diquinonetetra  2  : 4  dinitro  phenyi- 
hjdraz<Mie,  the  reduction  of  dinaphtha 
1:7:1':7'  diquinone,  by  H.  I.  Henry,  and 
Paget's  pjMper  on  chenopodium  oil  also  ap- 
pemed  at  this  time. 

Fargher  and  Perkin 's  paper  on  in  opianic 
acid  is  of  iuteiest,  and.  ot^tains  references  to 
homoveratrole,  kit.  nic  derivatives,  the  oxi- 
dation of  4:5  dimethoxy  o  tolyl  methyl  ke- 
tone, 4:5dimethoxy  pUthalonic  acid,  the 
action  of  aniline  on  4:5  dimethoxy  phthal- 
onic  acid,  in  opianic  acid  (4:5  dimethoxy  o 
aldehydro  benzoic  acid)  and  its  derivatives. 

In  September,  Head  and  Andrews'  paper 
on  studies  of  halogenohydrins  and  related 
derivatives  of  cinnamic  acid,  Part  1.,  was 
comnmnicated.  Among  the  questions 
studied  were:  The  addition  of  H  CI  O  and 
of  H  BrO  to  cinnamic  acid  and  to  methyl 
coumaric  acid. 

The  a4)plication  of  Holmann's  reaction  to 
substituted  phthalimides,  by  Moore,  Mar- 
rack  and  Proud,  appeared  at  the  same  time. 

Smiles  and  Stewarts'  paper  on  m  dithio- 
benzoic  acid  apjK'ared  at  this  time. 

Copisarow's  paper  on  Freidel  Crafts  Re- 
action, migration  of  alkyl  groups  in  benzene 
nucleus,  deserves  a  mention.  Smiles  and 
McClelland 's  research  on  the  derivatives  of 
8  oxy-(l)-thio  na^phthena  is  of  interest,  and 
contains  in  the  experimental  part  details  of 
the  interaction  of  ethyl  acetoacctate  and  2 
thiolbenzoic  acid,  and  the  isolation  of  con- 
densation pro<lucts  and  derivatives. 

Shimoitmra  and  Cohen's  new  method  for 
resolvition  of  asymmetric  compounds  was 
published  at  the  same  time,  and  contains  a 
description  of  the  pri>parations  of  1  menthyl 
(I  1  phenyl  chloroacetate,  C.H,  CH  d'COj- 
C,„H,,,  1  menthvl  dl  phenyl bronjoact^tate, 
(",H,  CH  Br  CO;C,„H„,  1  menthyl  dl  bro- 
mophenyl(propionat<\  C,H,  CH,  CH  Br- 
COjCjoH,,. 

The  action  of  SO  Cl^  on  1  menthyl  dl  man- 
delate  and  that  of  P  CI,  on  bromopropiono  d 
bomylamide  and  other  analogous  substi- 
tuted amid(>bo<lies  wa«  also  studied. 

In  Perkin  and  Plant's  research  on  deriva- 
tives of  tetra  hydrwarbazole,  the  reduction 
products  of  carbazolo  are  of  interest  because 
of  their  relations  to  strychnine. 

Tetra  hydrocarbazole  and  9  methyl  tetra 
hydro  carbazole  were  oxidised  to  9^  methyl 
carbazole. 

Bennet  and  Whincop's    paper  on  deriva- 


296 


THE  CHEMICAL  KfiWs. 


NOVEMBER  9,  1923. 


tives  of  monothio  ethylene  glycol  appeared 
in  September,  and  contained  descriptions  of 
a  number  of  new  and  conoiplex  aliphatic  sul- 
phur compounds,  such  as  jSj8'  di  p  nitix)  ben- 
zoyloxydiethyl  disulphide,  ethylene  bis  ft  hy- 
droxy ethyl  sulphide,  ethylene  bis  /3  chlor- 
ethyl  sulphide,  sulphido  bis  ft  hydroxy  di- 
ethyl sulphide,  and  2:4  dinitro  phenyl  ft 
hydroxy  ethyl  sulphide,  C6H3(N02)2  S ' 
CH^  CH^  OH. 

Crompton  and  Triffitt's  short  paper  on  Di- 
chloroacetates  and  Chlorobromoacetates 
from  a  ft  Dichlorovinyl  ethyl  ether  is 
worthy  of  note. 

In  October,  Morgan  and  Hickenbottom's 
paper  on  Studies  in  n  Butyl  Series,  Part  I., 
Aryl  and  n  Propyl  ketones,  appeared,  and 
the  extensive  experimental  part  contained 
much  that  was  important  in  connection 
with  these  comparatively  simple  bodies. 

Grant  and  Pyman's  research  on  the  Ni- 
tro-  and  Amino-derivatives  of  4  Phenylgly- 
oxaline  appeared  at  the  same  time,  in  which 
2  Thiol  4  phenylglyoxaline  and  4  phenylgly- 
oxaline  M^ere  described.  The  nitration  of  4 
phenylglyoxaline  led  to  the  isolation  of  4o 
and  4p  nitro  phenylglyoxalines.  The  nitra- 
tion of  4p  nitro  phenylglyoxaline  gave  5  ni- 
tro 4  p  nitro  phenyl  glyoxaline. 

The  benzoylation  of  4  phenylglyoxaline 
and  its  nitro  derivatives  was  also  accom- 
plished. 

Towards  the  end  of  August,  Ray  (pub- 
lished a  paper  on  synthesis  in  the  Thian- 
thren  series.  The  method  of  condensation 
employed  was  to  dissolve  the  substance  in 
dry  CSg  in  a  flask  filled  with  the  acid  of  a  re- 
flux condenser  and  dropping  funnel,  and 
containing  SgCI,.  The  catalyst  (aluminium 
foil)  was  inserted  previous  to  addition  of 
S2CI2.  The  following  were  studied:  Di- 
chloro  thianthren,  dichlorodimetliylthian- 
thren,  diacetyl  amino  thianthren,  dimethoxy 
thianthren,  diacetyl  thianthren,  dibenzyl 
thianthren,  thianthrendicarboxylic  acid. 

Singh  and  Lai's  studies  on  Aryl  deriva- 
tives of  bis  iminocamphor  are  worthy  of 
mention.  They  prepared  00'  di  tolylenebis 
imino  camphor,  00'  dimethoxy  diphenylene 
bis  imino  camjphor,  pp'  diphenylene  bis 
imino  camphor,  and  pp'  bis  iminocamphor 
diphenyl  amine. 

Duff's  paper  on  cis  phthalate,  cis  homo 
phthalate,  and  other  ethjdeno  diamine  co- 
baltic  salts  is  of  note.  Among  the  coin- 
pounds  studied  were :  cis  phthalatedicthy- 
lene  diamine  cobaltic  ■salts,  cis  o  sulphoben- 
zoate  diethylene  diamine  cobaltic  salts,  cis 
bromobenzene  3:4  disulphonate  diethylene 
diamine  cobaltic  salts,     cis    homophthalate 


diethylene  diamine  cobaltic  salts,  trans  di- 
chlorodiethylene  diamine  cobaltic  hydrogen 
benzyl  sulplioacetato,  and  trans  dichloro  di- 
ethylenediamine  cobaltic  hydrogen  sulpho- 
benzoate. 

Rowe  and  Levin's  researches  in  the  tlihy- 
dronophthalene  series,  the  ar  dihydro  a 
naphthols  and  derivatives,  were  published 
about  this  time. 

In  December,  1921,  there  appeared  Sil- 
berad's  researches  on  Sulphuryl  Chlcride, 
Part  I.,  Influence  of  catalysts.  Among  the 
catalysts  employed  were :  iodine,  thionyl 
chloride,  sulphur,  sulphur  chloride,  ferric 
chloride,  Al  Clg,  and  mixed  catalysts. 

Cohen  and  Crabtree's  paper  en  Structure 
and  Colour  of  Azine  Scarlets  appeared  at 
this  time,  and  was  summarised  by  them- 
selves in  this  way  :  — 

1. — The  formation  of  quaternary  metho- 
chloride  has  only  slight  effect  on  the  tint  of 
the  parent  hydrochloride. 

2. — Transition  from  a  simple  amino  groui) 
through  a  mono-alkylated  to  a  dialkylated 
amino  group  is  accompanied  by  gradation  in 
tint  from  pure  scarlet,  through  scarlet  ma- 
genta to  pure  magenta. 

3.  Transference  of  both  amino  groups  to 
same  nucleus  produces  a  fundamental 
change  in  colour. 

4. — Replacement  of  benzene  by  naphtha- 
lene or  tetra  hydroquinoiine  nucleus  pro- 
duces little  change  on  tint. 

5. — Absence  of  radicles  in  nucleus  en- 
hances the  blueness  of  shade. 

Among  their  work  were  preparations  of : 
3  amino  7  diinethylamino  2  methyl  phena- 
zine  metho  chloride;  3  amino  7  dimethylam- 
ino  2:8  dimethylphenazine  metho  chloride; 
5  aminonaphtha  phenazine  7  metho  chlor- 
ide 9  amino;  5  dimetliylamino  10  methvl 
naphthaphenazine  hydrochloride;  9  amino  5 
djmethylainino  10  methyl  naphtha  phena- 
zine metho  chloride;  3  amino  7  dimethyl- 
amino  phenazine  metho  chloride ;  3  : 7  tetra 
methyl  diaininophonazine ;  3  amino  2 
methyl  N  methyl  tetra  hydro  quinolino- 
phenazine  metho  chloride ;  3  amino  7 
methylamino  2  methyl  phenazine  metho 
chloride;  3  amino  7  methylamino  2:8  di- 
methyl phenazine  metho  chloride ;  3  amino 
7  benzylamino  2:8  dimethyl  phenazine 
metho  chloride;  3:7  diamina  2:8  dimethyl 
phenazine  metho  chloride;  3:7  diainino  8 
methyl  phenazine  metho  chloride;  and  5:9 
diamino  10  methyl  naphtha  phenazine 
metho  eh  1  or i fie-: 

FairboiuiH'  and  Toms'  new  synthesis  of 
osazines  appeared  in  December,  and  con- 
tained in  the  experimental  part  2:4  dinitro 


i^OVEMBER  9,  1923. 


THE  CHEMICAL  NEWS 


297 


phenyl  hydroxy  ethyl  ether,  and  6  amino 
2  :3  dihydro  1 :4  benzisoxazine. 

Dult,  Whitehead  and  Wormall's  paper  on 
the  action  of  diazo  salts  on  aromatic  sulphon 
amides,  Parti.,  appeared  at  the  same  time, 
and  contained  a  description  of  the  action  of 
benzenediazonium  chloride  on  |)  toluene- 
sulphoamide. 

The  action  of  o  toluenediazonium  chlor- 
ide on  the  same,  and  of  m  toluene  diazo- 
nium  chloride  on  the  same. 

The  action  of  p  toluenediazonium  chlor- 
ide and  p  chlorobenzenediazonium  chloride 
on  }>  toluene  sulphoamide. 

The  action  of  benzenediazonium  chloride, 
i>  toluenediazonium  chloride,  m  and  p  tol- 
uenediazonium chlorides  on  benzenesulpho- 
amide,  and  lastly  of  p  chlorobenzenediazo- 
nium chloride  on  benzenesulphoamidc. 

Mills'  and  Nodder's  paper  on  optically 
active  forms  of  keto  dilactone  of  benzophe- 
none  2:4:2:4'  tetracarboxylic  acid  deserves 
mention. 

The  last  paper  published  in  1921  was  by 
Ruth  King,  on  the  production  of  picric  acid 
from  sulphouic  acids  of  phenol.  The  work 
contained  the  examination  of  6  nitro  phenol 
2  :4  disuliphonic  acid  and  nitrolysis  of  suipho 
groups  in  the  ortho  and  para  positions. 


DR. 


MULLER'S  X-RAY  SPECTRO- 
GRAPH. 


To  meet  the  requirements  of  various 
classes  of  users,  including  crystaliographers, 
chemists,  metallurgists,  radiologists  ,  and 
others,  Dr.  Muller  has  designed,  and 
Messrs.  Adam  Hilger,  Ltd.,  75a,  Camden 
Road,  London,  N.W.I,  have  placed  on  the 
market  at  the  price  of  £44,  an  extremely 
compact  form  of  X-ray  Sipectrograph. 
While  of  sufficient  accuracy,  the  instru- 
ment is  made  of  simple  design  and  at  such 
cost  that  it  can  be  put  into  the  hands  of 
advanced  students  who  arc  capable  of  pro- 
fiting by  experience  of  this  important  class 
of  work. 

The  instrument  consists  of  a  support 
carrying  a  rotating  table  for  the  crystal 
mount,  and  jiassing  through  the  latter  a  bar 
of  triangular  section  upon  which  slide  car- 
riers for  slit  and  iplate-hoklers  respectively. 
This  support  is  mounted  on  a  box  contain- 
ing a  spring-motor,  to  tbo  shaft  of  which  is 
attached  a  cam.  A  lever,  which  can  be 
clamped  at  any  orientation  to  the  axis  of 
the  crystal  table,  is  kept  in  contact  with  the 


cam  by  a  spring,  and  is  thus  oscillated 
through  a  certain  angle  as  the  cam  rotates. 
With  the  cam  usually  supplied  an  angle  of 
oscillation  of  about  12°  is  obtained. 

The  crystal  mount  consists  of  a  vertical 
plate  with  lead  screen,  to  which  the  crystal 
can  be  attached  with  soft  adhesive  wax  and 
which  is  provided  with  tilting  adjustment 
about  a  horizontal  axis.  The  mount 'can  be 
traversed  in  a  slide  across  the  rotating  table 
so  as  to  bring  the  face  of  the  crystal  up  to  i^ 
the  axis  of  rotation.  The  edge  of  the  table 
is  divided  in  degrees  to  faciUtate  the  setting 
relative  to  the  lever  in  order  to  register  lines 
upon  each  side  of  the  n<wrmal  to  the  photo- 
graphic plate. 

The  sUt  consists  of  two  brass  blocks  26 
nans,  long,  which  can  be  clamped  at  a 
known  distance  apart,  one  of  a  number  of 
"feeler"  gauges  supplied  being  inserted 
between  the  jaws  before  clamping. 

The  plate-holder,  which  is  attached  to  its 
slide  by  two  milled  head  screws,  is  designed 
to  take  plates  12  cms.  x  1.9  cm.,  which  can 
be  cut  from  standard  size  plates  (-J-plate 
size).  It  is  provided  with  a  black  paper 
screen,  so  that  the  instrument  may  be  used 
in  daylight  without  risk  of  f<^ging  the 
plate,  and  no  special  sheath  for  the  plate  is 
necessary. 

In  order  to  measure  the  distance  between 
the  centre  of  rotation  and  the  surface  of 
the  phot<jgraphic  plate,  a  steel  rule  divided 
in  millimetres  is  supplied,  which  will  pass 
through  the  slit  mount.  The  centre  of  ro- 
tation of  the  table  is  determined  by  a  fidu- 
cial mark  upon  a  pin  which  can  be  inserted 
in  the  table  when  the  crystal  mount  is  re- 
moved. This  is  quickly  done  by  unscrew- 
ing the  ix'taining  screw  of  the  spring  top  and 
sliding  the  mount  out  of  its  grfX)ve. 

The  in8trum(>nt  is  mounted  on  three 
levelling  screws,  the  heads  of  which,  as 
wt>ll  as  those  of  other  adjusting  screws,  are 
inade  of  vulcanite  to  minimise  risk  of  shock 
in  case  the  instrument  is  charged  by  induc- 
tion from  the  tube  and  transformer,  etc.  A 
lead  screen  is  also  mounted  upon  the  in- 
stnnnent  to  prevent  fogging  of  the  plate  by 
stray  X-radiation. 

The  instiument  is  available  for  work  with 
a  single  crystal  by  the  Bragg  method.  Bv 
a  simple  interchange  of  parts  which  can  be 
effected  in  about  one  minute,  it  becomes 
suitable  for  the  investigation  of  powders  by 
the  Debye  metluKl.  The  slit' jaws,  crystal 
mount  and  j)lale  lif>lder  are  removed,  and 
the  carriers  moved  up  to  suipport  a  circular 
camera,  6  cms.  in  diameter,  which  carries  a 


298 


THE  CHEMICAL  NEWS. 


NOVEMBER  9,  1923. 


a» 


photographic  film.  The  camera  is  so  dis- 
posed that  a  powder-holder  can  be  inserted 
in  the  centre  of  the  rotating  table  and  ad- 
vantage taken  of  the  oscillating  movement 
foi-  this  work  also.  In  place  of  the  slit  is 
mounted  a  brass  block  pierced  with  an  aper- 
ture of  1  mm.  in  diameter.  The  end  of  this 
block  fits  into  an  aperture  of  the  camera  and 
points  directly  to  the  powder-holder  in  the 
centre. 


The  instrument  is  also  available  for  tak- 
ing photographs  by  Hull's  powder  method, 
a  small  spring,  which  can  be  quickly  at- 
tached to  the  slit,  being  supplied.  Thus 
the  three  standard  methods  now  in  use  are 
available  in  the  one  instrument. 


The  motor  is  such  as  to  give  about  40 
oscillations  per  hour  to  the  crystal,  and  to 
run  nearly  8  hours  without  rewinding. 


GENERAL    NOTES. 


MINERAL    PRODUCTION    OF 
CANADA,    1922. 

The  High  Commissioner  for  Canada  in 
London  has  received  from  the  Dominion 
Bureau  of  Statistics  at  Ottawa  the  follow- 
ing finally  revised  statistics  on  the  produc- 
tion of  Non-Metallic  Minerals  in  Canada 
during  1922. 

With  the  exception  of  arsenic  there  were 
no  outstanding  differences  between  the  pro- 
duction of  1922  and  the  previous  year  of 
the  connii(!(lities  listed  in  the  table  below 
as   miscellaneous  non-metallic   minerals. 

The  production  of  arsenic  in  1922  was 
2,576  tons,  an  increase  of  1,085  tons,  or  42 
percent.,  when  compared  with  1921.  Large 
quantities  of  this  commodity  are  being 
used  in  the  United  States  for  insecticides 
which  are  found  to  be  iparticularly  effective 
in  combating  the  boll  weevil,  an  insect 
which  has  caused  great  damage  in  the  cot- 
ton districts  during  recent  years. 


1922. 

Quantity.  Value  in  Dols. 

Actinolite •••■          Tons  50  575 

Arsenic  (white)  produced    from  Can-  ^  ^^  ^^^^  ^^.^ 

adian  ores       "  -'^gg  g'537 

g^rytes       , "  rjQrj  iilsoa 

^lif?"^i*«          "  27  727  248,402 

If^^P-^^'         "  41503  102,138 

Fluorspar • -  -^^  gi  353 

g^^Pjiite           "  ^005  43^742 

Grmdstones           "  ^'849  76,294 

Magnesite "  '^^l  24,017 

Magnesium  sulphate       "  '   ^^  2  044 

Manganese           "  ^  g^g  152,263 

JJ}^^    ,       •: Gals          ■  221*443  14,220 

Mineral  watir       ^^'S;  50  2  500 

Natro-Alunite          ^o^«  ^285  lloleOS 

Iron  oxides       "  g'^^Q  ^4500 

^f*    ,    , ';  'l90  1,796 

Phosphate          '  ^g  ^^3  74303 

I'yntes          "  i09'947  208,598 

§^1.^^^ " "  '202  3,027 

Sodmm  carbonate       "  -^^  -^-^  qqq 

Sodium  sulphate      "  13  195  188458 

Talc         "  '219  5,781 

Tnpolite  " . 

r^  .   ,  ...-  1,658,676 

Total  - ' 


NOVEMBEK  9,  1923. 


THE  CHEMICAL  NEWS. 


299 


THE    DESTKUCTIOX    OF    PLATINUM 
CKUGIBLES; 

The  destruction  of  platinum  crucibles, 
which  is  alwa_ys  attributed  to  a  chemical 
change  in  the  platinum,  can  be  prevented 
(according  to  a  publication  by  Heraens),  if 
unnecessarily  high  temii)t'ratures  in  heating 
the  crucible  are  avoided.  The  combinations 
of  platinum  with  carbon,  silicon,  boron, 
I)hosphoric  acid,  etc.,  arise  through  reduc- 
tion of  the  salt  being  heated  at  relatively 
high  temperatures.  Tlie  ease  with  which 
hydrogen  and  hydro-carbons  pass  through 
glowing  platinum  makes  sucB  a  reduction 
easy.  The  use  of  acitylene  for  heating 
platinum  is,  for  this  reason,  especially 
dangerous.  Melted  alkalis,  alkalijne  6ar- 
bonates,  in  the  preseiue  of  suipbur,  or 
potassium  cyanide,  strongly  attack  iplati- 
uum  at  high  temperatures. 

Easily  fusible  metals  and  easily  reducible 
metallic  oxides  cannot  he  treated  in  plati- 
num, and  the  sanu'  is  true  of  all  substances 
which  give  off  chlorine,  bromine,  iodine, 
sulphur  or  phosphorus. — Chemiker-Zeitung, 
Julu  21,  1923. 


THE  WORLD'S  AGJilCULTUKAL 
RESULTS. 

On  the  basis  of  statistical  data  and  other 
information  published  in  the  October  Inter- 
national Hciport  of  Agricultural  and  Com- 
mercial Statistics  of  the  International  In- 
stitute of  Agriculture,  Rome,  the  results  of 
the  Northern  Hemisphere  harvests  are  now 
ascertainable,  together  with  estimates  for 
some  of  the  more  important  crops  in  the 
Southern  Hemisphere. 

The  aggregates  for  the  Northern  Hemi- 
sphere (exclusive  of  Russia)  in  1923  surpafts 
those  of  1922  by  7.6  million  metric  tons  of 
wheat  (10  per  cent.),  by  3.2  million  of  rye 
(15  per  cent.),  2.8  million  of  barley  (13  per 
cent.).  6.4  million  of  oats  (14  per  cent). 
Thesi^  increases  mainly  arise  from  plentiful 
yields  in  Europe  and  Nnrth  Africa,  where  a 
favourable  season  was  experienced,  in  sharp 
contrast  with  the  drawbacks  suffered  la^t 
year  by  the  grain  crops.  In  North  America 
and  in  Asiatic  countries  the  totals  Are  very 
similar  to  last  year's,  which  showed  goo^ 
results. 

A  prelinu'nnry  estimnto.  quite  provisif>nal. 
from  the  Soutlu^rn  Hemisphere  is  available 
from  .Argentina,  wliere  th«*  wheat  yield  is 
forecasted  at  6.8  million  tons,  which  is  the 
highest  figure  on  record    for  that    country. 


and  shows  an  increase  of  1.6  million  metric 
tons  (31  per  cent.)  over  last  year.  Again, 
in  Australia,  the  area  under  wheat  is  nearly 
similar  to  that  in  1922,  and  good  yields  are 
anticipated,  as  conditions  are  favourable 
during  growth. 

It  may,  therefore,  be  regarded  as  certain 
that  the  aggregate  production  of  these  four 
grain  crops  is  considerably  larger  than  it 
was  last  year.  This  is  not  all,  for  the  re- 
cent crops  of  wheat  and  oats,  with  barley 
also  in  minor  degree,  are  actually  larger 
than  those  immediately  before  the  war. 
Comiparisons  are  available  from  the  recently 
published  International  Yearbook  of  Agri- 
cultural Statistics  issued  by  the  Institute. 
Apart  from  Russia,  the  harvests  of  1923,  in- 
clusive of  all  those  countries  which  have 
supplied  data,  exceed  the  averages  fur- 
nished in  the  Yearbook  for  1909  to  1913  by 
12.4  million  metric  tons  of  wheat  (16  per 
cent.),  3.3  million  of  oats  (7  per  cent.),  and 
0.7  million  metric  terns  of  barley  (3  per 
cent.).  Rye  alone  falls  short  by  1.4  mil- 
lioQ  ^5  per  cent.). 

Taking  the  several  continents  separately 
the  European  and  North  African  crops  are 
nearly  equal  to  those  of  the  pre-war  |)eriod, 
though  none  of  the  four  attains  a  parity. 
The  ascertained  increases  as  compared  with 
pre-war  figures  are  therefore  consequent  on 
extensions  in  the  other  continents,  particu- 
larly in  America. 

Available  data  for  the  Northern  Hemi- 
sphere maize  crops  are  not  quite  so  com- 
plete, as  data  are  not  yet  to  hand  from 
Rumania,  Jugoslavia  and  a  few  other  coun- 
tries. An  increased  yield  of  5.2  million 
metric  tons  (7  per  cent.)  may  be  already  in- 
dicated, however,  owing  almost  entirely  to 
the  plentiful  crop  in  the  United  States. 

As  regards  linseed,  special  reference  is 
due  to  the  exceptionally  large  yield  in  Ar- 
gentina, where  the  prelinunary  estimates 
are  for  1.9  million  metric  tons,  or  0.8  mil- 
lion more  than  lasl  year's  yield,  which  was 
in  itself  a  very  go<Kl  one.  Taking  into  ac- 
count the  fine  harvests  of  linseed  in  other 
countries  whence  data  are  to  hand,  the  yield 
already  tabulated  amounts  to  3.2  million 
metric  tons,  and  indicates  an  increase  of  55 
per  cent,  over  last  year's  yield. 

The  aggregate  yield  of  sugar-beet  in  the 
couritrii's  which  have  already  supplied  data 
—which  represents  rather  over  5()  per  cent, 
of  the  world's  total  yield — comes  out  de- 
cidedly larger  than  that  corresponding  of 
1922:  21.1  million  metric  tons  as  com- 
pared   with  19.2    million,    or    10  per    cent. 


300 


THE  CHEMICAL  NEWS. 


NOVEMBER  9,  1923. 


more.     It  would  seem    that  the  sugar  con- 
tent too  is  likely  to  be  higher. 

Potatoes,  on  the  other  hand,  are  exipected 
to  jield  a  much  poorer  aggregate  than  last 
year.  The  countries  which  have  furnished 
data,  representing  slightly  over  one-half  of 
the  world's  production  (apart  from  Russia), 
report  a  yield  of  65.5  million  metric  tons, 
as  compared  with  80.1  last  year,  showing  a 
decrease  of  18  pr  cent.  When  considering 
these  results  it  should,  however,  be  borne 
in  mind  that  1922  was  a  year  of  exceptional 
plenty  for  potatoes,  the"  then  yield  being 
far  above  the  average. 


AUSTRALIA'S  OVERSEAS  TRADE 
IN  JULY. 

The  Officer  in  Charge  for  His  Majesty's 
Senior  Trade  Commissioner  in  Australia 
has  forwarded  to  the  Department  of  Over- 
seas Trade  a  brief  resum^  of  the  returns  of 
the  Commonwealth's  overseas  trade  for  the 
month  of  July. 

These  returns  show,  in  comparison  with 
the  corresponding  month  last  year,  an  in- 
crease in  imports  of  nearly  £2,000,000, 
while  exports  show  a  decrease  of  over 
£2,500,000.  The  value  of  imports  ex- 
ceeded exports  by  £6,500,000. 

Imports  of  boots  and  shoes  showed  an 
increase  as  compared  with  the  correspond- 
ing period  in  1922,  while  cotton  and  linen, 
silk  and  woollen  piece  goods  showed  a  de- 
crease. Imports  of  petrol  (£453,828)  more 
than  doubled,  and  chassis  for  motors 
£679,659)  increased  by  £266,439. 

Exports  of  wool  were  over  £2,200,000  in 
value  below  those  of  July,  1922.  Ship- 
ments of  gold  exceeded  those  in  the  same 
period  by  £134,877.  Exports  of  Austra- 
lian products  from  the  States  were  :  — 

£ 

New  South  Wales  1,699,053 

Victoria        989,732 

Queensland        1,198,221 

South  AustraKa      687.443 

Western  Australia       784,696 

Tasmania 22,178 

The  Northern    Territory    imported    £930 
worth  of  merchandise ;  there    wei-e  no  ex 
ports. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 

Thursday,  November  1. 

Papers  read :  — 

E.  G.  T.  LiDDELii  and  Sir  Charles  Sher. 
RiNGTON,  Pres.  R.S.  :  A  Coiuparison  be- 
tiveen  certain  Features  of  the  Spinal  Flexor 
Reflex  and  of  the  Decerebrate  Extensor 
Reflex  respectively. 

J.  Barcuukt,  F.R.S.,  and  H.  Barcroft  : 
The  Blood  Fiyment  of  Arenicola. 

The  blood  pigment  of  Arenicola  Marina 
differs  from  the  hemoglobin  of  human 
blood  in  ct-rtaiu  respects. 

(1)  The  a  baud  of  the  oxy-hsmoglobin  is 
situated  18  Angstrom  units  nearer  the  vio- 
let, and 

(2)  The  a  band  of  the  CO-haemoglobin  is 
situated  11  A.U.  nearer  the  violet  than  the 
corresponding  human  band. 

(3)  The  dissociation  curves  show  a 
greater  affinity  for  both  oxygen  and  carbon 
monoxide  than  those  of  human  blood  under 
similar  conditions. 

(4)  The  affinity  for  CO  is  about  70  times 
that  for  oxygen,  as  compared  with  250  in 
man  and  140  in  the  mouse.  The  possibility 
of  a  relationship  between  the  position  of  the 
bands  and  the  affinity  of  the  pigment  for 
gas  is  discussed. 

(5)  The  main  unloading  of  oxygen  from 
the  pigment  of  Arenicola  would  appear  to 
be  between  1  and  3  mm.  pressure. 

(6)  The  mean  oxygen  capacity  of  the 
haemoglobin  per  gram  of  Arenicola  is  about 
0.01—0.013  cc. 

A  comparison  between  the  oxygen  capa- 
city of  the  pigment  and  the  total  oxygen 
consumption  of  the  worm  reveals  the  fact 
that  the  pigment  holds  sufficient  oxygen  to 
supply  the  animal  for  1-2  hours,  and  prob- 
ably acts  as  a  reserve  to  tide  it  over  the 
period  at  low-water  when  its  hole  is  closed. 

T.  Deighton  :  The  Basal  Metabolism  of 
a  Growing  Pig.  Communicated  by  Prof. 
T.  B.  Wood,  F.R.S. 

Various  alterations  in  the  calorimeter  de- 
scribed in  J.  Agric.  Sci.,  vol.  11  (1921),  are 
mentioned,  and  certain  modifications  of 
technique  described. 

The  basal  metabolism  of  a  pig  has  been 
measured  at  various  ages  from  75  days  up- 


i 


NOVEMBER  9,  1923. 


THE  CHEMICAL  NBWS. 


301 


wards,  and  it  has  been  shown  that  in  the 
pig,  as  in  human  beings,  the  metabolism 
per  unit  area  is  greater  in  mid-youth  tlian 
at  an;y  other  time  of  HlV. 

Experiments  are  adduced  to  show  that 
the  metabolism  after  the  ingestion  of  food 
reaches  a  maximum  after  o  hours  and  then 
declines. 

The  curve  of  basal  metabolism  showing 
its  variation  with  age  is  discussed,  and  rea- 
sons are  given  for  thinking  that  this  in- 
crease of  metabolism  in  youth  is  directly 
ascribable  to  growth. 

The  rationing  of  pigs  for^mainti-nance 
and  growth  is  discussed,  and  it  is  concluded 
from  the  experimental  results  achieved 
that  the  curve  of  rationing  for  growth  and 
maintenance,  without  fattening,  cannot 
ipossibly  be  a  two-thirds  power  curve 


ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

The  General  Monthly  Meeting  was  held 
on  November  5. 


THE  ROYAL  SOCIETY  OF  ARTS. 

On  Wednesday,  Novwmber  7,  the  in- 
augural address  of  the  170th  session*,  en- 
titled ExhihiiionH,  was  delivered  by  Lord 
AsKwiTH,  K.C.B.,  K.C..  D.C.L.,  Chair- 
man  of  the  Council,  and  a  Vice-President 
of  the  Societv. 


THE  INSTITUTION  OF  MINING 
ENGINEERS. 

Annual    General    Meeting — Preliminary 

Notice. 

The  thirty-fourth  annual  general  meet- 
ing will  be  held  at  the  rooms  of  the  Geo- 
logical Society,  Burlington  House,  Picca- 
dilly, London,  W.l,  on  Thursday,  Novem- 
ber 20,  1023.  An  agenda-programme  will 
be  sent  to  members  in  due  course. 


MINER ALOGICAL  SOCIETY. 

Anniversary  Meftixo,  Tuesday, 
novemrku  6,  at  6.80. 

The  following  papers  were  read:  — 
Dr.   L.  J.   Spencer:    Euclaae  and  Plati- 
num from  Diamond    Washinga    in    British 
Guiana. 


H.  E.  Buckley  :  The  Anomalous  Optical 
Properties  of  Freshly  Prepared  Mixed  Crys- 
tals of  Sciijncltc  Salt. 

Col.  N.  T.  Belaiew  :  On  the  Genesis  of 
\Vidmanstdtie7i  Structure  in  .  Meteorites 
and  Terrestrial  Alloys , 

Prof.  L.  R.  Wilberforce:  Illustration 
and  Detection  of  Inclined  and  Horizontal 
Dispersion  in  Bi-Axial  Crystals. 

A.  Russell  :  On  the  occurrence  of  the 
Hare  Mineral  Nadorite  in  Cornwall,  and  of 
Beraunite  (Eleonorite)  in  Co.  Cork,  Ireland. 

A.  F.  Hallimond  and  F.  R.  Ennos  :  On 
Moravite  from  North  Wales. 

Dr.  G.  T.  Prior  :  On  the  Chemical  Com- 
position of  the  Ashdan  Meteorite. 


THE  CHEMICAL  SOCIETY. 

Van  Der  Waalb  Memorial  Lecture. 

This  was  delivered  by  Dr.  J.  H.  Jeans, 
See.  R.S.,  at  the  Inc>titution  of  Mechanical 
Engineers,  Storey's  Gate,  Westminster, 
S.W  .1,  on  Thursday,  November  8,  1023,  at 
ti  p.m. 


The  following  papers  were  read  at.  the 
Ordinary  Meeting,  Nov.  1 :  — 

The  Rapid  Admixture  of  Hot  Combus- 
tible GascH  irilii  .\ir,  by  F,  M.  Cray  and  W. 
E.  Garner. 

The  minimum  temperature  at  which  hot 
combustible  gases  will  ignite,  when  mixed 
with  air  at  high  speeds,  must  be  higher  than 
the  normal  ignition  temiperature.  It  should 
l)e  possible  to  dem<Mistrate  the  cooling  effect 
i){  the  air  if  sufficiently  high  s|)eeds  of  pro- 
jection of  the  hot  gases  be  attained. 

Experiments  were  carried  out  in  which 
high  I'xplosives  in  steel  containers,  and 
acetylene  and  oxygen  mixtures  in  glass 
bulbs,  were  exploded  in  a  limited  volume  of 
air.  The  ignition  of  high  .explosives  is  to 
some  extent  determined  by  the  volume  of 
air  into  which  the  hot  gases  are  prf>jected, 
ignition  occurring    only    when  the    ratio    of 


302 


THE  CHEMICAL  NEWS. 


NOVEMBEK  9,  1923. 


weight  of  explosive  to  volume  of  air  ex- 
ceeds a  definite  value. 

In  the  experiments  with  acetylene  and 
oxygen,  the  velocities  of  projection  were 
not  sufficiently  high  for  this.  Partial  igni- 
tion occurred  whatever  the  ratio  of  explo- 
sive mixture  to  the  surrounding  air,  but  io-- 
nition  was  less  complete  the  higher  the 
velocity  of  projection.  Thus  the  greatest 
conversion  of  acetylene  to  carbon  mciu- 
oxide  was  attained  with  mixtures  of  equal 
proportions  of  acetylene  and  oxygen,  this 
mixture,  as  was  shown  by  Dixon,  possess- 
ing the  highest  velocity  of  explosion  of  any 
acetylene- oxygen  mixture. 

Although  carbon  monoxide  was  present 
in  the  products  from  the  explosion  of  all  of 
the  mixtures  investigated,  free  carbon  was 
found  only  in  those  experiments  where  the 
ratio  of  oxygen  t>o  acetylene  exceeded  unity. 
This  behaviour  is  in  agreement  with  the 
views  of  Bone  on  the  mechanism  of  the  pro- 
cesses occurring  during  .  the  combustion  of 
hydrocarbons. 

The  determination  of  Surface  Tension 
from  the  maximum  pressure  in  BvhhJes. 
Part  II.,  by  Samuel  Sugden. 

An  improved  form  of  apparatus  for 
measuring  surface  tension  by  the  method 
of  maximum  bubble  pressure  was  de- 
scribed. The  method  of  calculation  has 
been  simplified. 

The  variation  of  Surface  Tension  irith 
Temperature,  and  sonic  related  Functions, 
by  Samuel  Sugden. 

The  variation  of  surface  tension  with 
temperature  is  known  to  be  represented 
with  fair  accuracy  by  an  equation  of  van 
der  Waals  (1894), 

y  =  K,^,V,-f(l-m) 
in  which  B  is  a  universal  constant.  On  the 
other  hand,  Ferguson  (1916)  allowed  this 
exponent  to  vary  slightly  in  order  better  to 
express  the  data  of  Ramsay  and  Shields 
(1893).  Recently  it  has  assumed  a  new  in- 
terest, since  Ferguson  has  shown  that  the 
shuple  relation,  discovered  by  Maclend 
(1923),  between  surface  tension  and  density 
can  be  deduced  from  the  modified  Ramsay- 
Shields  law  and  the  equation,  if  B  is  con- 
stant (1.20). 

The  data  of  Ramsay  and  Shields  are  now 
known  to  be  in  error  owing  to  their  correc- 
tion for  capillary  rise  in  the  outer  vessel 
having  been  inadequate.  The  author  now 
calculates  the  necessary  correction  1)y  ap- 
plying an  earlier  (1921)  theory. 

From  the  available  figures  it  was  shown, 
for  six  non-associated  liquids,  that:  — 


(a)  The  variation  of  surface  tension  with 
temperatiu-e  can  be  ■  represented  accurately 
by: 

where  y^  is  a  constant  and  m  is  the  reduced 
temperature  : 

(b)  Macleod's  relation, 

y  =  C(])— d)\ 
where  C  is  a  constant  and  D,  d  are  the  den- 
sities of  liquid  and  vapour  respectively, 
holds  with  remarkable  accuracy  up  to  with- 
in a  few  degrees  of  the  critical  temperature ; 
*• 

(c)  Van  der  Waals'  relations  connecting 
■yo  with  the  critical  constants  are  only  ap- 
proximately true. 

Muconic  and  hydromuconic  Acids.  Part 
III.  :  Valency  interchange  in  the  Hydro- 
muGonic  system,  by  E.  H.  Farmer. 

It  was  shown  in  Part  I.  that  the  products 
of  interaction  of  sodiomalonic  and.  sodio- 
cyanoacctic  esters  with  ethyl  muconate 
possessed  the  general  structure  RO.,C-CH„ 
•CH^CXrCH-CO^R  and  not  RO,CCH:' 
CH  •  CHX  •  CH2  •  CO2R.  This  constituted 
an  addition  of  a  1 : 3-type ;  and  in  view  of 
the  difficulty  in  accounting  for  such  a  move- 
ment of  the  double  bond  as  is  necessitated 
if  1 :2-addition  be  supposed  to  take  place,  it 
was  suggested  that  the  muconic  system  was 
to  ome  extent  comparable  in  mobility  with 
the  glutaoonic  system. 

This  view  is  now  seen  to  be  incorrect. 
The  muconic  system  is  static,  conforms  to 
stereo-chemical  theory,  and  adds  the  com- 
ponents of  esters  at  the  1 :2-position.  The 
substituted  dihydromuconic  esters  thus  pro- 
duced represent  in  their  configuration  in- 
teresting instances  of  the  effect  of  an  equi- 
librium between  Aa-  and  A/^-dihydromu- 
conic  esters  in  the  presence  of  sodium  alk- 
oxide.  This  equilibrium,  which  favours  the 
Aa-form  in  the  esters  themselves,  results 
in  the  conversion  of  the  additive  products 
imder  consideration  into  /8-substituted  glu- 
taconic  esters. 

Experiments  on  the  Synthesis  of  Sub- 
stances possessing  the  Ladenhurg  Formu- 
la. Part  I.  :  Derivatives  of  cyclopropylcy- 
clopropane,  by  E.  H.  Farmer. 

Recent  syntheses  by  Beesley  and  Thorpe 
suggested  a  method  for  the  syntheses  of 
substances  possessing  the  Ladenb\u-g 
formula.  The  production  nf  considerable 
quantities  of  various  .derivatives  of  cyclo- 
propylc7/c/oipropane  was  described. 


NOVEMBER  9,  1923. 


THE  CHEMICAL  NEWS. 


303 


COEHESPO\'I)EXGE. 

To  the  Editors  of  Thk  Ciii.mical  Nkws. 

Sirs,' — Could  any  of  your  readers  inform 
me  what  is  tiie  lowest  pressure  at  which  the 
Joule  Thomson  Effect  is  prwlueed  on  pass- 
ing air  through  a  small  orifice  at  ordinary 
tom(peratures ".' 

The  lowering  of  temperature  may  be  ex- 
ceedingly small,  and  I  am  desirous  of  know- 
ing what  is  the  initial  pressure  which  will 
produce  the  slightest  cooling  effect  at  ordi- 
nary room  temptuature.  I  do  not  want  to 
prwluce  a  very  low  temperature,  only  down 
to  0°  C.  by  continually  cooling  the  incom- 
ing gas. — Yours.  .<o.. 

A.  J.  FnasLANi). 

Swansea,  November  1.   1920. 


ELECTH01>E  REACTIONS  AND 
EQUfUBRIA. 

A  general  discussion  on  this  subject  will 
Im'  held  by  the  Faraday  Society,  meeting  at 
the   Institution  of  Electrical  Engineers,  on 
Monday,  November  20  next.     The  first  ses- 
sion of  the  meeting  will  extend  from  8    to  o 
p.m.,  and  will  deal    with    "  Conditions    of 
Equilibrium  at  Reversible  ElectrfMles. "  Sir 
Robert  Robertson,   President,    will  preside, 
and  the  introductory  address  will  be  given 
by  Dr.  E.  K.  Rideal.     Among  the  speakers 
will  be  Professor  liiilman,    of  C()4>enhagen, 
who  will  read  a  paper  on  "  Somi'  ()xiilat:<  n 
and  Reduction  Electrodes  and  their  impor- 
tance to  Organic  Chemistry."     Aft^r  an  in 
terval  for  tea,  the  meetin;^  will    resume  ;it 
■).30  p.m.,  and  will  devote  itself  to  the  con- 
sideration of    "  Irreversible    Electrode  Ef- 
fects,      including      Passivity      and     Over- 
voltage."       Prof.    F.    Ct.    Donnan,     Vice- 
President,    will  preside    over  this    session, 
and  the  introductory    address  will  be  given 
by  Profos.sor  A.  J.  Allmand.       At  the  con- 
clusion of  the  meeting  a  dinner  will  be  he.ld 
at  the  Holbom  Restaurant,   to  bo  followed 
by  an  informal  conference.   Members  of  th(> 
Chemical  Society,  the  Physical  Society,  and 
the     Institution     oF     Electrical     Engineers 
have  been  invited  to  aitiiul  this  discussion. 
Others  interested  should  apply  to  the  Sec- 
retary   of  the    Faraday  Society.     10.  "Pssex 
Street,  London,  W.C.2.    from  whom  n'full 
programme  may  be  obtained. 


PUBLICATIONS  RECEIVED. 

The  Colour  Users'  Association  have 
issued  a  little  brochure  for  1923-4  contain- 
'ing  useful  general  and  special  information, 
including  lists  of  members,  dyestuff  statis- 
tics, regulations,  tables,  and  other  data, 
which  it  is  a  convenience  to  have  at  hand. 


BULLETINS  ISSUED  BY  THE 

DEPARTMENT  OF  THE  INTERIOR. 

UNITED  STATES  GEOLOGICAL 

SURVEY. 

Bismuth,  Selenium,  and  Tellurium,  by 
Victor  C.  Hkikks.    Pp,  16  to  24. 

Lead  in  1922,  by  C.  E.  Siebenthal  and 
\.  Stoll.    Pp.  27  to  86. 

Zinc  in  1922,  by  C.  E.  Siebenthal  and  A. 
SroLL.    Pp.  37  to  52. 

head  and  Zinc  Pegmenfs  and  Salts  in 
1922,  by  C.  E.  Siebenthal  and  A.  Stoll. 
I»p.  77  to  85. 

Asphalt  and  Related  Bitumens  in  1922. 
by  K.  W.  CoTTRELL.    Pp.  7  to  18. 

The  Lime  Belt  of  Massachusetts  and 
Parts  of  Eastern  Netp  York  and  Western 
Connecticut,  by  T.  Nelson  Dale.  Pp.  VI. 
+  71. 

Proffress  lirpnri  on  a  Sub-surface  Study 
of  the  Pershincj  Oil  and  (ins  Field,  Osage 
County,  Oklahoma,  by  W.  W.  Rurev.  Pp. 
1  to  70. 

Surface  Water  Supply  of  the  United 
States  1919-1920.  Part  I.:  North  Atlantic 
Slope  Drainage  Basins,  by  Nathan  C.  Gro- 

VEB. 

Surface  ]T'(//rf  Supply  of  the  United 
States,  1919-1920.  Part  X. :  The  Great 
liasin,  by  Nathan  C.  Grover.  Pp.  VI.  + 
348. 

Surface  Water  Supply  of  the  United 
States,  19W  and  1920.  Part  XII.:  North 
Pacific  Slope  l)rainagc  Basins,  by  Nathan 
(;.  Grover.     Pp.  V.  +  262. 


304 


THE  CKEMIGAL  NEWS. 


NOVEMBEE  9,  1923. 


Messrs.  Theqdor  Steinkopff,  of  Dresden, 
have  just  published  a  volume  on  Physical 
Cheinistry  as  Applied  to  Internal  Medicine, 
by  Prof.  H.  Shade,  Director  of  the  physico- 
chemical  division  of  the  Chnic  at  Kiel. 

The  development  of  physical  chemistry- 
has  assisted  in  the  progress  of  many 
sciences  in  recent  years.  That  it  has 
helped  in  medicine  is  well  borne  out  by  a 
perusal  of  this  work. 


This  list  is  specially  compiled  for  The  Chemical 
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Agents,  of  5,  Chancery  Lane,  Ixindon,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent   Applications. 
26037— Lantz,  K.— Manufacture  of  naphthaquinone 

derivatives.    Oct.  18. 
2616.3— Oechslin,   C— Manufacture     of     substituted 

products  of  an  aliphatic  arsenic  acid.    Oct. 

products  of  an  aliphatic  arsinic  acid.    Oct. 

19. 
25665— Pereira,   H.— Manufacture     of  perylene  vat 

dye.    Oct.  15. 
25666- Pereira,   H.— Manufacture   of     3-10-perylene 

quinone.    Oct.  15. 
25936— Soc.     rOxyhydrique      Prancaise.— Manufac- 
ture of  hydrogen.    Oct.  17. 

Specifications   Published   this    Week. 

184462— Moeller,  Dr.  F.— Waterproofing  cellulose 
or  carbohydrates  of  the  cellulose  group. 

199401— Pereira.   H.— Reduction   of   dioxyperylene. 

203347— Lilienfeld,  Dr.  L.— Manufacture  of  cellu- 
lose derivatives. 

Abstract  Published  this   Week. 

203077— Synthetic  drugs.— Pomaret,  M.,  of  92,  Rue 
Vielle  du  Temple.  Paris,  and  Mav  &  Baker. 
Ltd.,  Garden  Wharf,  Church  Road,  Rat- 
ter sea,  London.  _  ^^ 

Arsenobenzene  derivatives. — Stable  solutions  of 
3  :  3  -diamino-4  :  4  -dihydroxyarsenobenzene  and 
like  arseno  bases  with  reducing  sugars  are  pre- 
pared by  acting  with  an  organic  base,  for  example 
piperazine,  iipon  a  neutral  soluble  condensation 
product  of  the  arseno  base  having  one  or  more 
side  chains  directly  linked  to  a  nitrogen  atom, 
and  then  adding  a  solution  of  a  reducing  sugar: 
or  the  reaction  may  be  effected  in  the  presence  of 
a  sugar.  In  an  example  3  :  3  -diamino-4  :  4  -di- 
hydroxyarsenobenzene-N-methylene  sulphoxyl  ato 
dissolved  in  glucose  solution  is  treated  with  piper- 
azine; the  solution  is  readv  for  use  after  standing 
for  a  few  days.  Specifications  112,984  and  117.28^ 
are  referred  to.  The  Provisional  Specification 
also  mentions  hexamethylenetetramine  as  a  suit- 
able organic  base. 

^Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
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NOVEMBER  16.  1923. 


THE  CHEMICAL  NEWS. 


305 


THE   CHEMICAL  NEWS. 


VOL.  CXXVII.      Nf>.  3318. 


CHEMISTRY    AT   THE    BRITISH 
EMPIRE    EXHIBITION    (1924). 

At  the  British  Empire  Exhibition  at 
Wembley  the  national  life  of  this  country 
and  of  the  newer  nations  overseas  will  reveal 
itself  in  everj  branch  of  its  activities.  !n 
tvery.art,  craft  and  manufacture,  and  in 
agriculture,  we  hope  to  make  a  memoral)le 
display. 

Clearly,  therefore,  we  cannot  neglect  to 
make  an  exhibition  of  our  progress  and  pre- 
sent position  in  science,  more  ipartieularly  in 
chemical  science  which  is  imperceptible  to 
most,  but  nevertheless  clearly  intertwined 
with  our  progress  and  position  in  industry, 
with  the  preservation  of  our  health  anrl 
with  our  enjoyment  of  such  amenities  as 
our  civilisation  has  as  yet  provided. 

We  are  so  familiar  with  the  idea  that  we 
are  behind  othi-r  nations  in  chemistry,  par- 
ticularly behind  (iermany.  I  am  not  talk- 
ing about  the  application  of  chemistry,  but 
the  study  of  chemistry  and  of  researcli  in 
chemistry  at  our  universities,  that  the 
thought  may  arise,  is  it  wise  to  make  such 
an  exhibit?  Would  it  nf)t  be  better,  as 
chemistry  is  so  fundamental,  as  our  pro- 
gress in  industry  depends  so  much  upon  our 
progress  in  pure  chemistry,  to  conceal  our 
position  in  this  science — at  least  for  a  time 

from  the  prying  ga/.e  of  the  world  that 
will  visit  Wembley?  The  answer  to  that  is 
Ibis:  — 

The  pure  chemistry  exhibit  is  being  or- 
ganised by  a  connnittec  conipo«ed  of  repre- 
sentatives of  the  Association  of  British 
Chemical  Manufacturers,  of  the  Chemical 
Society-,  of  the  Society  of  Chemical  Indus- 
try, of  the  Institute  of  Chemistry,  of  the 
Society  of  Dyei^  and  Colourists,  of  the 
Federal  Council  of  Pine  and  Applied  Chem- 
istry, in  fact  of  all  rt-lovant  scientific  so- 
cieties, supported  and  greatly  assisted  by 
the  advice  and  co-operation  of  the  Royal 
Society.  It  would  appear,  therefore,  that 
in  the  minds  of  those  qualified  to  expn^ss 
an  opinion,  that  it  will  redound  to  the 
national  advantage  in  every  way  for  the 
world  to  see  what  the  British  men  of  science 
have  done  and    are  doinp  to    l)uild  up    tlie 


science    of  chemistry  as  it  is  known  in    the 
world  to-day.     That  is  the  answer. 

We  may  put  it  higher :  The  pure  chemis- 
try exhibit  at  Wembley  will,  without  a 
doubt,  for  ever  destroy  the  illusion,  which 
had  some  justification  in  the  past,  that  our 
university  training  and  research  in  chemis- 
try is  below  the  highest  standard  of  other 
countries. 

This  would  not  have  been  true  in  the 
same  sense  thirty  years  ago. 

We  have  always  had  masters,  giants  of 
science.  In  a  sense  the  exceptional  man  of 
genius  and  science  belongs  to  the  world.  In 
the  richness  and  the  output  of  the  many 
workers  of  talent,  in  the  vigour  of  the 
tt^aching  at  the  many  universities,  in  the 
output  of  first-class  work  in  every  branch  of 
chemical  science,  you  find  the  true  criterion 
of  the  national  position  in  chemical  science. 

Thirty  years  ago  we  could  not  have 
shown  this.  The  development  of  our  chemi- 
cal schools  which  we  know  to-day  is  com- 
paratively new,  and  is  as  yet  not  appre- 
ciated by  the  general  public.  What  is  the 
importance  of  this? 

It  is  of  importance  to  the  chemical  in- 
dustry for  the  world  to  know  that  behind  it 
are  great  schools  of  chemistry,  directed  by 
great  teachers  of  chemistry  and  inspired  by 
great  original  workers  in  chemistry  who 
can  supply  ideas  and  well-trained  students 
to  fertilise  the  chemical  factories — f>ther- 
wise  arid  wastes  of  pi|)e8  and  tubs  and  vats 
and  buildings. 

It  is  also  of  importance  to  our  university 
labf>ratorie8  that  their  work  and  influence 
should  be  more  widely  known  to  the  public 
who  support  them. 

However,  perhaps  it  has  not  occurred  to 
everybody  what  an  enormous  advantage  it 
is  to  the  public  to  see  with  its  own  eyes  and 
to  bo  able  to  comprehend  by  the  most 
charmingly  delightful  examples,  things 
which  were  a  few  years  ago  entirely  matters 
of  metaphysical  speculation.  To  quicken 
the  imagination  of  our  people,  to  give  them 
some  idea  of  the  enormous  interest — of 
which  they  are  for  the  most  part  entirely 
unaware — of  the  simple  things  which  sur- 
round their  daily  life,  is  one  consequence  of 
the  result  of  this  exhibit. 

Nothing  could  be  of  greater  importance 
than  to  give  the  f^eneral  public,  through  the 
eye  and  in  an  interesting,  fascinating  way, 
greater  appreciation  of  the  value  of  chemi- 
cal science  in  the  afifairs  of  life,  and  of  the 
steps  that  precede  groat  industrial  or  medi- 
cinal discoveries. 


306 


THE  CHEMICAL  NEWS. 


NOVEMBEK  16,  1923. 


The  following  sections  are  being  arranged 
by  the  conveners  mentioned. 


Physics  and  General  Chemistry. 

"Structure  of  the  Atom,"  Sir  Ernest 
Rutherford,   LL.D.,   F.R.S. 

"Sipectrosoopy,"  Professor  J.  C.  Mc- 
Lennan, F.R.S! 

"  Crystallography  and  Crystal  Struc- 
ture," Sir  Henry  Miers,  LL.D.,  F.R.S. 

"  Valency  Theories  and  Theories  of 
Chemical  Combination,"  Dr.  Arthur  Lap- 
worth,  D.Sc,  F.R.S. 

"  Photography,"  Dr.  T.  Slater  Price, 
O.B.E.,  F.I.C. 

"  General  Physical  Chemistry,"  Profes- 
sor F.  G.  Donnan,  C.B.E.,  F.R.S. 


Inorganic    Chemistry. 

"  Atomic  Weight  Determination,"  Dr. 
Alexander  Scott,  F.R.S. 

"Analysis:  Hydrogen  Ion  Concentra- 
tion," A.  Chaston  Chapman,  Esq.,  F.R.S. 

"  General  Inorganic,"  Professor  E.  C.  C. 
Baly,  C.B.E.,  M.Sc,  F.R.S. 

"Flame,  Fuel  and  Explosion  Waves," 
Professor  A.  Smithells,  C.M.G.,  B.Sc, 
F.R.S. 

"  Organic  Chemistry,"  Dr.  Henry  and 
Professor  F.  L.  Pyman,  D.Sc,  F.R.S. 

"  Biochemistry,"  J.  L.  Baker,  Esq., 
F.I.C. 

"  Agricultural  Chemistry,"  Sir  John 
Russell,  F.R.S. 

"  Sugars,"  Principal  J.  C.  Irvine, 
C.B.E.,  F.R.S. 

"  Terpenes,"  Professor  G.  G.  Hender- 
son, LL.D.,  F.R.S 

Plant  Colouring  Matters,"  Professor  T. 
M.  Heilbron,  D.S.O.,  F.I.C. 

"  Coal  Tar  Colouring  Matters,"  Dr.  J.  T. 
Hewitt,  F.R.S. 

"  General  Organic  Chemistry,"  Professor 
J.  F.  Thorpe,  C.B.E.,  F.R.S.' 

"  Cellulose,"  C.  F.  Cross,  Esq..  B..Sc., 
F.R.S. 

"  Catalysis,"  Dr.  E.  F.  Armstrong, 
D.Sc,  F.R.S. 

"  Explosives,"  W.  E.  Reid,  Esq.,  F.I.C. 

"  Plastics,"  Dr.  W.  R.  Ormandy. 

"  Apparatus,"  Commander  R.  E.  Stokes- 
Rees,  R.N. 

"  Chemical  Engineering,"  Professor  J. 
W.  Hinchley,  A.R.S.M.,  F.I.C. 

"  Historical,"  H.  B.  Pilcher,  Esq., 
O.B.E. 


PROPYL-STANNONIC    ACID. 

By  J.  G.  F.  Druce,  M.Sc.  (Lond.). 
R.Nat.Dr.  (Prague). 

Three  members  of  the  series  of  organic 
stannonic  acids  have  been  described  pre- 
viously, namely,  methyl-stannonic  acid 
{The  Chemical  Neivs,  1920,  CXX.,  229), 
ethyl-stanrionic  acid  (Trans.  Cheni.  Soc, 
1921,  CXIX,  758),  and  isopropyl-stannonic 
acid  {Trans.  Chem.  Soc,  1922  CXXl..  1859, 
and  this  Journal,  Vol.  CXXV.,  327). 

The  normal  propyl-stannonic  acid  has 
now  been  isolated.  The  potassium  salt  was 
formed  by  the  interaction  of  propyl  bromide 
(or  iodide)  and  an  alkaline  solution  of  potas- 
sium hydrogen  stannite  in  accordance  with 
the  equation  :  — 
CgH^X  +  KHSnOj  +  KOH  = 

C3H,  •  SnO  ■  OK  +  KX  +  H,0. 

From  this,  the  free  stannonic  acid  maj- 
be  obtained  by  careful  neiilialisation. 

The  reaction  is  not  quantitative,  although 
it  dot's  not  fall  far  short  of  being  so.  The  fil- 
trate which  remained  after  the  separation 
of  the  propyl-stannonic  acid  had  the  un- 
pleasant odour  associated  with  tri-alkyl  tin 
compounds. 

W^hen  this  solution  was  distilled,  a  quan- 
tity of  an  aqueous  distillate,  boiling  atnJo°, 
was  obtained.  It  was  found  to  contain  tin 
and  also  bromine.  Its  penetrating  odour 
suggested  the  probable  presence  of  tri- 
propyl  tin  bromide. 

The  residue  from  the  distillation  experi- 
ments yielded  a  further  distillate  when 
treated  at  a  higher  temperature  with  excess 
of  soda-lime. 

This  distillate  was  cloudy  and  oily,  and 
was  distinctly  alkaline,  although  it  left  no 
residue  on  evaporation. 

It  had  a  most  powerful  and  penetrating 
odour,  resembling,  but  distinct  fiom,  garlic, 
and  reacted  with  sulphuric,  hydrochloric, 
and  acetic  aeids,  but  owing  to  the  small 
quantity  available  the  amounts  of  the  salts 
obtainable  were  not  sufficient  for  analytical 
purposes.  In  all  probability  the  substance 
was,  or  at  least  contained,  tri-propyl  tin 
hydroxide. 

Recentlv,  Lambourne  (Trans.  Chem. 
Soc,  1922,  CXXL,  2533)  advanced  evi- 
dence which  indicated  that  methyl-stanno- 
nic acid  was  polymeric  and  had  the  struc- 
ture : 

CH3  ^0  ■  Sn  CH3 (OH)  -. 

Sn<  >0 

HO    ---^       \^0SnCH3(0H)-^^^ 


NOVEMBEK  16,  1923'. 


THE  CHEMICAL  NEW8 


SO'; 


since  he  was  able  to  isolate  tri-  and  penta- 
acotyl,  benzoyl,  anr]  other  derivatives. 

Investigations  are  in  progress  with  the 
object  of  ascertainiug  whethei-  this  is  the 
case  with  the  other  members  of  the  series, 
and  whether  it  is  supported  by  all  the  ex- 
perimental fficts. 

In  the  present  communication,  the  simple 
formula,  a-CjH,  •  SnO.OH,  has  been  ad- 
hered to,  since  it  is  possible  to  account  for 
ail  the  practical  data  presented  in  the  ex- 
perimental part. 

When  destructively  distilled,  the  acid 
gave  propyl  alcohol,  water,  propylene  and 
propane.  The  residue  chiefly  was  stannous 
oxifle,  but  stannic  oxide  was  also  present. 

The  decomposition  may    thus  follov»    the 
three  courses  t-xpressed  bV  the  eciuations:  — 
C'3H,   SnO  OH  =  C,H/)H  +  SnO 
C3H,    SnO  OH  =  C3H,  +  SnO  +  H,0 
('Jf,    SnO-OH   =  C3H,  +  SnO,. 

Experimental. 

i'niinralinn  of  a-Propyl-Htnnvonic  Acid. — 
Z  Sixt<'en  grams  of  propyl  bromide  (or  in 
some  experiments  22  gr.  of  thv  iodide)  were 
added  to  a  solution  of  potassium  hydrogen 
stannite,  obtained  by  treating  20  gr.  of 
stannous  chloride  mixed  with  60  oc.  of 
water,  with  enough  of  a  cold  lO  per  cent, 
so'ution  of  potassium  hydroxid<'  (about  240 
cc.)  to  dissf>lve  completely  the  precipitate  of 
stannous  hydroxide  first  formed. 

Alcohol  (about  200  cc.)  was  added  to 
make  the  mixture  homogeneous.  It  was 
shaken  at  intervals  during  fourteen  days. 

The  solution  wa-;  then  made  almost  neu- 
tral with  dilute  hydroehloric  acid  solution 
.  which  was  slowly  added  with  stirring.  The 
gelatinous  precipitate  was  filtered  off, 
washed  with  warm  water  until  free  from  al- 
kali, drained  and  dried. 

When  dry  it  was  easily  ground  to  a  white 
ntiior[)hr)us  powder. 

On  analysis — 

0.8448  gr.  gave  0.6480  gr.  SnO,; 

Sn  =  00.5  per  cent. 

0.7008  gr.  gave  0.2902  gr,  H.,0.  and  0.4047 
1.  CO,;        H  =  4.6  and  C  ='lH.l  percent. 

C,H,  SnO  OH  requires  Sn  =  60,  H  = 
1.1,  and  C=   18. f)  per  cent. 

Propyl  stannonic  acid  did  not  melt  on 
Inating.  but  decomposed  in  air  at  tempera- 
fnres  considerably  above  300°,  leaving  a 
\\  lute  residue  of  stannic  oxide. 

When  destructibely  distilled  out  of  con- 
tiict  with  air,  it  gave  a  little  propyl  aleohol 
(oxidised  by  chromic  acid  to  propionaldc- 
hydo),  some  water    (which  coloured    anhy- 


drous copper  sulphate  blue),  a  quantity  of 
an  unsaturated  hydrocarbon  (presumably 
propylene),  and  a  small  volume  of  a  satur- 
ated hydrocarbon  (propane).  Much  of  the 
dark  residue  was  soluble  in  a  hot  dilute 
solution  of  hydrochloric  acid,  yielding  a 
solution  of  stannous  chlcMide.  The  white 
insoluble  residue  was  reduced  to  tin  by  heat- 
mg  in  a  stream  of  hydrogen,  and  was  thus 
stannic  oxide. 

Properties  of  a-Propyl-Stannonic  Acid.— 
Propyl -stannonic  acid  was  not  soluble  in 
water  or  any  common  orcanic  solvent,  ex- 
cept glacial  acetic  and  other  acids.  It  ex- 
hibited amphoteric  properties,  being  soluble 
in  both  strong  acids  and  strong  solutions  of 
the  caustic  alkalis. 

Potasaitim  Propyl-Sfannonatc,  C,!!^- 
SnOOK. — The  potassium  salt  of  a-propyl- 
stannonic  acid  was  obtained  by  dissolving 
as  much  of  the  acid  as  possible  in  a  warm  15 
per  cent,  solution  o^  potassium  hydroxide. 
When  cold,  the  sutpernatant  liquid  was 
placed  in  a  vacuum  desiccator  over  both 
concentrated  sulphuric  ficid  and  sticks  of 
potassium  hydroxide. 

After  some  days  crystals  of  the  potassium 
salt  separated.  These  were  washed  several 
times  with  warm  alcohol,  to  remove  adher- 
ing potash,  and  dried. 

On  analysis — 

0,45.55  gr.  gave  0.2020  gr.  SNO, ; 

Sn  =  50.5  per  cent, 
0.4555  gr.  gave  0.1839  gr.  K^SO^; 

K  =   18.2  per  cent. 
C,H,   SnO  OK  requires  Sn    =   51,0  and 
K  =  16.7  per  cent. 

Potassium  propyl-stannonate  was  very 
hygroscopic,  and  was  obtained  free  from  ex- 
cess of  alkali  only  with  difficulty.  It  was 
soluble  in  water,  but  the  solution  readily 
hydrolysed,  being  alkaline  to  indicators  and 
giving  a  flf)eculent  deposit. 

The  sfxlium  salt  was  similarly  obtained, 
and  exhibited  the  same  general  properties 
as  the  potassium  coiiii)ound. 

With  solutions  of  calcium  and  barium 
chlorides,  solutions  of  the  alkali  salts  gav(> 
precipitates  of  the  l)asic  ipropyl-stannonates 
of  these  metals, 

Dipropyl  tin  oxide,  (CjH,),  SnO. — Dipro- 
pyl  tin  oxide  was  obtained  as  a  white  pre- 
cipitate by  heating  i)ropyl-stann(;nic  acid 
with  excess    of  a  ten  per  cent,  solution    Of 


308 


THE  CHEMICAL  NEWS. 


NOVEMBER  16,  1923. 


ipotassium  (or  sodium)  hydroxide,  under  a 
reflux  condenser  for  several  hours.  The 
precipitate  was  filtered  off,  washed  till  free 
from  alkali,  drained,  and  dried. 

On  analysis — 

0.2695  gr.  gave  0.1837  gr.  SnO^; 

Sn  =  53.4  per  cent. 

(C3H^)2BnO  requires  Sn  =  53.8  per  cent. 

The  oxide  did  not  melt  on  heating,  but  de- 
composed at  high  temperatures,  leaving  a 
residue  of  stannic  oxide. 

It  did  not  dissolve  in  water,  alkalis  or  or- 
ganic solvents.  Hot  concentrated  solutions 
of  hydrochloric  and  hydrobromic  acids  dis- 
solved it,  forming  the  corresponding  chlor- 
ide and  bromide. 

Propyl  tin  trichloride,  CgH.SnCla. — This 
compound  was  obtained  by  boiling  propyl- 
stannonio  acid  under  a  reflux  condenser  with 
a  benzene  solution  of  hydrochloric  acid  gas. 

When  the  resulting  solutirn  was  evaipora- 
tcd  in  vacuo,  colourless  deliquescent  pris- 
matic crj'stals  remained. 

On  analysis — 

0.5050  gr.  gave  0.2880  gr.  SnO^ ; 

Sn  =  44.93  per  cent. 

0.5050  gr.  gave  0.8224  gr.  AgCl ; 

CI  =  40.3  per  cent. 

C3H, -SnClg  requires  Sn  =  44.3  and  CI 
=  39.5  per  cent. 

The  crystals  of  propyl  tin  trichloride  were 
very  soluble  in  water  and  most  organic  sol- 
vents. The  aqueous  solutions  hydrolysed. 
especially  on  warming. 

Propyl  tin  tr'ihromide,  C3H7  SnBrg. — Pro- 
pyl tin  tribromide  was  obtained  by  dissolv- 
ing the  stannonic  acid  in  concentrated  hy- 
drobromic acid.  The  substance  possessed  a 
darker  colour  than  the  trichloride,  which  it 
resembled  in  being  deliquescent. 


THE  BRITISH  CAST  IRON  RESEARCH 
ASSOCIATION. 

The  various  researches  detailed  in  pre- 
vious announcements  are  progressing,  re- 
ports upon  same  will  be  given  in  Bulletin 
No.  4,  which  is  now  being  prepared. 

Semi-Steel. — During  the  recent  visit  of 
Dr.  Moldenke,  of  America,  to  this  country, 
he  expressed  some  very  interesting  re- 
marks as  to  the  manufacture  and  nomen- 
clature of  semi-steel.  There  is  no  doubt 
that  a  better  name  should  be  found  for  it, 
and  there  is  equally  no  doubt  that  better 
methods    of  manufacture  will    have  to>    be 


adopted  if  its  producton  and  use  are  to  pro- 
gress. The  Association  has  carried  out  nu- 
merous investigations  lor  its  members,  and 
has  collected  a  large  amount  of  data  upon 
the  methods  adopted  by  various  makers. 
Although  the  Association  are  not  yet  in  a 
position  to  state  that  definite  conclusions 
have  been  arrived  at,  they  can  offer  con- 
sidered advice  to  its  members  upon  the  best 
melting  practice  to  adopt.  This  has  been 
done  in  many  cases  with  the  result  that 
mixture  and  melting  processes  have  been 
improved.  When  the  Association  has  com- 
pleted its  investigation  there  is  no  doubt 
that  it  will  be  able  to  make  such  a  report  to 
its  members  as  will  enable  them  to  produce 
a  material  that  will  be  of  widespread  use. 

Supplying  Pig  Iron  oh  Analysis. — A  cir- 
cular giving  recommendations  for  suipplying 
pig  iron  on  analysis  has  been  circulated  to 
the  Blast  Furnace  Owners  in  this  country 
by  Dr.  R.  Moldenke  and  Mr.  W,  Wood,  on 
behalf  of  the  American  Society  for  Testing 
Materials.  The  recommendations  will  be 
carefully  considered  by  this  Association  in 
due  course. 

Problems  Sent  in  by  Members. 

Several  problems  have  been  sent  in  dur- 
ing the  past  month  for  assistance  by  the 
Association,  including  the  following: — De- 
fective gas  engine  cylinder  casting;  mixture 
for  cast  iron  permanent  mould;  nature  of 
cast  iron  scrap  for  Cupola  mixture;  quality 
of  ganister;  corrosion  of  cast  iron  propellers. 


GENERAL    NOTES. 

SAFEGUARDING  OF  INDUSTRIES 

ACT. 

Part  I. — Arbitrations  Under  Section  1. 

The  Board  of  Trade    has  received  formal 
notices  of  complaint   under   Sub-section   (5) 
of  Section  1,  that 
Rongalite, 
Sodium    Formaldehyde     Sulphoxylate, 

and 

Zinc  Formaldehyde  Sulphoxylate 
have  been  improperly    included  in  the  lists 
of  articles  chargeable  with  duty  under  Part 
I.  of  the  Act. 

These  complaints  will  be  submitted  in 
due  course  to  the  Referee  appointed  by  the 
Lord  Chancellor  for  the  purposes  of  the 
Sub-section,  and  any  person  interested 
should  communicate  immediately  with  the 
Assistant  Secretary,  Board  of  Trade  (Indus- 
tries and  Manufactures  Deipartment),  Great 
George  Street,  London,  S.W.I, 


NOVBMBEiR  16,  1923. 


THE  CHEMICAL  NI5WS. 


309 


DYESTUFFS    (IMPORT  REGULATION) 
ACT. 
Applications  fok  Licences  in  October. 
The  following  statement  relating  to  appli- 
cations for    licences    under    the    Dyestufis 
(Import  Regulation)  Act,   1920,  made    dur- 
ing October  has  been  furnished  to  the  Board 
of  Trade  by  the  DyestufiEs  Advisory  Licens- 
ing Committee. 

The  total  number  of  applications  received 
during  the  month  was  520,  of  which  42H 
were  from  merchants  or  importers.  To 
these  should  be  added  the  40  cases  out- 
standing on  October  1,  making  a  total  for 
the  month  of  560.  These  were  dealt  with  as 
follows  :  — 

Granted — 423  (of  which  381  were  dealt 
with  within  7  days  of  receipt). 

Referred  to  British  makers  of  similar 
products — 75  (of  which  03  were  dealt 
with  within  7  days  of  receipt). 

Referred  to  Reparation  supplies  avail- 
able— 53  (all  dealt  with  within  2  days  of 
receipt). 

Cancelled — 1. 

Outstanding  on  October  31,  1923- ft. 
Of  the  total  of  560  applications  received, 
49H,  oi-  89  per  cent.,  were  dealt  with  within 
7  days  of  receipt. 


CANADA'S    NON-FERROUS    METALS. 

Canada  exported  during  the  twelve 
months  ended  September  30  last  iron  and 
pnxlucts  thereof  valued  at  $63,400,239. 
compared  with  the  previous  year's  total  of 
$35,647,293.  The  total  value  of  non-ferrous 
metals  exported  was  $57,169,208.  as 
against  $32,831,376  for  the  preceding  twelve 
months,  and  shipments  of  these  included  : 
Quantity.  Value, 
cvvts.  $ 

Alunjinium,  bars  and 

blocks  107.439    8,059.445 

Copper  ore    351.128    3.469.307 

Copper  blister   431.719    6,042.H35 

Gold  ore,    dust,    &c.  —        10.443.61H 

Lead       -  3,230.634 

Nickel        5()1.508  10,080. 020 

ezs. 
Silver     ore     and   bul- 
lion     19,007,224  12. 422.865 

Zinc  -  2,556.332 

Non-MftaUic  \finerah. 
Exports    from     Canada    of    non-metallic 
Kiinerals  during  the  twelve    months    ond(>d 
September  30,  1923,  amounted  in  value  to 


$29,728,160,  as  against  $22,618,582,  the 
total  for  the  previous  twelve  months.  They 
included :  — 

Quantity.  Value, 

tons.  $ 

Asbestos   203,762  8,339,485 

Coal  1,807,973         11,510,343 


PnoCEHDIXdS  AND  NOTICES  OF 
SOCIETIES. 

THE  ROYAL  SOCIETY. 
Thursday ,  November  8. 

Papers  read  :  — 

A.  S.  Parkes  :  Studies  on  ihe  Sex-ratio 
and  related  Phenomena — Fa'tal  Retrogres- 
sion in  Mice.  Conuuunicated  by  Dr.  F.  H. 
A.  Marshall,  F.R.S. 

R.  A.  Fisher  :  The  Influence  of  liainfall 
on  the  Yield  of  Wheat.  Connnunicated  by 
Sir  Jolm  Russell.  F.R.S. 

The  Rothamsted  data  for  rainfall  and 
wheat  yields  extend  to  1854 ;  these  data 
have  been  utilised  to  calculate  the  overaj^ 
effect  on  the  yield  oi  rain  at  different  periods 
of  the  harvest  year,  for  plots  under  13  dif- 
ferent manurial  treatments.  The  method  is 
an  extension  of  the  method  of  partial  corre- 
lation, applicable  when  the  numl)er  of  in- 
de|H>ndent  variates  is  very  large  and  can  be 
arranged  in  a  eonlinuous  serii-s.  This  has 
involved  the  analysis  of  the  distribution  of 
rainfall  in  eaoli  of  the  years;  a  significant 
and  progressive  change  has  been  in  pro- 
gress in  the  distribution  pf  rain.  The  elimi- 
nation of  such  slow  changes  and  others 
which  appear  in  the  yields  has  been  effected 
by  the  method  of  (polynomial  fitting;  this 
niethod  is  shown  to  minimise  the  errors  in- 
volved in  such  alt^'rnative  processes  as  the 
use  of  Variate  Differences. 

The  several  plots  show  marked  differ- 
ences in  their  response  to  rain,  showing  that 
it  is  not  impossible  for  the  farmer  to  a(Ta|)t 
his  manurial  treatment  to  a  wet  or  dry 
seasot.  A  large  part  of  the  differences  may 
be  ascribed  to  the  effects  of  loss  of  soil  ni- 
trates by  percolaticm ;  other  effects  not 
susceptible  to  this  explanation,  and  not 
hitherto  anticipated,  include  the  losses  on 
the  highly  nitroj^'cnous  plots  due  to  late 
summer  rain.  The  residual  vahie  of  artifi- 
cial   nitrogenous     manures     ai[)pears     from 


310 


THE  CHEMICAL  NEWS. 


NOVEMBER  16,  1923. 


these    results     to     be  considerably    greater 
than  has  been  thought. 

Paper  read  in  title  only :  — 

D.  Thursby-Pelham  :  The  Placentation 
of  Hydrax  Capensis.  Communicated  bv 
Prof.  J.  S.  Gardiner,  F.K.S. 

Thursday,  November  15. 

Papers  read :  — 

Sir  William  Bragg,  F.E.S.,  and  Prof. 
G.  T.  Morgan,  F.K.S.  :  Crystal  Structure 
and  Chemical  Constitution  of  Basic  Beryl- 
lium Acetate  and  Propionate. 

G.  I.  Taylor,  F.R.S.  :  Experiments  on 
the  Motion  of  Solid  Bodies  in  Rotating 
Fluids. 

L,  G.  Jackson  :  Investigations  on  Para- 
magnetism at  Low  Temperatures.  Com- 
municated by  Prof.  H.  Kamerlingh  Onnes, 
For.  Mem.  R.S. 

L.  C.  Jackson  and- Prof.  H.  Kamerlingh 
Onnes,  For.  Mem.  R.S.  :  The  Magnetic 
Properties  of  some  Paramagnetic  Double 
Sulphates  at  Low  Temperatures. 

H.  H.  Potter:  Some  Experiments  on  the 
Proportionality  of  Mass  and  Weight.  Com- 
municated by  Prof.  0.  W.  Richardson, 
F.R.S. 

Paipers  read  in  title  only  :  — 

Lord  Rayleigh,  F.R.S.  :  Further  Studies 
on  the  Glow  of  Phosphorus  and  its  Extinc- 
tion by  Moist  Oxygen. 

Prof.  H.  A.  Wilson,  F.R.S.  :  An  Experi- 
ment on  the  Origin  of  the  Earth's  Magnetic 
Field. 

H.  Robinson,  D.Sc.  :  The  Secondary 
Corpuscular  Rays  produced  by  Homogene- 
ous X-Rays.  Communicated  by  Sir  Ernest 
Rutherford,  F.R.S. 

Lt.-Col.  J.  W.  GiFFORD  (with  an  Intro- 
duction by  Prof.  T.  M.  Lowry,  F.R.S.): 
Some  Reractive  Indices  of  Benzene  and  Cy- 
clohexane.  Communicated  by  Prof.  T.  M. 
Lowry,  F.R.S. 

J.  A.  V.  Butler:  A  Note  on  "The  Signi- 
ficance of  the  Electrode  otential."  Com- 
municated by  Prof.  J.  W.  McBain,  F.R.S. 


ROYAL  INSTITUTION. 

A  General  Meeting  of  the  members  of  the 
Royal  Institution  was  held  on  November  5, 
Sir  James  Crichton-Browne,  Treasurer  and 
Vice-President,  in  the  chair.  The  thanks  of 
the  members  were  returned  to  Mr.  F.  Cos- 
ton  Taylor,  for  his  donation  of  one  hundred 
guineas  to  the  Research  Fund,  and  to  Mr. 
Liobert  Mond,  for  his  gift  of  busts  and 
medallions  of  Dr.  Ludwig  Mond,  Canniz- 
zaro,  Liebig,  Berzehus,  and  others;  statu- 
ette of  Sir  James  Dewar,  and  many  por- 
traits and  photographs.  I'he  death  of  Pro- 
fessor Jules  VioJle,  an  honorary  member  of 
the  Institution,  was  announced,  and  a  re- 
solution of  condolence  with  the  family  was 
passed. 

Mr.  H.  A.  Gwyune,  Professor  J.  C.  Mc- 
Lennan, and  Colonel  H.  G.  Wait  were 
elected  members. 


H 


THE  PHYSICAL  SOCIETY  OF  LONDON. 

A  meeting  of  the  Society  w  as  held  on  Fri- 
day, November  9,  at  the  Imperial  College  of 
Science,  South  Kensington. 

A  Demonstration  of  "  Experiments  on 
the  Reproduction  of  Vowel  Sounds  "  was 
given  by  Sir  Richard  Paget. 

The  following  papers  were  read  :  — 
The  Scattering  of  Light    by   Carbon    Di- 
oxide and  Some  Organic  Vapours,  l)y  Prof. 
A.  L.  Narayan,  M.A.    (presented    by  Lord 
Rayleigh). 

Measurement  of  the  Surface  Tension  of  a 
Small  Quantity  of  Liquid,  by  Dr.  Allan 
Ferguson. 

Proceedings  of  the  meeting  held  on  Oct. 
26,  Alexander  Russell,  M.A.,  D.Sc,  in  the 
chair  :  — 

The  President  announced  that  Mr.  F.  E. 
Smith  had  been  forced,  owing  to  pressure  of 
work,  to  resign  his  position  as  Honorary 
Secretary  of  the-  Society,  and  expressed  the 
Society's  warm  appreciation  of  t'le  value  of 
the  services  he  had  rendered  in  that  office. 

The  President  further  announced  that 
Prof.  A.  0.  Rankine  had  been  elected  by  the 
CounciLto  succeed  Mr.  Smith  as  Secretary. 

Papers  read  :  — 

The  Fine  Structure  of  Some  Sodium  Salts 
of  the  Fatty  Acids  in  Soap  Curds,  bj  S.  H. 
Piper,  D.S.O.,  B.Sc,  and  E.  N.  Grindlky, 
B.Sc. 


NOVEMBER  16,  1923. 


THJS  CHEMICAL  NEWS. 


311 


X-ray  photographs  of  certain  sodium 
salts  of  the  fatty  acids  (soap  curds)  show 
lines  due  to  reflections  from  planes  with 
very  wide  spacings  of  the  order  40  A.U. 
These  planar  spacings  iiicivase  uniformly 
with  the  number  of  CH^  groups  in  the  mole- 
cule, indicating  an  effective  length  of  1.2o 
A.U.  for  the  CHj  group.  These  and  other 
lines  can  be  accounted  for  by  assuming  that 
the  curds  are  in  the  smectic  state  described 
I)y  Friedel. 

Discussion. 

Mr.  G.  Shearer  said  that  in  conjunction 
with  Dr.  Miller  he  had  recently  been  e.xam- 
ining  compounds  somewhat  similar  to  those 
referred  to  in  the  paiper,  with  similar  re- 
sults. The  compounds  he  had  dealt  with 
were,  however,  solids,  namely  the  heavier 
fatty  acids  and  their  esters.  He  also  had 
found  a  regular  increment  in  ihe  spacing  for 
each  CHj  radicle  added,  and  his  observa- 
tions confirmed  the  supposition  that  the 
a.xes  of  the  molecules  are  |)i  i[X'ndicular  («» 
the  strata  in  which  they  lie.  The  experi- 
luents  are  of  special  interest  in  that  they 
measure  the  actual  length  of  one  or  of  two 
molecules.  He  congratulalrd  the  authors 
on  the  excellence  of  their  photographs  for  a 
sumi-liquid  substance,  which  were  t\- 
hibited  at  the  meeting. 

X-liaij  Anoljfsis  of  Solid  Solutiont,  by  E. 
A.  Owen,  M. A.,  D.yc,  and  (!.  I).  Preston, 
B.A. 

The  atomic  structure  of  solid  solutions  of 
coipper-aluminium,  aluminium-magnesium, 
and  copper-nickel  has  been  examined  by 
the  X-ray  spectrometer.  In  each  case  it 
was  found  that  the  solute  atom  replaces  an 
atom  in  the  lattice  of  the  solvent,  the  sub- 
stituion  being  accompanied  by  a  distortion 
of  the  lattice. 

A  saturated  solution  of  aluminium  in 
copper  shows  that  the  aluminium  expands 
the  copper  lattice  from  BOO  A  to  3.G.")  A. 
Thi'  effect  of  adding  nickel  to  copper  was  to 
pro<luce  a  contraction  of  the  lattice,  thi>  con- 
traction being  approximately  a  linear 
function  of  the  atomic  percentage  of  either 
constituent.  The  addition  of  8  per  cent, 
magnesium  by  weight  to  aluminium  causes 
the  average  parameter  of  the  aluminimn 
lattice  to  increase  from  1.0.')  A  to  4.10  A. 
The  addition  of  8  per  cent,  aluminimn  by 
weight  to  magnesium  decreases  the  av«'rage 
pnranifter  (^f  the  hi'xagoii.il  lattice  of  mag- 


nesium from  3.17  A  to  3.15  A,  and  increases 
its  axial  ratio  from  1.63  to  1.66. 

An  examination  of  the  eutectic  alloy  of 
aluminium  and  copper  showed  that  this  al- 
loy consists  of  a  mixture  of  two  distinct 
substances  with  different  stpace  lattices. 
The  one  substance  bemg  Cu  Al^  and  the 
other  a  substance  the  space  lattice  of  which 
could  not  be  distinguished  from  that  of 
pure  aluminium. 

The  ^ntermetallic  compound  Cu  Alj  was 
found  to  possess  a  simple  tetragonal  lattice 
of  side  4.28  A  and  axial  ratio  0.562,  the 
copper  atoms  bein<:  at  the  corners  and  the 
aluminium  atoms  at  the  centres  of  the  four 
small  faces. 

The  atomic  structure  of  the  compound 
Cu  Al  resembles  that  of  a  solid  solution  of 
aluminium  in  copper,  but  the  distortion  is 
considerably  greater.  The  material  was 
found  to  have  a  faci'  centred  trigonal  lattice 
of  side  3.89  A  and  an  angle  between  the 
axes  of  94.6",  the  111  planes  being  connposed 
alternately  of  aluminium  and  copper  atoms. 

Discussion. 

.Mr.  1-.  1  wyman  commented  on  the  fine- 
ness of  the  definition  in  X-ray  photographs, 
remarking  that  it  might  have  been  expected 
that  r)win^  to  peiu't ration  of  the  rays  into 
the  material  and  from  other  causes,  con- 
siderable blurring  would  occur,  yet  the 
lines  shown  are  not  mote  than  a  hundredth 
of  an  inch  wide. 

Dr.  E.  A.  Owen,  in  reply,  said  that  the 
good  definition  might  he  ascribed  (1)  to  the 
fact  that  the  rays  do  not  penetrate  to  any 
great  depth  in  the  reflecting  material,  owing 
to  their  being  almost  completely  reflected 
by  the  outer  layers  of  atoms ;  and  (2)  to  the 
well-known  focussing  effect  obtained  when 
the  photographic  plate  and  the  source*  of 
radiation  are  equidistant  from  the  reflecting 
surface. 

Cohesion,  bv  ITeubbrt  Chatley,  D.Sc, 
A.Inst.P. 

The  paper  traced  the  consequences  of  as- 
suming that  the  alternately  positive  and 
negative  atoms  in  a  crystal  may  be  treated 
as  doublets  attracting  according  to  an  in- 
verse ourth-power  law,  while  the  electron 
fields  surrounding  the  atomic  nuclei  repol 
according  to  an  inverse  tenth-power  law.  It 
is  shown  that  the  numerical  results  agree 
fairlv  well  with  the  facts  as  regards  the 
strain  which  produces  rupture  in  solids,  and 


e^uptui 


312 


i^fiB  CHEMICAL  wfews. 


NOVEMBEB  16,  1923. 


as  regards  the  rate  of  change  of  conipressi- 
bihty  with  compression  in  liquids. 

Discussion. 

Prof.  A.  0.  Rankine  said  that  while  he 
recx>gnised  that  the  numerical  results  of  the 
theory  were  fairly  consistent  with  experi- 
mental values,  he  could  not  heltp  suspecting 
that  this  was  a  coincidence.  What  little  is 
known  of  the  nature  of  cohesion  seems  to 
indicate  that  the  laws  concerned  must  be 
far  more  complicated  than  a  simple  fnverse 
power  law.  The  doublets  would  only  at- 
tract according  to  an  inverse  fourth-power 
law  at  a  distance  great  compared  with  the 
distance  apart  of  their  components,  not  at 
the  distances  which  actually  obtain  in  a 
crystal;  and,  again,  in  a  ciystal  the  elec- 
tron swarms  of  neighbouring  atoms  must  be 
very  close  to  one  another  in  certain  regions, 
and  it  is  difficult  to  see  why  the  particular 
law  adopted  in  the  paper  should  hold.  Fur- 
ther, the  field  of  force  round  an  atom  must 
be  regarded  as  having  an  axis,  not  as  being 
sipherically  uniform  and  independent  of 
direction.  It  seems  unsatisfactory  also  to 
test  a  theory  based  on  the  structure  of  a 
solid  crystal  by  measurements  made  on 
water  in  the  liquid  state. 

Dr.  D.  Owen  said  that,  while  agreeing 
with  the  previous  speaker  that  the  formulae 
proposed  in  the  paper  were  open  to  objec- 
tion, any  hypothesis  seemed  better  than 
none.  Calculations  such  as  the  author  had 
made  might  be  of  value  in  suggesting  limit- 
ing values  of  elasticity  and  density  under 
great  stresses;  they  permitted,  for  example, 
of  interesting  speculations  as  to  the  condi- 
tions of 'matter  deep  in  the  earth's  interior. 


THE    FARADAY    SOCIETY. 
Papers  read  at  the    meeting  on  November 


12 


Part  I. — The    Electrodeposition  of    Man- 
ganese, by  A.  J.  Allmand  and  A.  N.  Camp- 

15ELL. 

The  problem  of  the  cathodic  deposition 
of  manganese  from  aqueous  solution  has 
received  little  attention  in  the  past.  Bun- 
sen  states  that  he  obtained  the  metal  by 
electrolysis  of  aqueous  manganous  chloride 
solutions,  using  the  a])paratus  ciniployed  jn 
the  deposition  of  chromium.  The  metal 
was  deposited  as  sheets  1  sq.  cm.  in  area;  it 
was  metallic  lookinf^   arid  oxidised  almost  as 


rapidly  as  potassium.  If  the  current  den- 
sity were  reduced,  mangano-manganic  oxide 
came  down.  Moore  states  that  metallic 
manganese  may  be  deposited  as  such  from  a 
neutral  solution  containing  a  large  excess  of 
ammonium  sulphocyanide ;  a  powerful  cur- 
rent is  necessary.  Smith  and  Frankel  find 
that,  if  an  excess  of  potassium  sulphocyan- 
ide be  present,  the  metal  comes  down  in 
gieyish- white  compact  form.  Under  the 
conditions  specified,  the  current  must  be 
low.  The  metallic  deposit  is  inclined  to 
oxidise  rapidly.  Van  Arsdale  and  Meier 
give  results  of  some  experiments  conducted 
on  the  electrolysis  of  manganese  sulphate 
solutions.  These  will  be  referred  to  in  more 
detail  below,  as  they  were  to  a  large  extent 
repeated  by  the  present  authors,  to  whom 
the  paper  was  unknown  when  the  work  was 
started.  Finally,  Foerster  quotes  some  re- 
sults obtained  by  Grube,  who  states  that 
very  pure  manganese  can  be  obtained  b}' 
electrolysis  of  a  6-7  N.  MnClg  solution, 
separated  by  a  diaphragm  from  the  anode. 
The  electrolyte  is  also  1.5  N.  with  respect 
to  NH^CI  and  0.1  N.  with  respect  to  HCl. 
The  current  density  is  20  amps./d.m.^  The 
electrolyte  is  strongly  stirred,  and  its  tem- 
perature 30°.  The  current  efficiency  is  said 
to  be  between  50  and  60  per  cent.,  and  the 
purity  of  the  deposit  99.9  to    100  per  cent. 

There  is  a  marked  tendency  for  the  de- 
posit to  sprout  at  the  edges  of  the  cathode, 
as  a  result  of  the  high  current  densities 
used.  This  can,  however,  be  overcome  by 
arranging  that  the  cathode  fills  the  whole 
cross-section  of  the  cell,  and  manganese  is 
then  obtained  as  a  smooth  miorocrystalline 
deposit,  which  can  be  removed  from  the 
cQpper  cathode  in  the  form  of  coherent 
sheet."  In  later  papers  Grube  and  Metzger 
refer  to  sheets  of  metal  1  inm.  thick  made 
by  this  method. 

The  problem  then  was  the  working  out  of 
the  conditions  for  the  'successful  electro- 
deposition  of  a  highly  electropositive  metal 
from  aqueous  solution.  We  decided  in  the 
first  instance  to  use  as  electrolytes  simple 
manganese  salts.  It  could  be  predicted  in 
advance  that  the  electrolysis  would  be 
favoured  by  a  high  metallic  salt  concentra- 
tir).n  and  by  a  low  hydrogen  ion  concentra- 
tion. A  high  current  density  was  also 
likely  to  be  advantageous.  With  regard  to 
temperature,  the  matter  was  more  complex. 
To  take  extreme  cases,  if  manganese  were 
a  metal  like  zinc,  with  high  hydrogen  over- 
voltage  and  small  irreve'-sible  resistance  to 
cathodic     deposition,     a     low     temperature 


NOVEMBER  16,  1923. 


THJ5  CHEMICAL  NEWS 


813 


would  be  better;  if  like  irou,  with  small  hy- 
drogen over-voltage  and  large  irreversible 
cathodio  efiects,  then  high  temperatures 
would  be  better.  We  connnrnced  on  the 
supposition  that  it  would  bL-have  more  like 
iron  than  like  zinc,  a  view  which  turned  out 
to  be  only  partly  correct,  as  both  high  hy- 
drogen over- voltage  and  high  irreversible  re- 
sistance to  nianganous  ion  discharge  were 
found. 

It  was  found  that  the  effects  of  changes 
in  composition  of  electrolytf,  current  den- 
sity, temperature,  and  tyi)e  of  cell  in- 
fluenced the  deposition. 

Pure  manganese  in  wjherent  form  can  Ix' 
prepared  in  small  quantity  with  a  current 
erticiency  of  40-5(J  per  cent . 

Attempts  to  prepare  larger  amounts  in 
coherent  form  have  so  far  been  unsuccess- 
ful. 

A  large  number  of  experiments  were  car- 
ried out  with  the  object  of  improving  the 
deposit  in  view,  without  any  striking  suc- 
cess. 

A  variety  of  addition  agents  were  tried, 
using  the  sti  ndard  manganese  sulphate  and 
"ammonium  sulphate  electrolyte.  Non;' 
jinMJuced  any  marked  improvement,  and  in 
several  cases  {e.g.,  gum  arabic,  dextrine, 
gelatine)  the  deposit  was  made  much  less 
pure. 

With  the  same  electrolyte,  an  experiment 
was  done,  making  use  of  a  burnisher  (an 
ebonite  strip)  pressed  against  the  rotating 
cathode.  The  deposit  obtained  was  smooth 
and  dense,  but  the  current  efficiency  was 
reduced  to  8.6  per  cent. 

Other  electrolytes  were  tri»(l.  The  use  of 
sulphocyanide  gave  a  more  coherent  but 
less  pure  deposit.  The  use  of  a  njixture  of 
mimganese  and  ammonium  perchlorates 
also  led  to  nothing,  as  the  whole  catholyte 
hydrolysed  with  great  rapidity,  becoming 
filled  with  manganous  hydroxide. 

Further  experiments  are  being  carried 
out. 

The  Cathodic  Behaviour  of  Aloys. — Part 
I. :  Iron — Nickel  AUoijh.  by  S.  Glasstone, 
M.Sc,  Ph.D.,  University  College,  Exeter. 

Very  little  work  has  been  done  on  the 
measurement  of  polarisation  voltage  at  elec- 
trodes composed  of  metallic  alloys,  and 
therefore  investigations  were  undertaken 
with  the  hQpe  of  throwing  some  light  on  the 
probletn  of  over- voltage  and  allied  pheno- 
mena. In  working  with  alloys  that  are  pre 
pared  from  a  fused  mixture  of  the  metals, 
the  structure,   and  no  doubt  the  properties 


of  the  allow  as  an  electrode,  will  depend 
upon  the  method  of  cooling.  Further,  the 
surface  skin  will  probably  be  different  from 
the  rest  of  the  alloy.  The  object  of  this 
work  was  to  investigate  the  cathodic  be- 
haviour of  alloys,  as  well  as  the  electrolyti- 
cally  deposited  pure  metals  for  oomtparison, 
along  three  lines :  (1)  to  measure  the  ca- 
th<xlic  potential  during  deposition  from  a 
solution  of  mixed  salts,  (2)  to  determine  the 
potential  required  for  hydrogen  liberation  in 
sulphuric  acid  and  sodium  hydroxide  solu- 
tions, i.e.,  "over- voltage,"  and  (3)  to  inves- 
tigate the  action  of  depolarisers.  Schlotter 
has  shown  that  the  reduction  efficiency  of 
any  particular  cathode  in  potassium  chlor- 
ate solution  is  greatly  influenced  by  deposit- 
ing upon  it  traces  of  another  metal  in 
amounts  insufficient  to  cover  the  surface  of 
the  cathode  com^jletely.  Thus  the  system 
electrode  metal — deposited  metal — hydro- 
gen might  be  more  or  less  efficient  for  the 
purposes  of  reduction  than  the  original  elec- 
trode system  before  metal  deposition.  Since 
an  alloy  at  which  hydrogen  is  being  evolved 
as  a  result  of  electrolysis,  resembles  to  a 
very  great  extent  the  electrode  system  used 
by  Schlotter,  it  appeared  that  a  systematic 
investigation  of  the  cathodic  behaviour  in 
the  presence  of  depolarisers  would  be  of  con- 
siderable interest. 

Examination  of  the  cathodic  behaviour  of 
iron-nickel  alloys,  deposited  from  solutions 
of  varying  proportions  of  ferrous  and  nickel 
suliphates,  from  several  standpoints  has 
brought  to  light  a  number  of  new  facts  con- 
cerning their  electrode  depcKsition,  over- 
voltage  and  action  in  the  presence  of  de- 
piilarisers.  Suggestions  have  been  offered 
to  account  for  some  of  the  observi'd  facts, 
but  a  fuller  discussion  of  their  significance 
in  connection  with  the  theories  of  over- 
voltage,  delayed  cathodic  deposition  and  of 
cathodic  reduction,  must  be  left  until  fur- 
ther information  is  available. 

The  Volumes  Occupied  by  the  Solute 
.itovia  in  certain  Metallic  Solid  Solutions 
and  their  Consequent  Hardenimj  Effects, 
by  A.  L.  Nokhury,  M.Sc,  University  Col- 
lege, Swansea. 

The  object  of  this  research  was  to  deter- 
mine the  densities  of  certain  copper  a-solid 
solution  alloys,  to  calculate  the  volumes 
that  the  solute  atoms  were  occupying  in 
each  case,  the  ultimate  object  being  to  ('om- 
pare  the  values  so  obtained  with  the  hard- 
n«'ss  values  of  the  same  alloys. 

In  order  to  obtain  accurate    values,    tht 


314 


THE  CHEMICAL  NEWS 


NOVExMBEK  16.  1923. 


effects  of  annealing  temperature  and  cold- 
work  on  the  density  of  cqpper  were  first 
studied.  The  densities  of  the  copper  a- 
solid  solutions  were  then  determined,  and 
the  results  calculated  in  a  certain  manner 
in  order  to  estimate  the  "atomic  volumes" 
occupied  by  the  solute  atoms  in  each  case. 

The  results  obtained  were  then  compared 
with  the  hardness  values,  and  a  certain  re- 
lationship was  brought  out.  It  was  also 
found  that  the  solute  atoms  were  not  occu- 
pying their  normal  atomic  volumes,  but 
that  in  each  case  a  contraction  or  expansion 
had  taken  place — the  amount  of  contraction 
or  expansion  apparently  increasing  as  the 
"chemical  affinity"  of  the  solute  for  the 
solvent  increased. 

The  paper  dealt  with  the  method  of  de- 
termining densities;  the  effect  of  annealing 
temperature  and  cold-work  on  the  density 
of  cathode  copper;  the  density  of  commer- 
cial copper,  and  of  certain  copper  a-solid 
solutions.  It  also  included  the  calculation 
of  "mean  atomic  volumes"  and  compari- 
son of  the  latter  with  hardness  data,  and 
suggested  an  explanation  of  hardening 
effects  of  elements  in  solid  solution. 

In  density  determinations  errors  due  to 
surface-tension  effects  between  the  surface 
water  and  the  suspending  wire  were  elimi- 
nated by  the  use  of  a  compensating  plati- 
num wire. 

Cold-hammering. had  the  effect  of  closing 
up  minute  blow-holes  in  copper.  Very 
severe  cold-hammering  set  up  stresses  and 
strains  in  the  metal  which  probably  caused 
local  increases  and  decreases  in  density. 
Otherwise  cold-hammering  did  not  affect 
the  density. 

Commercial  copper  has  a  distinctly  lower 
density  than  cathode  copper. 

For  theoretical  purposes  there  are  cer- 
tain advantages  in  calculating  density  re- 
sults as  "  mean  atomic  volumes." 

When  an  element  is  distributed  in  solid 
solution  as  single  atoms  replacing  single 
atoms  of  the  solvent  in  the  space-lattice  of 
the  latter,  the  hardening  effect  is,  in  gene- 
ral, proportional  to  the  difference  in  size  of 
the  solute  and  solvent  atoms.  The  above 
relationship  does  not,  however,  hold  in  cer- 
tain exceptional  cases  (viz.,  Si  in  Cu  and  Na 
in  Pb),  which  appear  to  arise,  when  the 
solute  has  an  exceptionally  strong  "chemi- 
cal affinity"  for  the  solvent.  In  such  cases 
it  is  suggested  that  the  'solute  exists  in 
solid  solntirm  in  the  foiTn  of  molecules  of  an 
inter-metallic  compound  having  a  different 
space-lattice  from  that  of  the  solvent.     The 


interference  with  slip  and  consequent  har- 
dening being  relatively  much  greater  in  this 
type  of  solid  solution. 

VVhen  an  element  forms  a  solid  solution 
with  another  element,  there  is  a  certain  con- 
traction or  expansion  which  seems  to  be 
large  or  small  according  to  whether  the 
"chemical  affinity"  between  the  elements  is 
large  or  small. 

From  the  theoa-etical  point  of  view  it  was 
thought  interesting  to  ascertain  whether 
cold-hammering  increased  the  hardness  of 
each  of  the  solid  solutions  to  the  same  ex- 
tent. 

The  solid  solutions  were  therefore  re- 
duced first  60  per  cent,  in  thickness  and 
later  90  per  cent,  in  thickness  and  their 
hardnesses  measured  after  each  reduction. 

It  was  difficult  to  hammer  all  specimens 
to  exactly  the  same  amount,  and  this  factor 
makes  the  results  somewhat  erratic;  they 
seem,  how^ever,  to  be  sufficiently  accurate 
to  show  that  the  nickel-copper  solid  solu- 
tions have  hardened  relatively  less  than  any 
of  the  other  solid  solutions,  which  a^ppear  to. 
have  hardened  to  equal  extents. 

The  Catalytic    Decomposition    of  Hydro- 
gen Peroxide    Solution  by  Blood    Charcoal, 
by  J.  B.  Firth,  D.Sc,  and  F.  S.  Watson 
M.Sc. 

Hydrv>gen  peroxide  has  been  shown  to  be 
decomposed  by  a  great  variety  of  sub- 
stances. Fillipi  showed  that  all  powders 
decompose  hydrogen  peroxide,  the  velocity 
of  decomposition  being  proportional  to  the 
exposed  surface  of  the  added  powder  and  in- 
dependent of  the  concentration  of  the  hy- 
drogen peroxide.  Lemoine  found  that  char- 
coals obtained  in  the  decomposition  of  wood, 
coconut  and  sugar  are  efficient  catalysts  of 
hydrogen  peroxide ;  the  catalytic  effect  be- 
ing apparently  correlative  with  their  sorp- 
tive  power  for  gases,  Clayton  showed  that 
hydrogen  peroxide  does  not  volatilise  appre- 
ciably from  its  aqueous  solutions  at  50°  to 
60°  C.,  and  the  rate  of  decomposition  is  not 
affected  by  stirring.  Rideal  and  Thomas 
show  that  hydrogen  peroxide  is  decomposed 
by  Fuller's  earth.  The  catalytic  activity  in 
th-e  decomposition  of  the  hydrogen  peroxide 
is  not  dependent  on  the  adsorptive  power; 
it  would  appear  that  the  iron  content  of  the 
Fuller's  earth  may  be  the  governing  factor. 
On  applying  the  equation  for  a  unimolecular 
surface  reaction  the  velocity  coefficient  is 
constant  for  a  given  sample  of  Fuller's 
earth.  The  authors  have  shown  that  ordi- 
nary pure  sugar    carbon    gives  rise    to    only 


NOVEMBER  16,  1923. 


THE  CfiEMICAL  NEWS. 


815 


very  slight  decomposition  of  hydrogen  per- 
oxide in  aqueous  solution,  but  the  rate  and 
extent  of  the  decomiposition  increases  con- 
siderably as  the  activity  of  ihe  carbon  is  in- 
creased, and  also  with  ri>^i  of  temperature. 
The  activity  of  the  carbon  gradually  decays 
during  the  reaction.  In  a  further  paper  the 
authors  described  experiments  with  speci- 
mens of  carbon  from  other  carbohydrates  in 
which  it  was  shown  that  the  rate  of  decom- 
pcsition  varied  considerably  with  the  differ- 
ent carbons,  but  the  fundamental  difference 
is  in  the  initial  activity,  'ihe  activity  falls 
rapidly  after  the  first  few  minutes,  becom- 
ing ultimately  very  slight,  wen  though  the 
solution  contains  a  fair  jiroportion  of  unfle- 
com posed  hydrogen  peroxide.  The  object 
of  the  present  investigation  was  to  study  the 
decomposition  of  hydrogen  peroxide  solu- 
tion by  bl(x>d  charcoal,  before  and  after  acti- 
vation treatment.  Whereas  in  previous  ex- 
periments relatively  pure  carbons  were 
used ;  in  the  present  case  the  charcoal  eon- 
tains  appreciable  quantities  of  impurity, 
mainly  iron.  Experiments  were  therefore 
carried  out  in  order  to  detirmino  as  far  as 
possible  the  influence  of  this  impurity  on 
the  rate  of  decomposition  of  the  hydrogen 
peroxide. 

The  blood  charcoal  used  gave  8.82  per 
cent,  of  ash  which  consisleil  almost  entirely 
of  iron  oxide.  After  tre.it  ment  with  hot 
aqua  regia,  the  ash  content  was  7.30  per 
cent.  It  was  then  subjected  to  treatment 
with  aqua  regia  for  a  month,  the  ash  con- 
tent becoming  6.32  per  cent.  Some  of  this 
charcoal  was  further  treated  with  bromine 
for  several  days,  after  which  the  ash  o<mi- 
tent  was  5.79  per  cent.  In  each  case  all 
soluble  material  was  extracted  by  washing 
with  boiling  distilled  water  until  the  filtrate 
showed  no  indication  of  iron  or  halogen. 

A  sample  of  the  charcoal  was  taken  after 
each  purification  process.  It  was  dried  at 
120°  C.  in  an  air  oven,  and  the  catalytic 
activity  determined  in  each  case.  The  hy- 
drogen peroxide  solution  used  c(mtained 
240.5  ce.  of  availabh'  oxygen  per  25  ce.  of 
solution.  0.25  grams  of  the  charcoal  and 
25  cc.  of  the  hydrogen  jK-roxide  solution 
were  used  in  each  experiment,  and  the  tem- 
perature of  experiment  18°  C.  The  reaction 
velocity  coefficients  were  calculated  from 
the  equation  for  a  unimoleeular  surface  r(>- 
action  <lx  df  =  K(a  -  x)  to  the  Naperian 
base  and  the  minute  as  unit  of  time. 

The  charcoal  showed  moderate  catalytic 
activity  in  the  decompcvsition  of  hydrogen 
peroxide  solution. 


This. was  considerably  increased  by  pre- 
vious heating  in  a  vacuum  at  600°  C.  and 
1KX)°  C,  and  was  still  further  increased  by 
previous  sorption  of  iodine  from  solution 
and  from  which  the  iodine  had  been  subse- 
quently completely  removed. 

The  activity  of  an  activated  charcoal  con- 
sists of  two  types,  one  which  is  termed  a 
activity  which  is  very  rapid,  but  ceases  after 
a  few  minutes,  and  a  second  termed  /8  activ- 
ity, whUch  may  persist  for  several  hours. 
Both  types  may  be  increased  by  activation 
methods.  In  ordinary  blood  charcoal  a 
activity  is  absi  nt. 

The  introduction  of  iron  into  sugar  solu- 
tion prior  to  carbonisation  considerably  in- 
creased the  activity  of  the  charcwil,  by  an 
amount,  greater  tban  can  be  accounted  for, 
by  the  iron  alone,  and  it  is  suggested  that 
the  iron  acts  as  a  spacing  agent  thereby  in- 
creasing the  aeti\ity  of  the  carbon  itself. 

The  velocity  of  decomposition  was  shown 
to  vary  with  tlu"  concentration  of  the  hydro- 
gen peroxide  solution. 

The  proportion  of  hydrogen  peroxide  de- 
composed was  (ktermined  by  both  the 
activity  of  the  charcoal  and  the  concentra- 
tion of  the  hydrogen  peroxide  solution. 

In  the  ca.se  of  the  highly  active  carbons, 
the  heat  generateii  by  the  rapid  decompo- 
sition of  the  hydrogen  peroxide  raised  the 
temperature  of  the  reaction,  temporarily, 
by  several  degrees,  which  further  facilitated 
the  decomposition  of  the  hydrogen  peroxide 
and  thereby  maintained  the  velocity  of  re- 
action at  a  higher  level,  until  this  heat  had 
been  dissipated. 

The  ProperticH  of  Powders. — Part  VIII.  : 
The  Influence  of  (he  Velocity  of  Compres- 
sion on  the  ApiHireni  Compressibility  of 
Powders,  by  E.  E.  Walker. 

When  a  powder  is  comiprcsscd  in  a  cylin- 
<ler  by  a  constant  load,  the  velocity  of  com- 
pression is  very  high  to  begin  with  and  then 
rapidly  falls  off,  but  no  case  has  been  ob- 
servetl  so  far  wlure  it  falls  off  to  zero  be- 
fore the  powder  is  completely  compressed. 

This  has  now  been  investigated.  Obser- 
vations were  made  on  the  height  of  the 
plunger  after  various  intervals  of  time,  the 
load  being  kept  constant.  As  a  rule  the 
load  was  applied  by  means  of  a  small  Tan- 
gye  press,  and  kept  constant  by  manipula- 
tion of  the  hand-operated  oil  pump — but  in 
certain  ca-ses  where  it  was  necessary  to  keep 
the  lr>ad  constant  for  several  hours  a  dead 
load  was  employed.  The  load  was  applied 
as  rapidly  and  gently  as  possible,    and  zero 


ai6 


THE  CHfeMICAL  NEWS. 


NOVEMBEU  16,  1923. 


time  taken  from  the  moment  at  which  the 
full  load  was  applied.  On  account  of  errors 
arising  from  the  estimation  of  zero  time, 
observations  made  in  less  than  20  seconds 
were  liable  to  considerable  error. 

The  isobaric  curve    has    been    correlated 
with  the  value  of  the  ratio: — ■ 

resistance  to  impact 


resistance  to  static  load 
and  further  evidence  for  the  validity  of  the 
classification  of  powders  suggested  in  Part 
VI.  of  these  studies  has  been  obtained. 

The  exceptional  readiness  with  which 
powdered  ammonium  nitrate  shrinks  has 
been  shown  to  be  dependent  chiefly  on  the 
high  value  of  its  velocity  coefficient. 

The  powders  examined  were  shown  to  fall 
into  three  classes. 

Substances  in  Class  I.  are  regfu-ded  as 
normal  substances,  which  are  compressed 
by  deformation  of  the  particles  both  when 
static  loads  are  employed  and  when  com- 
pression is  brought  about  by  the  imipact  of 
falling  weights. 

Substances  in  Class  II.  are  regarded  as 
behaving  normally  when  they  are  com- 
pressed slowly  by  static  loads,  but  when  the 
compression  is  Ijrought  about  suddenly  by 
blows  the  particles  are  broken  down  into 
fragments  which  fall  together  into  closer 
order,  so  that  the  resistance  to  compression 
is  much  less  than  the  calculated  value  to 
begin  with.  As  compression  proceeds  fur- 
ther disintegration  takes  place,  causing  an 
increase  of  resistance  analogous  to  the 
hardening  of  metals  by  cold  working. 

In  Class  III.  conditions  are  exceedingly 
complex  since  disintegi'ation  is  caused  both 
by  slow  and  by  rapid  compression  (imipact). 
and  accordingly  there  is  no  connection  be- 
tween calculated  and  observed  values.  Cal- 
cium carbonate  is  an  example  of  this  total 
lack  of  agreement. 

An  Investigation  of  SinoluchowsJ^i's 
Equation  as  Applied  to  the  Coagulation  of 
Gold  Hydrosol,  bv  Leonard  Anderson, 
B.Sc,  Ph.D. 

As  regards  the  kinetics  of  coagulation  of 
colloidal  soKitions  the  SmoluchoM'ski  equa- 
tion is  the  only  one  which  has  a  theoretical 
basis.  Freundlich  deduced  an  equation, 
based  on  measurements  of  the  variation  of 
the  viscosity  of  a  sol  during  coagulation, 
giving  the  relationship  between  time  and 
the  amount  of  precipitated  colloid.  How- 
ever, no  definite  relationship    is  known    to 


exist  between  the  size  of  particles  and  vis- 
cosity. 

According  to  Snioluchowski's  theory,  each 
particle  in  a  homogenous  sol  possesses  a 
sphere  of  attraction  E,  within  which  the 
attraction  is  so  strong  that  any  other  par- 
ticle, whose  centre  enters  this  sphere,  is 
firmly  held. 

In  an  originally  uniform  sol,  whose  par- 
ticles have  been  completely  discharged,  tlie 
initial  number  of  particles  whose  centres 
are  less  than  R  apart  is  vanishingly  small. 

In  course  of  time,  Brownian  movement 
brings  the  *nirticles  into  all  possible  con- 
figurations. In  consequence  of  Brownian 
movement  and  of  the  existence  of  "spheres 
of  attraction"  an  in'eversible  state  of  coagu- 
lation is  finally  set  up. 

Smoluchowski,  combining  probability 
considerations  and  the  laws  of  diifusion,  de- 
rives a  series  of  equations  which  give  the 
rate  of  disappearance  of  the  particles  in  a 
colloid  solution  duiing  "rapid"  coagulation. 
The  following  equation  gives  the  rate  of  dis- 
appearance of  primary  particles : 

V,   = 


(I  +  ftty 

where  y„  is  the  number  of  primaries  at  /.ero 
time,  Uj  is  the  number  of  primaries  at  a 
time  "f,"  and  ft  is  a  constant  equivalent  to 
AttDKv^,,  where  D  is  the  diffusion  coefficient 
and  R  is  the  radius  of  the  sphere  of  attrac- 
tion. 

Smoluchowski  also  attempted  to  extend 
his  theory  to  slow  coagulation.  Colorimet- 
ric  determinations  of  the  rate  of  coagulation 
of  gold  sols  by  HCl,  KCl,  BaCl,,  and  AlCl, 
were  can-ied  out  using  Hatschek's  method. 

These  experiments  now  brought  forward 
indicate  that  or  the  coagulation  of  gold  sols, 
by  means  of  the  electrolytes  chosen,  there 
is  a  "rapid"  region  in  which  Smoluchow- 
ski's  equation  holds.  The  constancy  of  /3 
is  quite  good,  especially  in  the  case  of 
barium  chloride  as  electrolyte.  In  a  region 
of  smaller  electrolyte  concentration,  an  ex- 
cessive slowing  down  in  the  speed  of  coagu- 
lation with  time  is  observed.  This  is  in 
agreement  with  the  data  of  Kruyt  and  Arkel 
and  also  with  the  one  case  of  Mukherjee  and 
Papaconstantinou  in  which  the  value  of  8 
falls. 

The  general  conclusion  arrived  at  is  that 
the  Smoluchowski  equation  is  strictly 
limited  in  its  application. 

Smoluchowski  asserts  that  the  curves  de- 
picting slow  and  rapid    coagulation  should 


NOVEMBER  16,  1923. 


THE  CHEMICAL  NEWS. 


817 


have  a  similar  form,  the  only  varying  fac- 
tor being  the  probability  that  an  unpact  will 
give  union. 

The  data  obtained,  however,  show  that 
coagulation  proceeded  even  more  slowly 
than  would  be  expected  on  the  basis  of  a 
biinolocular  process.  Furthermore,  if  pri- 
juaiies  did  disappear  simply  by  union  with 
e.ioh  other,  it  would  follow  that  once  coagu- 
lation has  commenced  it  should  proceed 
until  no  more  primaries  are  left.  On  thi< 
basis  incomplete  colour  change  from  red  to 
blue  should  not  be  possible,  since  any  red 
colour  remaining  would  indicate  unchanged 
priiiuiries  (attributing  the  rod  colour  to  the 
latter).  But  incomplete  colour  changi 
does  occur  and  depends  upcjn  the  concentra- 
tion of  the  electrolyte  present.  This  phe- 
nomenon a<liMit8  of  two  explanations  : 

1. — It  may  be  due  to  the  possibility  that 
the  rate  of  disappearance  of  primaries  i< 
counterbalanced  by  an  opposing  effect,  i.r., 
primaries  are  being  reformed  either  by  spon- 
taneous disruption  of  complexes  or  by  colli- 
sion of  complexes  with  each  other.  Such 
reversibility,  however,  would  seem  to  entail 
a  behaviour,  on  dialysis,  of  incompletely  co- 
agulated sol  which  has  not  yet  been  ob- 
served. 

2. — A  more  probable  explanation  woiild 
seem  to  be  tiuit  the  initial  primary  particles 
(giving  the  red  colour)  arc  nnrqualhi 
charged.  In  the  case  of  slow  and  eventu- 
ally incom|)lete  coagulation  very  small 
amounts  of  »'lectrolyte  are  used,  and  it  i-^ 
conceivable  that  the  amount  adsorbed  is  not 
suflficient  to  reduce  the  charge  of  some  of 
the  particles  (which  initially  carry  an  t'xees- 
sive  charge)  below  the  critical  limit  which 
will  permit  coagulation  to  take  place. 

If  this  conception  of  unequal  charge  is 
correct,  the  Smoluch(.wski  equation  could 
not  be  expected  to  be  applicable  in  general. 

In  reviewing  the  whole  problem  of  coagu- 
lation, it  would  appear  that  the  Rmolu- 
chowski  equation  in  its  |)re8ent  form  is 
limited  in  its  application.  Ticfore  it  can  bo 
applied  to  all  types  of  coagulation  it  appar- 
ently requires  modificatif)n  to  allow  for  the 
two  factors: 

(a)  The  decrea.se  of  the  probability  factor 
as  coagulation  proceeds. 

(h)  The  existtmce  of  incomplete  coagula- 
tion as  a  consequence  of  unequal,  and  in 
some  cases  therefore,  of  excessive  initial 
elactrical  charge  on  the  (primary  particles. 

{To  be  continued  next,  week.) 


THE  CHEMICAL  SOCIETY. 

UuuiNAuv  Scientific  Meeting, 

Thursd.w,  November  15. 

The  following  papers  were  read:  — 
Ring-chain      Tautomerisni.        Dynawical 
Evidence  relating  to  the  Mutarotation  of  the 
Siigars,  by  J.  W.  Baker,  C.  K.  Ingold,  and 

J.  F.  Thorpe. 

The  additive  Formation  of  Four  Mem- 
bered  Rings.  Part  III, — A  system  of  No- 
menclature for  Heterocyclic  Four  Mem- 
bered  Rings  and  the  Formation  and  Proper- 
tits  of  some  Derivatives  of  ft-mefhylencdi- 
imineoxide,  by  C.  K.  Ignold. 


THE  INSTITUTION  OF  PETROLEUM 

TECHNOLOGISTS. 

The  seventy-third    general    meeting    was 

held  at  the  hous<'  of  the    Royal  Society    of 

Arts,  on  Tuesday,  November  13.     The  fol 

lowing  paper  was  read  :  — 

Galician-Canadian       Pole     Tool     Fishing 
Methods,  by  Albkrt  Millar,  A.M.I.Mech.- 

E..    M.IN8T.P. 


THE  ROY.VL  SOCIETY  OF  ARTS. 

On  Monday,  November  12,  the  Cantor 
Lecture  (I.),  entitled  The  Cxiltiration  of 
Cocoa  in  British  Tropical  Colonies,  was  de- 
livered bv  Mr.  Samuel  Henry  Daviks, 
M.Sc.  F.'I.C. 

At  the  Ordinary  Meeting,  on  Wednesday, 
November  14.  a  lecture  entitled  Ti'lrphoto- 
graphie,  Trlanfographie,  Television  (Avcc 
Experiences  et  Projections),  was  delivered 
by  Monsieur  Epouard  Belin  (in  French). 
Mr.  Alan  A.  Campbell  Swinton,  F.R.S., 
late  Chairman  of  the  Council,  presided. 

The  Royal  Society  of  Arts,  which  was 
founded  in  1754  for  the  encouragement  of 
arts,  manufactures  and  commerce,  held  the 
opening  meeting  of  the  170th  session  on 
Wednesday  evening,  November  7,  when 
Lord  Askwith,  K.C.B..  the  Chainnan  of 
the  Council  and  a  Vice-President  of  the  So- 
ciety, delivered  his  address  on  Exhibitions. 

For  the  subsequent  meetings  before 
Christmas  the  following  arrangements  have 
been  made :  — 


318 


TUE  CHEMICAL  NEWS 


NOVEMBER  16,  1923. 


November  21. — J.  A.  Knowles,  For- 
geries of  Ancient  Sioiiied  Glass.  The  Earl 
of  Crawford  and  Balcarres,  K.T.,  P.C,  will 
preside. 

November  27. — The  Viscount  Burnham, 
C.H.,  LL.D.,  D.LiTT.,  M.A.,  The  West  In- 
dies. 

November  28.— Sir  Henry  John  Gau- 
VAiN,  M.A.,  M.D.,  M.Ch.,  Medical  Super- 
intendent of  the  Lord  Mayor  Treloar  Crip- 
ples' Hospital,  The  Effect  of  Sun,  Sea  and 
Open-air  in  the  Treatment  of  Disease.  The 
Rt.  Hon.  Arthur  Neville  Chamberlain, 
M.P.,  will  preside. 

December  o. — Arthur  William  Hill,  • 
M.A.,  Sc.D.,  F.R.S.,  F.L.S.,  Director  uf 
the  Royal  Botanic  Gardens,  Kew,  The 
Work  of  the  Royal  Botanic  Gardens,  Kew. 
Charles  Albert  Seward,  M.A.,  F.R.S., 
F.G.S.,  F.L.S.,  Professor  of  Botany  at  Ihe 
University  of  Cambridge,  will  preside. 

December  7. — William  Foster,  CLE., 
B.A.,  Registrar  and  Superintendent  of  Re- 
cords, India  Office,  The  Archives  of  ihe 
Honourable  East  India  Company.  (Sir 
George  Birdwood  Memorial  Lecture.)     ' 

December  12.  —  Sir  Frank  Bain-^^s. 
C.B.E.,  M.V.O.,  Director  of  Works,  H.M. 
Office  of  Work>i,  The  Preservation  of  His- 
toric Buildings  and  Ancient  Monuments. 
Sir  Aston  Webb,  K.C.V.O.,  C.B.,  P.P. A., 
will  preside. 


December  17.  —  William 
Agent-General  for  Ontario, 
within  the  Empire. 


C.     Noxox, 
Emigration 


CORRESPONDENCE. 


NATIONAL  CERTIFICATES  IN 
CHEMISTRY. 

To  the  Editors  of  The  Chemical  News. 

Sirs, — About  three  years  ago  the  Board 
of  Education  established  with  the  Institute 
of  Chemistry  a  joint  committee  for  the  pur- 
pose of  granting,  under  conditions,  Nation- 
al Certificates  in  Chemistry  to  students  in 
technical  schools  and  colleges.  These  cer- 
•  tificates  are  Part-time  Course  Certificates, 
(1)  Ordinary,  (2)  Higher,  and  Full-time 
Course  Certificates  in  (a)  Chemistry,  (h) 
Applied  Chemistry.     An  institution  wiihing 


to  prepare  students  for  any  of  these  certifi- 
cates must  submit  schemes  of  its  own, 
which  its  students  must  follow.  This 
seems  a  clumsy  feature  of  the  arrangement. 
Every  institution  devises  its  own  scheme  or 
schemes,  sets  the  examination  papers  at  the 
end  of  the  course,  and  marks  the  scripts  by 
means  of  its  own  teachers,  the  joint  com- 
mittee, having  ipieviously  approved  of  the 
local  schemes,  finally  apj)earing  as  asses- 
sors, ,who  supervise  the  questions  set,  re- 
vise the  marking  of  the  papers,  satisfy 
themselves  about  the  laboratory  work  done 
by  the  candidates,  and  finally  issue  certifi- 
eates  to  those  who  are  successful. 

AH  this  is  in  accordance  with  the  appar- 
ent policy  of  the  Board  of  Education  to 
make  technical  schools  quite  local  in  their 
character,  and  to  encourage  them  to  cater 
specially  for  the  technical  needs  of  their 
locality.  Hence,  the  idea  of  a  separate 
scheme  from  each  institution  has  been 
evolved. 

This  policy  of  localisation  does  not  satisfy 
the  best  type  of  students  in  the  technical 
schools,  who  are  not  able  to  express  their 
wants.  Localisation  does  not  tend  to  pro- 
mote good  general  education,  nor  does  it 
give  students  a  wide  outlook. 

The  students  in  the  technical  schools  are 
there  voluntarily.  For  various  reasons  they 
are  not  able  to  pursue  their  education  in  the 
day-time.  They  get  their  education  in  their 
spare  time,  generally  after  a  day's  work, 
and  large  numbers  attain  responsible  posi- 
tions and  become  as  efficient  as  those  who 
have  done  full-time  work. 

Such  earnest  students  develop  a  longing 
for  some  distinction,  in  the  form  of  a  de- 
gree or  diploma,  the  value  of  which  is  well- 
known  and  recognised  all  over  the  country. 
From  my  personal  acquaintance  I  know 
that  many  look  with  longing  eyes  at  London 
University  degrees,  but  they  are  met  with 
the  stumbling  block  that  they  did  not 
matriculate  at  the  outset.  For  those  in 
chemical  trades  there  is  the  Institute  of 
Chemistry,  whose  Fellows  and  Associates 
have  a  recognised  standing.  Spend  what 
time  they  may  in  a  technical  school,  study 
what  subjects  they  may,  make  themselves 
as  efficient  as  they  may,  all  their  work  does 
not  lead  in  the  direction  of  a  recognised  dis- 
tinction. True  it  is  that  certain  institutions 
provide  training  in  the  evening  which  is 
recognised  by  the  Institute  of  Chemistry, 
but  they  are  situated  in  only  13  large  towns 
in  England  and  Scotland  (not  in  Wales). 
What  are    the  prospects    of  students    else- 


NOVEMBER  16,  1923. 


THE  CHEMICAL  NEWS. 


;i9 


where?  They  are  in  a  local  groove,  with  no 
chance  of  getting  out.  The  National  Certi- 
ficates, after  all.  are  only  local  certificates, 
blessed  by  the  Joint  Comniiltce,  with  an 
iiBiplied  intimation,  not  an  open  one>  that 
the  holders  are  in  a  class  to  themselves,  in 
which  they  must  remain,  because  there  is 
no  intimation  anywhere  that  a  certificate 
can  be  used  by  the  holder  towards  gaining 
any  further  qualification. 

An  opportunity  has  been  missed  of.  fur- 
thering the  cause  of  education  by  assisting 
those  students  who  will  work  if  properly 
directed  and  encouraged. 

Something    should    be    done.        The    In- 
stitute    of    Chemistry     already     recognises 
evening  training  in  19  institutions.     Let  the 
InstituU'  say  that,    providing  a  student  han 
previously  passed  an  approved    preliminani 
examination,  the  sub-ecjuent  ^;aining  of  one 
or  more  national    certificates    shall  be    re- 
garded   as  so    much  training    towards    the 
qualification  for    the  assr.t'iatoship.       What 
would  be  the  effect    Uipon  students  in  tech- 
nical schools?     It  would  be  an  incentive  to 
those  who  do  not  possess  it,  to  work  first  of 
all   for  an  approved  preliminary  certificate, 
which  alone  wrmld  do  their    general   educa- 
tion some  gwxl.     Technical  school  students 
often  lack  a  good  general  education.     They 
are    so  (»ager    to  get  on    to  trade  work    that 
they  neglect  a  continuation  of  school  work. 
Having  passed  an  approved  preliminary  ex- 
amination which  the  Institute  will    accept, 
the  student    could  work  for  such    National 
Certificates     as     his     particular    technical 
school  is  apiproved  for,   fully  knowing,   and 
thereby    encouraged,    that    any    certificate 
gained    will    be  a  step    towards  a    coveted 
qualification.       If     he    finds     that     subse- 
quently the  varied  chances  of  life  bring  hiin 
within  reach    of  an  institution  on  the  Insti- 
tute    of    Chemistry's     recognised    list,     he 
could  take  advantage  of  it,  knowing  that  his 
previous  work    will  secure    some    rernission 
from  the  four  or  five    years'  period  now  re- 
quired.— Yours,  Ac,  A. P. 

Novemher  5,  1923. 


THE    PREPARATION    AND 
PROPERTIES  OF  SILVER  STIRIDE. 

To  the  Editors  of  The  Chkmical  News. 

Sfrs, — Silver  stibide  has  hoen  known 
^incc  the  year  1896  by  the  existence  of  fm 
angle  on  the  cooling  curve  of  silver  anti- 
monv  alloys  (Henri  Gautier,  ('ompieg  Ren- 
dns,' I8m,  CXXIII.,  172-174).     C.  T.  Hey- 


cock  and  F.  H.  Neville  (Proc-  Hoy.  Soc, 
1896,  X.,  160-164)  deduced  evidence  deti- 
nitely  giving  it  the  formula  Agg  Sb. 

In  1910  Th.  Liebisch  {Sii::unyfifcr  .'i. 
Akad.  Wiss.,  Berlin,  I^^IO,  365-370)  found 
that  most  specimens  of  silver  stibide  from 
Andreasberg  corresponded  to  the  formula 
Agj  Sb.  The  mineral  dyscrasite  (aj. 
crystallises  in  the  rhombic  system,  and  its 
colour  is  silver  white.  On  exposure  to  air 
and  light  it  acquires  a  dull  grey  or  yellow 
colour. 

In  a  previous  paper  by  the  author 
Chemical  Nens,  1023.  CXXVL.  27'))  it  was 
shown  that  stibine  could  be  detected  by 
jpassing  it  through  some  concentrated  silver 
nitrate.  If  this  is  performed,  using  dilute 
silver  nitrate  in  the  cold,  then  the  action  is 
found  to  go  according  to  the  equation  :  — 

SbH,  +  3Ag  NO,  =  Ag,  Sb  +  3HN(),. 

The  silver  stibide  formed  was  filtered  cff, 
washed  and  dried,  when  it  was  obtained  m 
the  form  of  silver  white  crystals,  which 
crystallised  in  the  rhombic  form. 

The  properties  of  silver  stibide  are  re- 
markable by  the  fact  that  it  is  totally  in- 
soluble in  both  hot  and  cold,  concentrated 
and  dilute,  sulphuric  and  hydrochloric 
acids.  It  is,  however,  soluble  in  boiling  di- 
lute nitric  acid,  giving  off  nitrous  fumes, 
but  is  insoluble  in  the  cold  dilute  acid. — 
Yours,  Ac, 

Edwakd  J.  Weeks,  M.Sc,  F.C.S. 

East  Duhvich,  S.E. 22, 


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drolysis by  means  of  a  film  of  oil,  vaseline  or  the 
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THE  CHEMICAL  NEWS. 


321 


THE    CHEMICAL  NEWS, 


VOL.  GXXVII.       No.  3319. 


THE  INTERMITTENT  GLOW  OF 
PHOSPHORUS. 

By  K.  R.  Krishna  Iyer. 

The  intormittent  luminosity  propagated 
in  pulsatory  fashion  when  the  last  trace.s  of 
oxygen  arc  being  removed  from  air  by  means 
of  phosphorus,  or  when  air  is  allowed  to  leak 
slowly  into  an  exhausted  vessel  containing 
phosphorus,  was  recently  dealt  with  by  the 
present  Lord  Rayleigh  (Proc.  Roy.  Soc, 
1021  (A)  XCIX.,  372).  He  showed  the  im- 
portance of  the  presence  of  water  vapour 
for  the  propagation  of  the  luminous  pulses, 
and  also  how  the  same  phenomenon 
occurred  in  the  presenct?  of  traces  of  sub- 
stances known  to  inhibit  the  glow  of  phos- 
phorus. 

Working  on  this  problem,  I  find  that  the 
intermittent  luminosity  and  formation  and 
I)rf>piigation  of  luminous  pulses  oould  be 
obtained  equally  strikingly  in  an  open  vessel 
containing  air,  such  as  a  test  tube,  flask,  or 
tube  open  at  both  ends,  if  traces  of  these 
inhibitors — e.g.,  naphthalene,  carbon  di- 
sulphide,  turpentine,  light  petroleum — are 
|)resent.  The  effect  is  particularly  goo<l  if 
the  vessels  be  wet  with  water.  No  inter- 
mittence  or  pulse-formation  is  obser^'ed 
with  water  alone.  It  is  also  found  that  the 
luminous  pulses  creep  along  the  surface  of 
the  vessels. 

It  is  well-known  that  the  luminosity  of 
phosphorus  is  inhibited  in  pure  oxygen 
above  a  critical  pressure  (depending  on  the 
temperature),  and  that  it  becomes  inter- 
mittent near  the  critical  pressure. 

The  explanations  offered  for  the  periwlic 
nature  of  the  glow  and  its  pro,pagation  in  the 
presence  of  water  and  inhibitors  (Rayleigh, 
/or.  ciL ;  Joubert,  Ecole.  Norm.  Annales, 
IH74,  III.,  209;  Jorissen,  Chem.  Weehblad. 
1918,  XV.,  705)  have  all  been  based  on  the 
view  that  here  we  are  dealing  with  the  pro- 
pagation of  combustion  Tn  an  explosive  mix- 
ture. The  fact  that  exactly  similar  effects 
are  produced,  even  in  open  vessels  contain- 
ing excess  of  air,  and  the  clearly  creeping 
nature  of  the  propagation  of  the  glow  neces- 
sitate a  modification  of  this  view.  It  ap- 
pears probable  that  the  effect  "in  oxygen  at 
the  critical  pressure  of  inhibition    and  that 


observed  in  tke  presence  of  the  "inhibitors" 
are  both  due  to  similar  causes. 

The  luminosity  of  phosphorus,  its  inliibi- 
tjon,  intermittent  nature  in  presence  of  "in- 
hibitors" and  the  formation  and  nature  of 
propagation  of  the  luminous  pulses  could 
all  be  strikingly  shown  a&  a  lecture  experi- 
ment by  the  following  simple  arrangement. 

A  very  dilute  solution  of  phosiphorus  in 
carbon  disulphide  is  prepared  and  poured 
over  a  long  narrow  strip  of  filter  paper  or  a 
cotton  thread,  suspended  from  an  open 
glass  tube  inserted  in  a  cork.  The  solvent 
is  allowed  to  evaporate  almost  completely, 
so  that  fumes  begin  to  appear  on  the  strip. 
The  cork  is  then  loosely  inserted  into  a 
conical  flask  of  height  greater  than  the 
length  of  the  strip.  Luminous  pulses  are 
seen  to  form  and  travel  up  and  down  along 
the  strip.  The  formation  of  the  pulses 
alternate  with  dark  intervals.  In  the  later 
stages  the  pulses  travel  along  the  sides  of 
the  flask  al.so.  If  the  strip  happen  to  be 
permanently  bright,  a  trace  of  carbon  disul- 
phide vapour  introduced  into  the  flask  will 
start  the  above  phenomena. 

Chemistry  Tjahoratory, 

H.H.  The  Maha  Rajah's  College, 
Trirandrum. 


I      THE  MECHANISM  UNDERLYING  THE 

REACTION  BETWEEN  ETHYL  (^YANO- 

ACETATE    .AND    TAUTOMERIC 

SUBSTANCES  OF  THE   KpyPO-ENOL 

TYPE. 

By  R.  F.  Huntkr,  F.C.S. 

The  condensation  of  ethyl  cyanoacetalo 
with  ketones  has  been  the  subject  of  numy 
investigations.  In  this  paper,  however,  we 
are  only  concernerl  with  the  recent  work  of 
I)r.  C.  K.  Ingold,  which  was  carried  out  at 
the  Royal  College  of  Science  a  year  or  two 
ago.  Usually  the  first  prcKluct  which  can 
be  isolated  is  an  unsaturated  cyano  ester, 
in  which  the  doul)ie  bcwid  is  situated  either 
in  the  a/3  or  I3y  j)osition  in  respect  to  the 
carboxyl  group.  For  instance,  acetone 
yields  the  afi  unsiiturated  condensation  pro- 
duct, whilst  cyclobexanone  gives  mainly  a 
eyano  ester  in  which  the  double  bond  occu- 
pies the  fty  position.  The  latter  type  of  re- 
action appears  to  he  the  one  most  mMpiently 
met  with,  and  it  is  possible  to  ascribe  the 
production  of  cyano  methylerotonic  ester 
from  acetone  to  the  instability  of  the  un- 
saturated is(Jmeride  that  is  intermediate  in 


322 


THE  CHEMICAL  NEWS. 


NOVEMBER  23,  1923. 


the  reaction.  In  such  cases  a  second  mole- 
cule of  ethyl  cjauo-acetate  may  enter  into 
the  reaction,  the  product  being  a  derivative 
of  glutaric  acid.  With  regard  to  the  prim- 
ary condensation,  there  can"  be  little  doubt 
that  it  is  the  enolic  modification  of  the  ke- 
tone which  enters  into  the  reaction,  because 
ketones  such  as  bcnzophenone,  of  which  no 
enolic  modification  can  exist,  fail  to  react, 
while  others  react  in  the  proportion  to  their 
capacity  for  tautomeric  change.  Again, 
tautoineric  ketonic  esters,  provided  they  are 
not  sufficiently  acidic  to  cause  the  dissocia- 
tion of  the  sodium  compound  of  ethyl  cy- 
anoacetate,  readily  react  to  give  condensa- 
tion products  with  this  substance,  but  once 
the  tautomeric  character  of  the  ketonic 
ester  has  been  destroyed,  say  by  alkylation, 
then  the  condensation  can  no  longer  be  ef- 
fected. Thus  ethyl  acetoacetate  yields 
ethvl  a-cyano  y8-methylglutaconate, 
CO;EtCH:CMe.OH  +CHNa(CN)C02Et-> 
C02EtCH:CMeCNa(CN)C02Et  +  H^O, 
whilst  ethyl  dimethylacetoacetate  shows  no 
tendency  to  condense. 

The  problem  was  to. discover  wherein  lay 
the  cause  of  the  reactivity  of  the  enolic 
forms.  Clearly  there  were  two  main  possi- 
bilities. The  equation  given  above  sug- 
gested that  the  prime  action  consisted  in  the 
elimination  of  water  through  the  union  of 
the  hydroxyl  group  of  the  enolised  sub- 
stance with  the  reactive  hydrogen  atom  of 
the  cyano  ester.  This  view  appeared  to  be 
the  one  accepted  without  any  reason  pre- 
vious to  Ingold's  work.  Now  it  is  possible 
that  the  reactive  feature  of  the  enolic  sub- 
stance is  not  the  hydroxyl  group,  but  the 
double  bond.  The  direct  addition  of  sodium 
cyanoacetic  ester  would  then  be  the  initial 
reaction,  the  elimination  of  water  being  a 
subsequent  occurrence.  We  can  illustrate 
the  view  by  :  — 

C02EtCH,CMe(OH)CNa(CN)C02Et 
->CO,Et.CH:CMeOH  +  CHNa(CN)C02Et 
-^C02EtCH:CMeCNa(CN)C02Et  +  H^O. 

The  decision  might  be  arrived  at  by  eli- 
minating alternately  the  two  possibilities. 
Thus  it  might  be  attempted  to  condense 
esters  in  which  there  is  a  double  bond,  but 
no  hydroxyl  group.  In  this  case  a  reaction 
of  the  first  type  would  be  impossible. 
Secondly,  it  might  be  attempted  to  employ 
esters  containing  one  hydroxyl  group  but  no 
double  bond.  In  this  case  the  occurrence  of 
the  reaction  of  the  second  "type  would  be 
eliminated.  The  evidence  obtained  by  In- 
gold  was  strongly  in  favour  of  the  second 
view,  namely,  that  in  all  cases  the  unsatur- 


ated linking  is  responsible  for  the  initial 
condensation,  and  the  elimination  of  water 
is  a  subsequent  effect.  Nine  hydroxy  esters 
were  examined.  Glycollic  ester,  the  smi- 
plest  of  all  the  esters  examined  alone, 
yielded  no  trace  of  condensation  product 
with  ethyl  sodiocyanoacetate  under  condi- 
tions which  gave  positive  results  in  all  other 
cases.  The  reason  being  that  glycollic  ester 
is  the  only  ester  which  cannot  pass  by  the 
loss  of  water  into  an  unsaturated  com- 
pound. The  three  other  hydroxy  esters  ex- 
amined all  gave  abnormal  condensation 
products,  such  as  could  only  be  derived  by 
the  direct  addition  of  ethyl  sodiocyanoace- 
tate to  the  unsaturatcKl  compound,  for  ex- 
ample, 1  actio  ester  gave  ethyl  a  cyanoglu- 
tarate,  from  which  glutaric  acid  could  be 
obtained  by  hydrolysis : 
CH3CH(OH)C02Et->  CH^iCHCO^Et-^ 
CHXH^CO^Et        CH.CH^CO^H 

I  "  ^1 

CH(CN)C02Et        CH^COJI 

Hydraoetio    ester,     on  condensaticn    r.nl 

hydrolysis,  gave  glutaric  acid : 

CR,{OIl)G}I,CO,-Et-^  CH,:CHC03Et-> 

CH^CH^CG^H 

^    I      " 
0H2(CN)C02Et  CH^CO^H 

The  condensation  of  hydroxyglutaric  es- 
ter afforded  very  direct  evidence  of  the  in- 
termediate formation  of  unsaturated  com- 
pounds in  the  reactions. 

The  Impeml  College  of  Science 
and  Technology,  S.W.7. 
September,  1923. 


CH^CH.COaEt 


GENERAL    NOTES. 


GERMANY'S  COMMERCE  AND 

INDUSTRY  DURING 

OCTOBER. 

Mr.  J.  W.  F.  Thelwall,  the  Commercial 
Secretary  at  Berlin,  has  forwarded  to  the 
Department  of  Overseas  Trade  a  review  on 
Germany's  trade  and  industry  during 
October. 

The  decline  in  economic  life  which  began 
to  be  accentuated  in  August  was  greatly  in- 
tensified in  October.  The  reason  lies  in  the 
internal  and,  particularly,  in  the  foreign 
political  situation  which  was  not  relieved, 
as  had  been  hoped,  by  the  abandonment  of 
passive  resistance  in  the  Ruhr.     Restriction 


NOVEMBEIl  23,  1923. 


THE  CHEMICAL  NEWS. 


323 


of  work,  dismissals  of  workmen,  low  wages 
and  high  prices  which  exceed  the  world's 
market  level  more  and  more,  are  chariic- 
teristic  of  the  low  condition  of  economic 
life. 

Mining. 

The  Uipper  Silesian  pit-coal  production 
was  normal  during  the  first  three  weeks  of 
the  month.  On  October  22  a  strike  broke 
out,  and  gradually  extended  to  all  mines, 
but  work  was  reported  to  have  been  resumed 
on  October  30. 

In  Central  Germany  conditions  in  the 
brown  coal  and  potash  mines  were  un- 
favourable. In  nil  districts  lack  of  sales 
was  complained  of.  The  curtailment  of 
working  hours,  the  dropping  of  shifts,  dis- 
missals, and  the  closing  of  one  mine  became 
necessary.  Up  to  three  shifts  a  week  were 
dropped.  In  the  Mansfeld  clipper  schist 
Tnines  the  position  became  so  bad  that  two 
shifts  had  to  be  dropped. 

In  the  Berlin  coal  trade  the  introduction 
of  gold  mark  invoicing  caused  ^'reat  difficul- 
ties. Payments  were  considerably  delayed. 
Delays  occurred  not  only  in  local  trade,  but 
also,  in  particular,  in  the  industry  which, 
owing  to  declining  employment  and  in- 
creases! paper  mark  prices,  'was  unablo  to 
effect  prompt  payment.  On  the  other  hand, 
the  pits  press  more  and  more  for  speedy 
payment  in  order  that  they  may  be  ready  in 
meet  wage  demands  whicn  increase  nlmot^t 
daily. 

Inland  business  in  the  Halberstadt  potash 
industry  was  almost  completely  stagnant, 
in  spite  of  the  fact  that  prices  were  reduced 
during  the  course  of  the  month.  Fc««ign 
trade  was  better,  but  still  quiet. 

In  the  iron  ore  industry  in  the  Siegesiand 
and  Dill  districts,  further  mines  were  com- 
pelled to  close  down  or  to  restrict  operations 
oc^siderably.  Conditions  in  the  mines 
where  the  work  is  exclusively  underground 
were  particularly  unfavourable,  ns  they  had 
to  bear  the  full  cost  of  pumping  t^e  water 
even  where  the  mines  had  been  closed  down. 

Iron,  Machinery,  and  Elcotro-Technical 
induHirics. 

The  abandonmont  of  passive  resistance 
did  not  change  the  position  in  the  Euhr.  As 
before,  the  pits  and  foundries  were  idle. 
Their  position  could  scarcely  be  imagined 
more  intolerable.  Coal  anrf  coke  supplies 
continued  to  be  despatched  by  the  French, 
The  supplies  of  bye-products,  such  as  am- 
monia, benzole,  ooal-tar,    rosin,  raw  naph- 


thaline, etc.,  were  completely  cleared  by 
the  French. 

In  Upper  Silesia,  employment  in  the  Op- 
peln  pig  iron  and  finished  products  works 
was  still  satisfactory.  Orders,  however,  de- 
clined  during  the "  course  of 'the  month. 
Foreign  trade  was  completely  stagnant. 

The  electro-technical  industry  reported 
that  prices  for  semi-manufactures  were 
high  and  delivery  periods  short.  The  mar- 
ket IS  small  and  stagnant.  Individual 
works  report  falling  prices.  Short-time 
work  has  been  introduced    on  a  fairly  large 

Chemical  InduBtry, 

The  business  position  was  such  that  more 
workers  had  to  bo  dismissed,  and  presum- 
ably a  further  restriction  of  operations  is  to 
be  reckoned  with  in  the  Wiesbaden  district. 
India-Rubhcr    Industrij. 

There  was  no  improvement  in  the  posi- 
tion of  the  Hanover  india-rubber  industrv. 
The  market  possibilities  at  home  have 
grown  worse,  so  that  a  curtailment  of  work- 
ing hours  and  further  dismissals  of  work- 
men could  not  be  avoided. 

Timber  Industri/. 
In  the  saw-mills  and  in  the  wood  trade 
business  was  almost  at  a  standstill.  Only 
small  transactions  were  conclude(i  which 
served  to  fill  up  stocks.  Business  with  Eng- 
land appeared  to  experience  a  slight  revival. 

Cloth ifuj  Industry. 

In  the  wool  wholesale  trade  business,  as 
before,  could  not  be  revived,  as,  owing  to 
the  large  amount  of  unemployment  in  the 
textile  industry,  the  demand  remained  very 
small.  Wool  prices  were  firm,  and  there 
was  the  less  anticipation  of  a  fall,  as,  in 
view  of  the  fact  that  the  wool  shears  have 
yielded  only  a  small  (]uantity  of  fine  wool, 
an  increased  demand  will  be  met  by  a  small 
supply.  Conditions  also  grew  worse  in  the 
carded  yam  spinning- mills.  In  occupied 
territory  the  demand  was  extremely  small 
owing  to  the  position  of  the  cloth  indiistry. 
Deliveries  to  districts  on  the  right  bank  of 
the  Rhine  were  out  of  the  question,  in  view 
of  the  difficulties  of  transport  and,  above 
all,  to  the  fact  that  the  costs  of  prcduction 
had  far  exceeded  the  world's  market  price. 

In  the  Aix-la-Chapclle  cloth  industry-,  the 
stock  of  orders  was  extremely  small.  Prac- 
tically no  new  orders  werg  received.  Foreign 
business  was  also  almost  at  a  standstill. 
The  high  costs  of  production  have  greatly 
impaired    the    power    to    compete    on    the 


324 


THE  CHEMICAL  NEWS. 


NOVEMBER  23,  1923. 


foreign  market.     In  the  cloth  trade  business 
was  irregular,  and  was,  in  general,  confined 
within  narrow  limits. 

4^6ather   Industry. 

The  prices  for  raw  hides  and  skins  of  all 
kinds  rose  continually,  both  at  the  auctions 
and  on  the  open  market.  A  much  larger 
turnover  would  have  been  obtained  had  not 
the  dearth  of  monej  made  itself  exception- 
ally felt. 


MEDICAL  SUPPLIES  FOR  THE 
DUTCH    GOVERNMENT. 

Mr.  R.  V.  Laming,  O.B.E.,  H.M.  Com- 
mercial Secretary  at  The  Hague,  reports 
that  the  Dutch  Government  are  calling  for 
tenders,  to  be  presented  by  November  27, 
for  the  supply  'of  various  medical  supplies. 

Applications  from  United  Kingdom  firms 
for  further  particulars  should  be  :addres.-;ed 
to  the  Department  of  Overseas  Trade 
(Room  52),  35,  Old  Queen  Street,  London, 
S.W.I.  (Reference  No.  30053/F.W./C.C. 
/(2). 


REPORT  ON  THE  CONSUMPTION  OF 

PREPARED    NON-METALLIC 

MINERALS  IN  CANADA. 

An  investigation  has  been  made  to  deter- 
mine the  extent  of  the  market  in  Canada  for 
finely-ground  non-metallic  minerals,  and 
this  report  on  the  consumption  of  certain 
non-metallic  minerals  in  Canada  has  been 
prepared  with  a  view  to  exploring  the  possi- 
bility of  establishing  plants  in  Canada  for 
the  production  of  finely-ground  non-metallic 
commodities  for  home  consumption.  The 
consumption  of  these  commodities  in  Can- 
ada is  considerable  in  the  aggregate,  and 
comprises  many  different  varieties.  Here- 
tofore, though  extensive  deposits  of  the 
crude  material  afe  known  to  exist  in  Can- 
ada and  though  these  deposits  are  in  certain 
cases  being  worked,  the  bulk  of  the  supply 
has  been  derived  from  importations. 


PROCEEDINQS  AND  NOTICES  OF 
SOCIETIES. 


THE  ROYAL  SOCIETY. 
Thursday,  November  15. 
Papers  read:  — 

Sir  William  Bragg,  F.R.S.,  and  Prof. 
G.  T.  Morgan,  F.R.S.  :  Crystal  Structure 
and  Chemical  Constitution  of  Basic  Beryl- 
lium Acetate  and  Propionate. 

Basic  beryllium  acetate  is  shown  by  X- 
ray  analysis  to  be  a  highly  co-ordinated 
compoimd.  The  molecule  is  a  perfect  tetra- 
hedron, having  an  oxygen  at  the  centre,  a 
beryllium  alone  at  each  corner  and  an  acetyl 
group  associated  with  each  edge.  The 
crystalline  structure  is  the  same  as  that  </f 
diamond.  The  propionate  forms  a  mono- 
clinic  crystal.  The  ipropyl  group  can  no 
longer  be  arranged  so  as  to  possess  a  plane 
of  symmetry,  as  in  the  case  of  the  acetyl; 
and  in  consequence  the  symmetry  is  much 
less. 

L.  C.  Jackson:  Investigations  on  Para- 
magnetism at  Low  Temperatures.  Com- 
municated by  Prof.  H.  Kamerlingh  Onnes, 
For.  Mem.  R.S. 

G.  I.  Taylor,  F.R.S.  :  Experiments  on 
the  Motion  of  Solid  Bodies  in  Rotating 
Fluids. 

Part  I.  Powdered  substances.  The  fol- 
lowing paramagnetic  substances  have  been 
investigated  from  atmospheric  temperatiu-e 
down  to  lowest  temperature  obtainable  with 
liquid  hydrogen  (about  14°  K.)j  anhydrous 
sulphates,  heptahydrated  sulphates  and  am- 
monium double  sulphates  of  cobalt,  nickel 
and  ferrous  iron.  New  phenomena  of  con- 
siderable interest  have  been  found  at  the 
lowest  temperatures.  Thus,  whilst  these 
substances  follow  the  Wejss  law  x  {'^  +  A) 
=  C  at  relatively  high  temperatures,  the 
following  types  of  deviation  from  this  law 
were  found  at  the  lowest  temperatures :  (1) 
Susceptibility  increases  more  rapidly  with 
fall  in  temperature  than  is    given  by  Weiss 

1 

law.       (2)    The  curve  of  —  against    T  pos- 

X 

sesses  a  point  of  inflection.     (3)  A  maximum 
and  a  minimum  value  of  susceptibility  occur 
in  region  of  lowest  temperatures. 
Part  II.      Crystals.       The   princiipal  sus- 


NOVEMBER  23,  1923. 


THE  CHEMICAL  NEWS. 


325 


coptibilities  of  crystals  of  cobalt  ammonium 
sulphate  and  nickel  sulphate  (heptahy- 
drate)  have  been  detennined  over  a  tem- 
perature range  of  290°  K.  down  to  14°  K. 
These  are  the  only  data  yet  available  as  re- 
gards the  principal  susceptibilities  of  crys- 
tals at  very  low  temperatures.  In  both 
cases  each  of  the  principal  susceptibilities 
follows  the  Weiss  law  at  higher  tempera- 
tures, but  deviates  therefrom  at  lower  tem- 
peratures. Th(^  Curie  constant  C  is  same 
for  each  of  principal  susceptibilities  of  any 
crystal.  Deviations  from  Weiss  law  in  caso 
of  cobalt  ammonium  sulphate  fall  into  cate- 
gory (1)  above,  while  those  of  nickel  sul- 
phate fall  into  category  (2). 

An  attempt  is  made  to  connect  magnetic 
phenomena  with  the  structure  of  crystals. 

L.  C.  Jackson  and  Prof.  H.  Kambrlinoh 
Onnes,  For.  Mem.  R.S.  :  The  Magnetic 
Properties  of  some  Paramagnetic  Double 
Sulphates  at  Low  Temperatures. 

In  fontinuation  of  a  previous  investiga- 
tion the  magnetic  susceptibilities  of  the  fol- 
lowing powdered  substances  have  been 
measured  over  a  range  of  temperature  of 
from  atmospheric  temperature  down  to 
about  14°  K. :  cobalt  potassium  sulphate, 
cobalt  rubidium  sulphate,  manganese  am- 
monium sulphate.  The  results  or  the  two 
cobalt  compounds  show  that  these  sub- 
stances follow  Ihe  law  x  (T+A)  ==  const,  ft 
not  U)o  low  temperatures,  but  deviate  there- 
from at"  the  lowest  temperatures,  in  such  a 
way  that  susceptibility  is  greater  than  value 
calculated  from  the  above  law,  thus  con- 
firming the  results  previously  obtained  with 
cobalt  ammonium  sulphate. 

Contrary  to  first  expectation,  it  was  found 
that  the  A's  of  the  three  above-mentioned 
coBalt  compounds  were  nearly  equal.  It  is 
shown,  however,  that  this  result  is  indeed 
to  be  expected  by  a  consideration  of  data 
already  published  for  the  principal  suscep- 
iibilities  of  cobalt  ammoniiun  sulphate  and 
the  conclusions  drawn  by  Tutton  as  to  the 
structures  of  these  monoclinic  double  sul- 
iphates  from  his  well-known  crystallographic 
investigations. 

Manganese  ammonium  sulphate  was 
found  to  obey  the  Curie  law,  x  T  =  const., 
down  to  the  lowest  temperature  mvesti- 
crated.  This  result  fits  well  with  the  known 
behaviour  of  other  manganese  salts,  show- 
ing that  in  this  series  of  compounds  the 
substance  follows  C\mo'>  law  more  closely 
the  greater  its  "  magnetic  dilution." 


H.  H,  Potter  :  Some  Experiments  ori  the 
Proportionality  of  Mass  and  Weight.  Com- 
municated by  Prof.  O.  W.  Richardson, 
F.R.S. 

The  gravitational  accelerations  of  lead, 
steel,  ammonium  fluoride,  bismuth,  paraffin 
wax,  duralumin  and  mahogany  have  been 
compared  with  that  of  brass,  and  no  differ- 
ence greater  than  that  attributable  to  ex- 
perimental error  has  been  found.  An  accu- 
racy of  one  part  in  5(),()00  has  been  obtained. 
Specaul  attention  has  been  given  to  two  sub- 
stances, ammonium  fluoride  and  paraffin 
wax,  which  have  large  hydrogen  contents. 

Papers  read  in  title  only  :  — 

J.oRD  Raylbioh,  F.U.S.  :  Further  Stiidies 
on  the  Glow  of  Phosphorus  and  its  Extinc- 
tion by  Moist  Oxygen. 

The  velocity  of  blast  necessary  to  blow 
away  the  glow  of  phosiphorus  increases 
enormously  with  rise  of  temperature.  On 
the  other  hand,  it  is  enormously  diminished 
by  enriching  the  air  blast  with  oxygen.  In 
either  case  the  range  examined  was  of  order 
1,000     times.  This     velocity     of     blast 

measures  rate  of  propagation  upstream  of 
glow  through  mixture  of  phosphorus  vapour 
and  oxygen. 

Where  velocity  is  reduced,  by  cooling  or 
by  adding  oxygen,  to  less  than  1  cm. /sec, 
the  condition  of  extinction  is  approached. 
From  this  viewipoint  the  known  (extinction 
by  moist  oxygen  alone  is  seen  to  be  the 
limiting  case  of  slow  propagation.  It  fol- 
lows that  extinct  ill!  is  due  to  failure  of  the 
process  causing  propagation.  This  was 
shown  before  to  be  in  all  probability  a  cata- 
lytic action  of  products  of  combustion.  Ex- 
cess oxygen,  like  other  inhibiting  sub- 
stances, "poisons"  these  prwlucts  or  makes 
them  unfit  to  act^-perhaps  by  a  process  of 
condensation,  similar  to  that  which  is  found 
to  clog  the  motions  of  ions  in  gaseous  com- 
bustion. 

Prof.  H.  A.  Wilson,  F.R.S.  :  An  Experi- 
ment on  the  Origin  of  the  Earth's  Magnetic 
Field. 

H.  Robinson,  D.Sc.  :  The  Secondary 
Corpuscular  Rays  produced  by  Homogene- 
ous X-Rays.  Communicated  by  Sir  Ernest 
Rutherford,  F.R.S. 

The  original  Robinson-Rawlinson  method 
of  investigating  velocities  of  secondary  ca- 
thode rays  produced  by  X-rays  has  been  de- 
veloped wHh  a  view  to  incre.ased  accuracy. 
Special   attention     has   befii   pnid   fo  homo- 


326 


THE  CHEMICAL  NEWS. 


NOVEMBEB  23,  1923. 


geneity  of  the  primary  X-ray  beam,  and  the 
effect  of  fluorescent  radiations  of  the 
material  under  investigation  has  been  there- 
by reduced. 

The  velocities  of  secondary  electrons  are 
measured  by  deflection  in  the  magnetic  field 
on  a  pair  of  large  Helmholtz  coils.  The 
copper,  Kd,  rays  are  used  as  primary  X 
radiation.  This  choice  permits  of  measure- 
ments being  made  in  regions  already 
mapped  out  by  X-ray  spectroscopy,  and  also 
allows  some  of  the  less  known  parts  of  the 
spectrum  to  be  investigated.  Satisfactory 
agreement  with  existing  data  has  been  found 
in  the  former  region. 

It  has  been  possible  to  separate  and 
measure  five  of  the  N  absorption  edges  of 
bismuth,  the  remaining  two  not  being 
separated  from  the  O  rings.  All  five  M 
edges  have  been  measured  for  atoms  as 
light  as  tungsten.  The  L  limits  have  been 
measured  as  far  as  copper,  and  the  K  limits 
to  oxygen.  The  very  soft  hmits  cannot  at 
present  be  measured  very  accurately,  but 
reasons  are  given  for  believing  that  K  limits 
of  light  atoms  may  be  higher  than  accepted 
values. 

Intensities  of  lines  of  corpuscular  spectra 
are  estimated  and  discussed.  Progressive 
changes  are  found  to  occur  along  the  series 
of  elements  in  relative  intensities  of  differ- 
ent members  of  the  same  group. 


Lt.-Col.  J.  W.  Gifford  (with  an  Intro- 
duction by  Prof.  T.  M.  Lowry,  F.E.S.): 
Some  Refractive  Indices  of  Benzene  and  Cy- 
clohexane.  Communicated  by  Prof.  T.  M. 
Lowry,  F.E.S. 


J.  A.  V.  Butler:  A  Note  on  "The  Signi- 
flcance^of  the  Electrode  Potential."  Com- 
municated by  Prof.  J.  W.  McBain,  F.E.S. 

1. — A  therm odynamical  argument  given 
in  Heyrovsky's  paper  on  The  Significance 
of  the  Electrode  Potential  is  examined,  and 
it  is  shown  that  certain  stages  of  the  cyclic 
process  employed  are  irreversible  and  that 
the  conclusions  are  therefore  erroneous. 

2. — ^A  method  of  conducting  the  cyclic 
process  reversibly  is  given,  and  it  is  shown 
that  the  sum  of  the  differences  of  potential 
round  the  cycle  is  zero;  it  follows  that  no 
information  regarding  the  relations  between 
the  electrode  potentials  and  the  various 
■  chemical  equilibrium  constants  is  obtained 
by  the  use  of  a  cyclic  process  of  this  kind. 


THE  EOYAL  SOCIETY. 
Thursday,  November  22. 

Papers  read:  — 

F.  Simeon:  The  Carbon  Arc  Spectrum  in 
the  Extreme  Ultra-violet.  II.  Communi- 
cated by  Prof.  A.  W.  Porter,  F.E.S. 

H.  J.  Cough  and  D.  Hanson,  D.Sc.  : 
The  Behaviour  of  Metals  subjected  to  Re- 
peated Stresses.  Coiinnunicateck  by  Sir 
Joseph  Petavel,  F.E.S. 

W.  SucKSMiTH  and  L.  F.  Bates:  On  a 
Null  Method  of  Measuriny  the  Gyro-Mag- 
netic Ratio.  Communicated  by  Prof.  A.  P. 
Chattock,  F.E.S. 

J.  H.  Shaxby  :  Studies  in  Brownian 
Movement,  II.  The  Determination  of  Avo- 
gadro's  Number  from  Observations  on  Bac- 
teria (Cocci).  Communicated  by  Prof.  S. 
W.  J.  Smith,  F.E.S. 

Papers  read  in  title  only  :  — 

H.  Hartridge,  Sc.D.,  and  F.  J.  W. 
EouGHTON  :  The  Kinetics  of  Hcenioglobin, 
II.  Commutiicated  by  Prof.  J.  N.  Langley, 
F.E.S. 

A.  F.  A.  Young  :  The  Thermionic  and 
Photo-Electric  Properties  of  the  Electro- 
Positive  Metals.  Communicated  by  Prof. 
O.  W.  Eichardson,  F.E.S. 

0.  F.  T.  Egberts  :  The  Theoretical  Scat- 
tering of  Smoke  in  a  Turbulent  Atmosphere. 
Communicated  by  Dr.  G.  C.  Simpson, 
F.E.S. 


EOYAL    INSTITUTION. 

The  98th  Course  of  Juvenile  Lectures  at 
the  Eoyal  Institution  to  be  delivered  this 
Christmas  by  Sir  William  Bragg,  F.E.S., 
'is  entitled  Concerning  the  Nature  of  Things, 
and  will  deal  with  I.,  The  Atovis  of  which 
Things  are  Made;  II.,  The  Nature  of  Gases; 
III.,  The  Nature  of  Liquids;  TV.,  V,,  and 
VI.,  The  Nature  of  Crystals,  (a)  Diamond, 
(b)  Ice  and  Snow,  (c)  Metals. 

The  first  lecture  will  be  given  on  Thurs- 
day, Dec.  27,  1923,  and  the  succeeding 
ones  on  Doc.  29,  1923,  and  Jan.  1,  3,  5,  and 
8,  1924. 


NOVEMBER  23,  1923. 


THE  CHEMICAL  NEWS. 


327 


THE  CHEMICAL  SOCIETY. 

Papers  read  at  the  Ordinary  Scientific 
Meeting,  November  15:  — 

Ring-chain  Tautomerisw.  Dynamical 
Evidence  Relating  to  the  Mutarotation  of 
the  Sugars,  by  J.  W.  Baker,  C.  K.  Ingold, 
and  J.  F.  Thorpe. 

An  earlier  paper  on  the  mechanism  of 
mutarotation,  dealing  not  only  with  dyna- 
mical, but  also  with  structural  and  other 
aspects  of  the  problem,  showed  that  the 
mutarotation-time  curves  have  (a)  a  form ; 
(b)  a  spacing,  on  the  mutarotation-timc- 
conoentration  diagram,  which  are  entirely 
at  variance  with  the  dynamical  conse- 
quences of  the  intermediate-hydrate  theory, 
but  are  in  complete  agreement  with  the  hy- 
pothesis of  ring-chain  taut<Mnerism,  to 
which  structural  evidence  also  points.  It 
has  been  objected  that  the  derivation  of  the 
dynamical  consequences  of  the  hydrate  the- 
ory was  based  on  a  fallacy.  The  authors  do 
not  accept  this,  and  now  present  the  com- 
plete mathematical  analysis  on  which  their 
conclusions  were  based. 

An  X-Ray  Investigation  of  certain  Or- 
ganic Esters,  and  other  Long  Chain  Com- 
pounds, by  G.  Shearer. 

By  means  of  an  accurate  X-ray  reflexion 
method,  measurements  have  been  made 
upon  solid  crystalline  films  of  methyl,  ethyl, 
octyl,  and  cetyl  palmitates,  of  methyl  and 
ethyl  stearates,  of  />-hexadecylphenol,  p- 
octadecylphenol,  and  of  ociadeoylbenzene. 
As  in  Miiller's  experiments  on  normal  fatty 
acids,  very  good  reflexions  were  obtained 
from  what  are  probably  the  crystal  cleavage- 
planes,  the  distances  or  "sipacings"  be- 
tween which  can  thus  be  d*  t(>rmined.  The 
cleavage  spacings  of  the  palmitic  esters  in- 
crease regularly  with  the  number  of  carbon 
atoms  in  the  alkyl  group ;  and  the  increment 
per  carbon  atom  of  the  eluinical  fcwmula  is 
the  same  for  these  esters  as  f<H:  the  two 
stearates  studied,  namely,  1.22  A.U.  for 
each  CHj  of  the  alkyl  radicle.  When  the 
palmitic  and  stearic  esters  of  a  given  alkyl 
radicle  are  compared,  the  increment  in 
spacing  per  CH,  of  the  acid  radicle  is  found 
to  bo  1.0.  This  figure  agrees  with  Miiller's 
value  of  2.0  in  the  case  of  the  free  fatty 
acids,  if  his  assumption  is  adopted  that 
there  are  two  molecules  pnd-to-end  between 
the  cleavage  planes  of  the  free  acids,  and  if 
only  one  ho  allowed  in  (he  cell  of  the  esters. 
The  accepted  and  iudei)endc'ntly  measured 


"diameter"  of  the  carbon  atom  is  1.5  A.U. 
In  order  that  chains,  built  of  atoms  of  this 
diameter,  shall  have  the  perpendicular  dis- 
tance of  1.22  A.U.  between  contiguous  cui- 
bon  atoms,  which  is  shown  to  prevail  in  the 
alkyl  chains,  it  is  necessary,  either  that  the 
chains  shall  be  tilted  at  an  angle  to  the 
cleavage  planes,  or  else,  if  their  lengths  are 
perpendicular  to  the  planes,  that  the  carbon 
atoms  should  be  linked  spirally  or  zig-zag. 
It  is  possible  to  calculate  the  observed, 
cleavage  sipacings  from  the  molecular  form- 
ulae, placing  one  or  else  two  molecules  be- 
tween successive  cleavage  planes  as  already 
indicated,  by  using  the  independently- 
known  "  atomic  radii,"  and  by  allowing 
that  an  acid  radicle  increases  by  1.0  A.U., 
an  alkyl  radicle  by  1.22  A.U. ,  per  CHj 
group;  where  necessary,  W.  H.  Bragg's 
value  for  the  dimcnsiwis  of  the  benzene  ring 
is  also  used. 

Further  X-Ray  Measurements  of  Long 
Chain  C&mpounds,  and  a  Note  on  their  In- 
terpretation, by  Alex.  Muller  and  G. 
Shearer. 

Data  were  given  tor  the  cleavage  spac- 
ings of  undecylic,  pentadecylic,  and  mar- 
garic  acids;  for  oleic,  elaidic,  and  tso-oleic 
acids;  and  for  orucic  and  brassidic  acids. 

A  systematic  exposition  was  given  of  the 
conclusions  which  can  legitimately  be 
drawn  from  these  experiments.  In  the  case 
of  stereoisomers  of  a  given  unsaturated 
acid,  the  observed  differences,  when  ex- 
pressed in  terms  of  the  two  types  of  chain, 
lead  to  the  inference  of  cis-trans  isomerism, 
and  point  to  a  definite  attribution  of  struc- 
ture as  between  the  two  isomers.  The  dif- 
ferences between  corresponding  saturated 
and  unsaturated  "  straight-chain  "  acids 
were  discussed. 

The  Constitution  of  the  Disaccharides. 
Part  IX.  :  Gentiobiose.  Its  identity  with 
Amygdalin  Biosc,  by  W.  N.  Haworth  and 
B.  Wylam. 

On  hydrolysis  of  completely  methylated 
gentiobiose,  2.3.5.6-tetramethylglucose  and 
2.3.5-trimethylglucose  were  obtained.  Gen- 
tiobiose thus  possesses  the  same  constitu- 
tion as  both  maltose  and  amygdalin  biose, 
and  since  the  latter  sugar  contains  a  /9- 
linking  imiting  the  two  glucose  residues 
exactly  as  does  gentiobiose,  this  is  the  di- 
saccharide  which  occurs  in  amygdalin. 
Synthetic  work  also  confirmed  this  result. 


328 


THE  CHEMICAL  T^BWS. 


NOVEMBER  23,  1923. 


The  Constitution  of  Rafflnose,  by  W.  N. 
Ha  WORTH,  E.  L.  Hirst  and  D.  A.  Ruell. 

Raffinose,  prepared  from  cotton  seed 
meal,  gave  rise  on  methylation  to  hendeca- 
methjl  ratfinose,  b.p.  238°  C.  /0.02  mm., 
[a]d  =  +  128°.  Hydrolysis  with  1  per  cent, 
hjdrochloric  acid  led  to  the  isolation  of 
three  partly  methylated  hexoses,  tetra- 
methyl  y-fructose  identical  with  that  iso- 
Uited  from  methylated  sucrose,  2.3.5-tri- 
methyl  glucose  (butylene  oxidic),  which 
gave  a  crystalline  methylglucoside  melting 
at  94°  C,  and  a  tetramethyl  galactose, 
which  gave  a  crystalline  anilide  identical 
with  that  prepared  from  methylated  lactose. 
A  structural  formula  was  rafl&nose  was  de- 
duced. 

It  appears  that  the  constitution  of  meli- 
biose  is  to  be  represented  by  a  formula  in 
which  the  glucose  unit,  through  the  hy- 
droxyl  group  attached  to  its  terminal  car- 
bon atom  6,  is  linked  with  the  reducing 
group  of  galactose. 


THE    FARADAY    SOCIETY. 
(Concluded  from  last  week.) 

Papers  read  at  the  meeting  on  November 
12:  — 

The  Effect  of  Sucrose  on  the  Rate  of  Co- 
agulation of  a  Colloid  by  an  Electrolyte,  by 
Leonard  Anderson,  Ph.D. 

The  concept  that  the  activity  of  ions, 
rather  than  their  concentration,  was  likely 
to  play  an  important  part  in  chemical  kine- 
tics was  first  suggested  by  Harned.  The 
interesting  problem  arises  as  to  whether  the 
activity  of  the  added  electrolyte  ions  does 
or  does  not  play  the  significant  roll  in  a  typi- 
cal colloidal  phenomenon,  namely  the  rate 
of  coagulation  of  a  colloid  in  presence  of 
added  electrolyte. 

The  work  of  Moran  and  of  Corran  has 
shown  that  sucrose  possesses  the  profperty 
of  causing  a  large  increase  in  the  activity  of 
various  ions  whilst  not  appreciably  altering 
their  concentration.  It  was,  therefore,  con- 
sidered of  interest  to  investigate  the  in- 
fluence of  sucrose  on  the  coagulation  of  a 
typical  colloid,  gold  hydrosol.  In  colloid 
systems  the  Smoluchowski^  equation  is  the 
only  one,  possessing    a  strictly    theoretical 

1  Smoluchowski,  Zeitschr.  physikal 
Chem.,  XCIL,  129,  1917. 


basis,  which  deals  with  the  kinetics  of  co- 
agulation. From  the  work  of  Anderson  and 
of  other  investigators,^  .however,  this  equa- 
tion appears  to  be  limited  to  raipid  coagula- 
tion. In  the  present  instance,  a  slow  or 
moderately  rapid  rate  of  coagulation  was 
considered  best,  since,  in  this  region,  the 
rate  of  coagulation  is  very  sensitive  to  slight 
variations  in  the  concentration  of  the  coagu- 
lant. In  view  of  the  inapplicability  of  the 
Smoluchowski  equation  to  this  region,  a 
more  arbitrary  method  of  measuring  the 
rate  of  coagulation  was  chosen,  namely,  the 
time  required  for  the  originally  red  gold  sol 
to  reach  the  tint  of  a  pai'tially  coagulated 
gold  sol,  stabilised  by  addition  of  gelatin. 

From  the  literature  it  appears  to  be  un- 
certain whether  sucrose  does  or  does  not  be- 
have as  a  peptiser  towards  colloidal  sols. 
Bancroft  enumerates  certain  cases  in  which 
sucrose  does  ipeptise.  Chatterji  and  Dhar, 
however,  state  that  true  peptisation  by  su- 
crose is  doubtful.  The  g,ddition  of  sucrose 
to  the  colloid  system  increases  the  viscosity 
and  should  thereby  lower  the  speed  of  co- 
agulation. The  sucrose,  however,  besides 
affecting  the  mobility  of  the  colloidal  par- 
ticles also  affects  the  mobility  of  the  co- 
agulating ions. 

The  experiments  indicated  that  the  su- 
crose had  a  two-fold  action.  The  first  was 
a  definite  peptising  effect,  and  the  second 
an  accelerating  effect,  upon  the  coagulation 
of  colloidal  gold  by  certain  electrolytes.  In 
the  case  of  potassium  chloride  as  electrolyte 
the  peptising  action  was  most  marked  and 
rapidly  increased  as  the  sucrose  increased. 
In  the  case  of  bariuin  chloride,  in  presence 
of  sucrose,  the  coagulation  proceeded  moi*e 
rapidly  (above  10  per  cent,  sucrose)  than  it 
should  do  on  the  basis  that  activity  is  the 
sole  factor  determining  the  rate  of  coagula- 
tion. From  this  it  would  appear  that  the 
sucrose,  in  addition  to  its  peptising  effect, 
also  introduced  a  specific  augmentation  of 
coagulation  in  excess  of  what  would  be  an- 
ticipated. The  latter  effect  is  apparently 
least  in  the  case  of  potassium  chloride  and 
greatest  in  the  case  of  barium  chloride.     In 


^  Anderson  (Trans.  Faraday  Soc).  Kruyt 
and  Arkel,  Bee.  Trav.  Chim.  Pays-Bas., 
XXXIX.,  656,  1920.  Westgren  arid  Reit- 
stotter,  Zeiinchr.  physikal  Chem.,  XCII., 
750,  1917.  Mnkherjcc  and  Vapaconsfanti- 
nou,  Phil.  Mag.,  XLIV.,  305,  1922. 


NOVEMBER  23,  1923. 


THE  CHEMICAL  NEWS. 


329 


the  case  of  hydrogen  ion  the  value   of  —  i» 

V 

constant  above  10  per  cent,  sucrose  which 
may  indicate  that  the  peptising  effect  of  thf 
sucrose  was  just  counterbalanced  by  the 
specific  augmenting  effect  and  consequently 
in  the  case  of  HCl  the  true  activity  appai- 
eutly  showed  itself. 

Sucrose  of  itself  had  no  ai)parent  coagu- 
lating power  on  gold  sol.  As  regards  the 
augmentation  of  the  coagulating  eftici<-'nc\ 
of  ions  produced  by  the  sucrose  it  might  b»' 
suggest<.'d  that  possibly  the  effect  was  due  to 
the  alteration  ip  the  dielectric  capacity  of 
the  medium  as  a  result  of  the  increase  in 
the  sugar  content.  Measurements  of  thf 
dielectric  capacity  of  sugar  soluticHis  indi- 
cated a  marked  fall  as  compared  with  that 
of  water.  The  electrical  adsorption  of  the 
ions  would  therefore  be  intensified,  involv- 
ing an  increase  in  neutralising  eflBcicncy  on 
the  electrical  charge  of  the  colloid  partick*, 
with  a  oous(  (juent  increase  in  the  rate  of 
effective  collisions,  i.e.,  effective  in  respect 
of  coagulation,  on  the  part  o!  the  colloid 
particles.  If  this  is  the  case  the  horizf>ntaJ 
line  obtained  in  the  case  of  hydrogen  ion 
was  largely  accidental,  and  the  result-s  cau 
only  be  regarded  as  qualitative  evidence  in 
favour  of  tne  activity  of  ions  as  a  significant 
factor  for  coagulation. 

It  was  established  from  the  experimental 
evidence  that  in  the  coagulation  of  ^old  sols 
by  hydrochloric  acid,  barium  chloride  and 
potassium  chloride  in  presence  of  varying 
amounts  of  sucrose  at  2.')°  C.  when  the  cmi- 
centration  of  the  hydrogen  ion  was  main- 
tained constant,  the  time  of  coagulation, 
corrected  for  viscosity,  was  found  to  pass 
through  a  maximum  at  about  10  per  cent. 
sucrose. 

When  the  activity  of  the  H  ion  was  main- 
tained constant,  the  time  of  coagulation 
corrected  for  viscosity  n^se  until  10  per 
cent,  sucrose  was  reached  and  then  became 
constant 

In  the  case  of  barium  chloride,  the  same 
conditions  were  observed,  and  in  both  eases 

T 

fhi'  value  of  —  passed  through  a  maxinniui 

at  about  10  per  cent,  sucrose. 

In  the  case  of  potassium  chloride  the  con- 
centration of  the  potassium  ion  was  main- 
tained constant.     It  was  found,  contrary  to 


anticipation,     that 


T 


increased     continu- 


ously as  the  sucrose  content  increased. 

Sucrose  exerts  a  definite  peptising  effect 
upon  colloidal  i,'ol(l.  and  it  also  exerts  a 
specific  augmentation  of  coagulation  in  the 
case  of  hydrogen  and  barium  ions  over  and 
above  that  of  iucreasng  the  activity  of  these 
two  ions.  It  is  thus  evident  that  sucrose  is 
by  no  means  inert  towards  ions  and  gold 
sols.  It  exhibits  apparent  antagonistic 
action. 

The  experiments  indicated  in  general, 
however,  that  tlu>  coagulating  power  of  an 
ion  is  4<?pendent  upon  its  activity  rather 
than  upon  its  concentration,  a  conclusion 
which  brings  the  typical  colloid  phenomenon 
of  coagulaticMi  into  line  with  the  kinetics  of 
chemical  change  in  homogenous  (molecular) 
systems. 

A  Method  of  Mcusurinn  the  Hale  of  Co- 
agulation of  Colloidal  Solutiona  over  Wide 
Ranges,  by  H.  H.  Paine,  M.A.,  B.Sc,  and 
G.  T.  K.  EvA.ss,  B.Sc,  University  of  the 
Witwatersrand,  Johannesburg. 

Considerable  light  was  thrown  on  the 
kinetics  of  coagulation  some  few  years  ago 
in  papers  by  Smoluchowski,  and  by  Fround- 
lioh.  These  writers  considered  a  colloidal 
solution  from  the  point  of  view  of  the  kine- 
tic theory.  Coagulation  is  regarded  as  the 
"coalescence"  of  "molecular"  particles  re- 
sulting from  their  mutual  collisien. 

Smoluchowski  was  concerned  primarily 
with  coagulation  when  it  occurs  at  its  nuixi- 
mum  rate — that  is,  when  all  collisions  be- 
tween colloidal  particles  result  in  coales- 
cence. The  existence  of  this  maxiiimm  is 
demonstrated  by  Zsigmondy  with  gold  sol, 
and  by  Kruyt  and  van  Arkel  with  selenium 
sol.  When  successive  samples  of  the  col- 
loidal solution  were  treated  with  increasing 
amoimts  of  an  electrolyte,  the  rates  of  co- 
agulation increased  to  a  maximum  or  limit- 
ing, value. 

Freundlich  extended  the  theory  to  slow 
I  coagulations,  and  made  a  further  inquiry 
into  the  forces  between  the  particles.  His 
theory  states  that  in  the  case  of  a  stable  col- 
loidal solution,  the  collisions  between  par- 
ticles are  "elastic,"  i.e.,  they  do  not  result 
in  coalescence.  A  repulsion  (something 
which  prevents  coalescence)  exists  between 
two  particles  arising  from  the  existence  of 
the  electrical  double  layer.  As  8cx>n  as  the 
potential     difference      across    this      double 


330 


THE  CHEMICAL  NEWS. 


NOVEMBER  23,  1923. 


layer  is  reduced  beyond  a  certain  critical 
value,  the  repelling  force  vanishes,  and  a 
collision  results  in  coalescence.  This  criti- 
cal point  has,  then,  many  of  the  properties 
originally  assigned  to  the  isoelectric  point. 

It  occurred  to  us  that  the  work  could  ho 
extended  by  the  use  of  a  "  protective  col- 
loid." The  addition  of  gelatine  or  starch 
results  in  making  the  colloid  less  sensitive  to 
electrolytes,  e.g.,  Luers  showed  that  the 
time  taken  for  a  change  to  be  observed  in  a 
Congo  ruby  sol  on  the  addition  of  an  elec- 
trolyte is  increased  if  gelatine  is  present. 

Coagulations  which  normally  proceed 
rapidly,  can  be  retarded  until  the  methods 
for  studying  relatively  slow  coagulations 
can  be  applied.  We  have  observed  coagula- 
tion proceeding  at  its  "limiting  rate"  for  a 
colloidal  copper  solution  to  which  a  suit- 
able quantity  of  starch  had  been  a"3ded. 

The  rate  of  coagulation  of  colloidal  cop- 
per solutions  was  studied  for  a  wide  range  of 
electrolyte  concentrations  by  making  use  of 
the  retarding  effect  of  starch.  Very  rapid 
coagulations  can  thus  be  brought  into  the 
region  of  observation  by  ordinary  methods. 
A  "Transformation  Factor"  can  be  obtained 
which  enables  us  to  calculate  what  the  rate 
rate  of  coagulation  would  have  been  for  the 
pure  colloid. 

The  results  of  these  experiments  agree 
closely  with  the  equation  deduced  by 
Freundlioh  'for  the  variation  of  the  rate  of 
coagulation  with  the  concentration  of  the 
electrolyte.  In  particular,  they  confirm 
the  existeilce  of  a  maximum  rate  of  coagu- 
lation. 

Concentrations  of  starch  below  a  certain 
minimum  do  not  influence  the  rate  of  coagu- 
lation. If  we  express  this  influence  by  the 
"  transformation  factors,"  a  linear  relation 
holds  between  the  logarithm  of  the  trans- 
formation factor  and  the  concentration  of 
the  starch  over  and  above  some  minimum 
value. 

Studies  in  Heterogeneous  Equilihria. — 
Part  I.  :  Conditions  at  the  Boundary  Sur- 
face of  Crystalline  Solids  and  Liquids,  and 
the  Application  of  Statistical  Mechanics,  by 
J.  A.  V.  Butler,  M.Sc. 

Equilibrium  between  two  phases  occurs 
kinetically  when  equal  numbers  of  mole- 
cules of  every  sipecies  concei'ned^  pass  the 
boundary  surface  in  both  directions  in  the 
same  time.  The  methods  of  statistical 
mechanics  have  been  applied  to  the  de- 
velopment of  the  kinetics  of  such  processes 
only  in  the  simplest  cases. 


Langmuir,  whose  pioneer  work  has  in- 
spired most  of  the  recent  progress  in  this 
direction,  was  concerned  with  vaporisation 
and  the  kinetics  of  gas  reactions  at  solid 
surfaces.  Rideal  and  liodebush  have  em- 
ployed special  forms  of  the  statistical  equa- 
tions with  some  success  in  the  calculation  of 
the  constants  of  vaporisation.  Langmuir 's 
treatment  has  been  extended  to  give  a  kine- 
tic theory  of  the  adsorption  of  gases  by 
Henry.  A  tentative  attempt  to  apply  sta- 
tistical equations  to  the  calculation  of  solu- 
biliy  is  uuntioned  by  Dushman. 

The  subject  is  here  approached  from  a 
somewhat  different  point  of  view,  which 
may  perhaps  be  made  clearer  by  analogy. 
In  the  study  of  homogeneous  equilibrium 
the  law  of  mass  action  proved  a  reliable 
guide  and  inspiration  for  many  years,  al- 
though it  gave  merely  the  form  of  the  equi- 
librium equation  and  did  not  lead  to^the  cal- 
culation of  the  equilibrium  constant  in  any 
case.  The  earlier  workers  on  heterogeneous 
equilibrium  aipproached  the  subject  from 
the  point  of  view  of  the  law  of  mass  action, 
but  the  results  were  comparatively  meagre. 
Certain  analogies  with  mass  action  obviously 
exist,  but  the  backward  state  of  our  know- 
ledge of  the  kinetics  of  phase  equilibria  may 
be  traced  to  the  fact  that  no  general  kinetic 
law  of  surface  action  has  been  available  to 
replace  the  law  of  mass  action. 

The  author  showed  that  although  it  is  not 
yet  possible  by  the  application  of  statistical 
methods  to  calculate  the  values  of  the  equi- 
■  librium  constants,  nevertheless  these 
methods  can  be  used  to  co-ordinate  diverse 
cases  of  heterogeneous  equilibrium,  in  par- 
ticular solubility,  the  solubility  product,  the 
electromotive  equilibria  of  metals  and  oxi- 
dation potentials. 

Although  this  treatment  does  not  aim 
primarily  at  the  calculation  of  equilibrium 
constants  and  may  have  a  very  distinct  use- 
fulness if  it  is  at  present  unable  to  achieve 
that  objective,  it  is  evident  that  every  op- 
portunity should  be  taken  of  making  a  com- 
parison with  numerical  data.  In  these  com- 
plex cases  the  exact  calculation  of  equili- 
brium constants  is  only  likely  to  be  achieved 
when  the  special  conditions  of  each  case 
have  been  qualitatively  explored. 

The  present  paper  was  devoted  to  a  pre- 
liminary discussion  of  the  conditions  at  the 
boundary  surfaces  between  crystalline  solids 
and  liquids  from  this  standpoint  and  the 
deduction  of  aippropriato  statistical  condi- 
tions. 

The  extension  of  the  methods  to  the  spe- 


NOVEMBER  23.  1923. 


THE  CHEMICAL  NEWS. 


331 


cial  case  of  metals  (lipping  into  their  salt 
solutions,  taking  into  account  the  electric 
factors  concerned,  have  led  to  a  physical 
interpretation  of  Nernst's  electrolytic  solu- 
tion tension,  A  further  extension  provided 
a  reasonable  explanation  of  the  mechanism 
whereby  reversible  oxidation  potentials  are 
set  up  at  inert  electrodes. 


THE  INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

Paper  read  at  the  Royal  Society  of  Arts 
on  Tuesday,  November  13:  — 

Galician- Canadian  Pole  Tool  Fiahiny 
Methods,  by  Albert  Millab,  A.M.I.- 
Mech.E.  (Member). 

"Fishing"  in  oil  well  nomenclature 
covers  a  great  variety  of  work,  an9  does  not 
merely  represent  the  recovery  of  lost  tools 
as  is  often  thought  to  be  the  case.  Side- 
tracking of  tools  or  casing  also  come  under 
the  heading  of  "  Fishing." 

In  all  these  operations  "touch"  plays  a 
most  important  part,  and  this  sense  can 
only  be  acquired  by  long  practice,  as  can 
also  the  knack  d!  constructing  suitable  fish- 
ing tools  to  suit  individual  cases. 

The  author  dealt  very  exhaustively  with 
all  the  aspects  of  the  problems  involved  in 
recovering  lost  tools,  and  in  dislodging 
those  that  became  stuck.  The  methods  to 
be  adopted,  it  was  pointed  out,  differed 
according  to  the  circumstances,  from  the 
case  of  slightly  bent  tools  to  a  troublesome 
accident  due  to  runaway  tools  or  casing. 


THE  INSTITUTION  OF  ELECTRTCAT. 
ENGINEERS. 

A  joint  meeting  with  the  Societe  des  In- 
genieurs  Civils  de  IVance  (British  Section) 
was  held  on  Thursday,  November  22.  A 
paper  entitled  The  iLlectrifioation  of  the 
Midi  RailuKiy  was  read  by  Monsieur  A. 
Bachellery. 

The  Wireless  Section  held  a  meeting  on 
Wednesday,  November  21.  Papers  entitled 
Periodic  Trigger  Reception,  by  Mb.  E.  V. 
Appleton,  M.A.,  D.Sc,  and  F.  S.  Thomp- 
son, B.A.  (Royal  Corps  of  Signals),  and  A 
Dynamic  Model  of  a  Valve  and  Oacillating 
Circuit,  by  Mr.  R.  C.  Clinker,  M.I.E.E., 
were  read. 


The  joint  meeting  with  the  Societe  des 
Ingenieurs  Civils  de  France  (British  Sec- 
tion), which  was  to  have  been  held  on 
Thursday,  November  16,  was  postponed  to 
Thursday,  November  22,  at  6  p.m.,  when 
Monsieur  A.  li.vcnELLERY  read  his  paiper  on 
The  Electrification  of  the  Midi  RaUuuy. 
Joint  Meeting  with  The  Physical  Society 
OF  LoNDOH,  Thursday,  November  29,  1928. 

The  above  meeting  will  begin  at  5.30  p.m. 
(light  refreshments  at  5  p.m.),  and  will  be 
in  two  sessions,  viz. :  5.30  to  7  p.m.,  and  8 
to  9.30  p.m. 

The  subject  to  be  discussed  will  be  :  Loud 
Speakers  for  Wireless  and  ofher  Purposes, 
and  among  those  who  wilT  contribute  short 
papers  (including  in  some  crises  practical 
demonstrations)  will  be  the  following:  — 

Mr.  S.  G.  Brown,  F.R.S. ;  Captain  P.  P. 
Eokersley;  Professor,  C.  L.  Fortescue, 
M.A. ;  Professor  J.  T.  MacGregor-Morris; 
Professor  E.  Mallett,  M.Sc.  (Eng.);  Mr.  L. 
C.  Pocock,  B.Sc. ;  Mr.  H.  L.  Porter,  B.Sc; 
Professor  A.  O.  Rankine,  D.Sc,  F.R.S. ; 
Mr.  E.  K.  Sandeman,  B.Sc;  Mr.  G.  A. 
Sutherland,  M.A. 

By  kind  (permission  of  the  British  Broad- 
castmg  Company  arrangements  are  being 
made  for  partiis,  limited  to  20  in  number, 
to  vis^  the  Company's  studio  at  No.  2, 
Savoy  Hill,  at  half-hourly  intervals  from  3 
io  5  p.m.  Members  wishing  to  visit  the 
studio  are  requested  to  send  their  names  to 
the  Secretary,  and  to  indicate  the  time 
which  would  be  most  convenient  to  them. 


THE    ROY.VL    AGRICULTURAL 
SOCIETY    OF   ENGLAND. 

The  proceedings  at  the  Monthly  Council, 
held  on  November  7,  Lieut. -Col.  E.  W. 
Stanyforth  (President)  in  the  chair,  in- 
cluded the  I  t  ion  of  various  reports. 
The  followin-  chemical  report:  — 

Mr.  J.  L.  Jiuddington  (Chairman)  re- 
ported that  a  letter  had  been  received  from 
the  Departmental  Cc«nmittoe  on  the  Ferti- 
lisers and  Feeding  Stuffs  Act,  inviting  evi- 
dence from  the  Society.  Arrangements-  had 
been  made  for  the  Chairman  to  give  evi- 
dence on  behalf  of  the  Society.  Several 
points  arising  on  a  memoranduin  received 
from  the  Ministry  of  Agriculture  had  been 
considered  by  the  Committee,  who  had  in- 
structed their  representative  as  to  the  action 
to  be  taken  thereon. 
The  Committee  recommended    that  a  re- 


33-i 


THE  CHEMICAL  NEWS. 


NOVEMBEE  23,  1923. 


port  by  the  Consulting  Chemist,  including 
the  names  of  the  vendors  of  the  materials 
mentioned,  be  published  as  a  private  and 
confidential  document  to  Governors  and 
Members. 

A  draft  of  a  proposed  new  by-law  defining 
the  duties  of  the  Connnittee  had  been  read 
and  approved. 


THE  KOYAL  MICROSCOPICAL 
SOCIETY. 

President :    Professor  Frederic  J.   Cheshire, 
C.B.E.,  F.Inst.P. 

Hon.     Secretaries:      Joseph     E.     Barnard, 
F.Inst.P.,  James  A.  Murray,  M.D. 

A  meeting  of  the  Society  was  held  on 
November  21.  The  following  paipers  were 
read  and  discussed:  — 

Sex-Reversal  and  Inter  sexuality,  by  Mk. 

F.  Rogers  Brambell,  B.A.,  B.Sc. 

Further  Evidence  on  the  Transition  of 
Peritoneal  Cells  into  Germ-Cells  in  Amj^hi- 
bia,  bv  Prof.  J.  Bronte  Gatenby,  M.A., 
D.Ph.,"M.R.I.A.,  F.R.M.S. 

Tlte  Preparation  of  Eel  Scales  for  Micro- 
scopic Examination,  by  Dr.  Miles  John- 
ston, M.B.,  Ch.B. 

The  Microscope  in  Physics,    bv  Mr.  F.  I. 

G.  Rawlins,  M.R.L,  F.R.M.S.^ 

Dr.  H.  M.  Woodcock  (Lister  Institute  of 
Preventive  Medicine)  exhibited  Bacterio- 
morphic  Granules  (or  Granules  simulating 
Bacteria)  resulting  from  Cell-lysis  or  Diges- 
tion, 

The  section  of  the  Royal  Microscopical 
Society  foi-med  to  deal  with  the  Industrial 
Applications  of  the  Microscope,  and  to 
assist  in  the  development  of  Industrial  Re- 
search in  British  Industries,  will  hold  its 
next  meeting  at  20,  Hanover  Square,  W.l, 
■  on  Wednesday,  November  28,  1923,  at  6.30. 
The  following  exhibits  have  been  arranged  : 

Mr.  Conrad  Beck,  C.B.E.,  F.R.M.S.:  A 
New  Projection    Microscope  for    measuring 

1 

Fine  Wires  and  Fabrics  to inch. 

50000 

Messrs.  Adam  Hilger,  Ltd. :  Dr.  Miillor's 


X-Raj^  Spectrograph  for  the  Examination  of 
Sub-Microecopio  Crystalline  Structures. 

Mr.  J.  E.  Barnard,  F.Inst.P.,  F.R.M.S., 
will  give  a  Lecture  Demonstration :  The 
characteristics  of  a  microscope  for  general 
and  special  purposes ;  the  tests  for  mechani- 
cal efficiency  that  should  be  satisfied. 

Dr.  Sidney  ,H.  Browning,  L.R.C.P., 
M.R.C.S.,  F.R.M.S.,  will  read  a  paper  en- 
titled The  xipplication  of  the  Microscope  to 
Industrial  Diseases. 

Mr.  Charles  A.  Newton,  F.R.M.S.,  will 
also  read  a  paper  entitled  The  Microscope  in 
the  Examination  of  Condensed  Milk. 


THE     SOCIETY    OF    GLASS 
TECHNOLOGY. 

A  meeting  of  the  Society  of  Glass  Tech- 
nology was  held  in  the  Lecture  Room  of  the 
Department  of  Coal  Gas  and  Fuel  Indus- 
tries, The  University,  l^eeds,  on  Wednes- 
day, November  21. 

The  following  i  papers  w  eiv  received  and 
discussed :  — 

Note  0)1  the  Influence  of  Rapid  Chilling 
on  the  Reversible  Expansion  of  Clay,  by  H. 

S.    HOULDSWOHTH,    M.Sc. 

Glasshouse  Pots:  Some  Notes  on  their 
Manufacture  and  Use,  by  P.  Marson. 

The  Casting  Process  for  Glasshouse  Re- 
fractories in  German  Glass  Plants,  by  Prof. 
Kurd  Endell,  Dr. Phil. 

By  the  courtesy  of  the  Directors  and  of 
H.  J.  C.  Johnstone,  Esq.  (General  Mana- 
ger), a  visit  was  made  to  the  Wortley  works 
of  Messrs.  Leeds  Fireclay  Co.,  Ltd.,  Wort- 
ley,  Leeds,  on  November  21 .  At  these 
works  members  had  an  opportunity  of  in- 
specting pot  clay  blocks,  firebricks,  blast 
furnace  linings,  coke  oven  bricks,  and  drain 
pipes. 


THE  MINERALOGICAL  SOCIETY. 
Anniversary  Meeting,  November  6. 

Dr.  A.  Hutchinson,  F.R.S.,  President,  in 
the  chair. 

Papers  read  :  — 


NOVEMBER  23,  1923. 


THE  CHEMICAL  NEWS. 


333 


Dr.  L.  J.  Spencer,  Eudase  and  Platinum 
from  Diamond-washings  in  British  Guiana.- 

Small  discs  resembling  lV>ssil  corals  con- 
sist of  a  radial  aggrcgatic^n  of  eiiclaw  crys- 
tals so  arranged  that  the  plane  of  symmetry 
is  always  parallel  to  the  surface  of  the  disc. 
These,  together  with  tounnalinc,  diamond, 
gold,  and  platinum,  were  found  in  the  con- 
glomerates near  the  Kaieteur  Falls  on  the 
Potaro  River.  Platinum  has  not  hitherto 
been  recorded  from  British  Guiana. 

Harold  E.  Buckley,  Some  Anomalous 
Optical  Properties  of  Freshly-prepared 
mixed  Crystals  of  the  Seifjnette  Salts. 

In  the  orthorhombic  and  isomonphous 
Seignette  salts  the  sodium-potassium  tar- 
trate has  the  optic  axial  plane  parallel  to 
the  bracl^y-pinacoid,  whilst  in  the  sodium- 
nmmonium  salt  it  is  parallel  to  the  macro- 
pinacoid.  Mixed  crystals  of  the  two  salts 
show,  as  would  bo  expected,  the  optic  axes 
for  difFerent  colours  in  two  planes  at  right 
angles  (as  in  brookite),  but  only  after  the 
(•i*ystnls  have  been  preipared  for  some  time. 
Freshly-prepared  mixed  crystals  exhibit 
crossed  dispersion  of  the  monoclinic  type 
(as  in  borax).  A  maximum  angle  of  75"  be- 
tween the  axial  planes  for  red  and  violet 
light  is  given  by  crystals  containing  45"  per 
cent.  Na-K  tartrate.  On  standing,  the  axial 
planes  slowly  migrate  to  the  planes  of  sym- 
metry, and  equilibrium  is  established  in 
from  two  to  thirteen  weel<>^,  this  being  has- 
tened by  increasing  the  temperature. 

C/OLONKL  N.  T.  Belaikw,  On  the  Genesis 
of  Widmanstiitten  Strticture  in  Meteorites 
and  in  Terrestrial  Alloys. 

The  Widnianstiitten  structure  belongs  to 
the  triad  of  secondary  structures,  the  other 
two  beinj;  the  structun-  of  large  crystals  and 
the  network  structure.  Under  suitable  con- 
ditions either  of  trhese  structures  may  occur 
in  iron-carbon  alloys,  or  in  any  other  alloys 
crystallising  in  the  face-centred  cubic  lat- 
tice and  exhibiting  the  same  kind  of  equili- 
brium diagram.  As  the  diagram  of  the  Fe- 
Xi  alloys  is  quite  similar  to  that  of  Fe-C, 
the  same  kind  of  crystallisation  may  be  ex- 
pected in  either  case  and  also  in  that  of 
inet<^orites.  The  well-knriwn  Widmanstat- 
ten  figures  in  meteoritos  are  also  arranged 
in  a  Widmanstatten  structure.  From  their 
aippearance  an  inference  can  be  made  as  to 
the  conditions  of  cooling  which  furthered 
their  appearance.  These  conditions  are  a 
very  slow  cooling  after  solidification  in  the 
granulation    zone    and    a    relatively    rapid 


separation  of  the  constituents  afterwards  m 
the  zone  of  secondary  crystallisation  leading 
to  their  lodging  theaiselveb  parallel  to  the 
octahedral  planes  in  every  gvanula. 

Prof.  L.  K.  Wilberforck,  Illustration 
and  detection  of  incliyied  and  horizontal  dis- 
persion in  Bi- Axial  Cry.'iials. 

If  the  optic  picture  of  an  ordinary  bi- 
axial crystal  is  viewed  through  a  prism 
whose  refracting  edge  is  parallel  or  perpen- 
dicular to  the  axial  plane,  the  appearances 
characteristic  of  horizontal  and  inclined 
dispersion  are  respectively  produced.  Such 
dispersions  in  a  crystal,  if  too  small  to  be 
detected  by  direct  observation,  can  be  dis- 
covered by  thus  using  a  prism  of  small 
angle  alternately  to  reinforce  and  oppose 
them,  and  noting  the  want  of  symmetry  in 
the  effects  produced. 

Arthur  Rissell,  On  the  occurrence  of 
the  Rare  Mineral  Nadorite  in  Comuall,  and 
of  Beraunite  (Eleonorite)  in  Co.  Cork,  Ire- 
land. • 

A  single  specimen  of  the  rare  mineral 
nadorite  was  found  by  the  writer  at  the 
small  antimony  mine  Bodannon,  St.  Endel- 
lion,  COTnwall.  The  nadorite  forms  aggre- 
gates of  nearly  square  platy  crystals,  trans- 
parent, of  a  yellowish-brown  to  reddish- 
brown  colour,  occupying  a  cavity  in  fibrous 
jamcsonite.  The  crystals  are  combinations 
of  a  (100)  and  r  (180),  and  are  twinned  on 
I  (Oil).  A  very  well-defined  specimen  of 
the  variety  of  beraunite  known  as  eleonor- 
ite wa«  found  by  the  writer  at  the  iron  and 
manganese  mine  of  Roury  Glen,  Glandore, 
Co.  Cork.  It  consists  of  a  mass  of  diverg- 
ing fibrous  crystals  of  a  reddish-brown 
colour,  between  walls  of  limonite.  Th(> 
fibres  are  elongated  in  the  direction  of  the  b 
axis,  and  show  very  strong  pleochroism. 

A.  F.  Hallimond  and  F.  R.  Ennos,  On 
Stilpnomclane  from  North    Wales. 

A  dark  scaly  vein-mineral,  strongly  re- 
sembling biotite,  proves  on  analysis  to  con- 
tain very  little  potash,  and  is  very  similar  in 
physical  properties  to  stilpnomclane  from 
Moravia.  The  composition  agrees  with  the 
formula:  6SiO,.2FeaO,.2Fe0.3H,0.  Sp.  G. 
2.85.  Apparently  uniaxial;  o  =  l.()87,  e  = 
1.595.  Pleochroic,  o  =  dark  brown,  e  = 
pale  yellow.  Brittle,  with  eminent  basal 
cleavage  and  marked  cleavage  normal  to 
this,  yielding  pleochroic  chips.  H  =  3.5. 
Insoluble  in  li  t  N72  HCl. 


334 


THE  CHEMICAL  NEWS. 


NOVEMBER  23,  1923. 


.    Dr.  G.  T.  Prior,    On  the  Chemical  Com- 
position of  the  Ashclon  Me'teofftc. 

This  meteoric  stone,  which  fell  at  Ashdon, 
near  Saffron  Walden,  Essex,  on  March  9, 
1923,  is  a  white'  hypersthene-ehondrite  con- 
taining 81  per  cent,  of  niekeUferous  iron  in 
which  the  ratio  of  iron  to  nickel  is  about  6. 


CORRESPONDENCE. 


THE  COLOURING  OF  POISONS. 

To  the  Editors  of  The  Chemical  News. 

Sirs, — In  a  recent  communication,  under 
the  above  heading,  Mr.  James  Sexton, 
M.P.,  advocates  the  colouring  of  poisons. 
and  mentions  several  points  against  it  put 
forward  by  the  General  Medical  Council. 
He  winds  uip  with  the  words,  "  These  four 
objections  may  be  just  or  they  may  not. 
What  I  submit  is  that  they  are  matters  of 
policy  to  be  determined  by  Parliament  in 
open  debate  rather  than  settled  autocratic- 
ally by  the  "most  conservative  of  our  trade 
unions." 

Mr.  Sexton  has  left  out  the  most  impor- 
tant people  concerned  in  this  matter.  I 
refer  to  —  I  was  going  to  have  said  "the 
chemiste" — but  to  a  Member  of  Parliament 
or  one  of  the  legal  profession  this  word 
would,  according  to  law,  designate  a  phar- 
macist, who  keeps  open  shop :  it  would,  of 
course,  include  him,  but  I  mean  it  in  the 
wider  sense  of  the  "  chemical  profession." 
If  Mr.  Sexton  does  not  know  what  I  mean  T 
shall  be  hatppy  to  explain  it  pi-ivately  to 
him,  if  he  so  wishes. 

I  say  he  has  left  out  the  chemical  profes- 
sion; those  men,  or  the  followers  of  those 
men,  who  have  discovered  or  synthesised 
the  greater  number  of  the  poisons.  Our 
contention  is  that  if  one  poison  is  to  be 
coloured,  others  will  follow,  and  where  is  it 
to  end  ?  Mr.  Sexton  •  uses  the  expression 
"deadly  poison";  what  does  he  mean  by 
that?  He  mentions  one  alkaloid,  viz., 
strychnine;  is  this  class  of  substance  the 
one  he  calls  "  deadly  poison,"  or  would  he 
also  include  prussic  acid  and  the  cyanides, 
compounds  of  arsenic  including  organic 
ones,  mercurous  and  mercuric  chlorides, 
lead  acetate,  phosphorus,  etc.?  Many  of 
these  are  quite  as  poisonous  as  strychnine. 
If  these  are  included,  then  try  and  imagine 
carrying  on  in  a  chemical  laboratory  with 
the  KCN  solution  coloured  with,  say.  gen- 
tian violet,  and  the  HgClg  solution  with 
malachite  green.   The  alkaloids  are  detected 


chiefly  by  means  of  colour  reactions,  with 
.which  a  colouring  matter  rnight  seriously,  in- 
terfere, esipecially  where  students  are  con- 
cerned. 

Parliament  is  notoriously  unscientific, 
otherwise  it  would  not  have  permitted  for 
one  day  the  importation  of  cotton  into  Ger- 
many during  the  war;  therefore  with  all 
due  respect  to  it,  Parliament  is  not  able  to 
give  a  properly  considered  decision  upon 
this  matter,  without  first  taking  council 
with  the  chemical  profession. 

In  the  event  of  this  matter  becoming  the 
law  of  the  land,  Mr.  Sexton  will  be  doing 
his  bit  towards  the  advancement  of  science, 
if  he  will  do  his  best  to  have  a  clause  in- 
serted in  the  Act,  permitting  all  chemical 
and  other  scientific  laboratories,  whether 
public  or  private,  and  those  firms  which 
supply  them,  to  obtain,  easily  and  without 
red  tape,  any  uncoloured  chemical,  whether 
poisonous  or  not.  W^e  are  put  to  no  end  of 
trouble,  as  things  are,  to  obtain  a  little  duty 
free  absolute  alcohol  for  use  in  unpaid  re- 
search work,  the.  expense  of  the  latter  fall- 
ing upon  the  person  doing  the  research,  but 
which  the  Inland  Revenue  calls  "a  hobby" 
and  refuses  to  allow  the  deduction  of  the 
income  tax  on  such  expense. 

I  mention  these  things  to  show  how  we 
are  hampered  in  ways  that  were  not  in- 
tended by  Parliament,  and  we  wish  to  avoid, 
if  possible,  this  further  and  probably  more 
serious  difficulty. — Yours,   &c., 

Herbert  Henstock,  M.Sc,  Ph.D., 

F.I.C. 

Chemical  Research  Laboratory, 
School  Gardens, 
Shrewsbury. 


NOTICES  OF  BOOKS. 

The  Expert  Witness,  by  C.  A.  Mit- 
chell, M.A.,  F.I.C.  Pp.  XV.  +  188. 
Cambridge:  Messrs.  Heffer  &  Sons,  Ltd. 
1923.     7s.  6d.  net. 

Chemists  are  very  apt  to  engross  them- 
selves in  their  subject,  and  to  leave  to  mere 
chance  the  important  task  of  bringing  to  it 
and  them  a  proper  recognition  of  the  high 
order  of  their  work. 

It  is  therefore  only  in  times  of  great 
stress  that  such  recognition  is  forthcoming, 
and  by  their  own  attitude  chemists  have 
themselves  to  thank  for  this. 

In  his  latest  work  on  the  applications  of 
science  (and  of  art)    to  human    identifica- 


NOVEMBER  23,  1923. 


THE  CHEMICAL  NEWS. 


335 


tion,  criminal  and  other  investigations,  and 
to  liistory,  Mr.  Mitchell  has  done  his  fellow 
workers  a  good  service.  This  hook  is  in- 
tended as  much  for  the  general  pubhc  as  for 
the  scientific  reader.  It  is  eminently  en- 
tertaining and  interesting,  and  the  re- 
viewer's regret  was  on  reaching  the  last 
page. 

Expert  evidence  in  general  is  discussed, 
and  then  the  author  deals  with  such  S(pe- 
ciaiised  cases  as  the  identification  by  skin- 
prints,  medical,  scientific  and  bacteriologi- 
cal evidence.  The  role  of  the  expert  m 
handwriting  and  in  art,  and  the  applications 
of  such  specialised  evidence,  is  very  ably 
described,  with  the  aid  of  many  illustrations. 

The  application  of  chemical  knowledge  in 
the  investigation  of  documents  and  writ- 
ings has  hitherto  not  received  adequate 
attention.  The  author  directs-  attentijon  to 
a  number  of  recent  investigations  in  legal 
cases  where  such  chemical  evidence  was  in- 
valuable. 

J^oubtless  these  will  become  more  and 
more  numerous  when  it  is  more  widely 
realised  what  a  valuable  part  chemistry  can 
play  in  such  matters.  J.G.F.D. 

Landscape  and  History,  Is.     London: 

Simpkin,     Marshall,     Hainiltwi,    Kent  A 

Co.,  Ltd. 

The  anonymous  author  has  addressed  this 
little  volume  more  especially  to  the  readers 
(and  distinguished  writers)  of  the  various 
Outlines  now  appearing. 

He  makes  apposite  quotations  from  Mr.  H. 
G.  Wells'  address  before  the  British  Science 
Guild  last  year,  and  his  theme  is  apparently 
to  draw  attention  to  the  geolf>gical  and  his- 
torical iniiportance  of  veins  and  strata  of 
iron.  These,  it  is  urged,  possess  very  great 
significance  to  an  extent  by  no  means  fully 
realised  in  scientific  circles.  Six  excellent 
photographs  are  included. 


The  Institute  of  Science  and  Industry  of 
Australia  has  issued  Bulletin  No.  24,  en- 
titU'd  Tlic  Production  of  TAqiiid  Fuels  from 
Qil  Shale  and  Coal  in  Australia,  by  R.  E. 
Thwaites,  M.A. 

It  is  pointed  out  that  the  rapid  depletion 
of  the  world  stocks  of  petroleum  and  the  ex- 
traordinary increase  in  the  use  of  oil-fuels, 
and  the  advancing  efl&ciency  of  oil-engines 
have  awakened  a  recognition  of  the  import- 
ance of  all  questions  touching  the  economic 
production  of  liquid  fuels.  The  necessity 
of  the  direct  value  of  researches  into  their 
production  is  universally  recognised.       In 


Australia  tlte  question  whether  natural 
petroleum  exists  in  payable  quantities  or 
not  is  unsettled,  but  large  supplies  of  coals 
and  shales  certainly  exist. 

Apart  from  their  direct  econamic  value, 
they  have  also  that  which  arises  from  the 
possibility  of  making  the  country  indepen- 
dent of  foreign  supplies. 

The  present  Bulletin  embodies  the  results 
of  the  inquiries  made.  For  some  years  past 
Mr.  Thwaites  has  made  a  special  study  of 
fuel  problems,  and  has  also  carried  out  ex- 
perimental investigations  on  the  distillation 
of  coal  and  the  production  ^of  liquid  fuels 
therefrom,  both  in  small  and  large  scale 
plant. 


The  Ministry  of  Agriculture  and  Fisheries 
has  issued  a  leallet,  No.  316,  dealing  with 
the  cultivation  of  lavender  for  marketing 
and  distilling.  Lavender  has  been  grown 
commercially  in  the  south  of  England  for  a 
great  many  years,  having  been  introduced 
in  1568,  and  where  the  soil  and  situation  are 
favourable,  there  is  no  doubt  that  it  is  a 
profitable  crop  and  worthy  of  consideration. 
It  is  grown  for  the  oil  for  perfumery,  for 
sale  in  a  fresh  state  as  "bunched  lavender," 
and  as  "dried  lavender"  for  sachet  making, 
etc.  A's  regards  oil  production,  it  is  pointed 
out  that  chemistry  has  not  yet  succeeded  in 
producing  a  synthetic  product  which  can 
claim  to  be  a  substitute  for  English  oil  of 
lavender,  and  hence  the  supiply  depends 
wholly  upon  the  natural  product. 


BOOKS  RECEIVED. 

The  Chemical  Elements,  by  F.  H.  Lor- 
iNo.  Pp.  VIIL  +  171.  1923.  Messrs. 
Methuen  A  Co..  Ltd.,  86,  Essex  Street, 
W.C.     88.  6d.  net. 

Konduktomefrische  Titrationen,  von  Dr. 
I.  M.  KoLTHOFF.  Pp.  VI.  +  94.  1923. 
Verlag  von  Theodor  SteinkopfT,  Residenzstr. 
12b.  Dresden,  Blascwitz.     28.  9d. 

The  Development  of  the  Sciences,  by  Er- 
nest WiTHAM  Brown,  Henry  Andrews 
BuMSTRAi),  John  Johnston,  Frank  Schle- 
8INOER,  Herijhrt  Ernest  Greoory, 
Lorande  JiOSE  Woodruff.  Pp.  XIV.  + 
827.  1923.  Humphrey  Milford,  Oxford 
University  Press,  Amen  Comer,  E.C.4.  168. 
net. 

A  Comprehensive    Treatise  on    Inorganic 
and  Theoretical  Chemistry,  by  J.  W.  Mel- 


336 


THE  CHEMICAL  NEWS. 


NOVEMBER  23,  1923. 


LOR,  D.Sc.  Pp.  X.  +  1074.  Vol.  IV.,  1923. 
Messrs.  Longmans,  Green  &  Co.,  39,'  Pater- 
noster Row,  E.G. 4.     63s.  net. 

Elcktrochemie  Nichtwdssrujcr  Losungen, 
von  Paul  Walden.  Pp.  XL  +  515.  1924. 
HeiT  Johann  Ambrosius  Barth,  Dorrien- 
strasse  16,  Leipzig,  Germany.  Bound  28s., 
unbound  24s. 

Organische  Chemie,  von  Dr.  Rudolf 
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NOVEMBER  30,  1923. 


THE  CHEMICAL  NEWS. 


337 


THE   CHEMICAL  NEWS, 

VOL.  CXXVII.      No.  3320. 


ARE    THE  NATURAL  OliOUriNGS    OF 

THE  ELEMENTS  AND  THE  SPECTRAL 

LINES  OF  HYDROGEN  RELATED? 

Part  IV. 

By  F.  H.  Lorino. 

In  continuing  the  study — see  The  Chemi- 
cal News,  1023,  CXXVII.,  pp.  225,  257,  272, 
290 — attention  should  again  be  drawn  to 
the  planetary  bodies,  in  particular  tho 
minor  planets,  or  asteroids  as  they  are  com- 
monly called  (see  Part  III.);  as  there  is 
some  likelihood  of  the  distribution  of  these 
small  bfKlies  in  space  following  a  place  law 
similar  to  the  distribution  of  lines  in  the 
hydrogen  spectrum.  With  this  view  in 
mind  the  writer  has  examined  the  distribu- 
tion of  the  minor  planets  as  given  in  the 
Kncycloptedia  Britannica,  1911,  11th  Edi- 
tion, Vol.  XXL.  p.  717. 

In  the  accompanying  diagram,  1.  shows 
the  distribution  as  given  in  the  Encyclopir- 
dia,  »vhile  IL  (explained  below)  is  taken 
from  Sommerfeld's  "  Atomic  Structure  and 
Spectral  Lines."  p.  210.  The  lett<>rs  nnd 
brackets  are  ndded  by  the  present  writer  for 
purpf>ses  of  comparison.  It  will  be  seen 
how  cUwely  the  maxima  nnd  minima  coin- 
cide in  these  two  curves,  like  letters  indicat- 
ing similar  characteristics,  and  the  brackets 
indicate  minimum  values  and  gaps.  In  the 
diagram  (II.)  reipresenting  trie  hydrf)gen 
spectrum,  the  place  where  the  a  line  would 


fall  is  on  tHe  left  side,  and  similarly  the 
planets  occur  in  greater  orbits  as  one  pro- 
ceeds from  right  to  left,  the  base  line,  if  con- 
tinued, passing  through  tihe  sun.  In 
both  cases  the  higliest  points  occur  at  A. 

In  explanation  of  the  curve  (II.)  for  hy- 
drogen, the  following  from  Sommerfeld's 
book,  pp.  2(M),  210,  will  make  the  matter 
clearer:  "  Besides  the  Balmer  spectrum  to 
be  understoo<l  in  the  general  sense  of  equa- 
tion (5),  hydrogen  possesses  another  sipec- 
trum  of  quite  a  different  nature,  the  so- 
called  'nintnj-linrs  spectrum'  (VieUinien- 
spektrum).  In  contradiction  to  Balmer's 
'four-line'  spectrum  (called  so,  occasionally 
in  view  of  its  four  lines  Ha,  H/?  .Hy.  H8  in 
the  visible  [though  some  writers  include  the 
He  line  which  is  in  the  ultra-violet]),  the 
nuiny-lines  spectrum  is  to  be  regarded  as  a 
band  apectnim,  although  it  does  not  exhibit 
the  external  signs  of  band-spectra,  namely, 
the  accumulation  of  the  lines  at  certain 
heads  of  the  bands  and  the  repetition  of 
these  bands,  constituting  flutings.  From 
the  great  number  of  lines  observed,  how- 
ever, individual  groups  of  lines  may  be 
separated  out.  which  follow  the  laws  nf  band 
lines  (set  up  bv  Deslandres — see  Fulcher, 
Phyftikal.  Zcifschr.,  1912,  p.  1140;  Crnse, 
Anti.  d.  Phys.,  I.,  p.  87).  and  which  also 
show  themselves  to  be  related  in  that  they 
behave  similarly  in  the  Ze(^man  eff(>ct.  The 
many-lines  spectrum  arises  in  the  (Jeissler 
tube  at  lower  discharging  j)f)tentials  than 
the  Balmer  spectrum.  The  question  as  to 
the  carrier  of  the  many-lines  spectrum  is  a 
subject  of  great  controversy.  The  lati  r  ex- 
perimental investigations,  in  particular  a 
work  of  E.  Gehrcke  (Cf.  lie  port  of  fhc  Phy- 
sih(fl-Tcchn.  Reich^ansfalt.  1921)    leave    no 


A 


D 

; 

:;.:ii:iisi   :.. 

::        K. 

::;:::::^    ::::: 

:  .  :  :          .     ' 

iJiil.. 

::t::::::: 

.It     i:::.: 

— J* 

t.,   _ 

-J 

tJ 

xZj- 

338 


THE  CHEMICAL  NEWS. 


NOVEMBEK  30,  1923. 


room  for  doubt  that  its  carrier  is  the  hydro- 
gen molecule  ami  not  the  hydrogen  atom. 
Fi'om  the  point  of  view  of  thi-ory,  only  the 
Hj  molecule  can  come  into  question  at  all 
as  the  carrier  of  the  many-iines  spectrum, 
on  account  of  the  great  comj)]exity  of  the 
latter.  Actiially,  we  shall  see  in  Chapter 
VII.  that  the  modern  theory  of  band-spee- 
tra,  even  if  it  cannot  predict  quantitatively 
the  frequencies  of  the  many-lines  spectrum, 
it  can  at  least  completely  account  for  its 
general  character  quaHtatively  if  its  calcu- 
lations are  based  on  the  mass  and  size  of 
the  Ho  molecule.  To  give  the  reader  at 
this  early  stage  a  general  survey  of  the  dis- 
tribution and  density  of  the  lines,  we  give 
here  as  a  resume  of  the  empirical  data  the 
accompanying  curve  [II.]  that  has  been  cal- 
culated and  drawn  by  K.  Glitscher  (S'tt.z- 
ungsbcr.  d.  hayer.  Ahad.,  1916,  p.  125).  At 
regular  intervals  of  100  wave-numbers  it 
gives  as  ordinates  the  total  intensity  of  the 
lines  that  have  been  measured  in  each  of 
these  int^'rvals,  and  the  intensity  of  which 
has  been  estimated.  The  end-points  of  the 
ordinat<>s  have  been  connected  by  a  smooth 
curve.  This  curve  is  the  schematic  picture 
of  the  distribution  of  intensity  in  the  many- 
lines  spectrum,  and  would  be  obtained 
directly  if,  for  example,  the  action  of  the 
Balmer  lines  were  eliminated  and  the  whole 
Stpoctral  region  were  photographed  with  a 
greater  width  of  slit  and  measured  photo- 
metrically." 

Commenting  on  the  above,  it  will  be  seen 
that  the  development  of  this  study  is  in 
general  harmony  with  the  foregoing  deduc- 
tions ;  and  the  inference  is  that  the  law  of 
distribution,  whether  it  involves  electrons. 
atoms,  molecules,  minor  planets,  or  planets, 
is  of  common  origin;  and,  as  was  already 
stated  in  Part  II.,  the  law  of  the  part  is  the 
law  of  the  whole.  Strictly  speaking,  per- 
haps one  should  say  that  the  law  of  the  part 
is  translatable  into  the  law  of  the  whole,  or 
vice  versa. 

This  idea  may  seem  strange  to  many  who 
have  not  followed  the  trend  of  modern  re- 
search in  directions  that  point  in  some  ways 
to  this  conclusion. 

Now  to  show  here  this  "trend,"  the  fol- 
low^ing,  taken  from  the  EncyclopcFdia  Tlri- 
fannica,  supplement,  1922,  vol.  XXXII.,  p. 
561,  will  suffice  :  "  Spectra  and  the  Periodic 
Table. — Attention  is  being  drawn  more  and 
more  to  the  relation  of  the  spectrum  to  the 
periodic  table  of  the  elements.  While  it 
cannot  be  said  that  the  relation  is  known 
with  any  approach  to  completeness,  a  num- 
ber of  important    facts    have    b^'en    noted 


which  may  ultimately  prove  of  great  service 
in  the  interpretation  of  the  table.  It  has 
long  been  know^n  that,  when  doublets  or 
triplets  occur  in  the  spectra,  the  wave- 
number  setparations  of  their  components 
(which  are  constant  in  the  sharp  and  diffuse 
series)  are  approximately  propoi-tioual  to 
the  squares  of  the  atomic  weights  of  the 
elements  producing  the  spectra — so  long  as 
those  elements  belong  to  the  same  family 
group.  The  Zeeman  effect  also  is  generally 
the  same  for  lines  of  corresponding  series 
in  the  spectra  of  elements  belonging  to  the 
same  group.  But  perhaps  the  most  com- 
prehensive connection  of  spectra  with  the 
periodic  table  is  established  by  the  '  dis- 
placement law  '  of  Ko&sel  and  Sommer- 
feld  {Verh.  Deut.  PJujs.  Gesell,  1919).  It 
has  been  observed  that  the  'complexity'  of 
the  lines  of  a  series — i.e.,  their  character  as 
singlets,  doublets,  or  triplets — is  constant 
throughout  a  group,  but  varies  from  one 
group  to  another.  The  displacement  law 
states  that,  when  an  element  is  ionised,  the 
enhanced  series  takes  on  the  same  type  of 
comiplexity  as  the  arc  series  produced  by  the 
element  to  the  left  {i.e.,  in  the  preceding 
group)  in  the  periodic  table.  It  is  assiuued 
that  electrons  arrange  themselves  round  the 
nucleus  in  rings,  and  that  spectrum  pheno- 
mena are  produced  by  electrons  in  the  outer 
ring.  If  the  outer  ring  contains  an  odd 
number  of  electrons,  the  spectrum  will  show 
triplets  and  singlets.  In  the  periodic  table 
each  element  contains  one  outer  electron 
more  than  its  neighbour  in  the  preceding 
group,  while  a  grouip  consists  of  elements 
having  the  same  number  of  electrons  in  the 
outer  ring.  It  follows  that  the  removal  of 
an  electron  from  an  element  [atom]  will 
make  the  outer  ring  similar  to  that  of  the 
immediate  forerunner  of  the  element  in  the 
table,  and  so  make  the  enhanced  lines  of 
the  first  element  of  the  same  type  of  com- 
plexity as  the  arc  lines  of  the  second.  Re- 
moval of  a  second  electron  would  restore 
the  arc  type  of  complexity,  for  the  number 
of  outer  electrons  would  again  become  odd 
or  even,  as  the  case  might  be.  A  second 
ionisation  is  difficult  to  bring  about  in  most 
cases,  but  with  silicon  it -is  probable  that 
one,  two,  and  even  three  electrons  have 
been  removed,  step  by  step,  thus  making 
possible  four  distinct  spectra.  These  ap- 
pear to  show  the  alteration  of  complexity 
required  by  the  displacement  law.  The 
table  here  gives  the  types  of  series  pro- 
duced by  the  neutral  and  ionised  elements 
of  the  various  groups,  so  far  as  they  are 
known  at  present," 


^ 


NOVEMBER  30,  1923. 


THE  CITBMICAL  NEWS 


389 


Group          VIII.  or  O.         I.                II.             III.  IV.  V.            VI. 

Arc.: N.C.A.                 D.  T.  &  S.         D.  T?           D?            T. 

Enhanced   (?)                 N.C.A.            D.        T.  k  S.  D?  T?            D? 

N.C.A.  =  not  completely  analysed.  S  =    singlets.     D  =  doublets.     T  =  triplets. 


VII. 

(?) 
T? 


"  The  spectra  of  the  liip;her  groups  are 
much  more  complex  than  those  of  the  lower 
ones.  Their  series,  if  they  possess  any,  are 
possil)ly  of  a  different  type  from  those  with 
which  we  are  familiar.  The  displacement 
law,  however,  suggests  that;  by  repeatt^d 
ionisations,  series — and  tliorefore  terms — 
might  be  detected  in  each  spectra,  of  the 
same  kind  as  those  of  the  j^upa  of  ele- 
ments on  the  left.  But  since,  with  each 
successive  ionisation,  the  torm  constant,  N, 
is  multiplied  in  the  ratio  1  :4:9:ir),  etc., 
the  chief  series  linos  might  tend  rapidly  to 
approach  the  far  ultra-violet  and  become 
dirticult  to  observe." 


Summary  of  Parts  III.  and  IV. 

It  was  shown  that  the  rarlial  distribution 
of  the  planets,  taken  in  mean  distances 
from  the  sun  in  millions  of  miles  divided  by 
10,  corresiponded  for  a  consecutive  series  of 


planets  with  the  a,  P,  y,  8,  e  group  numbers 
of  the  periodic  table,  which  can  be  derived 
from  the  five  correspondingly  lettered  lines 
of  the  Balmer  spectrum  of  hydrogen. 

It  is  here  shown  that  the  distribution  of 
the  minor  planets  in  groups  follow  some- 
what closely  the  line-intensity  curve  of  thi' 
many-lines  spectrum  attributed  to  H,  as 
the  carrier;  and  these  studies  seem  to  show 
that  the  law  of  the  part  can  be  transformed 
into  the  law  of  the  whole  or  vice  vertta,  so 
that  the  law  of  distribution,  whether  it  in- 
volves electrons,  atoms,  molecules,  minor 
planets,  or  planets,  is  of  common  origin ; 
and  underlying  all  this  iphenomena  there 
seems  to  be  something  that  may  be  referred 
to  a.s  a  "  plac<?  principle."  It  is  of  course 
known  that  all  the  minor  planets  have  not 
been  discovered,  their  number  being  of  the 
order  of  1,000,  but  a  sufficient  number  are 
known  to  show  a  characteristic  type  of  dis- 
tribution as  indicated  bv  the  diagram. 


INDIGOID    DYESTUFFS. 

Part  I. 
By  K.  F.  Hunter,  1  .C.8. 

S(HTie  months  ago  (see  The  Chemical 
ScicH,  .July  13,  this  Vol.  |),p.  17-18).  an 
article  was  j)ul)lished  on  "  Sulphur  Dyes." 
It  is  now  propr>sed  to  deal  in  something  of 
the  same  way  with  some  of  the  other  im- 
portant classes  of  synthetic  colouring  mat- 
ters, and  the  first  group  to  be  dealt  with  is 
the  indigoid  dye  family.  It  is  not  int<>nded 
to  deal  exhaustively  vvith  the  subject,  but 
only  a  few  standard  compounds  will  be 
d»alt  with.  The  practical  side  of  the  pre- 
parations will  not  be  considered,  since  it  has 
been  v(^ry  fully  dealt  with  in  the  last  two 
chapters'  (»f  Thorpe  and  Ingold's  "  Vat 
Colours." 

lii'fore  proceeding  to  the  subject  proper, 
it  might  be  of  interest  to  give  the  historical 
side  of  indigoid  dyestuffs  some  considera- 
tion. 

The  famous  Tynan  purple,  or  rather 
"  the  purple  of  the  ancients,"    is  the  only 


the  coasts  of  Tyre. 
prized    of    colours, 
emblem  of  royalty, 
services  of  religion. 


vat  dye  \\4iich  we  have  records  of  for  some 
fifteen  hundred  years  before  the  ('hristian 
era.  The  colour  was  obtained  from  an  ex- 
cretion from  certain  shell  fisli  found  along 
This  dye  was  the  most 
and  regarded  as  an 
and  fit  for  the  highest 
By  combining  the  in- 
fusions of  diflf<'rent  kinds  of  shell  fish,  the 
Phcpnicians  were  able  to  vary  the  colour, 
some  shades  tending  toward  red  and  .some 
toward  blue,  the  two  shades  most  men- 
tifmed  in  the  English  versions  of  the  Old 
Testament  being  descrilx^d  as  "blue"  and 
"  purple."  Accounts  of  the  manufacture 
nf  this  substance  are  given  by  various  T^atin 
writers,  among  whom  we  might  mention 
Cassidorus,  Pollux,  Vergil,  Lucretius,  and 
IMiny.  Probably  the  colour  was  introduced 
into  Europe  about  500  n.c.  The  Greeks 
paid  considerable  attention  to  colours,  the 
Romans  obviously  obtaining  their  know- 
ledge of  colouring  matters  from  th(^  Greeks. 
During  the  Middle  Ages,  the  knowledge  ot 
purple  was  lost,  save  in  the  writings  on  the 
ancients.       Canniparius.  writing  in  Italy  at 


340 


THE  CHEMICAL  NEWS. 


NOVEMBEli  30,  1923. 


the  beginning  of  the  17th  century,  speaks 
of  the  purple  as  being  known  only  through 
ancient  writings. 

Cole  made  observations  on  the  subject  in 
the  Phil.  Trans.  1685.  Reaumua-  in  1710  (in 
Mem.  de  VAcad,  Royale  des  Sciences,  1711) 
made  an  observation  on  a  number  of  purple- 
giving  molluscs  on  the  coast  of  Poitou. 
i)uhamel,  in  1736,  recorded  similar  observa- 
tions in  the  same  scientific  paper.  Ban- 
croft made  some  investigations  on  the  sub- 
ject in  1813.  Schunk  (1879)  investigated 
the^-substanoe.  Friedlander  took  up  the 
subject  in  1907.  He  isolated  the  colouring 
matter,  preparing  1.4  gm.  of  pure  sub- 
stance from  the  glands  of  12,000  specimens 
of  the  Murex  hrandaris.  The  substance 
was  insoluble  in  alcohol,  ether,  ligroin, 
chloroform,  acetic  acid  and  acetone ;  soluble 
with  difficulty  in  hot  pyridine,  in  which  it 
dissolved  to  give  red  violet  solutions.  Ana- 
lysis indicated  the  formula  Cj6HgBr2N202. 
This  represents  2  :8-dibromoinderubins  and 
1 :6-<iilbromo  indigos.  The  substance  was 
found  to  bo  identical  with  6 : 6'  dibromo- 
indigo  previously  synthesised  by  Sach's  and 
Kemp  from  p  bromo  o  nitro  benzaldehyde : 


BrC„H3 


/CO  /CO  V 

\^fH  /  \NH/ 


6:6'  Dibromoindigo. 

We  now  come  to  the  question  of  natural 
indigo.  From  the  earliest  times  the  indigo 
plant  was  cultivated  and  the  indigo  ex- 
tracted from  it  by  the  Hindus.  Its  prepara- 
tion is  described  in  old  Sanskrit  scripts, 
and  these  scripts  show  that  its  mode  of  pre- 
paration scarcely  underwent  any  alteration 
during  the  centuries  preceding  the  discovery 
of  India  by  the  Dutch. 

From  India  the  knowledge  of  indigo 
spread  along  the  trade  routes  through  Per- 
sia to  Syria  and  Arabia  and  thence  to 
Egypt.  The  Egyptians  used  indigo  exten- 
sively. This  is  revealed  by  analysis  of 
mummy  cloths.  The  knowledge  of  indigo 
reached  China  about  700  a.d.  From  Egypt 
the  knowledge  passed  to  Greece,  and 
thence  to  Rome.  During  the  dark  ages  be- 
tween 50O  to  1200  .\.D.,  the  knowledge  was 
almost  lost  in  Europe  save  in  a  few  Italian 
cities.  From  Italy  the  knowledge  spread  to 
France  and  Flanders  during  the  thirteenth 
century.  The  Flemish  and  Italian  dyers 
using  indigo  in  the  fourteenth  century  un- 
fortunately excited  the  enmity  of  the  older 
society  of    Black    Dyers.      The    feud    con- 


tinued well  into  the  sixteenth  century,  and 
the  Black  Dyers  were  so  successful  that  in- 
digo was  prohibited  as  being  a  newly  in- 
vented, deceitful,  eating  and  corrosive  dye. 
The  Dutch,  after  1602,  however,  began  to 
import  large  quantities  of  indigo,  and  the 
superiority  of  this  caused  it  to  take  the 
place  of  the  woad  industry  to  an  enormous 
extent.  In  France  the  use  of  indigo  was 
allowed  when  mixed  with  a  hundred  times 
its  weight  of  woad  in  the  "  woad  vat." 

The  principal  plants  cultivated  for  the 
{)urpose  of  obtaining  indigo  belong  to  the 
genus  Indigofera,  and  have  been  grown  in 
India,  China,  Japan,  Java  and  the  Philli- 
pine  Islands,  Central  America  and  the  West 
Indies,  Brazil  and  Madagascar. 

The  principal  Sipecies  are :  — 

Sumatrana, 

Acreta, 

Paucifolia, 

Tinchloride, 

Secundiflora, 

Dispenna,  and 

Argentea. 

The  colour-forming  principle  in  the  indigo- 
fera is  a  glucoside  of  indoxyl,  indican, 
which,  by  the  action  of  enzyines  present  in 
the  plant,  is  hydrolysed,  yielding  free  in- 
doxyl. This,  by  atmospheric  oxidation, 
proceeds  to  indigo.  The  manufacture  of  in- 
digo (natural)  hence  consists  of  the  two 
essential  operations :  firstly,  the  steeping  of 
the  plant  in  water  when  fermentation  takes 
place  and  .hydrolysis  of  the  glucoside  fol- 
lows; secondly,  the  precipitation  of  the 
colouring  matters  from  the  solution  of  in- 
doxyl by  the  action  of  air.  The  chemicals 
used  in  the  manufacture  of  natural  indigo 
have  three  purposes :  first,  to  purify  the 
water  for  steeping;  secondly,  as  an  adjunct 
for  steeping;  and  Lastly,  in  the  oxidising 
process. 

Natural  indigo  contains,  as  well  as  indigo 
and  indirubin,  traces  of  uncondonsed  isatin, 
a  yellow  colour  which  has  been  isolated  and 
identified      as     the     tetrahydroxy    flavone ; 
ksempborol    and  a  number  of  brown  amor- 
phous bodies  which  dissolve    in  alkaline  re- 
ducing   solutions    but    cannot    be    used    to 
colour  cotton  fibre.     There  is  also  present  a 
horn-like  substance  known  as  indigo  gluten, 
and  certain  mineral  matter.      The  most  im- 
portant   constituent    of     the    natural    sub- 
stance from  the  point  of  view  as  a  dye  is  in- 
digo or  indigotin,    the  dyeing  properties    of 
which  are  due  to  its    capability    of    passing 
into  a  leuco  compound,  "  indigo  white,"  in 


NOVEMBEK  30,  1923. 


THE  CHEMICAL  NEWS. 


341 


solution  when  treated  with  alkaline  reducing 
agents.  In  alkaline  solution  this  pene- 
trates the  fibres  of  cotton,  and  is  reoxidised 
to  indigo  by  atmospheric  oxidation  dyeing 
the  fibre.  Indirubin  undergoes  similar  con- 
VL-rtiion  with  alkaline  reducing  agents. 

We  now  come  to  consider  one  of  the  most 
important  questions  of  to-day,  viz.,  syn- 
thetic indigo.  In  1841,  Erdmann  and 
Jjuurcnt  oxidised  indigo  to  isatin.  Laurent, 
by  chloriuatiou  and  bromiuation  of  this,  iso- 
lated mono  and  dichloroisatin  and  dibromo- 
isatiu.  Bayer  commenced  his  researches  on 
isatin  in  1865  in  conjunction  with  Knop, 
attempting  to  reduce  the  substance  to  indi- 
go. The  attempt  failed,  but  resulted  in  the 
isolation  of  dioxindole  and  oxindole.  He 
regarded  oxindole  as  a  pbenol  of  a  substance, 
CgH^ :  C2H3N,  to  which  he  gave  the  name 
indole,  and  reduced  oxindole  to  indole  in 
1866  by  passing  the  vapour  of  oxindole  over 
heated  zinc  dust. 

In  1878  Bayer  synthesised  isatin  by  tlie 
scheme  suggested  originally  by  Kekuie. 
Starting  with  phenylacetie  acid,  he  con- 
verted this  into  successively  nitrophenyl- 
acetic  acid,  aminophenyl  acetic  acid,  oxin- 
dole, nitro  oso  oxindole,  amino  oxindole. 
and  finally  this,  with  ferric  chloride,  into 
isatin. 

Indigo  had    been  obtain(>d    in   traces    by 

Eimnerling  by  distilling  o  uitro  aceto  fihe- 
uone  with  zinc  dust  and  scxla  lime.  Tins 
reaction  was  shown  by  Bamberger  to  de- 
pend on  tiie  intermediate  reduction  pro- 
duct methylanthranol.  The  first  rational 
synthesis  of  indigo  was  accomplished  when 
Bayer  synthesised  isaoin.  for  Bayer  and 
Rmmeriing  had  sht  wn  in  1870  that  ieatin 
can  be  reduced  to  indigo  by  treatment 
with  PCI3.  followed  by  contact  with  atmos- 
phere. This,  however,  was  improved  a 
year  after  the  isatin  syntlu'sis  by  Bayer, 
who  prejjared  isatin  chloride  by  the  action 
of  [)h()sphorus  pentachlon'de  on  isatin,  and 
reduced  this  by  means  of  hydriodic  acid  to 
indigo  in  acetic  acid  solution. 

A  year  later,  Bayer  obtained  indigo  from 
f>  nitro  einnamic  acid  by  the  following 
scheme  :  By  the  action  of  KOH  on  the  di- 
brumide  he  obtained  o  nitro  phenyl  ipropio- 
lic  acid.  This,  on  heating  with  alkalis,  is 
converted  into  isatin,  and  by  heating  with 
alkalis  in  the  presence  of  glucose  is  con- 
verted in<o  indigo.  Also,  the  ethyl  ester  of 
o  nifro  plnnyl  propiolic  acid,  on  treatment 
with  CO  If  SOj,  proceeds  to  the  isotrieiic 
ester  of  isatogenic  acid.  This,  on  hydrolv- 
<{<.  j)M<«es  info  the  acid  and  (ben  info  i^.ifin 


and  on  reduction  yields  the  ethyl  ester  of 
indoxylic  acid.  The  free  acid,  on  heating, 
loses  COo  and  passes  into  indoxyl,  and  this, 
on  oxidation,  passes  into  indigo. 

(To  he  continued.) 


PliOCEEUlMlS  AND  XOTICES  OF 
SOCIETIES. 


THE  KOYAL  SOCIETY. 

TlIURSD.W,   NoVE.MBER  22. 

Special  General  Meeting  to  Consider 
THE  Annual  Report  of  Council. 

Papers  read :  — 

F.  Si.MEoN,  The  Carbon  Arc  Speclruni  m 
the  Extreme  Ultra-violet. — 7/.  Conununi- 
cated  by  Trof.  A.  W.  Porter,  F.H.S. 

The  results  may  be  summarised  as  fol- 
lows :  — 

(1)  The  spectrum  of  the  carbon  arc  in 
vacuum  extends  as  far  in  the  extreme  ultra- 
violet us  that  of  the  spark,  with  the  excej)- 
tion  of  a  very  faint  line  at  360.5  A,  and 
about  25  lincH  have  been  added  to  the  arc 
spectrum  an  already  recorded. 

(2)  The  L  series  of  carbon  can  be  excited 
by  a  potential  of  bi'tween  30  and  40  volts. 

(8)  Reasons  are  given  for  thinking  that  a 
number  of  lines  in  the  carbon  spectrum  are 
true  "arc"  lines. 

(4)  Providing  the  grating  will  give  radia- 
tion in  the  short-wave  region,  the  same 
technique  suffices  to  photograph  the  spec- 
trum from  185^)  A  to  870  A.  , 

H.  J.  Gouon  and  I).  Hanso.n,  D.Sc,  77»f 
liehaviour  of  McfuU  Hiibjrcied  fo  Hepcdtcd 
StrcHHVH.  CoMUMunicated  bv  Sir  Joseph 
Pefavel.  F.H.S. 

The  subject  of  the  paper  is  the  effect  of 
static  and  alternating  stresses  on  the  micro- 
structure  of  metals,  the  main  object  of  the 
research  being  to  determine  whether  the 
crystalline  .structure  of  a  metal  can  be 
aiffected  when  »iul)jt(cted  to  ranges  of  stress 
lens  than  the  limiting  range  of  stress 
(fatigue  range).  It  is  shown  that  with 
*'Armco"  iron,  mild  steel,  and  copper,  crys- 
talline "slip"  occurs  at  ranges  of  stress  con- 
siderably less  th.in  (he  fati;;ne  range. 

In  exi)lana(i(>n  <>\  this  result,  it  is  sug- 
gested that  metals  can  be  "strain-hardened" 
under  (lie  action  of  alternating  stresses,  as 


342 


THE  CHEMICAL  NEWS. 


NOVEMBER  30,  1923. 


well  as  under  static  stresses;  it  is  further 
suggested  that  fracture  occurs,  in  a  metal 
subjected  to  alternating  stresses,  when  a 
certain  limiting  strain  far  the  material  is 
exceeded. 

The  paper  is  divided  into  the  following 
sections :  — 

(1)  Preliminary  Mechanical  Tests. 

(2)  Study  of  the  Microstructure  under 
Static  Stresses. 

(3)  Study  of  the  Microstructure  under 
Alternating  Stresses. 

(4)  Discussion  of  the  Kesults  with  rc- 
sgect  to  other  known  Phenomena  of 
the  Fatigue  of  Metals. 

W.  SucKSMiTH  and  L.  F.  Bates,  On  a 
Null  Method  of  Measuring  the  Gyro- 
Magnetic  Ratio.  Conununicated  by  Prof. 
A.  P.'Chattock,  F.R.S. 

A  new  method  is  described  of  determining 
the  gyro-magnetic  ratio,  and  results 
obtained  with  it  are  given.  As  in  the  ordi- 
nary resonance  method,  the  specimen,  sus- 
pended vertically  by  a  fine  wire  along  the 
axis  of  a-  helix,  is  magnetised  by  an  alter- 
nating current  of  same  frequency  as  natu- 
ral frequency  of  the  system ;  but  the  result- 
ing resonance  amplitude  is  reduced  to  zero 
by  a  series  of  imipulses  timed  to  oppose 
those  due  to  gyro-magnetic  effect. 

As  no  measurement  of  magnetic  moment, 
frequency,  or  damping  is  involved,  a  con- 
siderable gain  in  precision  is  obtained.  The 
method  is  independent  of  time-lag  in  mag- 
netisation, and  so  can  be  applied  to  Heusler 
alloys. 

The  following  table  contains  mean  values 
of  ratio  obtained  for  iron,  nickel  and  Heus- 
ler alloys  :  — 
*  Metal.  K. 

Iron       0.503 

Nickel        0.501 

Heusler  alloys  0.501 

The  number  is  in  every  case  0.5  within 
the  limits  of  experimental  error,  and  corro- 
boration is  thus  afforded  of  measurements 
of  the  ratio  recently  carried  out  in  this  Uni- 
versity by  an  independent  method  by 
Messrs.  Chattock  and  Bates. 

J.  H.  Shaxby,  Studies  in  Brownian  Move- 
ment.— II.  The  Determination  of  Avo- 
gadro's  Number  frovi  Observations  on  Bac- 
teria (Cocci).  Communicated  by  Prof.  S. 
W.  J.  Smith,  F.R.S. 

A  determination  of  Avogadro's  number 
by  the  method  of  measuring  the  displace- 
ments, due  to  their    Brownian  movements, 


of  small  spheres  suspended  in  water,  was 
carried  out  with  cocci.  Their  surfaces  may 
fairly  be  supiposed  to  be  "wetted"  so  that 
there  is  no  slip  between  the  water  imme- 
diately adjacent  and  the  spheres  them- 
selves, and  the  resistance  w  hioh  might  arise 
from  electrical  sources  depending  on  slip  is 
avoided.  Precautions  were  taken  that  no 
mobements  other  than  Brownian  should  be 
recorded.  The  value  of  N  thus  found,  from 
the  large  number  of  observations  made  on 
Staphylococcus  albus,  is  0.08  x   lO^''. 

Papers  read  in  title  only  :  — 

H.  Haktkipge,  Sc.D.,  and  F.  J.  W. 
RouGHToN,  The  Kinetics  of  Hcemoylobin. — 
//.  Communicated  by  Prof.  J.  N.  Langlcy, 
F.R.S. 

A.  F.  A.  Young,  The  Thermionic  and 
Photo- Electric  Properties  of  the  Electro- 
positive Metals.  Coumiunicated  by  Prof. 
O.  W.  Richardson,  F.R.S. 

0.  F.  T.  Roberts,  The  Theoretical  Scat- 
tering of  Smoke  in  a  Turhulent  Atmos- 
phere. Communicated  by  Dr.  G.  C.  Simp- 
son, F.R.S. 


THE  ROYAL  SOCIETY  OF  ARTS. 

On  Monday,  November  19,  the  Cantor 
Lecture  (II.),  entitled  The  Cultivation  of 
Cocoa  in  British  Tropical  Colonies,  was 
given  by  Samuel  Henry  Da  vies,  M.Sc, 
F.I.C. 

On  Wednesday,  November  21,  at  the 
Ordinary  Meeting,  a  paper  entitled  For- 
geries of  Ancient  Stained  Glass  was  read  by 
J.  A.  Knowles.  The  Right  Hon.  the  Earl 
of  Crawford  and  Balcarres,  K.T.,  P.C, 
F.S.A.,  presided. 

On  Tuesday,  November  27,  at  the  meet- 
ing of  the  Dominions  and  Colonies  Section, 
a  paper  entitled  The  West  Indie.'i  was  read 
by  the  Viscount  Burnham,  C.H.,  LL.D., 
D . LiTT . ,  M . A .  The  Lord  Askwith ,  K .  C . B . , 
K.C.,  D.C.L.,  Chairman  of  the  Council, 
presided. 

On  Wednesday,  November  28,  at  the  Or- 
dinary Meeting,  a  paper  entitled  The,  Effect 
of  Sun,  Sea  and  Open  Air  in  the  Treat nirni 
of  Disease  was  delivered  by  Sir  Henhy  John 
Gauvain,     M.A.,    M.D.,     M.Ch.,    Medical 


NOVEMBER  30,  1923. 


THE  CHEMICAL  NEWS. 


343 


Superintendent  of  the  Ltnd  Mayor  Treloar 
Cripples'  Hospital.     Lord  Dawson  of  Penn, 
G.G.V.O.,      K.C.M.G.,        C.B.,        ^^  ^^ 
F.R.C.P.,  M.R.C.S.,  presided. 


M.D., 


SOCIETY  OF  PUBLIC  .\NALYSTS  AND 
OTHER    ANALYTICAL  CHEMISTS. 

The  no.xt  meeting  of  tlie  Society  will  he 
held  on  Wednesday,  December  5,  at  the 
Chemical  Society's  Rooms,  nt  8  p.m. 

The  following  papers  will  be  read :  — 

CrystaUine  Bromides  of  Linseed  Oil,  by 
Hakold  Toms,  M.Sc.  (under  the  Analytical 
Investigation  Scheme). 

The  Plea  for  Siandardisafion,  by  M.  S. 
Salamon,  B.Sc. 

Note  on  the  Estimation  of  Chromium,  bv 
Hubert  T.  S.  Britton,  M.Sc,  F.I.C. 

The  Colori metric  Estimation  of  Lead  in 
Cream  of  Tartar,  by  R.  L.  Andbbw. 


PHYSICAL    SOCIETY  OF  LONDON. 

A  meeting  of  the  Society  was  held  on 
Thursday,  November  29. 

A  joint  discussion  with  the  Institution  of 
Electrical  Engineers  took  place  on  the  sub- 
ject of  "  Fioud  Speakers  for  Wireless  and 
other  Purposes." 

First  Sessiok  of  Discussion. 

General  Principles  involved  by  the  Accu- 
rate Reproduction  of  Sound  by  Means  of  a 
Loud  Sprakrr.  by  Prof.  \.  O.  Rankink. 

Thcdiji  of  Loud  Speaker  Ifcmyn.  (^Somc 
factors  affecting  faithful  and  efl5cient  repro- 
(hiction.  Causes  of  incftieiency.  Economy 
in  amplifiers  resultant  on  improved  effi- 
ciency. With  demonstration).  By  Dr.  L. 
C.  PococK. 

The  Electrical  Side  of  the  Phenomena  of 
hou^- frequency  AvipUficalion  in  Wireless 
CirouitH.  Causes  of  distortion  and  means  of 
elimination.     Demonstration.     By  Prof.  ('. 

]..    F(»UTKStUE. 


The  Problem  of  Disiorfwn  in  the  Hepro 
duction  of  Sound  by  the  Gramophone,  b^ 
Mr.  H.  L.  Porter. 

General  Discussion, 


bj^ 


Second  Session  of  Discussion. 
Distortion  in  Atidio-Circuits.  Relative 
importance  of  various  frequencies.  Demon- 
stration of  eflfeel  of  elimination  of  various 
frequency  bands.  Demonstration  ol'  nodes 
and  anti-node-  in  .ai  audiLoiium.  Methods, 
direct  and  indirect,  of  Measurement  of  the 
Efficiency  and  Faithfulness  of  Loud-Speah- 
iny  Telephones.  By  Mr.  E.  K.  Saxueman, 
B.Sc. 


The  Overtones  of  the  Dutphraym  of  a 
Telephone  Receiver.  Their  effect  in  causing 
distortion.  With  Demoustrafion.  B\  Prof. 
J.  T.  Mc'Greuor-Morris  and  Prof.  E.  Mal- 

LKTT. 


Architectural  Acoustics.  Its  relation  to 
Loud  Speaker  operation.  By  Mr.  G.  A. 
Sutherland,  M.A. 

Some  Directions  of  Improvement  of  the 
Loud-Speakiny  Telephone.  Action  of  the 
Frenophone.  With  Demonstration.  By 
Mb.  S.  G.  Brown,  F.R.S. 

The  Characteristics  of  the  Gaumont- 
Jjumiirc  Loud  Speaker.  With  Demonstra- 
ticm.     By  Capt.  P.  P.  Eckkrsley. 

General  Discussion  (continuation  of). 

Visits  wore  arranged,  by  kind  permission 
of  the  British  Broadcasting  Company,  to 
their  Studio  on  Savoy  Hill. 

Proceedings  at  the  meeting  on  November 
9,  Alexander  Russell,  M.A.,  D.Sc,  in  the 
chair:  — 

A  Demonstration  of  Experiments  on  the 
Reproduction  of  Vowel  Sounds  wa.s  given 
by  Sir  Richard  Paget. 

The  author  found  that  each  of  the  vowel 
sounds  comiprises  two  component*  lying 
within  two  ranges  two  or  three  semitones  in. 
extent,  the  two  ranges  being  characteristic 
of  the  vowel  and  si'parated  by  an  interval  of 
from  three  tones  to  three  octaves,  accord- 
ing to  the  nature  of  the  vowel.  The  devices 
shown  for  roprrKlueing  vowels  consisted  in 
their  simplest  fonn  of  pairs  of  resrmators 
tuned  to  the  toTies  eharaetoristic  of  various 
vowels  and  <f>  arnmged  that  the  sf>und  from 


344 


THE  CHEMICAL  NEWS. 


NOVEMBER  30,  1923. 


an  artificial  larynx  or  squeaker  could  be 
passed  through  them  in  series  or  in  parallel. 
Certain  vowels  in  which  the  upper  reso- 
nance is  a  harmonic  of  the  lower  canl  a  so 
be  produced  by  means  of  a  single  resonator. 
Consonants  are  found  to  depend  in  part  on 
characteristic  resonances  and  their  rate  of 
change,  and  in  part  on  the  release  of  air 
pressure  in  the  compound  resonators,  some 
of  which  were  caused  to  emit  words  by  open- 
ing and  closing  their  orifices  suitably  by 
hand.  The  author,  in  illustration,  an-anged 
his  hands  to  form  a  double  resonator  in  imi- 
tation of  the  human  mouth,  and  passed 
through  them  the  sound  from  a  squeaker 
representing  the  larynx.  By  manipulating 
the  fingers  and  hands,  he  was  able  to  pro- 
nounce easily  recognisable  sentences. 
A  discussion  followed. 

A  paper  on  Scattering  of  Light  by  Carbon 
Dioxide,  Nitrous  Oxide,  and  some  Organic 
Vapours,  by  A.  L.  Narayan,  M.A.,  A. Inst. - 
P.,  was  read  by  Lord  liayleigh  in  the  ab- 
sence of  the  author. 

It  has  been  shown  by  Lord  Rayleigh  that 
the  light  scattered  laterally  by  the  mole- 
cules of  gases  is  not  completely  polarised, 
but  contains  a  com.ponent  polarised  at  right 
angles  to  the  direction  which  is  predicted 
by  theory  for  a  spherical  molecule,  the  twf> 
components  being  conveniently  referred  to 
as  the  "wrong"  and  the  "right"  compo- 
nents respectively.  The  author  was  able 
to  employ  sunlight  for  illuminating  gases 
and  vapours,  which  he  enclosed  in  a  joint- 
less  tube.  The  strengths  of  the  components 
were  compared  both  by  direct  photometry 
and  by  photometric  comparison  of  their 
effects  on  a  photographic  plate,  improved 
thermo-electric  apparatus  being  employed 
for  the  latter  purpose.  Lord  Rayleigh's  re- 
sults were  confirmed,  particularly  in  the 
case  of  CO2  and  NgO.  It  is  suggested  that 
the  difference  in  the  scattering  power  of 
these  two  gases  is  contrary  to  the  predic- 
tion of  the  Lewis-Langmuir  theory  of  the 
atom . 

Discussion. 
Prof.  A.  O.  Rankine  said  that  his  experi- 
ments, referred  to,  merely  showed  that  the 
collision-area  of  the  molecules  in  question 
varies  with  orientation  in  a  manner  consis- 
tent with  the  Lewis-Langmuir  theory;  it 
may  be  possible  to  invent  other  molecular 
models  with  which  tHc  experimental  results 
will  be  equally  consistent.  These  results, 
however,  are  relevant  only  to  the    external 


form  of  the  molecules,  for  viscosity  may  be 
presumed  to  be  unaffected  by  the  distribu- 
tion of  mass  between  the  nuclei.  Thus  the 
ma-sses  of  the  nuclei  would,  according  to 
theory,  be  8,  6,  and  8,  in  CO2,  and  7,  8,  and 
7,  in  N2O;  and  since,  as  Sir  J.  J.  Thomson 
has  suggested,  these  molecules- would  have 
different  moments  of  inertia  though  their 
masses  would  be  equal,  it  might  be  expected 
that  they  would  differ  in  tiieir  polarising 
effect. 

Mr.  J.  Guild  said  that  in  the  measure- 
ment of  such  small  intensities  of  light  a 
large  experimental  error  must  be  expected, 
so  that  the  agreement  between  the  author's 
and  Lord  Rayleigh's  results  was  much  bet- 
ter than  might  have  been  expected.  Parti- 
cularly in  the  case  of  vatpours,  where  the 
percentage  of  the  "wrong"  component  is 
small,  the  Nicol  system  is  beiug  used  under 
the  most  disadvantageous  conditions, 
which  are  calculated  to  evoke  various  de- 
fects even  in  the  most  perfect  apparatus. 
As  regards  the  photographic  method  of 
photometry,  would  not  the  actinic  effects  of 
the  "right"  and  of  the  "wrong"  oompo- 
nents  be  different  ?  In  the  case  of  the  Tyn- 
dall  effect  due  to  larger  aggregates,  the  in- 
tensities of  the  corresponding  components 
are  resipeetively  proportional  to  the  inverse 
fourth  and  the  inverse  eighth  powers  of  the 
wave  length,  so  that  the  "wrong"  compo- 
nent would  be  much  bluer  than  the  "right" 
and  have  a  disproportionate  effect  on  the 
plate.  The  author  mentions  tlTat  many  iri- 
<lescent  colours  in  Nature  are  due  to  scatter- 
ing of  light.  It  is  interesting  to  note  that 
many  other  common  colours  have  been 
traced  to  the  same  cause,  e.g.,  the  blues  of 
the  sky,  of  birds'  feathers,  and  of  the  eyes 
of  blondes. 

Lord  Rayleigh,  in  reply,  said  that  he  did 
not  suppose  the  authors  of  the  Lewis- 
Ijungmuir  theory  regarded  their  model  as  a 
real  representation  of  the  atom,  consistent 
with  all  the  latter's  properties.  It  is  rather 
a  schematic  diagram  ada,pted  to  summarise 
certain  groups  of  properties,  and  might  well 
be  inconsistent  with  others.  The  chromatic 
difference  between  the  components  in  the 
Tyndall  effect,  though  not  cofpletely  ac- 
counted for,  is  a  fact;  but  the  effect  is  not 
comparable  with  that  under  discussion,  the 
smallest  particles  which  show  the  Tyndall 
effect  being  large  compared  with  molecules. 
That  there  is  no  substantial  chromatic 
effect  on  the  photographic  plates  is  proved 
by  the    agreement    of    the    results    of    the 


NOVEMBEB  30,  1923. 


VHB  CHEMICAL  NEWS. 


345 


photographic  method  with    those  of    direct 
photometry. 

On  the  Measurement  of  the  Surface  Ten- 
sion of  a  Small  Quantity  uf  Liquid,  by 
Allan  Ferguson,  M.A.,  D.bc. 

If  a  small  quantity  of  liquid — one  cubic 
millimetre  or  less — be  placed  in  a  vertical 
capillary  tube,  its  surface  tension  may  be 
determined  by  applying  pressure  to  the 
Uipper  end  of  the  tube,  and  measuring  the 
pressure  necessary  to  force  iht-  liquid  into 
such  a  position  that  the  meniscus  at  tht- 
lower  end  of  the  tube  is  plane. 

Interfacial  tensions  may  also  be  deter- 
mineil  in  this  way. 

If  no  restriction  be  placed  un  the  amount 
of  liquid  available,  a  simple  apparatus  niay 
In;  used,  by  means  of  which  the  ordiuars 
surface  tension  of  a  liquiil,  or  the  interfacial 
tension  between  two  liquids,  may  be 
measured  in  several  different  ways. 


THE  GEOLOGICAL  SOCIETY  OF 

LONDON. 
At  the  meeting  on  November  7,  Prof.  A. 
C.  Sewaid,  ScD.,  F.K.S.,  President,  in  the 
chair,   the  following  cominunications    were 
read: — 

On  the  Skeleton  of  Iouanddon  athekkikl- 
DKNSis  sp.  nov.,  from  the  Wealden  ShaliH 
of  Afherfield  {Isle  of  Wiyht),  by  the  lat<' 
Keoinald  Walter  Hoolky,  F.G.S.  Read 
by  Dr.  A.  Smith  Woodward,  F.R.S.,  F.G.S. 

The  Igneous  Rocks  of  the  Tortworth  In- 
Her,  by  Prok.  Sidney  Hugh  Kbynolds, 
M.A.,  Sc.D.,  F.G.S. 

At  the  meeting  held  on  \\edne8day,  Nov. 
'Jl,  the  following  communication  was  read: 

The  Development  of  the  Severn  Valley  in 
the  Neiyhbourhooct  of  Iron-Bridge  and 
Bridgnorth,  by  L.  J.  Wills,  M.A.,  Ph.D., 
F.G.S.  With  a  Section  on  the  Upper  VVorfe 
Valley,  in  collaboration  with  E.  E,  L.  Dixon, 
B.Sc.,  F.G.S. 


THE  liNSTlTl'TION  ol    MINING 
ENGINKEUS. 

The  thirty-fourth  aimnnl  <,'enera]  niot'tin;; 
of  the  Institution  of  Mininj,'  I'^nginecrs  was 
held  on  Thursday,  November  29. 


The  following  pampers  were  read,  or  taken 
as  read,  and  submitted  for  discussion:  — 

Hydraulic  Stoicage  at  the  Dalzell  and 
Broomside  Collieries,  by  Prof.  K.  W.  Dron, 

M.lNST.C.E. 

Some  Effects  of  High  Air-Temperatures 
upon  the  Miner,  by  Prof.  K.  Neville  Moss, 
x\LSc.  (Sixth  Report  to  the  Committee  on 
"  The  Control  of  Atmospheric  Conditions  in 
Hot  and  Deep  Mines.") 

Strata  Temperatures  in  Sotith  Wales,  in- 
clu(fing  Pembrokeshire,  by  T.  D.  Jones, 
M.Sc.  (Seventh  Report  to  the  Comnutteo 
on  '*  The  Control  of  Atmospheric  Condi- 
tions in  Hot  and  Deep  Mines.") 

The  Specific  Heat  of  Coal,  by  G.  Coles, 
B.Sc.  (Eighth  Report  to  the  Counnittee  on 
"  The  Control  of  Atmospheric  Conditions  in 
Hot  and  Deep  Mines.") 

The  following  paper  wilj  be  submitted  for 
further  discussion :  — 

The  position  of  Mechanical  Engineering 
in  Colliery  Operations,  by  Sir  William 
Ellis,  G.B.E.,  D.Eno.  (see  Trans.  Inst. 
M.E.,  1923-1924,  vol.  LXVI.,  page  85). 


THE  OPTICAL  SOCIETY. 

The  1923  Thomas  Young  Oration. 

A  meeting,  of  the  Society  was  held  at  tlio 
Imperial  Colleec  of  Science  and  Techno- 
logy*, on  Tuesday,  November  27,  when  the 
Thomas  Young  Oration  was  delivered  by 
Dr.  M.  von  Rouk,  Jena,  the  subject  being 
Contributions  to  lite  History  of  the  Spec- 
taclc  Trade  front  the  earliest  times  to 
Thomas  Young's  Appearance. 


THE    INSTITUTION    OF   ELECTRICAL 
ENGINEERS. 

Periodic  Trigger  Reception,  by  E.  V. 
Appleton,  M.A.,  D.Sc,  and  F.  S.  Thomp- 
son, B.A.,  Royal  Corps  of  Signals, 

The  phenomenon  of  oscillation  hysteresis 
exhibited  by  simple  triode  generators  was 
discussed  theoretically.  A  practical  method 
of  reception  in  which  this  plu^nomcnon  is 
utilised  in  a  periodic  nianncr  was  <lfscrll)ed. 
This  nietho<l,  wliich  fta:  oonvenieua;  niMV  be 
termed    "  periodic    trigger    reception,'      is 


346 


THE  CHEMICAL  NEWS. 


NOVEMBEK  30,  1923. 


suitable  for  continuous-wave  and  sipark  sig- 
nals. 

A  low-frequency  electromotive  force  is  in- 
troduced in  the  grid  circuit  of  a  simple  tri- 
ode  oscillator  in  such  a  way  that  high- 
frequency  oscillations  are  not  produced  in 
the  absence  of  an  incoming  signal.  A  small 
signal  of  high  frequency  is,  however,  suffi- 
cient to  produce  a  train  of  free  oscillations 
once  every  low-frequency  cycle.  Such  free 
oscillations  are  rectified  by  the  triode,  and 
a  signal  of  the  impressed  low  frequency  is 
heard  in  the  receiver  telephones. 

The  system  differs  fundamentally  from 
the  Armstrong  super-regenerative  receiver 
in  the  following  respects  : — 

(a)  The  ordinary  oscillation-hysteresis 
characteristic  is  followed  "adiabatically" ; 

(b)  No  self-oscillations  are  produced  m 
the  system  in  the  absence  of  an  incoming 
signal;  and 

(c)  The  amplitude  of  the  telephone  signal 
is  practically  indeipendent  of  the  amplitude 
of  the  incoming  signal  and  not  proportional 
to  it  as  in  super-regenerative  receivers. 

It  has  been  discovered  experimentally 
that  oscillations  may  be  maintained  in  a 
simple  triode  generator  with  extreme  nega- 
tive grid  potentials  such  as  would  cut  off 
the  anode  current  entirely  under  normal 
conditions.  A  simple  theory  for  the  condi- 
tions necessary  for  such  maintenance  is 
given.  An  oscillator  of  this  type  is  very 
efficient  in  that  anode  and  grid  currents  are 
only  permitted  to  flow  for  a  very  small  part 
of  the  cycle. 

A  Dynamic  Model  of  a  Valve  and  Oscillat- 
ing Circuit,  by  E.  C.  Clinker,  Member. 

A  mechanical  model  was  described  which 
reipresented  the  action  of  a  3-electrode  valve 
when  coupled  to  an  oscillatory  circuit.  A 
string- moving  around  pulleys,  one  of  which 
is  driven  by  a  small  motor,  represents  by  its 
motion  the  current  through  the  valve.  The 
oscillatory  circuit  is  represented  by  a  spring 
and  a  weighted  pulley.  By  a  mechanical 
coupling  between  the  spring  and  a  brake  on 
the  driving  motor,  the  effect  of  the  inter- 
mittent current  through  the  valve  is 
obtained,  and  the  system  exhibits  self- 
maintained  oscillations. 


THE  SOCIETY  OF  PUBLIC  ANALYSTS 
AND  OTHEK  ANALYTICAL  CHEMISTS. 

Ordinaky  Mkkting. 

Held  at  the  Chemical    Society's    Rooms 


on  Wednesday.  November  7,  Mr.  P.  A.  Ellis 
Richards,  President,  in  the  chair. 

Certificates  were  read  for  the  first  time  in 
favour  of :  Mr.  Robert  Charles  iYederick 
and  Hubert  Thomas  Stanley  Britton,  M.Sc. 
(Lond.),  E.I.C. 

Certificates  were  read  for  the  second  time 
in  favour  of :  Messrs.  Laurence  Eversley 
Campbell,  M.Sc.  (Lond.),  F.I.C. ;  John 
Troubridge  Hannen,  B.A.  (Cantab.),  A.R.- 
C.Sc,  A. I.e.;  Cyril  Langley  Hintou, 
F.I.C. ;  Douglas  William  Kent-Jones, 
B.Sc.  (Lend.),  F.I.C;  Thomas  William 
Alan  Shaw,  M.Sc.  (Liv.);  William  Hall 
Simmons,  A.I.C. ;  Kenneth  Edward  Nether- 
coate  Williams;  Percy  Noel  Williams, 
M.Sc.  (Liv.),  A.I.C. 

The  following  papers  were  read: — • 
The  Gold-Beaters'  Skin  Test  for  Tannins, 
by  Phyllis  H.  Price,  B.Sc. 

Tanning  consists  in  the  fixation  of  the  tan- 
nins by  animal  fibre.  A  reliable  tannin  test 
must  therefore  demonstrate  this  specific 
property,  and  such  a  test  was  described 
from  Dr.  Nierenstein's  laboratory  by  Miss 
E.  Atkinson  and  Miss  E.  O.  Hazleton  (Bio. 
Chem.  Jo^im.,  1922,  XVI.,  516).  1  heir 
method  consisted  in  the  fixing  of  the  tannin 
on  gold-beater's  skin  and  the  subsequent 
staining  of  the  skin  with  ferric  chloride. 
Non-tannins  are  not  fixed  on  the  gold- 
beater's skin  and  consequently  not  stained. 
The  author  has  further  developed  the  test, 
and  finds  that  it  is  possible  to  detect 
0.00005  grm.  of  gallotannin  in  1  cc.  of  solu- 
tion with  the  use  of  either  ferrous  sulphate, 
ferrous  chloride  or  amyl  nitrite  fumes  in 
place  of  ferric  chloride.  It  was  also  noticed 
that  on  decolorisation  with  dilute  hydro- 
chloric acid,  skins  previously  treated  with 
pyrogallol  tannins  are  completely  de- 
colorised, whereas  those  treated  with  cate- 
chol tannins  have  a  reddish  stain  left  on 
them.  This  is  suggested  as  a  test  for 
Phlobaphenes. 

Determination  of  Nitrogen  in  Coal,  by  W. 
Donovan,  M.Sc. 

The  author  confirms  the  work  of  Fieldner 
and  Taylor,  Terrea,  Fleischer,  and  others, 
who  observed  that  the  Dumas  process,  as 
described  in  the  report  of  Research  Com- 
mittee of  the  Institute  of  Oas  Engineers, 
and  the  Kjeldahl  method  both  gave  results 
below  the  correct  one,  the  former  owing  to 
incomplete  combustion,  the  latter  by  loss 
of  gaseous  nitrogen,  but  points  out  that  the 


NOVEMBEB  30,  1923. 


THE  CHEMICAL  NEWS. 


d47 


Dumas  process  makes  no  provision  for  the 
complete  removal  of  hydrocarbons.  Cou- 
cordant  results  are,  howevir,  obtained  with 
the  Dumas  process  (hydrocarbons  having 
been  completely  removed)  by  the  addition 
of  a  constant  0.2  per  cent,  to  the  Kjeldahl 
gure,  using  mercury  as  a  catalyst. 

The  Estunation  of  Lead  in  PufaJdc 
Waters  and  in  Urine,  by  John  C.  Tiikesii, 
M.D.,  D.Sc,  F.I.C. 

In  estimating  traces  of  h  iJ  in  coloured 
nKK>rland  waters  the  influoiif  of  the  colour 
is  not  always  removed  l>y  making  the 
.standards  with  the  same  water  diluted  with 
distilled  water.  The  proscnoe  of  even  one- 
part  of  copper  in  100  millions  roducos  the 
depth  of  the  tint  given  by  lead,  and  iron  in 
solution  also  interferes  witH  the  colori- 
mctric  estimation  of  lead,  and  accounts  for 
most  of  the  discrttpancics  obtained  with 
moorland  waters.  It  is  essential  that  the 
standard  should  have  the  same  acidity  and 
contain  the  same  acid  as  th<  water  or  urine 
under  examination.  A  sensitive  method  of 
testing  for  lend  in  urine  is  de^scribed,  and  it 
is  shown  that  three  kiifds  of  filter  paper 
contained  suflficient  leaid  to  cause  urine 
which  was  free  from  lend  to  srive  a  positive 
result  in  the  test. 


THE  INRTITUTION  OF  ELECTKICAT. 
ENOTNEEl^S 

A  paper,  entitled,  The  KUctnfication  of 
ihe  French  Midi  Railway,  was  read  by  MoN. 
A.  Bachkllery,  Ing^nieur-en-Chef,  Che- 
mins  de  Fer  du  Midi,  France,  and  discussed 
at  a  joint  meeting  of  the  Institution  of  Elec- 
trical Engineers  and  the  Soei^t^  des  Inge- 
nieurs  Civils  de  France  (British  Section), 
held  on  Thursday,  November  22. 

After  a  brief  dl'scriplion  of  the  cxtperi- 
ments  made  before  the  war  on  the  Midi 
.Railway  in  the  way  of  electric  traction,  the 
author  gives  an  account  of  the  extensive 
electrification  work  now  pursued  by  that 
company  in  accordance  with  the  new  stand- 
ard regulations  of  the  Froneh  Government, 
and  of  the  first  results  alreidy  obtained  on 
the  electrified  lines. 


T.F/'TUHES  IN  CHEMISTRY. 

A  course  of  three  lectures  on  Somr  Choi>- 
fern  in  ihe  Recent  Devrlnpment  of  the 
Theory  "/  Electrolytic  Disaociation    will  be 


given  at  University  College,  London  (Grower 
Street,  VV.C.l),  by  Prof.  J.  N.  Bronsted 
(Professor  of  Chemistry  in  the  University 
of  Copenhagen),  at  5.30  p.m.  on  Monday, 
Dec,  10,  Wednesday,  Dec.  12,  and  Friday, 
Dec.  14. 

At  the  first  lecture  the  chair  will  be  taken 
by  Professor  F.  G.  Donnan,  C.B.E.,  F.K.S. 

The  lectures  arc  addressed  to  tulvanced 
students  of  the  University  and  to  others  in- 
terested in  the  subject.  Admission  is  free, 
without  ticket. 


WHAT  CHEMISTRY  SHALL  BE 

TAUGHT  IN  HIGH  SCHOOL  AND  HOW 

IT    SHALL  BE  CORREL.\TED  WITH 

COLLEGE    CHEMISTRY. 

By  Louis  W.  Mattkrn. 

Chemical  Department  McKinlcy  Technical 
High  iSchool,  Washington,  D.C. 

{Abridged  from  the  "School  Science  and 
Mathematics,"  Vol.  XXIII.,  No.  7,  Octo- 
ber, 1923.) 

No  endeavours  are  so  prolific  of  far- 
reaching  benefits  to  the  betterment  of  man- 
kind as  those  which  contribute  to  the  aim  of 
education,  as  expressed  by  William  C. 
Ruediger,  "To  educate  a  person,  means  to 
adjust  him  to  those  elements  of  his  environ- 
ment that  are  o  concern  in  modern  life,  and 
to  develop,  organise  and  train  his  powers  so 
that  he  may  make  efficient  and  proper  use 
of  them."  What  a  fine  instrument  chemis- 
try may  become  as  a  contributor  to  develoip 
and  to  carry  out  the  two  aspects  of  life  as 
implied  in  that  definition,  first  the  objec- 
tive, and  second  the  subjective. 

Objectively,  first,  cnemical  principles 
touch  our  every  day  physical  environment 
at  every  turn  in  life  with  an  illiunination 
that  reveals  its  indispensable  usefulness  in 
manufacturing  processes,  in  furnishing  the 
basic  supplies  of  mankind  through  agricul- 
ture, in  tlu'  rapi<l  (k'velf.ipments  of  fofnis  and 
medicine,  and  in  tliat  proper  understanding 
of  certain  plu-nomena  and  substances  which 
is  essential  to  their  best  usage  in  connec- 
tion with  personal  welfare. 

With  regard  tt)  the  subjective  aspect,  the? 
qualities  needed  in  the  study  of  chemistry 
and  therefore  to  be  accordingly  developed 
in  the  student.  an>  those  which  operate  pro- 
min(>ntly  in  the  production  of  success  in 
modern  life,  namely,  accuracy  in  observa- 
tion, correlation  of  observations  and  the  de- 


348 


tHB  CHfiMlCAL  NEWS. 


NOVEMBER  30,  1923. 


duotion  therefrom  of  princijples  or  laws  and 
the  relation  of  new  observalions  to  these 
laws,  independent  judgment  based  on  ex- 
perimental evidence,  the  ability  to  check 
thought  and  imagination  with  experimental 
evidence,  the  indispensable  virtue  of  thor- 
oughness, and  the  very  important  matter  of 
expressing  clearly,  either  written  or  oral, 
experimental  work. 

Subsequent  to  the  great  developments  of 
the  possibilities  of  chemistry  due  to  the 
urge  of  the  researches  of  Bla-ck  (1728-99), 
Cavendish  (1731-1810),  Priestley  (1733- 
1804),  and  Lavoisier  (1743-94),  those  in- 
terested in  education  not  only  gave  chemis- 
try a  place  in  the  colleges  as  early  as  1767- 
1839,  but  also,  later  on,  in  the  American 
Academy,  which  was  developed  out  of  a 
desire  to  do  the  people  at  large  more  good 
than  the  then  existing  Latin  grammar 
school.  At  this  time  a  new  spirit  in  Ameri- 
can education  was  struggling  for  bith.  The 
American  spirit  in  education,  animated  by 
such  sipirits  as  Benjamin  Franklin,  William 
Peim,  Rensselaer,  Lawrence  of  Harvard, 
Williams  of  Michigan,  and  Pugh,  the  first 
President  of  the  Pennsylvania  State  Col- 
lego,  the  blacksmith  apprentice,  who  man- 
aged to  get  enough  elementary  education  to 
s;);'nd  four  years  abroad,  returning  as  an 
accomphshed  educator  in  agricultural 
science,  and  others — all  brought  science  to 
bear  upon  the  welfare  of  the  people  at  large, 
both  from  a  practical  and  cultural  point  of 
view.  Pugh  states,  "  The  facts  of  science 
discipline  the  mind  to  habits  of  thought  and 
enable  one  fully  to  comprehend  the  abstract 
principles  involved  in  the  practical  opera- 
tions of  life."  From  1819  to  1840  in  North 
Carolina,  Massachusetts,  Connecticut  and 
New  York  alone,  thirty-five  academies  and 
secondary  schools  taught  chemistry.  It  is, 
therefore,  not  surprising  that  the  increased 
revelations  of  the  wonderful  ])assibilities  of 
chemistry  since  those  early  days  caused  a 
large  number  of  students  in  the  high  scbonls 
of  this  country  to  study  chemistry. 

This  increasingly  large  number  of  chemi- 
cal students  is  a  very  important  field  of 
chemical  education  :  first,  because  students 
in  high  schools  are  especially  sensitive  to 
visions  of  their  life's  work  and  a  long  list  sec 
chemistry;  second,  they  have  the  ability  to 
successfully  learn  chemistry  when  there  is 
not  an  attempt  to  put  a  quart  in  a  pint  mea- 
sure— remembering  that  the  rest  of  the 
quart  can  better  be  administered  at  college ; 
third,  the  large  number  whose  formal  edu- 
cation ceases  with    the  high    school    carry 


into  citizenship  that  which  will  be  helpful 
in  creating  more  of  an  intelligent  apprecia- 
tion at  large  of  the  importance  of  chemistry 
and  the  value  of  its  many  current  publica- 
tions to  the  material  well-being  and  benefit 
of  mankind. 

The  problem  of  correlating  the  chemistry 
taught  in  high  schools  with  college  chemis- 
try is  a  doubly  complex  problem.  The  col- 
lege professors  of  chemistry  receive  from 
liigh  schools  those  wKo  have  had  chemistry 
and  those  who  have  not.  The  high  school 
teachers  of  jhemistry  have  in  their  classes 
those  who  intend  to  go  to  college  and  those 
who  do  not.  Different  high  schools  treat 
chemistry  differently,  both  as  to  content 
and  method  of  teaching,  tsus  presenting  to 
the  colleges  a  variety  of  preparation.  Since 
chemistry  may  logically  play  an  increas- 
ingly important  part  in  sigh  school  educa- 
tion, should  not  the  American  Chemica. 
Society,  with  its  rich  knowledge  of  chemis- 
try, and  its  wealth  of  educational  ability, 
help  to  solve  the  problem  of  how  and  what 
ehemistry  should  be  taught  in  the  high 
schools  ? 

How  chemistry  is  taught  during  the 
highly  sensitive  period  of  lii^h  school  educa- 
tion, as  well  as  what  is  taught,  is  exceed- 
ingly important,  because  the  habits  and 
attitude  of  mind  then  formed  will  help 
mightily  to  determine  the  extent  of  further 
development  in  college  chemistry.  I,  there- 
fore, suggest  tho  following  method  and  con- 
tent for  high  school  students  of  chemistry, 
either  for  those  not  going  to  college  or  those 
who  do;  however,  the  latter  is  the  class  for 
shecial  consideration  at  this  time. 

Stress  the  develoyment  of  accuracy  in 
observation,  without  which  there  can  be  no 
real  progress  in  chemistry.  Rober  E.  Rose, 
in  discussing  the  weakness  of  chemists,  lays 
particular  emphasis  on  a  positive  need  for 
more  training  of  the  ability  to  observe 
accurately,  and  ascribes  a  lack  of  that  abil- 
ity to  "  faults  of  our  secondary  schools." 
The  wide  variation  of  materials  and  their 
actions  afforded  by  a  properly  systemised 
series  of  elementary  chemistry  experiments 
give  an  unparalleled  opportunity  for  train- 
ing of  the  power  to  observe. 

Student  laboratory  experiments  should 
precede  <'lass-room  development,  thereby 
getting  information,  not  second-hand,  but 
first-hand,  which  arouses  curiosity  and 
stimulates  keen  observation.  These  obser- 
vations should  become  the  basis  of  cla^ss- 
room  development  and  further  expansion  of 
the  principles  taught  by  these  experiments 


NOVEMBER  30.  1923. 


THE  CHEMICAL  NEWS. 


349 


into  their  applications  in  evury-daj  life.  lu 
tlie  adiuiiublu  "Report"  oi  the  CoimnittLC, 
appointed  by  the  Prime  Minister  to  inqunv 
into  the  "Position  of  Natural  Science  iu  thr 
Educational  System  of  Chvat  Britain, 
attention  is  properly  called  to  the  danger  of 
carrying  the  heuristic  method  to  an  ex- 
treme; that  is,  to  discover  things  through 
their  experiments,  with  very  little  aid  from 
their  teacher.  While  the  spirit  of  iuquiry 
should  saturate  every  experiiiunt,  it  wouM 
be  a  waste  of  time  to  compel  the  students 
to  rediscover  all  that  tliey  ar.'  expected  to 
know  during  the  limited  time  given  to  h»b- 
or.iioiv  work. 

{To  be  contimied.) 


GENERAL    NOTES. 


ANGLO- SWISS  TRADE  IN  1922. 

The  Department  of  Overseas  Trade  has 
received  from  the  British  Legation  at  Berne 
the  following  survey  of  Anglo-Swiss  trade 
during  1022. 

According  to  the  recently  published  Cus- 
toms Statistics  for  the  entire  twelve  months 
of  1022,  Great  Britain  maintains  her  posi- 
tion as  Switzerland's  chief  customer. 
France  coming  next,  then  the  United  States 
of  .\merica,  and  then  Germany. 

Aoxx>rding  to  the  Suuhs  Exporter  toe  Octo- 
ber, the  favourable  marketing  conditions 
for  Swiss  artificial  silk  an-  causing  the 
"Viscose  S.A."  of  Emmobriuke  (Lucerne) 
to  contemplate  the  erection  of  a  second  fac- 
tory in  this  country.  Moreover,  a  new  un- 
dertaking for  the  manufacture  of  artificial 
silk  is  about  to  be  established  at  Steckborn, 
bv  the  "Borvisk"  Artificial  Silk  Works. 
Ltd..  of  Ziirich. 

With  regard  to  exports  of  chemicals,  the 
increase  of  10.1  million  francs  can  be  attri- 
but<^d  almost  entirely  to  aniline  and  other 
coal  tar  dyes.  There  is  alsf)  a  slight  increase 
in  these  particular  chemical  exports,  as 
crvinpared  with  1021  (13.1  as  against  10.0 
million  francs),  whereas  there  is  a  decrease 
to  be  not+'d  in  respect  of  the  a^'gregate  total 
of  chemicals  exported  to  the  United  King- 
dom. This  decrease  applies  more  particu- 
larly to  iperfumery,  cosmetics;  and  vege- 
table nikaoids.  There  is  a  notable  increase 
in  exports  of  technical  oils  and  fats,  which 
have  risen  from  10.7  million  francs  in  1021 
to  58.5  million  francs  in  1022. 


CORRESPONDENCE. 


BRITISH    EMPIRE    EXHIBITION 
(1924). 

To  the  Editors  of  The  Chemical  News. 

Sirs, — It  is  well  known  to  most  people 
that  at  the  foithcoming  Exhibition  next 
year  at  Wembley  there  will  be  shown  a  very 
complete  representation  of  our  ipresent 
state  of  knowledge  of  natural  science.  The 
details  of  the  arrangements,  perhaps,  are 
not  so  well  known,  and  with  a  view  to  fur- 
nishing informatif>n  to  those  already  inter- 
ested and  p.)ssibly  enlisting  the  assistance 
of  those  who  havt;  not  already  offered  it,  I 
shall  be  glad  to  bi'  allowed  to  make  the  fol- 
lowing statement :  — 

A  Committee  of  the  Royal  Society  is 
dealing  with  an  exhibit  illustrating,  so  far 
as  space  permits,  researches  in  various 
branches  of  pure  science  other  than  Chemis- 
try. 

The  Chemistry  Exhibit  is  being  organised 
by  a  Committee  of  representatives  of  all  the 
other  scientific  societies  dealing  with  science 
and  application  of  chemistry.  The  two 
Committees  are  working  in  the  closest  ipos- 
sible  co-operation,  having  three  members  in 
common  in  order  to  prevent  overlapping. 

The  space  at  the  disposal  of  the  Commit- 
te«»s  is  limited,  but  those  who  are  able  and 
willing  to  assist  in  the  Chemistry  Exiiibit 
should  communicate  with  Dr.  Levinstein, 
at  166,  Piccadilly,  W.l,  or  any  of  the  Con- 
venors of  Sections,  whose  names  are  given 
below,  with  regard  to  exhibits  dealing  with 
chemistry. 

Subjects  which  are  on  the  borderland  of 
Physics  and  Chemistry,  such  as  the  Stmc- 
ture  of  the  .\tom,  the  Inner  Structure  of- 
Crystals,  and  recent  Spectroscopic  work, 
will  be  dealt  with  by  the  C/ommitt^e  to 
which  it  is  most  appropriately  referred. 
Arrangement's  will  be  made  between  the 
two  Committees  to  exhibit  the  work  in  its 
most  aippropriate  place. 

CrKMisTRY  Exhibit. — Convenors  : 

Dr.  E.  F.  Armstrong,  F.R.S.,  Green- 
back. Latchford,  Warrington;  Catalysis: 
Fat,  Hvdrogenation  of. 

J.  L.^  Baker.  Esq.,  F.I.C.,  Dial  Cottage. 
Cookham  Road.  Maidenhead;  Biochemistrv. 

Professor  E.  C.  Baly.  C.B.E.,  M.Sc.. 
F.R.S.,  The  University,  Liverpool;  Gene- 
ral Inorganic. 

A.  Chaston  Chapinan,  Esq..  F.R.S.,  ft. 
Duke  Street,  Aldgat<».  E.C.8;  Hydrogen  Ton 
Concentration . 

C.  F.  Cr(jes,  Esq..  B.Sc,  F.R.8.,  4,  New 


350 


THE  CHEMICAL  NEWS. 


NOVEMBER  30,  1023. 


Court,  Lincoln's  Inn,  W.C.2;  Cellulose. 

Professor  F.  G.  Donnan,  C.B.E.,  F.R.S., 
University  College,  Gower  Street,  W.C.I; 
General  Physical  Chemistry. 

Professor  G.  G.  Henderson,  LL.D., 
F.P.S.,  The  University,  Glasgow;  Terpenes. 

Dr.  T.  A.  Henry,  The  Wellcome  Chemi- 
cal Research  Laboratory,  6,  King  Street, 
Snow  Hill,  E.C.I;  Organic  Chemistry  Alka- 
loids. 

Professor  I.  M.  Heilbron,  D.S.O.,  Chem- 
istry Department,  The  University,  Liver- 
pool; Plant  Colouring  Matters. 

Dr.  J.  T.  Hewitt,  F.R.S.,  Manor  House, 
Sutton,  Heston,  Hounslow,  Middlesex ; 
Coal  Tar  Colouring  Matters. 

Professor    J.    W.    Hinchley,    A.R.S.M.. 
F.I.C.,    The  Institution    of    Chemical    En 
gineers,  !7.307,  Abbey  House,  Victoria  St.. 
Westminster,    S.W.I;    Chemical  Engineer- 
ing. 

Principal  J.  W.  Irvine,  C.B.E.,  F.R.S., 
The  University  House,  St.  Andrews,  Fife ; 
Sugars. 

Dr.  Arthur  Lapworth,  D.Sc,  F.R.S., 
The  University,  Manchester;  Valency  The- 
ories and  Theories  of  Chemical  Combination. 

Professor  J.  W.  McBain,  M.A.,  F.R.S.. 
The  University,  Bristol;  Colloids. 

Sir  Henry  Miers,  LL.D.,  F.R.S.,  Birch 
Heys,  Cromwell  Range,  Fallowfield,  Man- 
chester; Crystallography  and  Crystal  Struc- 
ture. 

Dr.  W.  R.  Ormandy,  F.I.C.,  18,  Belsizo 
Grove,  Belsize  Park,  N.W.3;  Plastics. 

Professor  F.  L.  Pyman,  D.Sc,  F.R.S., 
College  of  Technology,  Manchester;  Alka- 
loids. 

R.  B.  Pilcher,  Esq.,  O.B.E.,  The  Insti- 
tute of  Chemistrv,  30,  Russell  Square, 
W.C.I;  Historical.^ 

Sir  John  Russell,  D.Sc,  F.R.S.,  Lawes 
Agricultural  Trust,  Rothamstead  Experi- 
mental Station,  Harpenden;  Agricultural 
Chemistry, 

Dr.  T.  Slater  Price,  O.B.E.,  F.I.C., 
British  Photographic  Research  Association, 
30,  Russell  Square,  W.C.I ;  Photography. 

Professor  A.  Smithells,  C.M.G.,  B.Sc, 
F.R.S.,  68,  Lissenden  Mansions,  Highgato 
Road,  N.W.8;  Flame,  Fuel  and  Explosion 
Waves. 

Commander  R.  E.  Stokes-Roes,  R.N., 
The  Institution  of  Petroleum  Technolo- 
gists, 5,  John  Street,  Adeliphi,  W.C.I;  Ap- 
paratus. 

Professor  J.  F.  Thorpe,  G.B.E.,  F.R.S., 
The  Imperial  College  of  Science  and  Tech- 
nology, South  Kensington.  S.W.7;  General 
Organic  Chemistry. 


The  next  meeting  of  the  Committee  is  to 
be  held  on  DeceiiiDer  19,  and  it  is  hoped 
that  prior  to  this  date  sufficient  information 
will  be  in  the  hands  of  each  Convenor  to  en- 
able him  to  make  a  close  estimate  of  the 
amount  of  space  he  will  require  and  the  ex- 
penses which  will  be  incurred  in  his  sec- 
tion. It  is  essential  that  this  date  be  ad- 
hered to,  if  the  subsequent  work  is  to  be 
efficiently  carried  out. 

The  idea  of  having  standard  specimen 
bottles  has  been  abandoned,  and  specimens 
will  be  shown  in  exhibitoi's'  own  bottles, 
except  in  special  circiunstances.  The  im- 
portance of  the  Scientific  Exhibits  has  al- 
ready been  well  recognised  by  the  technical 
press,  and  I  am,  therefore,  encouraged  to 
hope  that  the  widest  publicity  may  be  given 
to  the  details  of  the  arrangements  which 
have  already  Been  made. — Yours,  &c., 

W.    J.    V.    WOOLCOCK. 

The  Association  of  British  Chemical 

Manufacturers. 
166,  Piccadilly,  London,  W.l. 
November  21,  1923. 


RED  SULPHIDE  DYES, 
To  the  Editors  of  The  Chemical  New^s. 
Sirs, — In  a  recent  paper  communicated 
to  this  Journal  on  the  subject  of  sulphur 
dyes,  the  author  remarked  that  sulphide 
dyes  are  known  in  every  colour  but  red  (The 
(fhemical  News,  1923,  CXXVIL).  The  re- 
cent research  of  Watson  and  Dutt  on  the 
subject  of  these  dyes  deserves,  in  view  of 
this,  some  mention.  The  first  paper  on  this 
subject  communicated  to  The  Chemical  So- 
ciety in  1922,  expressed  the  view  that  the 
lack  of  fastness  of  these  dyes  was  due  to 
the  fact  that  they  contained  ordinary  auxo- 
chromes,  such  as  amino  or  hydroxy  1  groups, 
as  weir  as  mercaiptan  groups,  and  the  pre- 
sence of  these  ordinary  auxochrrmes  caused 
the  dyeings  to  be  stripped  to  a  certain  ex- 
tent by  acids  or  alkalis.  Some  substances 
were  therefore  prepared  containing  chromo- 
phores  and  mercaptan  groups,  but  no  auxo- 
chromes.  Thus  4  benzeneacinaphthylmer- 
captan  was  found  to  be  soluble  in  sodium 
sulphide,  but  only  to  dye  in  light  brownish 
shades.  Despite  this  it  was  hoped  that  the 
mercaptan  derivatives  of  the  various  groups 
might  prove  more  valuable  red  sulphide 
dyes  than  the  compounds  prepared  by  vari- 
ous previous  workers.  But  the  various  new 
comipounds  of  the  azine,  oxazine,  phthalein, 
nitroso  and  acridine  groups  all  failed  for 
one  reason  or  another.  Thus  2-amino-8- 
thiol-10-phenyl     phenazonium      hydroxide. 


NOVEMBEK  30,  1923. 


THE  CHEMICAL  NEWS. 


351 


though  a  sulphide  dye,  was  found  to  dye 
only  in  dull  violet  jhadcs ;  3-amiuo-7-di- 
iiicthylaiuino-4-thiolphcnaziuo  only  to  give 
red-brown  shades  very  sensitive  to  acids 
an  dalkalis ;  9-diuiethylamiuo-2-thiol-3-plien- 
oxazone  to  be  soluble  in  sodium  sulphide, 
but  only  to  give  blue  shades.  The  follow- 
ing compounds  were  pr^^pared  :  — 

Ethyl  4  Bcuzeneazo  1  naphthyl  xanthate, 
4  Benzeneazo  1  naphthyl  mercaptan, 
pp'p"  trithioltriphenylciirbinol, 

2  amino  8    thiol    10    phenylpheoazonium 
hydro.xide, 

3  Amino  7    dimethylamino     i    thiolphen- 
azine, 

0  J  dimethylamino  2  thiol  3  phenoxazonc, 
Dithiolfluorescein, 
DinitrosothiolresOTcinol,  mil 
2:2':4:4'     Tetra    amino    .'>:ii'    dithioldi- 
phenylmethane. 

Yours,  &c., 

R.  F.  HuNTBR,  F.C.S. 
Ilufhhury,  N.E. 


NOTICES  OF  BOOKS. 
Recent  Developmcnls  jx    Atomic  The- 

on/,  by  TiEo  Ghaktz  (Profe>sor  of  Physics 

in  the  University  of  Munich),  Translated 

from  the  Geniian  by  G.   Bakr.     Pp.  XI. 

+     174     (with     index).       1928.      Messrs. 

Methuen  A  Co.,   I.td.,    SO.  Essex  Street. 

\V.C.2.     Os.  net. 

This  is  a  welcome  book,  coming  just  at  the 
time  when  so  much  interest  is  developing  in 
connection  with  atomic  theories. 

The  book  opens  on  somewhat  conven- 
tional lines,  dealing  with  molecules  and 
atoms.  In  passing  we  notice  the  state- 
ment that  "  Molecules  are  the  units  of 
structure  of  compounds."  This  is  really 
only  a  half  truth,  and  there  are  several 
«;uch  half  truths  noticeable  in  the  book.  It 
has  been  extperimentally  demonstrated  that 
iji  ci'itiiin  crystals,  for  exainplc,  the  atom 
f>r  m()le(!ule  loses  its  identity,  so  that  the 
attem()t  to  sub-divide  all  mattiT  by  hard  and 
fast  degrees  breaks  down  in  this  type  of 
case. 

The  book  is.  however,  strong  on  the  phy- 
sical, f>r  more  particularly  the  electrical, 
side,  and  the  chapter  on  atoms  and  ions  is 
excellent. 

The  usual  statement  that  Helmholtz 
(1881)  was  the  first  to  draw  important  con- 
clusions from  Faraday's  experiments  in- 
volving the  conception  of  atomic  or  mole- 
cular electricity,  appears  in  this  book;  but 
some  time  prior  to  1881  the  idea  of  mole- 
cular eleetricitv  was  known.       Still    we    do 


not  wish  in  any  way  to  minimise  the  value 
of  Heludioltz's  suggestions. 

The    statement    appears    on    i>.  29    that 

electricity  behaves  like  a  special  chemi- 
cal element,  whose  atoms  combine  with 
those  of  the  other  known  elements  to  form 
ions."  Hydrogen  without  its  electron 
would  be  an  ion,  so  that  this  statement  is 
again  in  the  nature  of  a  half  truth  according 
to  recent  views.  These  should  be  correcteti 
in  the  second  edition. 

Disintegration  of  atoms.  X-ray  spectra, 
line  spectra,  Bohr's  model,  and  the  "decom- 
pcjsition"  of  nuclei  are  dealt  with  clearly. 

Balmer's  law  is  representi'd  in  a  very 
clear  manner,  which  points  to  the  desirabil- 
ity ol  physicists  making  their  I'quations 
attractive  m  appearance  to  the  lay  mintl 
and  also  businesslike  for  quick  appreciation. 

l^e  table  of  isotopes  on  p.  88,  head  ( f 
third  column,  should  read  II.  The  system 
of  closed  branching,  see  p.  fio,  as  is  use<l  in 
Germany,  is  adopted,  notwithstanding  the 
International  Committee's  Report. 

The  usual  error  of  tacitly  accrediting  As- 
ton with  the  discovery  of  the  two  neon  iso- 
topes is  made  in  this  book.  As  a  matti'r  of 
fact,  Sir  J.  J.  Thomson  was  the  first  defi- 
nitely to  isolate  the  component  isotopes  of 
neon  by  means  of  his  pf>sitive  rays ;  but  we 
have  few  impartial  historians  in  science  as 
yet. 

The  book  is  well  illustrated,  while  the 
translator  is  to  be  congratulated  on  the 
luciditv  of  his  style. 


The  A. B.C.  of    Atoms,    by    Bertrand 
RrssELL,  F.R.S.      Pp.    175    (no  index). 
1023.   Messrs.  George  Routledge  &  Sons, 
]A4.,     Broadway    House,    68-74,    Cart<'r 
Lane,  E.C.4.     48.  6d.  net. 
This  little  book,  as  a  popidar    exposition 
of  the  atom,  is  well  worth  perusal  by  all  in- 
terested in  the  subject,  but  there  are    some* 
statements  which  should  be  corrected  in  the 
second  edition.     For  example,  on  page  13, 
the  end-pr<)dtict  of  disintegration  is  referred 
to  as  a  lead  "of  a  sort."    As  we  all  know,  it 
is  lead  in  every    sense  of   the  chemical    and 
physical   meaning    we  attach    t-o    common 
lead.    On  page  62  it  is  stat-ed  that  the  atonj 
has  least  energy  when  the  orbit  is  smallest. 
This  does    not    necessarily    follow.       What 
energy     the     electron    retains,     and    what 
energy  the  electron  absorbs  and    gives  out 
are  two  quantities  that  should  not  be  con- 
fused with  each  other.     On  p.  129  the  fol- 
lowing   appears:      "When    two    elemeats 
have  the    same    atomic    number    they    are 


352 


THE  CHEMICAL  NEWS. 


NOVEMBER  30,  1923. 


called  'isotapes.'  "  dhlorine  35  and  chlor- 
ine 37  have  the  cuninion  atomic  niuuber  17, 
but  isotope  35  is  not  one  element  and  iso- 
tope 37  another.  The  word  element  in  this 
case  embraces  all  atoms,  whatever  their 
difference  in  atomic  weight  may  be.  The 
above  statement  was  made  in  connection 
with  radio-activity,  when  two  differently- 
named  elements  may  be  isotopically  alike, 
but  such  statements  are  not  satisfactory. 

The  book,  however,  abounds  in  many 
happy  statements,  and  it  should  have  a 
wide  circle  of  readers.  The  absence  of  the 
visual  diagrams  and  an  index  are  a  disad- 
vantage  to  a  book  of  this  kind. 


BOOKS  RECEIVED. 

Industrial  Filtration,  by  Arthur  WRiftiiT. 
M.E.  Pp.  X.  +  330.  Vol.  I.,  1923.  The 
Chemical  Catalog  Co.,  Inc.,  19,  East  ■24th 
Street,  New  York,  U.S.A.    $5.00. 

Kolloide  in  der-Technik,  von  Dr.  Eaphaf.l 
Ed.  Liesegang.  Pp.  157.  1923.  Hen- 
Theodor  Steinkopff,  Residenzstrasse  12b, 
Dresden  and  Leipzig.     3s.  6d. 


STll- 


-Pro- 


This  list  is  specially  compiled  for  The  Chemical 
News  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 
Latest  Patent  Applications. 
28156— Bachalard,    G.— Preparation     of     sulphnrio 

anhydride.    Nov.  8. 
1780*— Coppee,   E.— Manufacture     of  pure  alcohol. 

Nov.  5. 
28008— Dreyfus,  H.— Manufacture     of  cellulose  de- 
rivatives.   Nov.  7. 
2774— Koppers   Co.— Manufacture     of  alkali 
phides  from  thiosulphates.    Nov.  5. 
Specification  Published   this    Week. 
IP.'adS- Holzverkohhmgs-lndustrie     Akt-Ges.- 
cess  for  the  ehlorination  of  methane. 
Abstract  Published  this   Week. 
204223— Lead  arsenate.— McDougall,  I.,  of  66,  Port 
Street,  and  Howies,  P.,  of  Glenluce,  Water 
Park  Road,  Broughton  Park,  both  in  Man- 

Lead  arsenate  is  obtained  by  reacting  with  at,- 
senic  acid  upon  a  colloidal  solution  of  lead  oxide 
in  water,  aqueous  solution,  or  other  suitable  dis- 
persion medium,  preferably  at  a  raised  tempera- 
ture. The  arsenate  precipitates  in  a  finely 
divided  form.  An  example  describes  the  produc- 
tion of  the  arsenate  PbHAsO  in  this  manner,  the 
colloidalising  of  the  lead  oxide  in  water  being 
effected  in  a  Plauson  mill,  steam  being  passed 
through  the  jacket  of  the  mill  so  as  to  raise  tlio 
temperature  to  80-100°  C.  The  arsenic  acid  is  run 
into  the  mill  and  the  reaction  is  effected  in  a  teAv 
minutes.  .     ,  .    .  .    .    i 

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THE  CHEMICAL  NEWS. 


353 


THE   CHEMICAL  NEWS, 

VOL.  OXXVn.      No.  3221. 

THE  SEPARATION  OF  HAFNIUM 
FROM  ZIRCONIUM. 

By  G.  Hevesy  and  V.  Thal  Jantzen. 

In  the  issue  of  The  Cluniical  News  dated 
July  20,  1923  (Vol.  CXXVIL,  p.  33),  a 
fthort  account  of  the  methods  generally  used 
in  the  separation  of  hafnium  from  zir- 
conium was  given.  We  have  received  re- 
quests from  different  sources  to  give  a  more 
complete  account  of  our  experimental  work, 
and  of  the  efficiency  of  tl\e  methods  em- 
ployed. In  deference  to  these  requests  we 
propose  to  give,  in  the  present  paper,  a  de- 
tailed description  of  the  preparation  of  haf- 
nium by  the  double  fluoride  method. 

When  working  with  Inrirer  nmoimts  of 
minerals,  we  abandoned  '  '   )d  f>ri;^in- 

ully  used,  of  preparing  an  llising  the 

potassium  zirconium  fluoride.  Under  such 
conditions  the  method  of  crystallisation  of 
the  corresponding  ammonium  salt  was 
found  more  suitable.  This  compound  pos- 
sesses a  solubility'  about  Icn  times  as  large 
as  that  of  the  potassium  sjilt.  Moreover,  it 
is  very  stable,    it  can  be  et  ystnllised  out  in 


/  ,1 //      •»'»      nftf     *Wf     **''t     «*!''      HI*      «*       ^**^* 


porcelain  dishes  without  these  showing  any 
indication  of  having  been  attacked,  and  it 
crystallises  in  beautiful  crystals. 

To  prepare  this  compound,  the  pulverised 
mineral  is  first  treated  with  hot  concen- 
trated hydrrK-hioric  acid,  to  remove  the  iron 
and  other  soluble  impurities  present,  and 
the  mineral  which  has  been  thus  ipurified  is 
then  mixed  in  small  portions  with  fused 
acid  ammonium  fluOTide  in  a  large  platinum 
crucible. 

Using  the  zirconium  mineral  alvite,  it 
was  found  that  a  part  of  its  zirconium  and 
hafnium  content  is  soluble  in  concentrated 
hydrochloric  acid.  In  view  of  this,  the 
preparation  of  the  double  salt  of  ammonium 
was  carried  out  in  two  parts  :  (a)  The  frac- 
tion insoluble  in  hydrochloric  acid  was 
fused  with  about  four  times  its  weight  of 
acid  auunonium  fluoride;  (b)  the  hydro- 
chloric acid  soluticm  was  evaporated  t;0  dn,- 
ness  to  render  the  silica  insoluble,  and  the 
ZrOCIj  +  HfOClj  was  extracted  with  cold 
water,  purified  from  iron  and  other  impuri- 
ties by  crystallisation,  and  converted  into 
ammonium  zirconium  and  ammonium  haf- 
nium fluorides  rcsipectively. 

In  what  follows,  we  shall  give  a  detailed 
description  of  the  treatment  of  the  portion 
(a). 

After  the  mineral  has  been  fused  with 
acid  ammonitmi  fluoride,  it  is  extracted  re- 
peat<»dly  with  boiling  water,  which  dissolves 
zirconium,  hafnium,  titanium,  niobium, 
tantalum,  vanadium,  germanium,  iron,  and 
manganese,  some  of  which  are  present  only 
in  very-  minute  quantities,  and  very  con- 
siderable amounts  of  ammonium  silicon 
fluoride.  Thorium,  the  higher  homologue 
of  hafnium,  and  also  the  rare  earth  elementiP 
present,  remain  insoluble,  together  with 
juiattacked  mineral  and  insoluble  zirconium 
and  hafnium  fluoride  compoimds,  such  as 
sodium  zirconium  fluoride. 

On  cooling  down  the  solution,  denoted  in 
the  diagram  by  I.l,  the  great<'st  part  of  the 
double  fluorides  crystal lis<>s.  supplying  the 
crystals  indicated  by  II. 1,  and  a  mother 
liquor  1.2.  The  next  step  consists  in  dis- 
solving ILl  in  boiling  water,  from  which, 
on  cooling,  the  crystals  II I.l  and  the  mother 
liquor  II. 2,  arc  obtained.  The  mother 
liquor  1.2  is  now  partly  evaiporated,  and  on 
cooling  it  supplies  the  crystals  II. 2,  together 
with  the  mother  liquor  1.8.  The  mother 
liquor  II. 2  is  u.sed  to  dissolve  the  crystals 
11.2.  The  successive  steps  in  the  crystal- 
lisation are  indicated  in  the  following  dia- 
gram, the  black  dots  representing  crystals 
andtthe  circles  raotbcr' liquors  :  — 


354 


THE  CHEMICAL  NEWS. 


DECEMBER  7.  1923. 


Desckiptive  T.\ble 

OF  Crystals  Removed. 

Fraction. 

Total  Weight  of 
Double  Fluorides. 

%  of  ZrO^. 

%  of  HfO^in 
ZrO^ 

vi,i 

VIII,2 
XIII,4 

848 
415 
310 

0.5 

0.5 

XVI,6 
XVII, 7 
XVII,8 

190 
120 
165 

1.6 

2.5 

XVIII,9 
XXI, 12 
XXI, 13 

134 
117 

198 

XXII,  14 

XXV,16 

XXVI,  17 

101 
91 
64 

11.2 

<2 

XXVI,  18 

XXVII,  19 

XXVIII, 20 

84 
35 
35 

13 

XXIX, 21 

XXIX, 22 

XXX,23 

39 
56 
79 

XXXI,24 

XXXII, 25 

XXXIII, 26 

130 
124 

88 

36 

<2 

XXXIV,27 
XXXV,28 
XXXV,29 

93 

74 
90 

C.50 

<2 

XXXVI,30 

XXXVI, 31 

XXXVII, 32 

45 
97 
41 

<2 

XXXVIII,33 
XXX  VIII.  34 
XXXV1II,35 

32 
83 

42 

XXXVIII, 36 

XXXVIII,37 

XXXIX,  38 

56 
98 
25 

<2 

XXXIX, 39 
XXXIX, 40 

XLI,42  "^ 
XLI,43 
XLII,44       ■ 

25 
40 
12.4 

21.4 
13.2 
14.2 

8 
2 

XLIII,45 

XLIV,46 

XLV,47 

7.6 

6.5 

14.4 

9 
15 

XLVI,48 
XLVI,49  I 
XLVI,60t 

VhhiII^^^ 

12.2 
15.9 
12.1 

25 

XLVI,51  i 
XLVI,62  i 

^^Hi- 

13.4 
16.9 

86 

DECEMBER  7.  1923. 


THE  CHEMICAL  NEWS 


355 


The  results  of  crystallisatioQ  were 
checked  by  first  determining  the  sum-total 
of  zirconium,  plus  hafnium,  plus  traces  of 
impurity  present.  This  was  performed  by 
weighing  the  oxides  obtained  by  treatment 
of  the  double  fluoride  with  ooncentratod 
sulphuric  acid,  and  igniting.  On  the  other 
hand,  the  hafnium  content  was  determined 
by  using  the  methods  of  quantitative  X-ray 
stpectroscopy,  as  described  by  D.  Coster  in 
The  Chemical  News,  dat^d  August  3,  1023 
(CXXVII.,  pp.  65-70). 

As  shown  in  the  accompanying  table, 
fractions  first  removed  contained  practi- 
cally only  ammonium  silicon  fluoride.  As 
we  proceed  downwards  in  the  table,  the 
amount  of  this  compound  diminished,  and 
the  fraction  XXXV/20  is  practically  pun- 
zirconium  salt,  with  about  2  per  cent.  h:if- 
nium  contf-nt. 

Not  until  fraction  Xrjn/46  has  been 
reached  (loon  the  hafnium  content  begin  to 
increase  in  the  removed  crystal  fraotion^ 
considerably;  this  fraction  contains  9  per 
cent,  of  hafnium. 

Whereas  the  major  part  of  the  crystal 
fractions  obtained  by  the  process  described 
was  found  to  bo  practically  free  from  haf- 
nium, the  bulk  of  the  hafnium  was  present 
in  high  concentration  in  the  mother  liquors. 
The  fraction  of  these  which  was  first  re- 
moved from  the  system  was  V.ll.  It  con- 
sisted chiefly  of  highly  soluble  impurities 
such  as  the  double  fluorides  of  iron,  man- 
ganese and  niobium,  and  about  4  to  5  per 
cent,  of  hafnium  salt.  Fraction  XIII / 21 
still  contained  about  10  per  cent,  of  impuri- 
ties, 20  per  cent,  of  ZrOj.  and  70  per  cent, 
of  HfOj.  On  the  other  hand,  fraction 
XXXVI/48  revealed  a  hafnium  content  of 
about  99  per  cent.,  a  zirconium  content  of 
not  more  than  1  per  cent.,  traces  of  tita- 
nium, niobium  and  manganese,  and  very 
minute  traces  of  vanadium  and  germanium. 
The  existt^nce  of  the  elements  present  only 
in  traces  was  detected  by  Oiptical  spectro- 
scopy. Fraction  XLI/51  contained  97.5  per 
cent.,  fraction  XLni/53  95  per  cent.,  of 
hafnium. 

When  a  mixture  of  hafnium  and  niobium 
double  fluorides  is  heated  carefully,  and 
afterwards  treated  with  boiling  water  and 
acid  ammonium  fluoride,  only  the  hafnium 
salt  dissolves.  This  method  was  repeatedly 
used  to  remove  niobium  Jrom  our  prepara- 
tions. 


The  elaborate  work  of  650  crystallisations 
was  performed  in  order  to  extract  in  a  con- 
centrated form  the  major  part  of  the  haf- 
nuim  present  in  the  mineral. 

^  We  propose  to  give  a  detailed  account  of 
the  solubility  measurements  in  a  subsequent 
issue  of   "The  Chemical  News." 

Institute  of  Theoretical  Physics, 
Copenhagen  University. 
September,  1923. 

ARE    THE  NATURAI.  GROUPINGS-   OF 
THE  ELEMENTS  AND  THE  SPECTR  \L 
LINES  OF  HYDROGEN  RELATED? 
Part    V. 
By  F.  H.  LoBiNG. 
In  developing  this  study— see  The  Chemi- 
cal News,    1923    CXXVII.,    pp.    225,    257, 
273,    290,    337— some    further    interesting 
features  are  brought  into  consideration ;  but 
before  making  deductions  therefrom  it  will 
be  necessary  to  acquaint  the    reader  with  a 
line  of  research  of  very    considerable  scien- 
tific importance.     Moreover,  the  digressions 
here  made  have  a  direct  bearing  on  the  argu- 
ment, and  give  support  to  it,  as  will  be  seen 
presently. 

IVof.  L.  Vegard,  in  the  Philosophical 
Magazine  for  October,  1923,  oontribut<>s  a 
paper  entitled  "  The  Constitution  of  the 
Upipir  Strata  of  the  Atmosphere,"  in  which 
he  propounds  a  theory,  based  upon  experi- 
ment, that  in  the  higher  regions  of  the 
earth's  atmosphere,  where  the  aurora  cur- 
tain phenomenon  is  confined,  clusters  of  ni- 
trogen molecules,  forming  a  sort  of  dust 
(crystals),  exist. 

It  is,  moreover,  suggested  that  this  dust 
IS  carried  upwards  and  maintained    at  high 
atmospheric  levels  bv  reason  of  the  electric- 
ally charged  state  of  the  particles,  and  that 
this  charged  state  is  due  to  a  iphoto-electric 
effect  arising  from  the  incident  rays,  includ- 
ing ultra-violet  light,  of  the  sun.     It  will  be 
rememl)ered  that  ultra-violet  light  falling  on 
substances  causes'  the  emission  of  electrons 
therefrom,  leaving  the  substance  positively 
charged.     In  this  case,  however,  corpuscu'- 
lar  rays  from  the  sun  may  be  involved,  and, 
indeed,  the  magnetic  field  of  the  earth  plays 
a    part    in    these    phenomena,    and    conse- 
quently the  aurora  is  locally  produced.  The 
negative  electric  charge  of  the  eart>h  is  sup- 
posed also  to  influence  the  auroral  displays. 
The  spectrum  lines  of  the  aurora,  in  par- 
ticular the  famous  green  line,    occurring  at 
the  altitudes  within  which    this  phenomena 


350 


THE  CHEMICAL  NEWS. 


DECEMBER  7,  1923. 


is  observed,  and  a  eertain  agreement  be- 
tween this  spectrum  and  that  of  normal  ni- 
trogen, is  advanced  as  goud  evidenct*  that 
the  aurora  is  due  to  the  sun's  ra^s  imping- 
ing upon  solid  nitrogen  particles.  Electron 
rays  are  mentioned  in  this  connection. 

Prof.  Vegard  further  suggests  that  it  ii^ 
these  particles  which  give  rise  to  optical 
scattering,  so  that  the  sky  is  rendered  blue 
by  reflected  light.  The  twinkling  observed 
in  the  case  of  fixed  stars  is  attributed  to  the 
same  fundamental  cause.  Prof.  Vegard 's 
paper  is  summarised  at  the  conclusion  of 
this  section. 

Of  immediate  interest  to  the  present  ar- 
gument, however,  is  Vegard's  view  that  the 
bending  of  Hertz  waves  so  that  they  con- 
form to  the  general  curvature  of  the  earth 
is  due  to  the  state  of  affairs  arising  from  the 
layer  of  charged  nitrogen  crystals  surround- 
ing the  earth  as  a  dust  layer  situated  at  a 
high  altitude. 

The  problem  of  the  bending  or  reflecting 
downwards  of  the  electric  waves  has  been 
under  discussion  for  many  years;  and  Prof. 
Fessenden  and  Dr.  Elihu  Thomson  have 
contributed  towards  its  solution,  the  former 
supporting  the  view  that  at  high  altitudes, 
beginning  at  the  lower  termination  of  the 
aiu'oral  draperies,  there  were  ionised  gas 
particles,  this  ionisation  being  induced  by 
direct  rajs  from  the  sun;  while  the  latter 
advocated  a  gliding  theory,  the  waves  being 
as  it  were  attached  to  the  earth  so  as  to  fol- 
low its  contour,  much  in  the  same  way  as 
electric  waves  become  attached  to  conduct- 
ing wires.  The  layer  of  ionised  gas,  sup- 
posed to  act  as  a  dt  fleeting  mediimn,  has 
been  mathematically  studied  by  Professors 
Fleming,  Ecoles,  and  others,  this  layer  l)eing 
known  as  the  Heaviside  layer  owing  to 
Heaviside's  mathematical  work  in  general 
in  connection  with  such  matters. 

Thus  it  will  be  seen  that  there  are  three 
theories  involved  in  the  elucidation  O'f  this 
phenomenon,  which  arose  from  researches 
in  connection  with  wireless  work.  These 
may  be  referred  to  as  (1)  the  gliding  theory, 

(2)  the  ionised  gas  Heaviside  layer    theory, 

(3)  the    nitrogen     crystals    Heaviside    layer 
theory. 

No\\",  Prof.  Vegard  shows  that  the  gas 
theory  is  untenable;  that  is  to  say,  ionised 
gas  will  not  account  for  the  spectrum  ob- 
tained, and  it  is  therefore  supposed  that  the 
bombardment  of  the  nitrogen  crystals  by 
corpuscular  rays  from  the  sun  will  account 
for  the  peculiarity   of  the    sipectrum  of    the 


aurora  draperies  observed  at  the  lower  edge 
and  at  the  highest  region. 

It  frequently  happens  that  whtn  theories 
are  first  established,  there  are  phciiouiena 
involved  which  coincide  in  their  effects  so 
that  the  theory  is  not  the  whole  truth,  but 
only  an  overlaid  truth,  which  would  become 
modified  when  more  knowledge  is  brought 
to  bear  upon  the  subject. 

In  the  case  of  the  Heaviside  layer,  it  is 
quite  possible  that  the  radiation  may  tend 
itself  to  describe  what  might  be  termed  a 
ground  orbit  round  the  earth.  This  idea  is 
made  possible  from  the  following  considera- 
tions:  In  Parts  I.  and  II.  of  this  paper  it 
has  been  shown  that  the  first  five  Balmer 
emission  lines  of  the  hydrogen  atom  are 
linearly  related  to  five  natural  groups  and 
groupings  of  the  elements  in  the  periodic 
table;  and  in  Part  III.  of  this  series,  that 
these  same  values  are  iti  close  agreement 
with  the  spacing  of  five  consecutive  planets 
(regarding  the  asteroids  as  collectively  one 
planet);  and  in  Part  IV.,  also  of  this  series, 
that  the  many-lines  spectiTim  of  the  hydro- 
gen molecule  accords  very  well  in  its  inten- 
sity distribution  with  the  distribution  of  the 
asteroids. 

To  be  able  to  pass  in  this  manner  from 
the  smallest  known  phenomenon  to  one  on 
the  huge  scale  of  the  planetary  system 
seems  to  involve  a  place  princijde  of  univer- 
sal significance,  which  gives  to  space  round 
all  bodies  a  controlling  feature  of  its  own. 
quite  apart  from  the  mass  magnitudes  of  the 
outer  bodies  concerned.  If  this  is  true,  as 
seems  to  be  the  case,  then  it  is  only  a 
natural  step  to  consider  whether  radiation 
will  not,  under  suitable  conditions,  describe 
closed  orbits  round  bodies  including  atomic 
nuclei.  Iliis  is,  of  course,  a  new  idea  as 
applied  to  the  atom,  as  it  had  been  supposed 
that  radiation  could  only  travel  in  straight 
lines  through  space,  though  Einstein's 
theory  shows  that  light  from  the  stars  is 
slightly  bent  in  its  course  past  the  sun,  and 
Hertz-wave  experiments  seem  to  show 
bending  round  bodies.  Just  what  the  con- 
ditions are  is,  of  course,  speculation,  but 
the  strong  fields  round  atoms,  or  rather 
round  atomic  nuclei,  and  presumably  also 
the  positively  charged  particles  in  the 
Heaviside  layer,  may  account  for  the  inter- 
pretation of  the  phenomena  indicated. 

If  there  is  a  germ    of   truth  in   this    idea, 
then  it  may  be  that  all  the  atomic  orbits  are 
not    due    to    electrons    actually    describing 
them;  but  that  they  are  described    by  pure 
radiation,   while  the  electron  as  the  opera^ 


DEiCEMBJlR  7,  1923. 


TfiE  CHEMICAL  NlilWS. 


35*? 


tor  may  only  vibrate  and  pass  from  one  prac- 
tically fixed  radial  abode  to  another,  linear 
or  radial  radiation  being  given  out  when  thi 
orbit  is  broken  or  detached.  The  electron, 
on  this  view  gives  rise  to  the  orbital  radia- 
tion, but  to  all  intents  and  (purposes  the 
electron  is  stationary,  so  that  the  Lewis- 
Langinuir  theory  can  be  retained  in  its  pre- 
sent form  with,  of  course,  modifications  in 
detail,  as  ha«  lx;en  made  by  ri'cent  investi- 
gators. In  the  ca.se  of  the  Bohr  orbits, 
these  are,  on  this  view,  ekctrodynaniically 
equivalent  to  an  electron  describing  sucli 
orbits. 

Considering  the  stability  of  the  electron 
in  its  stationary  position  outside  the  nucleiu- 
part  of  the  atom,  it  is  quite  (possible  to 
regard  the  electric  fields  involved  as  so 
disposed  that  the  electrons  accommodate 
the  most  electric  lines  when  they  are  at 
places  a  little  distant  frf>ni  the  nucleus, 
just  as  an  iron  disc  will  not  remain  face 
down  on  the  flat  face  of  a  magnet,  for  the 
simple  reason  that  in  its  upnght  or  edge 
position  it  can  accommodate  more  mag- 
netic lines  of  force.  It  must  be  remem- 
bered that  the  lines  of  electric  force  in  the 
atom  are  reduced  to  their  lower  numerical 
limit  in  joining  uip  with  one  electron,  and  on 
this  account  something  in  the  nature  of  a 
limiting  condition  must  prevail.  This  is 
discussed  in  the  writer's  "  The  Chemical 
Elements,"  Chapter  IX. ;  i^ne  also  page  161. 

Considering  now  Planck's  radiation  theory 
involving  energy  quanta,  this  would  not 
be  interprettnl  in  quite  the  satne  way  as  at 
present,  since  the  quanta  would  merely  l)e 
apportionments  of  closed  radiations  (orbits), 
and  open  radiations,  so  to  speak  (see  Notes 
to  follow).  The  clwed  radiation  is  atomic  or 
quantum  like,  while  the  open  radiation  be- 
haves in  acoord  with  the  lUKhdatorv-  theory 
of  light.  On  this  view  n  moiel  could  he 
constructed  showing  the  vaiious  quanttim 
groups  emitted  ns  the  vnrif>us  orbital-radia- 
tions are  broken  or  detachid,  which  would 
accord  with  Planck's  energy  equation.  See 
the  writer's  "  The  Chemical  Elements." 
page  82. 

SUMMAKIKS. 

The  Heaviside  layer,  which  is  suppus.  d 
to  cause  Hertz  waves  to  conform  to  the 
general  contour  of  the  earth,  is  discussed  in 
the  light  (»f  Vegard's  thef>ry  that  the  higher 
regions  of  the  atmosphere  contain  minut<" 
po'iiitively  charged  crystals  of  nitro«^'en,  but 
it  is  suggested  that  these  waves  m;iy  tend 
to  describe  a  ground  orbit  round  the  earth, 
because  orbital  phenomena  do  not  depend 
upon  the  mass  of  the  circulating  body,  as  is 


evident  from  the  fact  that  the  five  Balmer 
lines  of  the  hydrogen  atom  are  linearly  re- 
lated to  the  groupings  of  the  elements  in  the 
periodic  table,  to  the  radial  positions  of  five 
consecutive  planets  of  the  solar  system,  and 
the  many-lines  sipectrum  of  molecular  hy- 
drogen is  possibly  related  to  the  distribution 
of  the  asteroids.  This  leads  to  the  idea  that 
the  Bohr  orbits  arc  closed-radiation  orbits, 
which  only  give  rise  to  emission  lines  when 
the  electron  is  displaced  so  as  to  allow  thi' 
radiation  to  expand  as  a  radially-directed 
wave,  which  conforms  in  its  be- 
haviour after  leaving  the  atom  with 
the  undulatory  theory  of  Hght.  Hav- 
ing thus  practically  stationary  elec- 
trcms,  the  Lewis-Langmuir  theory  may 
be  a  true  cme.  The  quantum  theory  is  then 
an  apportionment  of  open  and  closed  radia- 
tions, for  each  closed  element  of  radiation 
is  of  the  nature  of  a  quantum.  The  closed 
radiation  being  mathematically  equivalent 
to  a  moving  electron,  while  the  electron  may 
only  vibrate.  Is  it  not  possible  UiV  the  laws 
established  by  Bohr  and  othi'rs  to  be  re- 
tained with  only  a  slight  alteration  in  th(>ir 
interpretation,  as  will  be  seen  by  consider- 
ing the  action  of  a  model  liberating  various 
closed  orbits  of  radiation  which  become 
"linear"  or  "rarlial"  radiations'.' 

Vegard's  summary  of  his  paper  follows 
here.     It  contains  much  of  general  interest. 

1. — Photographs  of  auroral  sipectra  oor- 
responding  to  ditTerent  altitudes  have  been 
obtained. 

2. — The  intensity  of  the  green  line  rela- 
tive to  that  of  the  nitrogen  bands  does  not 
inurt'ase  as  we  pass  upwards,  but  shows  a 
small  but  noticeable  diminution. 

3. — The  observations  show  that  the  green 
line  cannot  be  due  to  any  light  elementary 
gas,  such  as  II,  He,  or  the  hypothetical 
geocoronium. 

4. — The  green  line  must  originate  from 
nitrogen  or  from  some  substance  attached 
in  some  way  to  nitrogen.  Arguments  are 
given  for  considering  the  latter  possibility 
to  be  excluded. 

5, — Independent  of  any  hypothesis  with 
regard  to  the  origin  of  the  green  line,  obser- 
vations show  that  nitrogen  is  a  prominent 
component  of  the  atmosphere  to  its  very 
iiipper  limits. 

6. — To  explain  this  fact  we  must  either 
assume  for  the  auroral  region  an  increasing 
temperature  nmoimting  to  scleral  hundnnl 
degrees  centigrade,  or  we  must  assume  that 
nitrog«'n  i.s  kept  up  by  the  effect  of  electric 
forces.  Various  circumstances  seem  to  ex- 
clude the  first  possibility. 


358 


TfiB  CKteMICAii  NfiWS. 


JDECEMBER  7,  1923. 


7. — The  differential  equation  for  the  varia- 
tion of  density  in  an  electrified  atmosphere 
has  been  found,  but  its  solution  has  not  been 
carried  farther  because  some  simple  calcula- 
tions have  shown  that  a  highly  electrified 
upper  gas  layer  cannot  exist. 

8. — if  we  adhere  to  the  hypothesis  that 
nitrogen  is  driven  upwards  by  electric  forces 
we  are  led  to  the  assumption  that  the  nitro- 
gen in  the  upper  layer  is  condensed  into 
small  crystal  particles,  which  are  then  elec- 
trified through  the  photo-electric  effect  of 
the  sun's  rays  of  very  short  wave-lengths. 

9. — The  auroral  spectrum  should  be  pro- 
duced when  electric  rays  from  the  sun  pene- 
trate into  the  layer  of  nitrogen  dust. 

10. — The  colour  changes  of  the  aurorse  are 
explained  through  disintegration  or  evapora- 
tion of  the  dust  particles  caused  by  the  cos- 
mic electric  rays. 

11. — Our  view  with  regard  to  the  physical 
state  of  the  atmosiphere  gives  a  simple  ex- 
planation of  the  following  phenomena:  — 

(a)  The  sudden  change  of  colours  along 
the  track  of  a  meteor. 

{b)  The  increase  of  the  maximum  height 
of  aui'oral  rays  as  we  pass  towards  lower 
latitudes. 

(c)  The  zodiacal  light. 

(d)  The  blue  colour  of  the  sky. 

(e)  The  twinkling  of  fixed  stars  and  the 
absence  of  twinkling  in  the  case  of  planets. 

(/)  The  reflection  of  electric  waves  and 
sound  waves  from  the  upper  layer  of  the  at- 
mosphere. 

(g)  The  secondary  auroral  phenomena. 

(h)  The  absence  of  an  upper  layer  con- 
sisting of  the  light  gases,  hydrogen  -and 
helium. 


INDIGOID    DYE  STUFFS. 

Part  I. 

By  R.  F.  Hunter,  F.C.S. 

(Continued  from  Page  341.) 

Bayer's  synthesis  of  1880  was  improved 
two  years  later  by  his  synthesis  from  o  nitro 
benzaldehyde.  o-Xitrobenzaldehyde  was 
condensed  with  acetone  in  the  presence  cl 
alkalis  to  o  nitro  phenyl  lactone  methyl  ke- 
tone. This,  on  treatment  with  alkalis,  eli- 
minated water  and  acetic  acid  passing  into 
indigo.  The  hydroxy  ketone,  on  dehydra- 
tion with  acetic  anhydride,  yielded  o  "nitro 
styrl  methyl  ketone  which,  with  alkalis, 
gave  indigo. 


These,  however,  were  not  of  commercial  j 
value,  since  toluene  was  the  starting 
material.  In  1890  Heumann  published  a 
new  synthesis  of  indigo,  the  starting 
materials  of  which  were  benzene  and  acetic 
acid.  Aniline  was  obtained  from  benzene 
and  monochloracetic  acid  from  acetic  acid, 
and  these  were  condensed  to  give  phenylgly- 
cine.  This,  on  fusion  with  alkalis  at  300° 
or  above,  eliminated  water,  giving  indoxyl. 
This,  by  atmospheric  oxidation,  gave  indigo, 
the  yield,  however,  was  bad.  Three  years 
later  accomplished  the  synthesis  in  exten- 
sive use  to-day,  viz.,  the  anthranilic  acid 
synthesis.  Anthranilic  acid  condensed  with 
chloracetic  acid  yields  phenyl  glycine  o  car- 
boxylic  acid.  This,  ou  alkali  fusion,  gives 
indoxylic  acid,  and  this,  on  oxidation,  gives 
indigo.  Seven  year's  later  the  process  was 
being  worked  on  a  conmiercial  scale  by  the 
Badische  anilin  and  Soda  Fabrik.  The 
trouble  was,  of  course,  to  obtain  a  suitable 
source  of  anthranilic  acid;  naphthalene  pro- 
vided this.  Naphthalene  being  oxidised  to 
phthalic  acid  by  means  of  sulphuric  acid 
and  mercury,  this  being  converted  into  its 
anhydride,  and  thence  to  the  imide  by 
means  of  sulphuric  acid  and  juercury,  this 
being  converted  into  its  anhydride  and 
thence  to  the  imide  by  means  ot  ammonia, 
and  this,  on  treatment  with  caustic  soda 
and  chlorine,  giving  anthranilic  acid.  The 
process  of  condensation  has  been  recently 
modified,  the  acids  being  condensed  in  the 
form  of  their  alkali  salts.  A  still  better 
modification  is  to  treat  the  sodium  salt  of 
anthranilic  acid  with  sodium  bisulphite 
compound  of  formaldehyde  and  with  sodium 
cyanide;  a  nitrite  is  obtained  which  hydro- 
lyses  to  phenyl  glycine  car  boxy  lie  acid. 

A  synthesis  allied  to  Heuman's  consists 
of  condensing  aniline  with  ethylene  chloro- 
hydrin  ant  fusing  condensation  product 
with  caustic  soda,  the  melt,  on  oxidation, 
yielding  indigo.  Another  synthesis  is  by 
heating  glycollide  with  aniline  at  200°,  the 
product  being  glycollanilide.  This,  on  al- 
kali fusion,  gives  a  mixture  of  indoxyl  and 
indoxylic  acid,  and  this,  on  oxidation,  yields 
indigo. 

Sandemeyer's  synthesis  is  worthy  of  note. 
Aniline  is  converted  into  thio  carbanilide. 
This,  warmed  with  KCN  and  white  lead  in 
aqueous  alcohol  at  60°,  yields  hydrocyano 
diphenyl  carbimide.  This,  on  treatment 
with  AmjS  for  two  days  at  30°  proceeds  to 
the  thioamide.  This,  with  H,SO^  at  110°, 
gives  isatin  and  anilide.  This,"  on  reduction 
with  Am^S,  yields,  firstly,  thio  isatin,  and 
finally  indigo.      Another    synthesis    by  the 


DEOEMBliR  7,  1923. 


THE  CHEMICAL  NEWS. 


35d 


same  author  depends  on  the  preparation  ol 
isatin  anilide  by  action  of  concentrated 
HjSO.,  on  aniidine  obtained  by  condensa- 
tion of  aniline  and  chloroloxime. 

Among  the  other  syntheses  of  indigo,  we 
might  mention  Nencki's  synthesis  of  indigo 
by  action  of  ozone  on  indole.  Camp's  syn- 
thesis from  o  nitro  acetophenone.  Homol- 
ka's  preparation  from  o  amino  aceto  phe- 
none,  which  on  heating  at  '200°  with  sul- 
phur in  a  high  boiling  solvent,  eliminnted 
hydrogen  as  HjS  giving  indigo.  Simoni's 
synthesis  from  dianilinomaleic  acid  from 
aniline  and  dibromomaleic  acid  ie  worthy  of 
note. 

Bauer's  preparation  from  oxanilide  is  Hke- 
wise  of  interest,  and  Keissert  prepai'ed  in- 
digo in  the  following  way  :  o  nitro  toluene 
was  condensed  with  ethyl  oxalate  in  (pre- 
sence of  sfKlium  ethoxide  tf>  give  ethyl  o 
nitro  phenyl  pyruvate,  which  on  reduction 
gave  N  hydroxy  indole  carboxylic  acid, 
which  he  oxidised  to  indigo.  Indple,  the 
starting  point  of  Madolung's  preparation, 
has  been  synthesised  in  a  number  of  wa\8. 
o  nitro  w  chloro  styrene  obtained  by  bleach- 
ing powder  on  o  nitro  cinnamic  acid  is  re- 
duced to  aminochloro  compound.  This,  on 
heating  with  sodium  ethoxide.  gives  indole : 
o  nitro  benzaldehyde  can  be  o<Miverted  into 
o  aminobenzaldehyde,  this  to  o  aminoben- 
zaldoxime,  and  this  to  corresponding  o  al- 
dehyde glycine ;  this  is  converted  into  indoh- 
by  ring  closure  brought  about  by  heating 
first  with  acetic  anhydride  and  anhydrous 
srxJium  acetate,  and  then  with  aqueous  al- 
kalis. 

Indole  treated  with  amyl  nitrite  and 
sodium  ethoxide  gives  isonitroso  indole. 
This  can  b<'  reduced  to  aminoindolo,  this 
oxidised  to  indigo  doiminc.  and  this  hydro- 
lyaed  by  boiling  HCl  to  indigo. 

It  is  now  propcwed  to  deal  with  some  of 
the  derivatives  and  analogues  of  indigo, 
and  it  is  further  prajiosed  to  use  the  classi- 
fication used  by  Thorpe  and  Ingold  in  their 
recent  work  on  Vat  Dyestuffs.  The  first 
group  of  compounds  to  be  considered  are 
the  halogen  derivatives  of  indigo.  The  fol- 
lowing compounds  habe  been  described  : 

5  Monochloro  indigo; 

5:5'  dichloro  indigo; 


5:7:5'  Thichloro  indigo;  . 
5  : 7  : 5' :  7'  Tetrachloro  indigo ; 
5  Monobromoindigo ; 
5:5'  Dibromo  indigo; 
5:7:5'  Tribromo  indigo; 


5:7:5' 


Tetra  bromo  indigo; 


4  : 5  : 7  : 5' :  7'  Penta  bromo  indigo ; 

4  : 5  : 7  : 4' :  5' :  7'  Hexa  bromo  indigo ; 

5  Chloro  5'  bromo  indigo ; 

5  Chloro  7:5'  dibromo  indigo; 
5  Chloro  7  :5'  :7'  tri  bromo  indigo; 
5:7:5'  Triohloro  7'  bromo  indigo ; 
4:4'  Dibromo  indigo; 
5:5'  Dibromo  indigo; 
G:6'  Dibromo  indigo; 
7  : 7'  Dibromo  indigo ; 
5:7:4:7'  Tetra  chloro  indigo ; 
5  :6  :5'  :6'  Tetra  chloro  indigo; 
Oct  a  chloro  indigo. 
Octa  bromo  indigo; 
5  : 7  Dibromo  indigo ; 
6:6'  Dichloro  indigo. 
The  following  nitro  and  amino  compounds 
have  been  described  :  — 

5  :5'  Diamino  indigo; 
6:6'  Dinitro  indigo; 

6  :6'  Diamino  indigo; 

6:6'  Diamino  5:7:5':7'  tetra  bromo  in- 
digo. 

Among  the  sulphonic  and  carboxylic  acid 
derivatives  we  might  mention:  — 

Indigo  5  mono  sulphonic  acid; 

Indigo  5:6'  disulphonic  acid; 

Indigo  5:5:7'  tri  sulphonic  acid  ; 

Indigo  4:4'  dicarboxylic  acid. 

As  hydroxy  and  methoxy  derivatibes,  we 
have  :  — 

4:4'  Dichloro  7:7'  dihydroxy  indigo; 

4  : 4' :  6  : 6'  Tetra  chloro  7  : 7'  dehydroxy 
indigo ; 

5  : 5'  dihydroxy  indigo ; 

7  : 7'  Dihydroxy  indigo ; 

4  : 4'  Dimethoxy  indigo ; 

5  : 5'  Dimethoxy  indigo. 

6:6'  Dimethoxy  indigo;  and  the 
7  : 7'  Dimethoxy  indigo. 
As  homologues  of  indigo  there  are:  — 
7  : 7'  Dimethyl  indigo ; 
a  Naphthalene  indigo;  and 
P  Naphthalene  indigo. 
A  diphenyl  derivative    has  recently  been 
preipared :  — 


CO  NH 

NH,C,H,-C.H,   <j^j^>^  =  <'    <^^  >aH,CeH.NH, 

5:0'  Di  p  amino  pbonyl  indigo. 


The  Royal  College  of  Science,     South  Kenaingfon,  S.W.I. 


September,  1923. 


360 


tfiE  CHEMtCAL  WBWS. 


MCEMBEK  7,  1923. 


WHAT  CHEMISTRY  SHALL  BE 

TAUGHT  IN  HIGH  SCHOOL  AND  HOW 

IT    SHALL  BE  CORRELATED  WITH 

COLLEGE    CHEMISTRY. 

By  Louis  W.  Mattern. 

Chemical  Department  McKinley   Technical 
High  School,  Washington,  D.C. 

{Abridged  from  the  "School  Science  and 
Mathematics,"  Vol.  XXIII.,  No.  7,  Octo- 
ber, 1923.) 

{Continued  from  Page  349.) 

At  the  very  beginning,    the  high    school 
student  in    chemistry  should  be    brought  in 
full  harmony  with  the  fact  that    chemistry 
is    guided    by    fundamental    principles,     or 
laws,  which  find  a  great  variety  of  material 
expressions,     and  is  not  a  mere  memorisa- 
tion of  unrelated,    isolated  facts,    and  bug- 
bear equations.     Professor  Remsen's  state- 
ment to    a  class  of    students  in    chemistry- 
might  well    be  a  motto  for    all  high    school 
students  in    chemistry  :     ' '  Those    who  are 
looking    for  anything    else  than    a  clarifica- 
tion of  fundamental  principles  need  not  stop 
Jiere."     All  experiments  should  lead  to  the 
development  of  fundamental  principles,  and 
their     application    in     experiments    having 
problems    to  solve,    and  not  merely    enter- 
taining tests,    revealing    no  principles    nor 
relationships.       Too  often,     students    have 
been  pushed  into  the  applications  of  chem- 
istry without  a  knowledge    of  those  funda- 
mental principles  of  which  the  applications 
are  but  the    expressions,    and    thus  in    the 
wild  rush    to  be  practical,    the  very    thing 
that  will  produce  practical  results  has  been 
omitted.      As  time  peiTnits,  many  applica- 
tions should  be  presented,  but  always  illus- 
trative of    fundamental  principles.        Prin- 
ciples and    applications  are    the    combina- 
tions that    will  produce    far  more    interest 
and  permanent  benefit  than  short  industrial 
{^nd  applied  courses    m  chemistry    without 
the  proper  foundation  of  fundamental  prin- 
ciples.      George  W.  Walker,    of  the  Hupp 
Motor  Car  Corporation,  even  goes  so  far  as 
to  state:     "  For  the  best  training  and  edu- 
cation of  the    individual  coemist,    the  first 
and  most  important  thing    is    to   forget    all 
about    industry,"    and,    "  A    student    who 
intends  to  make  a    life  work    of    chemistry 
should    study    it  from  the    standpoint  of    a 
scientist  rather  than  the  standpoint  of  a  fae- 
tory  manager." 

The  chief  chemist  of    one  of  the    leading 


scientific  chemical  commercial  laboratories 
made  this  statement:  "  A  working  know- 
ledge of  fundamental  principles,  rather  than 
routine  ability  alone,  should  be  emphasised 
in  the  training  of  a  successful  chemist." 
William  C.  Ruediger  states:  "  The  person 
who  understands  the  theory  underlying  a 
line  of  activity  can  see  the  reasons  for  modi- 
fications and  advances  and,  having  a  basis 
for  assimilation,  can  adjust  himself  accord- 
ingly." 1  am  sure  that  college  professors 
of  chemistry  will  agree  that  a  firm  grasp  of 
certain  fundamentals  should  be  given  in  the 
chemistry  of  high  schools,  because  they  are 
essential  for  the  solution  of  the  many  im- 
portant problems  in  the  ever  widening  field 
of  chemistry. 

The  ability  to  make  a  correct  report, 
either  written  or  oral,  of  laboratory  work, 
seems  like  too  small  a  matter  to  mention  at 
this  time,  but  it  is  exceedingly  important. 
The  high  school  student  in  chemistry  should 
ptssess  this  ability  before  continuing  his 
collegiate  chemistry,  when  he  is  too  nmch 
engrossed  with  what  seems,  to  him,  to  be 
weightier  matters.  The  Chemical  Engineer- 
ing Education  Conference  "regards  English 
as  one  of  its  most  effective  tools,"  and  re- 
commends "a  special  course  in  report  writ- 
ing and  the  oral  ipresentation  of  projects." 
The  haste  to  cover  ground  in  a  limited  space 
of  laboratory  tdme  has  often  resulted  in 
abbreviating  laboratory  records,  until  they 
are  simply  answers  to  questions.  The  re- 
cord of  high  school  chemical  experiments 
should  contain  clear  cut,  accurate  state- 
ments of  the  purpose,  operation,  observa- 
tions, based  on  the  operation,  and  conclu- 
sions drawn  from  the  observations.  The 
conclusion  should  be  the  goal  of  the  pur- 
pose, and  between  these  the  logical  steps  of 
operation  and  observation  should  be  stated. 
AH  should  be  written  in  the  student's  own 
language,  except  the  purpose.  The  repeti- 
tion of  this  at  the  experiment  table  as  soon 
as  the  experiment  is  performed  will  fix 
habit.  It  is  just  as  important  to  know  the 
conditions  under  which  observations  were 
made  as  it  is  to  know  the  observations. 
Waiting  them  both  serves  to  unite  and  fix 
this  important  combination  in  the  student's 
mind,  as  well  as  to  acquaint  him  with  a 
method  of  making  records  that  will  be  of 
service  in  the  further  study  of  chemistry. 

Plainly,  if  the  high  school  students  in 
chemistry  nre.  to  possess  in  a  marked  degree 
the  ability  to  observe,  have  a  clear  working 
knowledge  of  certain  fundamental  ])rin- 
ciples,  and  can  make  good  clear    complete 


I 


t)BGEMBER  7,  1923. 


I'HB  CHEMICAL  NEWS. 


361 


records  of  experimental  work,  then  the  high 
school  teaoher  of  chemistry  must  not  be  a 
high  pressure  sipeed  arlisl,  drivmg  on  the 
highways  to  college  chemistry,  for  the  desire 
to  cover  too  nmch  ground  is  dangerous. 
The  high  school  is  distinctively  a  place  for 
the  development  of  those  three  things,  with 
the  paramount  virtue  of  thoroughness. 
Again,  too  much  speed  in  high  school  chem- 
istry is  detrimental  to  the  all-important 
matters  of  relationships  and  generalisations. 
Isolated  facts  nmst  be  co-ordinated  into  a 
system,  if  they  are  to  have  power.  It  is  not 
enough  to  know,  for  example,  that  sodium 
chloride  and  sodium  nitrate  will  produce, 
respectively,  hydrogen  chloride  and  hydro- 
gen nitrate,  but  that,  in  general,  all  chlor- 
ides and  all  nitrates  behave  in  a  similar 
manner;  or  that  oarbon  not  only  reduces 
copper  oxide,  but  acts  on  many  other  oxides 
in  the  same  way. 

How  might  any  view  be  correlated  with 
college  chemistry  and  college  chemistry 
with  the  high  school  view'.'  Just  as  the  So- 
ciety for  the  Promotion  of  Engineering  Edu- 
cation, and  the  National  En;^'iiieering  Socie- 
ties and  the  National  Committee  on  Mathe- 
m.atics,  appointed  committees  which  have 
recently  made  reports  on  the  improvement 
of  education  in  their  respective  brfinche«,  so 
I  would  suggest  that  thi-  pioper  officers  of 
the  American  Chemical  Society  appoint  m 
nucleus  committee,  and  this  conunittee  en- 
large its  number  to  include  a  sufficient  r« - 
presentation.  This  committee  should  be  a 
clearing  house  of  the  best  information  ol)- 
tainable,  and  make  a  comprehensive  study 
of  how  to  imiprove  educjitioUj  covered  by 
high  schools,  and  articulate  it  with  col- 
legiate chemistry  and  make  a  report  of  the 
same  to  the  American  Chirnical  Society  for 
its  approval.  Such  a  repoit  would  streng- 
then the  central  science  of  chemistry, 
which  plays  an  important  role  in  our  uidi- 
vidual,  national,  and  international  pros- 
perity. 

QEUERAL    NOTES. 

HISTORY  OF  THE  SPECT.\CLE 
TKADE.      . 

At  a  meeting  of  the  Optieal  Society,  lield 
at  the  Imp«'rial  College  of  Science  and 
Tochnologv.  South  Kensington,-  on  Tues- 
dav.  Nove'iiiber  27.  10-28,  Dr.  M.  von  \{<>\\i\ 
of  Jena,  delivered  the  1028  Thomas  T(Ming 
Oration.     The  date  was  the  123rd  anniver- 


sary of  the  delivery  by  Thomas  Young  of 
his  famous  Bakerian  Lectme,  "  On  the 
Mechanism  of  the  Eye."  The  subject  of  the 
oration  was  "  Contributions  to  the  history 
of  the  spectacle  trade  from  the  earliest 
times  to  Thomas  Young's  appearance." 

The  lecturer  divided  the  subject    chrono- 
logically into    six  parts,     and  detailed    the 
work  done  by  different  nations.       The  first 
period,    beginning  in  the  13th  century,  ex- 
tends   to  the    invention    of  printing,    about 
1148.      Comparatively   few   spectacles  were 
then  in  use,  and  our  knowled^'e  of  their  pro- 
duction,     distribution    and    price    is    very 
limited.     The  second  peri<xl,   relating  prin- 
cipally to  the  growth  of  the    South  German 
sipectacle    factories  from  about  1450  up    to 
1620,    is    much    better    known.        Thanks 
mainly  to  an  oculist  (Dr.  v.  PHugk,  of  Dres- 
den),   our  knowledge    of  the    statutes    and 
trauc    customs    is    quite    remarkable,    and 
exact  details  as  n^gards  the  outward  appear- 
ance of  the    spectacles    then    in  use,    their 
oonstructi<Mi,  distribution,    and    prices    are 
available.     At  about  the  same  time  Venice 
nmst  have  been  another  important  centre  of 
spectacle    manufacture,     but  vni fortunate- ly 
our  knowledge  of  the  glasses  produced  there 
is  deplorably  deficient.     We  are  aware  that 
in  the  early    davs    of    the    telescope     (the 
Dutch  form    and!    the    terrestrial    telescope, 
l)oth  made  of  single,  unachromatised  lenses) 
Venetian  craftsmen  were  supplying  these  in- 
stnnnents;  but  of  Venetian  spectacles    pro- 
per only  some  casual    hints    are    ascertain- 
able.      In    both    these    centres,    however, 
'near"  spectacles  (for  reading  and  working) 
only  were    made.       Notable    developments 
t(¥>K  place  in  Spain    from  about  1560  up  to 
1710:   distance-spectacles    fastened    to  the 
head    were  worn  everywhere,    even    in    the 
highest  circles  of  Spanish  aristocracy.     This 
we  know,  not  only  from  certain  French  his- 
t^H-ies  that  are    not    free    from    satire    and 
irony,     but    also    from    such    incontestable 
relics     as     pictures,     engravings,     medals. 
There  we  find  high  Spanish  dignitaries,    in- 
cluding   a  Viceroy    of    Naples,    represented 
with    nose-spectacles.       At  this    time    also 
Spanish    spectacles,    which    were    held    in 
position  by  threads  over  the  ears,    were  in- 
troduced to   China  and    Japan  by    Spanish 
Jesuits.      Another  chapter,    devoted  to  the 
decline  of  the  South  German  spectacle  fac- 
tf>ries  between  1620  and  1780  shows  the  de- 
velopment of  the  cheapest  n<>s<'  spectacles. 
The    chief    development    in    this    direction 
<^)ccurred  in  Niimberg,    between  about    1640 
and  1740,  in  a  clever  an  deflective  manner; 


362 


THE  CHEMICAL  NEWS. 


DECEMBEE  7,  1923. 


it  is  only  a  pity  that  the  makers'  princiipal 
object  was  to  turn  out  the  greatest  quantity 
of  extremely  cheap  (and  sufficiently  nasty) 
goods.  The  last  part  of  the  lecture  de- 
scribed the  growth  of  the  spectacle  grinding 
optician,  and  related  principally  to  the  Lon- 
don opticians  of  the  18th  century.  The 
patent  sipeoifications  have  preserved  exact 
data  with  regard  to  the  aims  and  methods  of 
these  old  craftsmen.  The  greater  accuracy 
indispensable  with  achromatic  objectives 
(invented  by  Chester  Moor  Hall  in  1733  and 
put  on  the  market  by  John  Dolland  after 
1758)  placed  the  London  spectacle  maker 
proper  on  a  much  better  footing  than  his 
Niirnberg  competitor  working  with  bad  tools 
and  to  a  very  small  degree  of  accuracy. 

THE  PEEPAEATION  OF  PUEE  SILVEE 
STIBIDE. 

By  EDViTARD  J.  Weeks,  M.Sc,  F.C.S.,  and 
William  V.  Lloyd,  B.Sc,  F.C.S. 

In  a  previous  communication  (The  Chemi- 
cal Neifs,  1923,  CXXVIL,  319),  one  of  us 
(E.J.W.)  showed  that  silver  stibide  could 
be  prepared  by  passing  stibine  into  dilute 
silver  nitrate  in  the  cold.  It  has  now  been 
found  possible  to  prepare  this  compound  in 
tiie  pure  state  in  the  following  way. 

Stibine  is  prepared  electrolytically  by  re- 
duction of  a  pure  antimony  cathode  in  N. 
sulphuric  acid  (Sand,  Weelis  and  Worrell, 
J.C.S.,  1923,  CXXIIL,  456-470),  and  after 
being  washed  and  dried  it  is  passed  through 
some  half  noiinal  silver  nitrate  in  the  cold. 
Silver  stibide  is  then  deposited  in  the  pure 
state.  The  silver  was  estimated  in  the  fol- 
lowing way  : 

The  silver  stibide  was  boiled  with  con- 
centrated nitric  aci  dfor  about  half  an  hour 
and  then  concentraterl  hydrochloric  acid 
was  added  and  the  whole  further  boiled  for 
half  an  hour.  The  antimony  went  into  solu- 
tion and  the  silver  was  deposited  as  silver 
chloride.  The  solution  was  diluted,  and  the 
chloride  estimated  in  the  Gooch.  The 
theoretical  percentage  of  silver  is  72.92  per 
cent.,  and  the  estimated  amount  was  found 
to  be  73.01  per  cent. 

The  fact  that  the  nitric  acid  produced  by 
the  action  of  the  stibine  on  the  silver  nitrate 
does  not  oxidise  the  silver  stibide  as  shown 
by  H.  Eeckleben  (Ber.,  1909,  XLIL,  1458- 
1464)  is  no  doubt  accounted  for  by  the  fact 
that  in  this  method  of  preparation  the  whole 
action  is  conducted  in  an  atmosphere  of  hy- 
drogen produced  from  the  antimony  cathode. 

Sir  John  Cass  Institute,  Aldgate. 
November  10,  1923. 


PROCEEDINGS  AND  NOTICES  OF 
SOCIETIES. 


THE  EOYAL  SOCIETY  OF  AETS. 

On  Monday,  December  3,  Cantor  Lecture 
(1),  entitled  Recent  Progress  in  the  Wool 
Industries,  was  read  by  Aldred  F.  Barker, 
M.Sc,  Professor  of  Textile  Industries,  the 
University,  Leeds. 

On  Wednesday,  December  5,  at  the  Ordi- 
nary Meeting,  a  paper  entitled  The  Work  of 
the  Royal  Botanic  Gardens,  Kew,  was  read 
by  Arthur  William  Hill,  M.A.,  Sc.D., 
F.E.S.,  F.L.S.,  Director  of  the  Eoyal  Bo- 
tanic Gai'dens,  Kew.  Prof.  C.  A.  Seward, 
M.A.,  F.E.S.,  F.G.S.,  F.L.S.,  presided. 

On  Friday,  December  7,  at  a  meeting  of 
the  Indian  Section,  a  paper  entitled  The 
Archives  of  the  Honourable  East  India  Com- 
pany, will  be  read  by  W^illiam  Foster, 
CLE.,  Historiographer,  India  Office.  (Sir 
eGorge  Birdwood  Memorial  Lecture.)  The 
Eight  Hon.  Viscount  Peel,  G.B.E.,  Secre- 
tary of  State  for  India,  will  preside. 


THE  FAEADAY  SOCIETY. 

General  Discussion  on    "  Electrode 
Eeactions  and  Equilibria,"  November  26. 

The  Mechanism  of  the  Reversible  Elec- 
trode, by  Eric  H.  Eideal. 

One  of  the  oldest  unsolved  problems  in 
physical  chemistry  is  the  source  of  E.M.F. 
in  the  simple  galvanic  cell  and  the  mechan- 
ism of  its  production.  Ever  since  the  in- 
vestigations of  Vo'lta,  opinion  has  swung  to 
extremes,  oscillating  between  the  contact 
and  the  chemical  theories.  At  the  present 
time  there  are  supporters  of  each  view, 
whilst  a  centre  party  of  opinion  wishes  to 
ascribe  the  observed  potential  differences  to 
both  effects. 

For  our  purpose  we  must  exclude  all  irre- 
versible effects  caused  by  film  formation  at 
the  electrodes  or  alteration  in  concentration 
of  the  electrolytes  at  the  electrode  surfaces 
due  to  a  difference  in  the  rate  of  removal  of 
the  ions  from  the  skin  in  contact  with  the 
electrode  and  the  rate  of  supply  by  diffu- 
sion. 

A  close  examination  of  I'ho  literature  on 
the  capillary  electrometer  may  readily  lead 


DECEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


363 


to  the  conclusion  that  the  problem  of  the 
factors  influencing  the  surface  tension  of  a 
curved  mercury  surface  in  contact  with  an 
electrolyte  have  not  yet  been  solved.  It  is 
possible  that  the  Quincke  double  layer  has 
no  objective  existence,  and  that  the  inter- 
facial  electrification  is  the  result  of  ionic  ad- 
sorption. The  data  of  Smith  and  others 
clearly  point  to  both  cationic  and  anionic 
adsorption,  whilst  the  Lipmann  curve  may 
be  as  readily  deduced  from  the  Gibbs  sur- 
face tension  equation  as  from  the  hypothe- 
sis of  a  Quincke  electric  double  layer. 

Oxidation  and  Reduction  Potentials  of 
Organic  Compounds,  by  Einar  i3uLM.\NN. 

The  affinity  of  organic  chemical  proceaees 
has  only  been  measured  iu  very  few  cases  of 
distinct  transformations.  Since  1920  seve- 
ral investigations  on  affinity  giving  numeri- 
cal values  have  been  carried  out  on  reduc- 
tion-oxidation potentials,  otspeoially  of  tho 
typti  qiiinone-hydroquinoue.  1  have  tried  to 
study  the  leduction  potentials  <rf  some  few 
quinones  in  electrolytes  with  different  hy- 
drion  concentration. 

The  quinhydrone,  the  quinone-quinhy- 
droue,  imd  the  hydroquinone-quinhydrone 
electrodes  were  described,  and  an  account 
was  given  of  the  reduction  potentials  of  dif- 
erent  quinones  and  of  azo-compounds. 

The  Processes  at  the    Mercury    Droppiny 
(Uithode.       Part     I. —  the      Deposition     of 
Metals,    by  Jaroslav    Heykovsky,     n.S( 
Ph.]).,  Charles'  University,  Prague. 

Experimental  results  have  «hown  that  a 
polarised  drop  of  a  mercury  ca^pillary  ca- 
thode represents  a  reversible  state  of  equili- 
brium. On  each  polarised  drop  instantly 
the  numl>er  of  ions  is  dopostod  sufficient  to 
charge  it  by  tiieir  solution  tension  to  the 
balancing  back  E.M.F.  The  almost  stream- 
less  condition  of  polarisation  excludes  the 
secondary  effects  of  the  current  so  far  that 
the  potentials  at  which  ions  are  deposited 
from  various  concentrations  change  like 
the  potentials  of  e-oncentration  cells  with  re- 
versible metallic  electrodt  s.  Thus  this  ar- 
rangement allows  an  extension  to  the  study 
of  tri-  or  telra-valent  ionic  concentration 
cells.  Further,  since  the  freshly  deposited 
atoms  arc  always  in  an  active  condition;  the 
con(!lusion  seems  justified,  that  any  retar- 
dation (phenomena  oberved  in  the  deposition 
cannot  bo  due  to  surface  conditions,  but 
must  be  rather  sought  in  an  imperfect  ionic 
equilibrivun  of  the  solution  {e.g.,  in  the  case 
of  arsenic). 


This  circumstance  enables  us  also  to  de- 
cide whether  some  metallic  compounds 
exist  as  a  true  or  as  a  colloidal  solution. 

The  applicability  of  this  method  is  limited 
on  one  side  by  the  most  unnoble  lithium  de- 
position-potential at  about  -2.1  volts  from 
the  normal  calomel  electrode,  on  the  other 
it  stretches  to  +0.2  volt,  where  the  oxida- 
tion of  mercury  begins. 

Finally  it  may  be  pointed  out  that  tho 
method  can  be  equally  adapted  for  tho 
study  of  monaqueous  solutions  (see  Dr. 
Shikata's  subsequent  communication). 

The  Processes  at  the  Mercury  Dropping 
Cathode.  Part  II.— The  Hydrogen  Over- 
potential,  by  Jaroslav  Hbyrovsky,  D.Sc, 
Ph.D.,  Charles'  University,  Prague. 

The  chief  circumstance  that  allows  us  to 
follow  the  metallic  deposition  at  the  drop- 
ping mercury  cathode  up  to  cathodic  polari- 
sations over  -2.0  volts  (from  the  calomel 
electrode  potontial)  is  the  high  overpoten- 
tial  displayed  at  the  dropping  mercury. 

The  real  value  of  the  overpotential  of  hy- 
drogen, i.e.,  the  potential  at  which  bubble 
formation  takes  place  referred  to  the  hydro- 
gen electrode  in  the  same  solution,  is  thus 
in  normal  hydrochloric  acid  above  -0.9 
volt  (-1.2  from  the  calomel  electrode);  the 
ovenpotenti  •'  m>  inore  dilute  acids  is  still 
greater. 

It  seeiii>  .!>  1 1  the  presence  of  hydrogen 
ions  catalvses  the  production  of  hydrogen ; 
probably  bivause  the  more  acidic  solution 
exerts  a  stronger  oxidising  influence  upon 
the  diffusing  gas,  which  is  then  more  readily 
removed  from  the  electrode. 

However,  before  the  increase  due  to  the 
deposition  of  hydrogen  is  reached  (below 
-1.0  volt)  the  dropping  electrode  behaves  in 
the  presence  of  hydrogen  ions  exactly  as  in 
neutral  or  alkaline  solutions,  indicating  a 
similar  state  of  polarisation  equilibrium  in 
the  drop  surface. 

The  experience  with  polarisation  pheno- 
mena at  the  dropping  mercury  cathode 
leads  necessarily  to  the  view  that  only  hy- 
drogen atoms  are  electrochemical ly  activi- 
at  an  overcharged  electrode,  its  potential  de- 
pending on  the  relatively  very  few  hydrogen 
atoujs  present  at  the  cathode;  after  the 
union  to  molecules  the  gas,  which  is  far 
from  being  in  equilibrium  wifli  the  atoms, 
is  electrochemically  inactive  and  escapes. 

Tho  abnormally  high  overpotential  at  the 
dropping  cathmle  is  certainly  largely  due  to 
the  clean  freshly  formed  mercury  surface; 
however,  the  chief  factor  of  the  overpoten- 


364 


THfi  CHBMICAL  NEWS. 


DECEMBER  1,  192a. 


tial  must  not  be  sought  in  the  ideal  smooth- 
ness of  the  surface — as  is  sometimes  be- 
lieved-^but  rather  in  the  cathode  material 
itself. 

The  author  suggests  that  ions  of  unnoble 
atoms,  when  depositing  at  the  charged  elec- 
trode below  their  deposition  potential,  pass 
instantly  again  into  solution ;  the  number  of 
depositions  is  slightly  greater  than  the  num- 
ber of  atoms,  which  leave  the  surface,  so 
that  each  atom  stays  only  a  very  short  in- 
stance at  the  surface.  If  now  an  electrode 
material,  like  mercury,  has  no  affinity  for 
hydrogen  nor  exerts  any  physical  adhesion 
to  keep  the  hydrogen  atoms  longer  at  its 
surface  or  absorbs  them  inside  the  metallic 
phase,  the  atoms  of  hydrogen  stay  too  short 
a  time  to  have  sufficient  chance  to  come 
closer  together  and  to  combine ;  only  at  very 
negative  potentials,  when  their  deposition 
is  more  dense,  union  to  nrolecules  can  pro- 
ceed. The  molecules  then  freely  diffuse  off 
or  collect  into  bubbles.  If,  however,  the 
electrode  is  capable  of  absorbing  to  some  ex- 
tent the  deposited  atorns,  and  thus  shields 
them  against  the  dissolving  action  of  the 
olution,  the  atoms  have  occasion  to  com- 
bine below  the  surface,  and  escaping  as 
molecules  affect  in  such  cases  the  polish  of 
the  electrode. 

Some  influence  of  a  real  chemical  hydride 
fcn'mation  could  explain  disturbances  some- 
times encountered  at  the  dropping  cathode 
during  electrolysis  of  calcium  and  lithium 
salts,  which  were  due  to  occasional  bubble 
formation  at  the  mercury  drop.  The  hydro- 
gen here  evolved  might  be  due  to  the  union 
of  the  deposited  atoms  Li  +  H  or  Ca  +  2H 
to  hydrides,  which  arc  well  known  to  be 
highly  unstable  in  water  and  would  in  the 
aqueous  layer  at  once  form  molecular  hy- 
drogen. 

Noie  on  the  Standardisation  of  the  Sign 
of  the  Potential,  by  Prof.  A.  W.  Porter, 
F.ll.S. 

Determination  of  the  Affinity  Constants 
of  Bases  bi/  the  Hydroge^  and.  Quinhydrone 
Electrodes',  by  J.  N.  Puing,  M.B.E.,'D.Sc. 

A  determination  has  been  made  of  the  hy- 
drolysis and  affinity  constants  oi  a  number 
of  amino  bases  in  water  and  in  acetone- 
water  mixtures. 

Both  hydrolysis  and  affinity  constants  are 
affected  by  the  nature  of  tEo  solvent  to  an 
extent  which  it  has  not  yet  been  possible  to 


correlate  with  any  other  property  such  as 
dielectric  constant. 

With  a  few  exceptions,  bases  which  are 
arranged  in  order  of  decreasing  basicity  in 
water  have  the  same  order  as  a  similar  series 
in  the  other  solvents  employed. 

A  determination  of  the  dissociation  con- 
stant of  water  has  been  made  in  acetone- 
water  mixtures.  As  in  the  case  of  the  affin- 
ity constants  of  bases,  the  value  of  the  dis- 
sociation of  water  falls  rapidly  with  in- 
creasing acetone  content.    • 

The  author  expressed  his  indebtedness  to 
Mr.  a.  M.  Westrip  and  Mr.  T.  K.  Brown- 
son  for  their  collaboration  in  this  investiga- 
tion. 

Electrode  Potentials  in  Non-Aqueous  So- 
lutions, by  Emil  Baur. 

Only  one  single  method  is  available  for 
the  determination  of,  a  single  potential  dif- 
ference between  an  electrolyte  and  a  metal- 
lically-conducting electrode.  The  method 
is  base'd  upon  an  evaluation  of  the  electro- 
capillary  curve  of  mercury.  Investigating 
this  curve,  G.  Lippmann  showed  that  the 
surface  tension  of  mercury  passes  through  a 
maximum  when  the  polarisation  is  gradually 
being  raised.  At  this  maximum  the  charge 
on  the  mercury,  and  hence  potential  of  the 
mercury  against  the  liquid  with  which  it  is 
in  contact,  must  be  zero.  From  this  con- 
sideration Helmholtz  and  W.  Ostwald  con- 
cluded, that  the  measurement  of  the  poten- 
tial required  for  attaining  the  maximum  of 
the  Lippmann  curve,  would  determine  the 
potential  which  is  effective  at  the  mercury 
electrode  under  examination  in  its  polarisa- 
tion. When,  and  in  so  far  as,  this  potential 
is  identical  with  the  voltaic  potential,  i.e., 
the  change  in  free  energy,  under  the  condi- 
tions prevailing,  of  the  transition  of  mer- 
cury into  mercurous  ion,  it  must  be  permis- 
sible to  determine  the  voltaic  potential  with 
the  aid  of  the  maximum  of  the  Lippmann 
curve. 

It  has  subsequently  become  clear  that 
the  assumption  of  this  equality  is  not  al- 
ways justifiable.  When  so-called  capillar- 
active  ions  are  being  adsorbed  at  the  phase- 
boundai'y,  the  double  layer  of  ionic  adsorp- 
tion will  be  superposed  upon  the  Nernst- 
Helmholtz  double  layer. 

Recent  measiu'ements  allow  us  to  con- 
clud(>  that  in  the  case  of  inorganic  salts  the 
interface  potentials  corresponding  id  the 
partition  equilibrium  will  generally  be  of 
little  significance,  amounting,  perhaps,  lo  1 


DECEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


365 


centivolt.  Consequently  we  can  fix  abso- 
lute values  for  the  electrode  potentials  in 
utiy  nun-aqueous  solutions. 

Cu)i,centratiun  Cells  and  Electrolysis  of 
Sodium  Eihoxide  Solutions,  by  Dr.  M.\suzo 
Shikata,  IniiK^rial  University  of  Kyoto. 

To  investigate  the  nurcury  dropping 
electrode  for  the  study  of  electrolysis  in 
non-aqueous  solutions,  this  method  lias 
been  tested  on  scxliuni  I'thoxidu  solutions. 
The  reason  for  selecting  thi-  i  thoxide  solu- 
tions was  not  only  their  simplicity  of  coui- 
pfwition  and  preparation,  but  the  lack  of 
information  on  this  subject. 

The  chief  aim  concerning  the  droipping 
mercury  method  was  to  «ho\\  tiiat  the  de- 
position of  sodium  into  the  mercury  drops 
from  ethoxide  solutions  proeeids  reversibly. 
This  can  be  proved  by  compjiring  the  shift>< 
of  the  current-voltage  curvis  with  the  po- 
tentials of  ordinary  coneentr.ition  cells  with 
sodium  amalgam  electrodes. 

According  to  Heyrovsky,  tliu  sudden  in- 
crease of  current  observnblo  from  a  certain 
potentini  of  the  polarised  drop  is  duo  to  the 
formation  of  a  very  dilute  ;imalgam  of  a 
certain  composition,  which  begins  to  diflfuw 
into  the  interior  of  the  drops.  This  amal- 
gam then  must  have  the  same  comipoeiti<^>n, 
whether  coining  from  any  aqueoua  or  non- 
aqueous electrolysis. 

Therefore,  if  we  could  refer  the  "deposi- 
tion potentials"  of  the  polarised  drops  in 
alcohol  or  water  to  the  same  sodium  an)al- 
gam  electrode,  we  shotild  obtain  in  either 
case  an  identical  potential  Hifference. 

The  deposition  of  sodium  from  alcoholic 
ethoxifle  solutions  at  the  dropping  mercury 
cathode  was  found  to  proceed  reversibly  n-<5 
in  aqueous  solutions. 

The  activities  of  sodium  ions  meanured  by 
concentration  cells  with  soHiuip  amalgam 
electrodes  showed  an  abnormal  increase  in 
concentrated  solutions. 

Conductivities  and  vapour  pressures  of 
these  solutions  suggest  tliis  nnomaly  to  be 
due  to  the  diminution  of  solvation  of  sodium 
ions, 

(To  be  continucfl.) 


THE  CTTEMTCAL  SOCIETY . 

Oroinarv   Scirntific   MFKTiNfi,   Thursday. 

December  6. 

The  following  papers  were  read  :  — 

The  Additive    Formation    of    Four-Mem- 

hrrrd   lint, JIT    Part  TIT.     .1   SjiHtetu  of  No- 

menrlntnre  for  Heterocyclic  Fnur-Memhered 


Rings  and  the  Formation  and  Properties  of 
some  Derivatives  of  fi-Methylenedi-Imtne- 
oxidc,  by  C.  K.  IngoLD. 

^fhc  Dcixndencc  of  I'olurisation-ovvr- 
coltagc  on  Hydroxtjl  and  Hydrogen  Ion 
Concentration.  Part  I.  PoJarisation-over- 
voltage  of  an  Antimony  Cathode  in  Aqueous 
AlLalinc  Solution,  by  H.  J.  S.  Sanu  and  E. 
.J.  Weeks. 

Stereoisomerism  and  Local  Ancesthetic 
Action  in  the  fi-Eucaine  Group.  Resolution 
of  P-  and  Iso-fi-Euclaine,  by  H.  Kino. 

ft- Alizarin.  An  Isomeric  Form  of  Alizar- 
in, by  A.  CrREEN. 

The  Isomerism  of  the  Oximes.  Part  XV. 
The  Supposed  Fourth  Benzildioxinie,  by  O, 
L.  Braoy  and  F.  P.  Dunn. 

The  Alternation  in  the  Heats  of  Crystalli- 
sation  of  the  Normal  Monobasic  Fatty 
Acids,  bv  W.  E.  Garner  and  F.  C.  IUndall. 


ROYAL  INSTITUTION  OF  GREAT 

BRITAIN. 
A  general  monthly  meeting  was  held  nn 
December  3. 


THE  INSTITUTION  OF  ELECTRICAL 

ENGINEERS. 

The  Relations  between  Damping  and 
Speed  in  Wireless  Reception,  by  L.  B.  Tur- 
ner, M.A. 

The  first  part  was  devoted  to  an  examina- 
tion of  the  ordinary  method  of  reowder 
working  in  wireless  telegraph  receivers,  as 
affected  by  the  dannping  of  the  receiver  cir- 
cuits. After  a  re^sum^  of  the  significances  of 
the  decrement  of  any  oscillatory  system,  its 
l)earing  on  the  possible  speed  of  recording 
Morse  signals  is  investigattvl.  The  quality 
(approach  to  correct  Morse  "shaping")  is 
estimated  from  calculated  curves  of  ampli- 
tude of  os<Mllation  set  up  in  the  receiver  by 
the  incoming  dots  and  dashes  constituting 
the  letter  "  I."  By  comparing  several  such 
curves,  a  minimum  practical  value  is  found 
ff>r  the  product  of  frequency  and  decrement 
and  duration  of  Morse  dot.  The  relation 
between  stpeed  of  signalling  and  the  requi- 
site transmitter  power  is  then  investigated. 
Part  I.  concludes  (Section  5)  with  a  sum- 
marj'  and  discussion  of  the  results  arrived 
at. 
An  improved  method  of  reception,  called 


366 


THE  CHEMICAL  NEWS. 


DECEMBER  7,  1923. 


"receiver  curbing,"  wa-s  described  and  ana- 
lysed. An  estimate  is  made  of  the  improve- 
ment obtainable,  and  practical  circuits  arc 
given  for  putting  the  method  into  effect. 


NOTICES  OF  BOOKS. 

Systematic  Organie  Chemistry,  by 
William  M.  Gumming,  B.Sc,  F.I.C,  I. 
Vance  Hopper,  B.Sc,  A.R.C.Sc.L, 
F.I.C,  and  T.  Sherlock  Wheeler, 
B.Sc,  A.R.C.Sc.L,  A.I.C.  Pp.  XXII. 
+  535.  1923.  London :  Constable  & 
Co.,  10-12,  Orange  Street,  W.C.2.  25s. 
net. 

Organic  Chemistry  has  become  so  com- 
plex, abounding  in  complicated  formulae, 
and  including  long  series  of  preiparations  and 
catalogues  of  constants  and  properties,  that 
the  task  of  writing  a  systematic  practical 
volume,  such  as  this,  is  very  great. 

The  three  authors  have  endeavoured  to 
produce  a  complete  laboratory  guide  for  the 
up-to-date  methods  of  preparation  and  esti- 
mation of  organic  comipounds.  The  intro- 
ductory ohajiters  deal  with  general  hints 
and  practical  information.  The  compounds 
are  then  studied  in  groups,  and  according  to 
the  linkings  of  the  carbon  atoms,  e.g.,  car- 
bon to  carbon,  hydrogen  to  carbon,  oxygen 
to  carbon,  etc.  Aliphatic  and  aromatic 
bodies  are  discussed  together  in  their  sys- 
tematic groups.  Altogether,  in  this  sec- 
tion, 178  reactions  are  studied,  involving 
the  description  of  381  preparations.  This  is 
not  all,  however,  since,  in  the  chapters  on 
dyes,  drugs,  electrolytic  and  miscellaneous 
preparations  the  number  is  brought  up  to 
nearly  500. 

Many  methods  given  in  recent  researches 
have  been  included. 

There  are  nine  chapters  dealing  with  the 
various  processes  of  qualitatively  estimat- 
ing different  elements  and  radicals  in  vari- 
ous types  of  compounds;  many  of  them  are 
of  very  considerable  technical  and  indus- 
trial importance.  The  last  two  chapters 
are  concerned  with  the  reagents  and  with 
qualitative  tests. 

Great  care  has  evidently  been  taken  in 
arranging  the  matter,  which  is  very  ably- 
presented,  and  it  would  be  out  of  place  to 
make  more  than  reference  to  the  small 
omissions  (e.g.,  the  alternative  method  of 
estimating  the  NO2  group),  which  might 
have  been  incorporated  in  this  very  comipre- 
hensive  volume. 


The  book  should  commend  itself  to  those 
engaged  in  directing  advanced  organic  lab- 
oratory work.  It  is  the  type  of  book  speci- 
ally suited  for  students  reading  for  final 
examinations,  and  for  post-graduate 
workers.  J.G.F.D. 


Practical  Mathematical    Analysis,     by 

HoRST    VON    Sanden,    translated    by    H. 

Levy,  M.A.,  D.Sc,  F.R.S.E.      Pp.  XV. 

+  195.      London:    Methuen    &  Co.,    36, 

Essex  Street,  W.C.2.     1923.      Price  10s. 

6d.  net. 

This  translation  on  applied  mathematical 
methods  is  of  interest,  since  it  bridges  the 
gap  between  the  theories  and  their  practical 
applications.  The  methods  are  developed 
with  the  object  of  expressing  the  results  in 
a  numerical  form. 

In  the  ipreface,  the  author  urges  that  the 
slide-rule  should  be  made  a  subject  of 
school  study.  An  explanation  of  its  prin- 
ciples would  certainly  enable  the  conception 
of  a  function  and  the  relative  limits  of 
accuracy  to  be  introduced  with  more  ease. 

The  book  is  of  interest  to  experimental- 
ists in  the  various  pure  and  applied 
sciences. 


Landolt-Bornatein,  Physikalisch-Chem- 
ische  Tabellin.  Funfte  Umgearbeitete 
und  vermehrte  Auflage,  herau.sgegeben 
von  Dr.  W.  A.  Koth  und  Dr.  K.  Scheel. 
In  zwei  Banden  Berlin  :  Verlag  von  Ju- 
lius Springer.  1923.  £9  7s.  6d. 
Eleven  years  have  elapsed  since  the 
fourth  edition  of  Landolt-Bomstein  ap- 
ipeared. 

During  this  period  physics  and  chemistry 
have  developed  very  considerably,  adding 
data  to  the  enormous  amount  already  accu- 
mulated. 

The  new  matter  in  the  present  edition  in- 
cludes chapters  on  Radioactivity,  Spectrum 
Analysis,  The  Physics  of  the  Atom,  Crystal 
Structure,  etc.  Other  sections  have  been 
enlarged,  so  that  the  work  is  a  really  re- 
markable achievement,  reflecting  great 
credit  upon  the  authors  and  their  collabora- 
tors. 


The  Journal  of  Scientific  Instruments  : 
Issued  By  the    Institute    of    Physics,    10, 
•  Essex  Street,  Strand,  London,  W.C.2. 
The  first  issue  of  this  Journal,    October, 
1923,  brings  to  our  notice  its  purpose  in  de- 
scribing methods  for  measurement  and    the 


DECEMBER  7,  1923. 


THE  CHEMICAL  NEWS. 


367 


construction  of  instruments  in  connection 
with  all  branches  of  scientific  work.  This 
is  the  first  publication  of  its  kind  in  Eng- 
land, and  we  h^ve  much  pleasure  in  heartily 
welcoming  it  as  being  a  medium  of  great 
utility  to  the  scientific  worker. 

Under  the  management  of  the  Institute  of 
Physics,  and  with  the  co-Qperation  of  ihf 
National  Physical  Laboratory,  tills  montlily 
publication  should  become  a  medium  of 
national  value. 

The  Editorial  Board  is  a  strong  one,  in- 
cluding Sir  R.  T.  Glazebrook,  K.C.B.. 
F.R.S.,  Sir  J.  J.  ITiomsfm,  O.M.,  F.R.S. 
and  others  of  eminence.  The  secretary,  F. 
S.  Spiers,  O.B.E.,  B.Sc,  may  be  commu- 
nicated with  in  regard  to  all  matters  otlur 
than  those  customarily  dealt  with  by  th'' 
editor,  such  as  MSS. 

BOOKS  RECEIVED. 

Uses  of  Waste  Materials,  by  Prof.  Ak- 
TURo  Bruttini.  Pp.  XX.  +  367.  1023. 
Messrs.  P.  S.  King  &  Son,  litd.,  Orchiud 
House,  2  &  4,  Great  Smith  St.,  Westmin- 
ster.    128.  net. 

Lead,  by  J.  A.  Smythe,  Ph.D.,  D.Si . 
Pp.  VI.  +  343.  1923.  Messrs.  Longmans, 
Green  &  Co.,  39,  Paternoster  Row,  E.C.4. 
lOs.  net. 


PUBLICATIONS    RECEIVED. 

The  Royal  Technical  College,  Glasgow, 
has  just  issued  the  Annual  lieport  on  the 
One  Hundred  and  Twenty-stVLnth  Session. 
It  contains  an  account  of  the  Studies  (pur- 
sued and  the  successes  obtained,  and  also 
the  general  information  to  be  found  in  Col- 
lege Calendars. 

The  publications  and  papers  on  research 
vvr>rk  carried  (Kit  by  investigators  at  the 
(yollege  indicate  that  there  is  great  activity 
in  the  Chemical  Department. 

licport  1921-22,  with  the  Supplement  t 
the  "Guide  to  the  ExperiTiiental  Plrts.  " 
containing  the  yields  per  aer(>,  etc.,  has  just 
been  isused  by  thi'  Rothamst<^d  Experimen- 
tal Station,  Harpenden,  and  may  l)e  (tb- 
tained  from  the  Secretary,  price  2s.  6d. 

'J'he  work  done  during  the  period  under 
review  is  given,  and  there  is  a  summary  of 
the  results  of  original  investigation*  whieh 
have  been  published  in  various  journals. 

The  report  is  a  further  striking  indication 
of  what  can  be  achieved  by  the  constant  and 


continued  application  of  science  and  scien- 
tific principles  to  crop  productiiai  and  culti- 
vation. 


The  Department  of  Overseas  Trade  has 
issued,  through  H.M.  Stationery  Office,  a 
Report  on  the  Economic  Situation  of  the 
Netherlands  East  Indies,  to  June,  1923,  by 
H.  A.  N.  Bluett,  British  Commercial 
Agent  for  the  Netherlands  East  Indies, 
Hataviii.     1923.     Price  3s.  net. 

The  reiport  contains  a  general  review  of 
the  trade  of  the  Netherlands  East  Indies  for 
tlie  period,  and  indicates  the  prospects  for 
the  near  future. 

The  fact  that  the  Netherlands  East  Indies 
is  a  considerable  consumer  of  chemicals  and 
ciemical  manures  is  now  fully  realised  by 
British  manufacturers,  and  exports  to  this 
country  from  the  Uniti>d  Kingdom  have 
been  well  maintained. 

For  several  of  the  principal  iines  con- 
sumed tliere  is  an  increased  import  which 
has  largely  favoured  Great  Britain.  Many 
home  manufacturers  previously  not  repre- 
sented in  this  market  have  during  the  past 
two  years  established  trade  relations  with 
leading  importing  firms,  so  that  if  our  com- 
ipetitive  prices  are  maintained  there  is  now 
every  indication  tliat  in  future  the  United 
Kingdom  will  be  the  principal  supplier  of 
heavy  chemicals. 

In  addition  to  heavy  chemicals  there  is  a 
good  demand  for  refined  chemicals,  medi- 
cines, patent  medicinal  foods  and  photo- 
graphic chemicals,  also  chemicals  required 
for  the  manufacture  of  aerated  waters, 
syrups  and  cordials. 

Artificial  Dyes  and  Paints. — The  import 
of  dyes,  which  are  much  needed  for  the 
batik  industry,  remains  steady,  although 
with  the  exception  of  synthetic  indigo  the 
impwts  for  1922  show  a  decrease  on  1921. 
It  should  be  noted,  however,  that  stocks  at 
the  end  of  December,  1922,  were  much 
lower  than  at  the  beginning  of  that  year, 
and  as  the  present  demand  for  the  batik  in- 
dustry is  good,  it  is  expected  that  imports 
for  the  current  year  will  show  an  int^'ease  on 
1922. 


Livingstone     College 
1922-23. 


.Annual       Report, 


Chains  for  General  Entjinerring  Purposes. 
Price  List.     Hans  Reynold,  Ltd. 


368 


THE  GHEMIQAL  NEWS. 


DECEMl^ER  7,  1923. 


BULLETINS  ISSUED  BY  THE 

DEPARTMENT  OF  THE  INTERIOR, 

UNITED  STATES  GEOLOGICAL 

SURVEY. 

Gold,  Silver,  Copper,  Lead  and  Zinc  in 
the  Eastern  States  in  1922,  by  J.  P.  Dun- 
lop.     Pp.  77  +  14. 

Bauxite  and  Aluminum  in  1922,  by  James 
M.  Hill.    Pp.  87  +  96. 

Antimony  in  1922,  by  Edward  Sampson. 
Pip.  107  to  112. 

Fluorspar  and  Cryolite  m  1922,  by  Hu- 
bert W.  Davis.    Pp.  15  to  22. 

Salt,  Bromine,  and  Calcium  Chloride  in 
1922,  by  K.  W.  Cottrell.    Pp.  23  to  29. 

Asbestos  in  1022,  by  Edw.\rd  Sampson. 
Pp.  31  to  37. 

Nitrates  in  1922,  by  George  Rogers 
Mansfield.    Pp.  39  to  40. 

Graphite  in  1922,  by  Arthur  H.  Red- 
field.    Pp.  63  to  68. 

Boundaries,  Areas,  Geographic  Centres 
and  Altitudes  of  the  United  States  and  the 
Several  States  (with  a  brief  recor^l  of  impor- 
tant changes  in  their  territory),  bv  Edward 
M.  Douglas.    Pp.  VI.  +  234. 

Triangulation  and  Primary  Traverse. 
1916-1918,  by  C.  H.  Birdseye.    Pp.  914. 

Rock,  Formations  in  the  Colorado  Plateau 
of  South-eastern  Utah  and  NorThem  Ari- 
zona, by  C.  R.  Longwell,  H.  D.  Miser,  R. 
C.  Moore,  Kirk  Bryan,  and  Sidney  Paige. 
Pip.  23. 


« 


This  list  is  specially  compiled  for  The  Chemical 
News  by  Messrs.  Rayner  &  Co.,  Registered  Patent 
Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks. 

and  Designs  can  be  obtained  gratuitously. 
28997— Chemisohe     Fabrik      Griesheim-Elektron.- 
Manufacture  of  ac ylacetyl  compounds.  JNov. 
16.  „,     , 

Specifications  PtibUshed  this  Week. 
p-Nitrophenetol  is  prepared  by  heating  an 
aqueous  aicoliolic  solution  of  p-nitrochlorbenzene 
of  low  concentration  with  a  quantity  of  an  alka- 
line reagent,  such  as  sodium  ethoxide,  not  sub- 
stantially in  excess  of  that  chemically  equivalent 
to  the  ohloro-derivative,  at  or  above  the  normal 
lK)iling-point  of  the  aqueous  alcohol  and  without 
ebullition.  For  concentrations  of  the  chloro- 
derivative  of  3  per  cent,  and  upwards,  less  tlian 
the  equivalent  of  the  alkali  may  be  used.  Accord- 
u\s  to  examples,  concentrations  ot  3  and  .■>  per 
cent  of  p-nitrochlorbenzene  in  85  per  cent,  aico- 
liol  are  heated  with  sodium  ethoxide  and  caustic 
soda  reswotively  in  an  autoclave  and  at  tem- 
peratures of  90-120°  C.  To  piievent  reduction  to 
azoxy-compounds  the  autoclave  is  lined  with 
enamel,  silver,  or  nickel.  .  .    ,    ■, 

Messrs.  Ravner  &  Co.  will  obtain  printed  cx)pie6 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  bd. 
»ach. 


NOTICES. 


EDITORIAL.-— All  Literary  communica- 
tions and  Books,  Chemical  Apparatus, 
&c.,  for  review  or  notice  to  be  addressed 
to  the  Editors. 

SUBSCRIPTIONS  £1  10s.  per  annum, 
payable  in  advance,  should  be  addresse*! 
to  the  Manager. 

BACK  NUMBERS  and  VOLUMES  can  be 
purchased  on  application  to  the 
Manager. 

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rent week's  publication  should  be  for- 
warded to  the  Advertisement  Manager, 
The  Chemical  News,  Limited,  97,  Shoe 
Lane,  E.C.4. 

All  Cheques  and  Post  Office  Orders  should 
be  crossed  "  The  Westminster  Bank. 
Limited,"  made  payable  to  the  order  of 
The  Chemical  News,  Limited,  and 
addressed  to  the  Manager,  The  Chemical 
News,  97,  Shoe  Lane,  London    E.C.4. 


DECEMBER  14,  1923, 


THE  CHEMICAL  NEWS. 


869 


THE    CHEMICAL  NEWS, 

VOL.  CXXVII.      No.  3322. 


ARE    THE  NATURAL  GROUPINGS    OF 

THE  ELEMENTS  AND  THE  SPECTRAL 

LINES  OF  HYDROGEN  RELATED? 

Part  VI. 
By  F.  H.  LoRiNG. 

In  continuation  of  the  above  study  from 
The  Chemical  News,  1923.  CXXVII.,  p. 
355,  the  following  observations  will  be 
given  :  — 

Notes  and  Commknts. 

1. — The  advent  of  the  octet  theory  of 
atomic  structure  and  the  pnlnetary  theory 
of  the  atom  as  developed  by  Niels  Bohr  has 
placed  before  chemists  a  quantitv  of  valu- 
aWe  theoretical  matter  which  is  difficult  to 
harmonise ;  for.  How  can  the  electrons  de- 
scribe elliptical  and  circular  orbits  round 
atomic  nuclei  and  at  the  same  time  function 
as  practically  stationary  bodies  dispos«;d 
round  each  nucleus  in  various  patterns  us 
demanded  by  the  followers  of  the  octet 
theory  V 

It  nas  been  suggested  in  this  paper  that 
the  Bohr  orbits  are  in  reality  radiation  or- 
bits, and  thai  the  vibrations  of  the  electrons 
are  elcctro-niechanically  equivalent  to  such 
orbits.  It  was  shown  that  ponderable  mass 
as  such  need  not  be  a  factor  in  the  pheno- 
mena of  orbital  paths,  since  the  orbits  were 
not  finally  governed  by  the  moving  mass 
magnitudes;  but,  on  the  other  hand, 
velocity  is  an  important  factor.  In  addi- 
tion to  this,  the  entranf  direction  of  the 
moving  entity  should  be  takin  into  account. 
For  example,  a  comet  entering  the  solar 
system  in  a  certain  direction,  i.e.,  moving 
towards  the  immediate  region  of  the  sun. 
while  then  travelling  with  a  certain  velocity, 
will  fall  under  the  sun's  influence  and  de- 
scril)e  a  certain  orbit  round  it.  At  the  most 
distant  part  of  its  orbit,  that  is  to  say,  at  its 
aphelion,  the  comet  is  moving  at  a  momen- 
tary zero  velocity  relative  to  the  sun,  and  it 
is  then  that  it  changes  its  direction  and  re- 
turns to  the  region  of  the  sun,  the 
f>rbit  Ix'ing  elliptical :  just  as  a  ball 
thrown  upwards  from  the  earth  comes 
instantaneously  at  rest  relative  to  the 
earth  at  a  certain  height,  and  then 
falls  back  to  the  earth,  describing  an  ellipse 
having  no  area — which  is  a  straight  line. 
Whether  the  ball  bo  light  or  heavy,  wi*,hout 


air  friction  it  could  be  made  always  to 
describe  the  same  path  or  orbit  of  zero  area, 
and  its  acceleration  would  be  the  same  also. 
In  this  case  the  mass  of  the  ball  is  not  a 
factor  in  the  time-rate-of-change  of  velocity. 
The  planets,  that  travel  out  orbits  in 
accordance  with  the  place  law  of  Bode, 
vary  irregularly  in  mass  in  respect  to  one 
another,  so  that  no  direct  connection  be- 
tween mass  and  the  particular  orbit  selected 
is  possible.  Again,  the  effect  of  mass  is  an 
antecedent  one,  and  this  is  an  important 
matter,  for  mass  is  functionally  a  prior  con- 
diti<m  in  the  phenomenon,  which  is  related 
to  the  energy  expended  in  producing  the 
initial  velocity,  and  of  course  the  mapping 
of  the  subsequent  velocities  as  well,  for  it 
determines  the  velocity  at  which  a  given 
body  may  enter  a  planetary  system ;  or,  in 
the  instance  of  the  ball,  the  height  to  which 
it  is  thrown  by  the  thrower. 

Now,  if  the  orbits  which  the  planets  de- 
scribe be  regarded  as  definitely  predeter- 
mined places  in  space,  this  "predetermina- 
tion" must  rest  upon  the  antecedent  factors 
just  indicated,  so  that  any  orbit  is  possible, 
according  to  the  entrant  direction  and  velo- 
city, which  may  be  ctwisidered  jointly ;  and 
this  joint  effect  in  turn  rests  upon  the  pre- 
ceding event  in  which  the  energy  (1)  acting 
on  the  mass  (2)  were  the  predominating  fac- 
tors. The  whole  phenomenon  dates  back, 
as  it  were,  to  the  initial  energy  and  mass 
conditions,  which  have  to  \m^  considen^d  re- 
trospectively with  regard  to  the  entrant 
direction  and  speed  at  a  given  place  relative 
to  the  sun. 

The  orbit  in  the  hydrogen  atom  must 
similarly  depend  upon  the  initial  energy 
conditions  if  the  phenomena  discussed  are 
of  a  parallel  nature,  as  would  seem  to  be  the 
case.  The  formation  of  the  planetary 
system  then  is  akin  to  the  ccndition  of 
affairs  that  takes  place  in  the  spectrum 
processes  of  hydrogen;  but,  the  question 
arises — How  far  back  are  the  antecedent 
conditions  to  be  carried? 

Considering  the  atom,  since  there  is  only 
one  electron  belonging  to  hydrogen,  the 
antecedent  conditions  do  not  in  the  several 
processes  of  radiation  go  back  as  they  do  in 
the  planetary  system,  containing  nine 
planets  (counting  the  asteroids  collectively 
as  one).  Moreover,  since  the  hydrogen  or- 
bits are  mathematically  regular  and  always 
the  same  when  they  are  rendered,  so  to 
speak,  visible  by  the  resulting  emission 
lines,  the  energy  conditions  as  regards 
direction  nrjd  velocitv    is  nhvavs  the    same 


370 


THE  CHEMICAL  NEWb. 


DECEMBEK  14,  1923. 


for  each  line.     How,  theu,  can  this  state  of 
affairs  be  explained? 

It  seems  that  the  electron  can  only  take 
up  energy  in  multiples  of  a  given  quantum, 
and  give  out  energy  in  the  same  multiples, 
according  as  the  electron  is  driven  from  one 
"orbital"  place  (radial  place)  to  another,  and 
this  is  quite  in  accord  with  Bohr's  quantum- 
energy  theory  of  the  hydrogen  atom.  The 
electron  can  only  take  up  and  give  out  a 
quantum  of  energy  which  corresponds  to  its 
position  relative  to  the  nucleus,  and  there- 
fore it  must  be  under  a  constraining  in- 
fluence to  do  this ;  so*that  what  corresponds 
to  the  antecedent  event  in  the  case  of  the 
planetary  system  is  practically  concurrent 
with  the  radiation  phenomena  of  the  atom. 

This,  then,  involves  the  energy  and  viass 
of  the  electron,  if  the  case  is  like  that  of 
the  planetary  system ;  but  since  the  mass' 
factor  under  consideration  is  not  necessary 
to  the  orbit  as  such,  it  can  be  regarded  as 
the  determining  factor  in  the  vibration  of 
the  electron.  In  other  words,  in  the  case  of 
the  atom  the  antecedent  factor  is  the  vibra- 
tion of  the  electron.  The  immediately  sub- 
sequent factor  is  the  radiation  which, 
according  to  this  view,  describes  practically 
closed  orbits  round  the  nucleus,  and  the 
final  occurrence  is  the  passage  of  this  radia- 
tion out  as  a  radial  radiation  when  the 
electron  is  driven  or  falls  towards  the  nu- 
cleus into  another  position  of  equilibrium 
in  which  it  vibrates  according  to  its  place. 
The  influence  of  the  sun,  or  the  atomic 
nucleus,  is  of  course  most  important;  but 
the  observations  are  here  concerned  more 
particularly  with  the  behaviour  of  the  orbits 
in  resipect  of  their  relafive  spacial  positions. 

2. — One  difHculty  that  arose  from  the 
many-electrrn  orbits  of  Bohr's  theory  was 
the  complex  magnetic  phenomena  which 
should  theoretically  aiise  from  so  many  cir- 
culating negative  electrons  correspcmding 
in  effect  to  closed  electric  circuits.  The  hy- 
drogen atom  should  then  behave  like  such  a 
circuit  and  exhibit  magnetic  effects,  and 
many  elements  should  show  siiTiilar  effects ; 
whreas^  only  a  few  elements  give  rise  to 
strong  magnetic  phenomena,  these  being 
iron,  cobalt,  nickel.  Now,  in  the  atoms  of 
these  three  elements  there  may  be  elec- 
trons so  situated  that,  \mder  certain 
related  conditions,  they  are  free  to  de- 
scribe orbits,  but  in  practically  all  other 
elements  the  electrons  can  only  vibrate,  as 
according  to  this  study  such  a  conclusion 
seems  inevitable. 

3. — Beferring  to  the  wedge  periodic  table. 


attention  should  be  drawn  to  a  feature  of 
some  suggestive  value ;  that  is  to  say,  the 
characterisation  of  the  element  by  the  width 
of  the  wedge  where  the  element  falls.  In 
science,  geometric  representation  of  a  quan-  • 
tity  or  qu;Uity,  in  which  the  origin  of  the 
plan  is  not  known,  is  often  more  truly  scien- 
tific because  of  its  non-committal  nature ; 
for  truth  is  often  better  expressed  by  a  non- 
commital  scheme  than  by  one  based  upon 
highly  artificial  and  ingenious  hypotheses. 

4. — In  referring  to  the  spectral  lines  of 
hydrogen,  it  should  be  noted  that  there  are 
several  types  of  spectra,  namely  :  (1)  the 
Balmer  series  lines;  (2)  the  many-lines 
spectrum,  called  the  secondary  spectrum  of 
hydrogen;  (3)  the  Lyman  series  lines;  (4) 
the  Paschen  series  lines ;  (5)  the  Brackett 
series  lines ;  (6)  a  continuous  spectrum  with- 
out lines;  (7)  a  fine-line  series  due  to  the 
reliitivity  effect  in  connection  with  each  so- 
called  single  line.  In  the  case  of  the  Balmer 
series,  it  is  frequently  expressed  mathe- 
mathematically  in  v  terms,  as  are  also  the 
others  of  like  type,  as  follows: — • 
1      1 

V  =   N    — - —     (Lyman.) 

1^  n" 
1      1 

V  =   N    — - —     (Balmer.) 

2^  n2 
1      1 

V  =   N    — - —     (Paschen.) 

3^  n^ 
1      1 

V  =   N    — -—     (Brackett.) 

4^  n^ 
N   =   the  Rydberg  constant. 

The  frequency  equals  the  velocity  of  light 
(c)  in  centimetres  per  second  divided  by 
wave  length  (A),  also  in  centimetre  mea- 
sure; but  the  Rydberg  constant  is  usually 
evaluated  by  the  equation  in  which  v  = 
ivave  number,  or  1/A  cm.,  so  that 

_  N  =  (4wVn2-4)   X    (1/A  cm), 
in  which  n  for  the  Balmer  series  runs  3,  4, 
5,  6,  7,  &c. 

5. — Referring  to  the  planets  and  the  group 
numbers,  the  average  percentage  of  eiror, 
not  counting  the  asteroids,  is  as  follows:  — 
(-0.29)  +  (-1.16)  +  (-0.33)  =  (-2.78). 
(-2.78/3)  =  (-0.926).  (-0.926)  -  (+0.28) 
=  (-0.646).  6.72  +  9.29  +  14.16  +  48.33 
=  78.50.  78.50/0.646  =  121.  100/121  = 
0.8  per  cent.  The  resipective  summations 
are  77.0  and  78.50. 

6. — Referring  to  Bode's  law,  it  will  be 
seen  that  it  is  not  mathematically  regular 
in  respect  of  the  iTrst  term  ;  and  that  it  de- 


DECEMBER  14,  1923. 


THE  CHEMICAL  NEWS 


371  - 


parts  appreciably  from  the  planetary  values 
above  52.02.  Similarly,  the  group  rule  in- 
dicitted  agrees  with  the  pfauetary  values 
just  where  Bode's  law  agrees,  thus  suggest- 
ing that  the  complete  law  of  the  planets  is 
iperhaps  expressible  by  two  formulae. 

7. — The  coronium  line,  5303,  would  by 
the  fra-mula  given  correspond  to  the  upper 
limit  of  the  asteroids,  for  it  would  give  a 
value  28.7.  The  mean  28.7  +  21  =  24.8, 
which  is  clf>se  to  the  asteroid  mean  of  25. 
No  importance  whatever  can  be  attached  to 
this  observation ;  but  it  is  given  to  show 
that  strange  lines  might  be  considered  in 
connection  with  the  relations  given. 

8. — Having  accorded     preference    to  Ve- 
gard's     theory     in     resipect    of    the    con- 
stituent of  the  upper  atmospHere,  attention 
may    be     here    drawn    to    another    theory, 
equally  valuable  for  the  pui  pose  of  the  main 
argument,  due  to  H.  Bongards  (Pfct/«.  Zeit., 
1023,    Vol.  XXIV.,  p.  270).      This  paper  is 
abstracted  in  Science  Abstracts  for  Novem- 
ber, 1023 ;    and  to   give  the  readers  of    Thr 
Chrwiral  News    this    informati<Mi,    the  ab- 
stract is  mainly  reproduced  here:    "Rlipher 
found  for  the    wave-length    of  a  green    line 
discovered  by  Wiechert    in  the  night  sky  of 
middle  latitudes  the  wave-length  5578.05  A, 
while  Vegard  found  A  =  5578.2+1  for  what 
is  generally  regarded  as  the  same  line  in  the 
aurora.     A  faint    line  in  the  multipbj    line 
spectrum    of    hydrogen.    A  =  6578.3,    can 
.hardly  l)e  identified  with  this;    and  the  only 
other  known  line  of  the  right  wflve-length  is 
A  =  5577.08  in  the  blue  spectrum  of  argon. 
There  are  many  other  lines  in  this  spectrum 
and  in  that  of  the  aurora  .  but  so  far  the  lat- 
ter has  not  been  measmcd    with    sufficient 
accuracy  to    alk)w  of  identification,    as  the 
mniil)er  in  both  cases  is  so  large  at  the  violet 
end  of  the  sipectrum ;  but  there  is  additional 
evidence  in  the  fact  that  in  the  red  portions 
of  the  aurora  Vogel  found  two  bright  lines. 
A  =  0207  and  A  =  5180;    these    measure- 
ments were  taken  in  1871,  and  are  regarded 
as  fairly  accurate.      In  the  red  argon  spec- 
tnun,  which    appears    to    be  due    to  argon 
atoms  which  have  lost  one  electron,  Paschen 
found  a  bright  line.  A  =  ()207.15,  and  Kay- 
ser  another.  A   =   5188.40:    these  are  pr«)b- 
ably  identical  with  the  al)Ove  auroral  lines. 
In  spit<>  of    its  high  d<>nsity  argon    may  be 
present    normally    in     the    atm<^>«phere     at 
h«'ight^  above  100  km.  where  the  aurora  is 
seen;  volcanic  eruptions  may  carry  this  gas 
to  great  heights,    and  the  thermodynamieal 
properties  of  mf>natomie    gases  favour  their 
renuiining    at  high    elevaHons    when    tliev 


have  attained  them;  the  author,  however, 
favours  the  view  that  argon  particles  are 
ejected  from  the  sun,  with  very  high  veloci- 
ties, and  entering  the  earth's  atmosphere 
produce  the  aurora.  There  are  difficulties 
in  the  way  of  this  theory.  The  absence  of 
Doppler  effect  indicates  a  velocity  less  than 
3  X  10'  cm.,  which  would  not  enable  the 
particles  to  penetrate  so  deep  into  the  at- 
mosphere; the  argon  particles  may  leave 
the  sun  strongly  positively  charged,  with  a 
very  high  velocity,  and  being  devoid  of  the 
electrons  which  are  concerned  in  radiation 
do  not  begin  to  emit  light  until,  by  colli- 
sions with  the  atoms  of  the  air,  they  have 
lost  much  of  their  velocity,  and  picked  up 
the  necessary  electrons.     . 

A  Modified  View    of  the  Atom  Arising 
Out  of  this  Study. 

0. — If  the  extended  argument  of  this 
study  is  in  general  true  in  its  purport,  then 
it  can  be  said  that  the  natural  grouipings  of 
the  elements  are  linearly  related  to  the 
wave-lengths  of  the  first  five  Balmer  lines 
of  hydrogen ;  but  still  further  evidence  is 
nei'ded  before  the  argument  as  a  whole  can 
reasonably  be  considered  sound.  It  was 
suggested  that,  in  conformity  with  the  find- 
ings of  this  study,  the  Bohr  atom  was  really 
static  as  regards  the  electron  movement 
other  than  vibration  and  radial  displace- 
ment, and  that  the  Lewis-Langmuir  theory 
could  stand  on  its  own  merits  as  a  conse- 
(juence. 

Now  it  is  not  out  of  order  to  consider  an 
atom-model  along  the  lines  suggi^sted.  In 
the  first  place  it  will  be  conducive  to  clear- 
ness to  state  the  facts  and  concepts  upon 
which  such  a  model  can  be  constructed. 
These  are :  — 

(a)  Rutherford's  monumental  work  on 
the  nucleus  theory  of  the  atom  is  basi-d 
on  such  fine  experiments  and  consistent 
reasoning  that  it  is  everywhere  accepted 
as  a  fact.  Stated  otherwise,  the  atom 
has  a  nuclear  part  which  is  a  positive 
charge  corresponding  in  magnitude 
exactly  with  the  atomic  number,  the  lat- 
ter having  been  experimentally  estab- 
lished by  the  work  of  Moseley.  which  is 
well  known. 

{h)  In  view  of  this  study  it  is  suggested 
that  the  electron  can  vibrate  to  and  fro 
relative  to  the  positive  nucleus  in  all 
.positions,  but  only  in  those  in  which  the 
radiation  closes  synchronously  on  the 
electron  can  it  be  held  in  a  fixed  place, 
(r)  Under  these  circumstanees,     when 


372 


THE  CHEMICAL  NEWS. 


DECEMBER  14,  19^3. 


the  electron,  as  the  operator,  is  forced  by 
the  nature  of  events  out  of  the  fixed  place, 
the  closed  radiation  passes  out  from    the 
atom  at  the  velocity    of  light  as  light    or 
radiant  energy. 

In  general,  for  a  series  of  energetic  vibra- 
tions, the  spacing  of  the  lines  will  be  wide; 
but  for  a  series  of  minor  vibrations  the  spac- 
ings  will  be  close,  which  follows  partly  from 
(a)  and  (b)  above. 

Certain  antecedent  factors  may  govern 
the  "energetics"  of  the  electron.  (See  note 
1  above.) 

The  position  of  the  electron  relative  to 
the  nucleus  is  governed  by  its  amplitude  of 
vibration  or  vice  versa;  so  that  for  high  fre- 
quencies it  is  able  to  be  nearer  the  nucleus 
than  for  low  frequency  vibrations. 

The  high  frequency  vibrations  are  emitted 
in  more  widely  spaced  quanta,  in  accord- 
ance with  Planck's  equation,  than  the  lower 
frequency  vibrations,  being  no  doubt 
governed  by  the  probability  of  the  occur- 
rence owing  to  the  nature  of  the  mechanism. 
It  is  as  if  the  inner  position  is  more  difficult 
to  attain  to  frequently,  whereas  the  outer 
positions  are  more  vulnerable,  so  to  speak, 
and  consequently  the  phenomenon  occurs 
oftener. 

Corrections. 
Owing  to  illness  when  the  proofs  arrived, 
the  writer  was  unable  to  make  all  the  cor- 
rections and  amendments  necessary.       The 
following  may  therefore  be  noted  :  — 

On  page  275,  25th  line  from  top,  insert 
"of  molecular  or"  next  to  the  words  "ato- 
mic weight."  On  page  200,  right-hand 
column,  14th  line  from  bottom,  "con- 
tinued" should  read  "concluded."  On 
page  337,  1st  column,  2nd  line  of  text, 
"272"  should  read  "273."  On  same  page. 
2nd  column,  14th  line  from  top,  "contradic- 
tion" should  read  "contradistinction."  On 
page  338,  right-hand  column,  28th  line  from 
bottom,  next  to  the  word  "will"  insert: 
"consist  of  doublets,  while,  if  the  number 
is  even  the  sipectrum."  On  page  339,  left- 
hand  column,  8th  line  from  top  of  para- 
graph beginning  with  "  The,"  "  each  " 
should  read  "  such." 

INDIGOID    BYE  STUFFS. 
Part  II. 

By  R.  F.  Hunter,  F.C.S. 
{Continued  from  Page  359.) 

We  now  have    to  study    the  indigo  ana- 
logues, and  we  shall    first  deal  with  indigo 


analogues  derived  from  two  similar  compo- 
nent nuclei,  following,  as  before,  the  classi- 
fication of  Thorpe  ami  Ingold. 

The  first  dye  to  be  eousidered  as  derived 
from  indole,  apart  from  indigo  or  2:2'  bis 
indole  indigo,  which  has  already  been  dealt 
with,  is  indirubin,  indigo-red,  or  2:3  bis 
indol  indigo.  This  was  synthesised  by 
Bayer  by  condensing  indoxyl  and  isatin. 
This  was  modified  by  Forrer,  who  replaced 
indoxyl  with  indoxylic  acid  smd  obtained  an 
80  per  cent,  yield. 

Wahl  and  Bagard's  synthesis  consists  of 
condensing  oxindole  with  isatin  chloride, 

Among  the  substitution  products  men- 
tion may  be  made  of  the  following  :  — 

5  Methyl  indirubin; 

7  Methyl  indirubin; 

5'  Methyl  indirubin; 

5': 7'  Dimethyl  indirubin; 

5'  Bromoindirubin; 

5' :  7'  Dibromo  indirubin ; 

5:5'  Dimethyl  indirubin; 

6:6'  Dibromo  indirubin; 

6:5': 7'  Trichloro  indirubin. 

The  next  analogue  is  3:3'  bis  indol  indigo 
or  iso  indigo,  obtained  by  Laurent  in  1841 
by  heating  isatyde.  As  derivatives  we 
have:— ^ 

5  Bromo  isoindigo; 

5:7  Dibromo  iso  indigo; 

5  Nitro  iso  indigo;    and  as  homologuos : 

5  Methyl  iso  indigo. 

This  brings  us  to  the  indigoid  dyes  from 
thionaphthen,  the  most  important  of  wliich 
is  thio  indigo,  or  2:2'  bis  thionaphthen  in- 
digo, 

CO  CO 


S 


s 


prepared  in  1906  by  Friedlander,  by  an  ap- 
plication of  the  Badischo  modification  of 
the  Heumann  synthesis,  in  which  thio  sali- 
cylic acid  replaces  anthranilic  nc:d.  The 
present  synthesis  consists  of  the  conver- 
sion of  phenyl  thio  gly collie  acid  into  hy- 
droxy thio  napEthen,  this  to  thio  indigo 
white,  and  thence  to  thio  indigo.  Another 
method  is  to  convert  anthranilic  acid  into 
the  diazoniura  salt,  this  to  dithio  salicylic 
acid,  this  to  thio  salicylic  acid,  this  to  o  car- 
boxy  phenyl  thio  glycol  lie  acid,  thence  to 
hydroxy  thio  naphthen  carboxylic  acid  to 
hydroxy  thio  naphthen,  and  thence  to  thio 
indigo. 

Another  method  is  to  convert  aniline  into 
o  amino  thio  phenol,  to  o  amino  phenyl  thio 
glycol  lie  acid,  to  o  cyano  phenyl  thiogly- 
collic  acid,  to  3  amino  thio  naphthen  2  car- 


DECEMBER  14,  1923. 


THE  CHfeMlCAL  NEWS. 


873 


boxylic  acid,  and  this  to  3  hydroxy-  thio 
uaphthen.  Another  method  depends  on  the 
condensation  between  thiosalicyHc  acid  and 
acetylene  dichloride,  the  bis  thiosaUcviic 
derivative  of  ethylene  formed  on  dehydra- 
tion proceeds  directly  to  thio  indigo. 

Hydroxy  thio  naiphthen  can  be  converted 
into  thio  indigo  by  other  means  than  oxida- 
tion. Thus,  vvljen  hydroxy  thio  naphthen 
is  brominated  there  are  f  irmed  ni  no  broiiio 
and  dibioino  compounds,  both  of  whicli 
readily     pass    into    thio    indigo.  These 

methods  are,  of  course,  of  no  commercial 
baiue. 

Thionaphthenquinone,  the  thio  analogue 
of  isatin,  deserves  mentic.n.  It  can  Ik-  pre- 
pared in  a  variety  of  way?;.  For  instance, 
the  dibromo  derivative  above  can  be  directly 
hydrolvsed,  or  it  can  be  treated  with  ani- 
line, the  product  being  the  anilide  of  thio 
naphthen(piinone  from  which  aniline  residue 
is  removed  by  acid  hydrolysis. 

Further,  hydrothio  naphthen  with  nitrous 
acid  yields  a  nitroso  cojiipound  which,  on 
hydrolysis,  yields  thio  naphthenquinone. 
Am(^ng  the  substitution  iproducts  and  homo- 
logues  of  thio  indigo,  we  might  mention  :- 

7:7'  Dimethyl  thio  indigo; 

4:6:4:6'  Tetramethyl  thio  indco; 

5:7:5': 7'  Tetramethyl  thio  indigo; 

Bis  1  :2  naphtha  thiophen  indigo; 

Bis  1  :8  naphtha  thiophen  inSIgo; 

Bis  2:3  najjhtha  thiophen  indigo; 

Bis  2:1  naphtlia  thiophen  indigo; 

5:5'  Dichloro  thio  indigo ; 

5:5'  Dichloro  6  :6'  dimethyl  thio  indigo; 

7:7'  Diamino  thio  indigo; 

6:6  Dichloro  thio  indipo; 

6:6'  Diethoxy  thio  indigo; 

5:6'  Dibromothio  indigo; 

4:4'  Dimethyl  6:6'  dibromo  thio  indigo; 

&:6'  Dimethyl  thio  indigo; 

5:5'  Dichloro  6:6'  diethoxy  thio  indigo. 

2:3'  Bis  thio  naphthi-n  indigo,  or  thioin- 
dirubin,  is  worthy  of  note,  and  has  been 
|)repared  from  hydroxy  ihio  naphthen  and 
thionaphthenquinone. 

Thi-  indigoid  dyes  from  coumarone  are  of 
interest :  — 

2:2'  Bis  coumarone  indigo,  unlike  its 
sulphur  and  nitrogen  analogues,  is  not  of 
technical  importance.  It  has  been  prepared 
by  condensation  of  coum.iranone  with  p  m- 
troso  dimethylaniline,  followed  by  hydroly- 
sis with  HCl  to  getn  dimethyl  p  phenylene- 
diaminc  and  oxindigo. 

2:3'  Bis  eoumarone  iiuligo,  or  oxindiru- 
bin,  has  not  lK>.n  preipsnv.l,  but  methyl  de- 
rivatives are  known.     We  might  mention  : 


from 
We 


1 : 1'  bis 


5:5'  Dimethyl  oxindirubin; 

6:6'  Dimethyl  oxindirubin; 

5:6'  Dimethyl  oxindirubin; 

6:5'  Dimethyl  oxindirubin. 

Symmetrical  indigoid  dyes  derived 
other  component  nuclei  are  known, 
might  mention :  — 

2  : 2'  Bis  indenone  indigo ; 

1 :1'  Bis  acenaphthene  indiyo; 

3:3'    Dimethyl    5  : 5' dimethoxy 
benzene  indigo ; 

1 : 1  Bis  phenanthrene  indigo ; 

4:4'  Diphenyl  bis  2:2  furan  indigo; 

5:5'  Diphenyl  2:2'  dimethyl  3:3'  bis  py- 
razole  indigo; 

3:3'  Bis  isn  carbostyril  indigo. 

This  brings  us  to  the  indigo  analogues  de- 
rived from  two  dissimilar  nuclei,  of  which 
ceba  violet  A,  or  2  indole  2  thio  naphthen 
indigo,  is  an  example 

The  first  class  of  these  dyes  are  those 
formed  by  the  union  of  any  two  or  three 
component  nuclei;  indole,  thio  naphthen, 
and  coumarcme,  following  the  classification 
of  Thorpe  and  Ingold.  As  dyi's  from  indole 
and  thionaphthen,  we  have  2  indol  2  thio 
naphthen  indigo,  or  ciba  violet  A,  deriva- 
tives of  this  being  2(6  liromoindole)  2  thio 
naphthen  indigo  2(6:7  dibromoindole)  2 
thio  naphthen  indigo  3  indol  2  thio  naphthen 
indigo,  or  thioindigo  scarlet  K,  from  which 
derivatives  have  been  obtained. 

As  dyes  from  indole  and  coumarone,  we 
have  2  indol  2  ooumaronu  indigo  and  8  in- 
dole 2  coumarone  indigo. 

The  sole  dye  from  thionaphthen  and  cou- 
marone is  2  thionaphthen  3  coumarone  in- 
digo. 

The  second  class  of  dyes  are  formed  by 
the  union  of  either  of  the  component  nuclei; 
indole  and  thionaphthen,  with  a  six  mem* 
bored  hom(X5yclic  ring  of  the  benzene  type. 
We  consider  firstly,  the  dyes  derived  from 
indole  by  union  with  six  membered  homo- 
eyelic  rings.     We  have:  — 

2  Indole  benzene  indigo;  this  indigo  has 
not,  as  yet.  been  prejpared,  but  derivatives 
of  it  are  knoNvn.  "  Derivatives  with  hydroxy  I 
groups  in  the  benzenoid  component  nucleus 
have  been  prepared  by  Friedlander  bv  con- 
densing the  appropriate  polyhydric  phenols 
with  isatin  chloride.  We  might  mention 
the  dyes  froin  resorcinol,  catechol  and  py- 
rogallol.  An  amino  derivative  has  been 
prepared  by  condensing  isatin  chloride  with 
in  hydroxy  diphcnylamine. 

2  Indole  2  napthtalene  indigo  was  pre- 
pnivd  by  Friedlander  by  condensing  a  naph- 
thol  with  isatin  chlori(ie    in  benzene    solu- 


374 


THE  CHEMICAL  NEWS. 


DECEMBEK  14,  1923. 


tion.  Derivatives  have  been  prepared  from 
substituted  a  naphthols.  We  might  men- 
tion the  d^^es  obtained  from  monomethyl 
1 : 4  dihydroxy  naphthalene  from  1:5  di- 
hydroxy  naphthalene  and  5  acetamino  1  hy- 
droxy naphthalene.  Derivatives  containing 
substituents  in  the  indole  nucleus  have 
been  obtained  by  condensing  substituted  isa- 
tin  with  natphthol. 

Derivatives  have  been  made  by  using  azu 
dyes  from  diazotised  base  by  coupling  with 
a  naphthol  in  conjunction  with  isatin  a  ani- 
lide.  i 

2  Indole  1  naphthalene  indigo  has  been 
prepared  by  Friedlander  from  isatin  chlor- 
ide and  naphthol. 

2  Indole  2  anthracene  indigo  has  been 
prepared  by  the  same  author  from  isatin  a 
anilide  and  a  anthrol.  Derivatives  are 
known. 

Hydroxyl  derivatives  have  been  prepared 
by  condensation  of  1:5  and  1:8  dihydroxy 
anthracene  with  isatin  a  anilide.  Some  im- 
portant dyes  have  l>een  prepared  by  con- 
densing 5  chloro,  5  bromo,  5:7  dichloro. 
5:7'dibromo  isatins  with  anthrol  and  1  :5 
and  1:8  dihydroxy  anthracene.  Similar 
compounds  have  been  prepared  by  condens- 
ing 7  methyl  isatin  chloride,  5:7  dimethyl 
isatin  chloride,  and  5:6  methylene  dioxy 
isatin  chloride  with  a  anthrol  and  1  : 5  and 

1  :8  dihydroxy  anthracene.  Blue  dyes  have 
been  prepared  by  condensing  hydroxy  an- 
throne  with  isatin  chloride  and  5  :7  dibromo 
isatin  chloride. 

2  Indole  1  anthracene  indigo  has  been 
prepared  by  Bezdrik  from  13  anthrol,  just 
as  2  indole  2  anthracene  indigo  is  prepared 
from  a  anthrol. 

2  Indole  3  acenaphthene  indigo  has  Ijeen 
obtained  from  isatin  a  anilide  and  4  hy- 
droxy acenaiphthene,  by  replacing  5:7  di- 
bromo isatin  chloride  in  place  of  the  anilide 

2  (5:7  dibromoindole)  3  acenaphthene  indi- 
go is  obtained. 

As  dyes  derived  fi-om  thio  naphthen  by 
union  with  six  membered  homocyclic  rings, 
we  have  :  — 

2  Thionaphthen  2  naphthalene  indigo 
from  a  anilide  of  thio  naphthen  quinone  and 
a  naphthol ; 

2  Thionaphthen  2  anthracene  indigo 
from  a  anthrol  and  a  anilide  of  thio  naph- 
then quinone; 

2  Thionaphthen  2  naphthapheno  carba- 
zole  indigo  and  2  thio  naphthen  2  nnplTthn 
pheno  carbazole  indigo. 

This  brings  us  to  the  third  class  of  dyes, 
those  formed  bv  the    union  of  either  of  the 


component  nuclei,  indole  and  thionaphthen, 
with  a  five  membered  homocyclic  ring  of 
the  type  contained  in  indene.  We  consider 
first  the  dyes  from  indole  and  5  carbon 
rings.  An  example  of  these  is  2  indole  2 
indene  indigo,  prepared  by  Friedlander,  by 
condensing  isatin  chloride  with  a  hydrin- 
done. 

2  Indole  1  indene  indigo  has  been  ipre- 
pared  from  hydrindone  and  isatin  a  anilide 
in  the  presence  of  pyridine. 

2  Indole  1  acenaphthylene  indigo  has 
been  prepared  from  indoxyl  and  acenaph-. 
thenquinone,  and  also  by  condensation  of 
acenaphthone  and  isatin  chloride. 

Halogen  derivatives  have  been  prepared 
by  using  dibromo  diacetyl  indoxyl  in  the 
place  of  indoxyl  or  dibromoisatin  in  place  of 
isatin  and  by  direct  halogenation  of  the 
parent  dye. 

The  dyes  from  thionaphthen  and  five  car- 
bon rings  are  of  interest. 

2  Thionaphthen  1  indene  indigo  has  been 
prepared  by  treating  hydrindone  with  ace- 
tic anhydride  aoid  with  the  condensation 
product  of  p  nitrosodimethylaniline  and  3 
hydroxy  thionaphthen.  2  thionaphthen  2 
acenaphthylene  indigo,  better  known  as  ciba 
scarlet,  has  been  prepared  by  condensing  3 
hydroxy  thionaphthen  with  acenaphthaqui- 
none  in  an  acetic  acid  solution  in  the  pre- 
sence of  hydrochloric  acid  in  small  quan- 
tity as  condensing  agent.  It  has  also  been 
prepared  by  heating  acenaphthaquinone 
with  3  hydroxy  thio  naphthen  3  carboxylic 
acid.  Halogen  derivatives  of  ciba  scarlet 
are  known. 

2  Thionaphthen  1  aceanthrylene  indigo 
has  been  prepared  from  3  hydroxy  thionaph- 
then and  aceanthraquinone. 

The  fourth  class  of  dyes  are  those  formed 
by  union  of  the  component  nucleus  indole 
with  six  membered  heterocyclic  rings,  of 
which  2  indole  3  isocarbostyril  indigo  is  an 
example. 

We  conclude  with  the  fifth  class  of  dyes, 
those  formed  by  union  of  either  of  the  com- 
ponent nuclei,  indole  and  thionaphthen, 
with  five  membered  heterocyclic  rings.  2 
indole  dihydroxy  pyrimidine  indigo  is  an 
example  of  a  dye  containing  a  simple  six 
membered  heterocyclic  ring  as  one  of  its 
compound  nuclei,  and  is  prepared  by  con- 
densation of  isatin  a  anilide  with  barbituric 
acid  in  the  presence  of  acetic  anhydride. 

2  Indole  4  pyrazolo  inrligo  is  the  (parent  of 
!i  class  of  dyes  of  which  only  two  are  known 
at  present.  The  3'  methyl  'and  1'  phenyl  3' 
methyl  derivatives  have  been    obtained  by 


DECEMBER  14,  1923. 


THE  CHEMICAL  NfiWS. 


875 


condensation  of  isatin  anilide  with  3  methyl 
and  1  phenyl  3  methyl  pyrazolone. 

2  Indole  2  isoxazole  indigo  has  been  pre- 
pared by  condensing  isatin  chloride  with  the 
corresponding  aromatic  isoxazolone. 

2  Indole  5  thia  zolthiole  indigo  has  been 
prepared  by  condensing  isatin  anilide  and 
rJKKlaninic  acid  in  the  presence  of  acetic 
anhydride. 

2  Thionaphthen  5  thiazol  thiole  indigo, 
the  last  dye  we  shall  consider,  has  been 
obtained  from  the  a  anilide  of  thio  naph- 
thenijuinone  and  rhodaninic  acid. 

The  Royal  College  of  Science, 
October,  1923. 


GENERAL    NOTES. 


A  report  on  the  present  poeition  of  the 
stocks  of  drugs  and  chemicals,  etc.,  in 
-Japan  has  been  received  from  the  Acting 
British  Consul  at  Osaka,  copies  of  which, 
together  with  lists  of  importws  in  Japan, 
may  be  obtained  by  British  firms  upon  ap- 
plication to  the  De^jartment  of  Overseas 
Trade. 


ATMOSPHERIC  CORROSION. 
'  The  First  Experimental  Report  to  the  At- 
mospheric Corrosion  Committee  of  the 
British  Non-Ferrous  Metals  Research  Asso- 
ciation will  be  presented  and  discussed  at  a 
meeting  of  the  Faraday  Society  to  be  held 
on  December  17,  at  8  p.m.,  in  the  rooms  of 
the  Chemical  Society,  liurlington  House, 
W.l.  The  very  comprehensive  series  of 
field  tests  and  laboratory  experiments  de- 
scribed in  the  Report  were  carried  out  by 
Mr.  W.  H.  J.  Vernon  on  behalf  of  the  Com- 
mittee. Persons  interested  in  the  subject 
desirous  of  attending  the  discussion  may 
obtain  a  ticket  of  admission  from  the  Secre- 
tary of  the  Faradav  Sf>ciety.  10,  Essex  St., 
London,  W.C.2. 

PROCEEDINGS    AND  NOTICES  OF 
SOCIETIES, 

THE  ROYAL  SOCIETY. 
TiiuttSDAV,  Dkck.mbbr  6. 
Papers  read  :-- 

E.  O.  T.  LiDPKi.L  and  Sir  Charles  Siier- 
RiN(iToN,  PuKS.  R.S.,  RfcivHwrnf  Type  of 
Reflexes. 


G.  S.  Carter,  The  Structure  and  Move- 
ments of  the  Latero-F rental  Cilia  of  the 
Gills  of  Mytilus.  Communicated  by  Prof. 
J.  S.  Gardiner,  F.R.S. 

Papers  read  in  title  only  :  — 

V.  B.  WiGGLKswoRTH  tmd  C.  E.  Wood- 
row,  The  Relation  between  the  Phosphate 
in  Blood  and  Urine.  Communicated  by 
Prof.  F.  G.  Hopkins,  F.R.S. 

It  has  bein  si'.jv. n  that  ingestion  by  man 
of  doses  of  the  acid  and  alkaline  sodium 
phosphates  containing  1^-2  grammes  of 
phosphorus  causes  a  rapid  50-00  per  cent, 
increase  in  the  blood  phosphate,  which  then 
returns  very  gradually  to  the  normal  level. 
The  work  of  others  has  shown  that  ph(xs- 
phate  is  so  rapidly  excreted  by  the  kidneys 
of  the  dog  that  no  such  increase  occurs  in 
that  animal  under  similar  ccmditions. 

In  such  experiments  the  curve  of  urinary 
excretion  of  phosphate  runs  roughly  parallel 
to  that  of  the  bIcKxl  concentration,  but  the 
former  varies  much  more  widely  than  the 
latter,  and  is  roughly  proportional  to  the 
excess  above  a  certain  value  in  the  bhxxl. 
Moreover,  thi'  rate  of  excretion  in  the  urine 
is  independent  of  the  amount  of  water  ex- 
creted. 

In  a  study  of  the  partiticm  of  the  in- 
organic phosphate  between  the  plasma  and 
corpuscles  of  the  blood,  it  has  been  shown 
that  under  conditions  in  which  the  blood 
phosphate  is  subnormal,  normal,  or  slightly 
above  normal  in  amount,  the  concentrations 
in  plasma  and  corpuscles  are  identical. 
When  the  concent raticm  in  the  plasma  rises 
far  above  normal  the  value  for  the  cor- 
puscles is  always  lower,  whether  the  plas- 
nui  value  is  rising  or  falling.  This  unequal 
partition  is  not  to  be  e.xplained  by  the  for- 
mation of  an  organic  *'acid-solublc"  phos- 
phorus compound  in  the  corpuscIe*j,  for  the 
organic  fraction  of  the  acid-soluble  phos- 
phorus is  not  increased  by  the  ingestion  of 
phosphate;  nor  is  this  fraction  increased  by 
taking  glucose  or  a  mixture  of  glucose  ancl 
phosphate,  as  niight  have  been  expected  if 
one  of  its  constituents  were  a  hexosephos- 
phoric  ester. 

J.   B.   S.   HaLDA.NK,   V.   B.    WlOOLKSWORTII 

and    C.  E.  Woodrow,    The    Effect    of    Re- 
action Changes  on  Human  Inorganic  Meta- 
bolism.     Communicated    by    Prof.    F.    G 
Hopkins,  F.R.S. 

Over-breathing  diminishes  the  phoK< 
phates  in  bloml  and  urine,  while  carbon  di- 
oxide inhalation  and    sleep  increase    them. 


376 


THE  CHEMICAL  WEWS. 


DECEMBER  14,  1923. 


In  acidosis  caused  by  ammonium-chlorid© 
ingestion  the  urinary  tphosphate  is  in- 
creased; v,?hile  the  phosphate  of  the  blood, 
and  also  its  organic  acid-soluble  phos- 
phorus, is  diminished.  Ammonium- 
chloride  acidosis  leads  to  an  increased  ex- 
cretion of  water,  sodium,  and  potassium, 
probably  owing  to  a  partial  loss  of  electric 
charge  by  the  body  colloids.  This  is  fol- 
lowed by  a  retention. 

J.  B.   S.  HaLDANE,  V.  B.  WiGGLESWORTH 

and  C.  E.  Woodrow,  The  Effect  of  Ee- 
action  Changes  on  Human  Carbohydrate 
and  Oxygen  Metabolism.  Communicated 
by  Prof.  F.  G.  Hopkins,  F.R.S. 

The  alkalosis  of  over- breathing  or  bicar- 
bonate ingestion  converts  the  blood  sugar 
into  a  highly  dextrorotatory,  unoxidisable 
form,  and  also  prevents  glucose  storage; 
thus  causing  acetonuria  and  lowered  respira- 
tory quotients  and  glucose  tolerance.  Am- 
monium-chloride acidosis  interferes  with 
the  storage  of  glucose,  but  not  with  its  oxi- 
dation. Bicarbonate  ingestion  raises  the 
resting  oxygen  consumption;  ammonium- 
chloride  ingestion  usually  lowers  it. 

J.  A.  Campbell,  Concerning  the  Influence 
of  Atmospheric  Conditions  upon  fTie  Pulse 
Rate  and  "Oxygen-Debt"  after  Running. 
Communicated  by  Prof.  L.  Hill,  F.R.S. 

The  "oxygen-debt"  for  25  minutes  after 
ceasing  to  run  showed,  under  fixed  condi- 
tions of  experiment,  a  range  of  variation  of 
38  percent,  from  day  to  day;  7-minute 
debts  showed  a  mnge  of  33  per  cent.,  so 
should  do  as  well  for  comparative  purposes 
as  25-minute  debts.  Atmospheric  cooling 
power  had  no  effect  on  the  "oxygen-debt"; 
the  blood  sent  in  greater  volume  through 
the  skin  in  warm  conditions  is  not  then 
taken  from  the  muscles.  "Stitch"  was  the 
commonest  cause  of  cessation  of  running  in 
the  subjects — not  first-class  athletes — 
under  observation.  Pulse  rate  is  markedly 
increased  under  warm  conditions.  This  is 
not  always  shown  clearly  in  short  experi- 
ments in  cool  conditions,  because  it  takes 
time  for  the  body  mass  to  become  heated 
up.  The  oxygen  tension  surrounding  the 
muscles  was  increased  after  exercise. 

J.  Gray,  The  Mechanism  of  Ciliary  Move- 
ment. TV. — The  Relation  of  Ciliary  Activ- 
ity to  Oxi/gen  Consumption.  Communi- 
cated by  Prof.  J.  S.  Gardiner.  F.R.S. 

In  the  absence  of  atmosipheric  oxygen 
ciliary  activity    continues     for    about     one 


hour.  From  a  study  of  the  effect  of  various 
reagents  upon  the  mechanical  activity  and 
on  the  oxygen  consumption  of  ciliated  cells, 
it  is  concluded  that  the  whole  ciliary 
mechanis  mis  divisible  into  three  distinct 
parts :  (i)  a  reaction  which  is  sensitive  to 
cations  (particularly  the  hydrogen-ion),  any 
interference  with  which  involves  a  change 
in  the  rate  of  the  ciliary  beat,  but  only  ulti- 
mately leads  to  a  change  in  the  amount  of 
oxygen  consumed;  (ii)  a  mechanism  which 
appears  to  be  brought  into  operation  by  the 
presence  of  an  activating  acid  substance. 
This  mechanism  is  inoperative  in  the  ab- 
sence of  calcium,  and  in  the  absence  of  a 
certain  critical  amount  of  water  in  the  cell. 
The  events  associated  with  this  mechanism 
are  independent  of  and  have  no  influence 
upon  the  amount  of  oxygen  absorbed ;  (iii)  a 
reaction  of  an  oxidative  nature  which  is 
necessary  for  prolonged  activity. 

As  far  as  they  are  at  present  known,  the 
properties  of  the  ciliary  mechanism  form  a 
very  close  parallel  to  those  of  cardiac 
muscle,  as  illustrated  by  the  sinus  region  of 
the  heart. 


THE  INSTITUTION  OF  ELECTRICAL 
ENGINEERS. 

An  Ordinary  Meeting  was  held  on  Thurs 
day,  December  13.  A  paper  entitled  Fiil- 
vcrised  Fuel  and  Efficient  Steam  Genera- 
tion, was  read  by  D.  Brownlie. 

Pulverised  Fuel  and  Efficient  Steam 
Generation — A  Detailed  Consideration  of 
the  Perfor^nance  of  Pulverised  Fuel  as  com- 
pared with  Mechanical  Stoking  under  the 
most  Modern  Conditions,  by  David  Brown- 
lie,  B.Sc. 

The  paper  is  a  detailed  consideration  of 
the  latest  developments  in  the  use  of  pul- 
verised coal  for  steam  generation,  and  a 
cormparison  of  the  advantages  and  disad- 
vantages of  this  method  of  firing  as  compared 
with  mechanical  stoking,  in  each  case  under 
the  latest  improved  conditions  and  more 
particularly  as  applied  to  very  large  power 
station  boiler  plants.  Since  the  starting  up 
in  December,  1920,  of  the  pioneer  large  in- 
stallation, Lakeside,  Milwaukee  (40, (XX) 
k.w.  on  "Lopuloo"  pulverised  fuel),  the 
progress  made  in  the  United  States  has  been 
remarkable,  and  3,500,000  tons  of  pul- 
verised coal  will  shortly  be  burnt  per  annum 
imder  water-tube  boilers. 

The  paiper  contained  a  full  account  of  the 


DECEMBER  14,  1923. 


VHB  CHEMICAL  NEWS. 


377 


Lakeside  station,  particularly  the  exact 
working  costs,  whilst  a  description  was  also 
given  of  the  River  Rouge  plant  at  Dearborn, 
Detroit,  as  representatives  of  the  latest 
(pulverised-fuel  practice.  For  comparison, 
a  similar  account  is  given  of  the  Dalmar- 
nock  power  station,  Glasgow,  characteristic 
of  the  best  British  mechauical  stoker  prac- 
tice. 

The  author  is  of  the  opinion  that  the  ad- 
vantages in  the  aggregate  of  pulverised  fuel 
are  so  remarkable  that  they  constitute  al- 
most a  revolution  in  steam  boiler  practice. 
The  paper  also  contained  a  large  amount  of 
general  statistical  matter. 

A  Wireless  Section  Meeting  was  held  on 
Wednesday,  December  5.  A  paper  entitled 
The  Relation  between  Damping  and  Speed 
in  Wireless  Receptipn  was  read  by  L.  B. 
TuRNEK,  M.A.  (Member). 

THE  INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

The  Seventy -Fourth  (Jeneral  Meeting 
was  held  on  Tuesday,  Di  eeinber  11,  when 
the  following  paper  was  read  :  — 

The  Modem  Rotary  Drillituj  Syslcni,  by 
L.   R.    McCOLLUM. 

The  chair  was  taken  by  the  Pregident,  H. 
Barringer,  M.Inst.C.E.,  M.I.Mech.E., 
M.IN.A..  M. Inst. Mar. Eng. 


PROCEEDINGS  OF  THE  GEOLOGICAL 
SOCIETY  OF  LONDON. 

November  21. 

Prof.  A.  C.  Seward,  Sc.D.,  F.R.S.,  Pr. 
sident,  in  the  chair. 

The  following  communicatiMi  was  re;  d 
and  discussed  :  — 

The  Development  of  the  Severn  Valley  in 
the  Nci(fhbourhood  of  Iron-Bridge  and 
liridqnorih,  by  Leonard  .Johnston  Wills. 
M..\'.,  Ph.D.,  F.G.S.  ;  with  a  Section  on  \hv 
Uipp»r  Worfe  Valley,  in  collaboration  with 
Ernest  Edward  I>eslie  Dixon,  B.Sc..  F.(J.S 

A  meeting  of  the  Society  was  held  on 
Wednesday,  December  5,  when  the  follow- 
ing communications  were  read:  — 

The  Geology  of  Southern  Quernscy.  by 
D.  J.  Farquharson,  M.Sc.  Commimi- 
cated  bv  Pmf.  O.  T.  Jones,  D.Sc,  M..^  . 
F.G.S. ' 

Thr  (fcolngy  of  thf  Northrrn  Border  nj 
Dartmoor  he-tu'ecn  Whiddon  Doivn  and  Ihit- 
tcrdon  Down,  by  C.  W.  Osman,  M.Inst.- 
C.E., F.G.S. 


Specimens  and  lantern-slides  of  Arach- 
nid remains  from  the  Rhynie  Chert  were  ex- 
hibited by  Dr.  F.  A.  Bather,  M.A.,  F.R.S., 
on  behalf  of  Mr.  A.  S.  Hirst,  F.Z.S. 


THE    SOCIETY    OF   GLASS 
TECHNOLOGY. 

A  meeting  was  held  in  Leeds  on  Novem- 
ber 21,  the  President,  Prof.  W.  E.  S.  Tur- 
ner, D.Sc.,  in  the  chair.  Three  papers  were 
presented. 

Notes  on  the  Influence  of  Rapid  Chilling 
on  the  Reversible  Expansion  of  Clay,  by  H. 

S.   HoULDS WORTH,   M.Sc. 

The  author  gave  resulte  of  measuring  the 
reversible  thermal  expansion  of  fireclay 
test  pieces  cooled  slowly  and  rapidly.  Test 
pieces  were  moulded  from  Fai:nley  fireclay, 
dried  and  fired  in  the  surface"  combustion 
laboratory  furnace  to  Cone  9  (1280°  C.)  in 
three  houi-s  and  maintained  at  that  tein- 
iperature  for  two  hours  more.  One  piece  was 
removed  from  the  fuiuaoe  and  plunged  into 
cold  water,  and  another  was  placed  on  a 
steel  plate  to  air  cool,  while  a  third  was 
slowly  cooled  in  the  furnace.  A  glass  pot 
mixture  of  clay  and  gi-og  obtained  from 
Stourbridge  in  a  leathery  condition  was 
next  examined.  There  was  a  considerably 
greater  difference  in  the  temperature-ex- 
pamjion  curves  of  the  rapidly  chilled  and 
slowly  cooled  specimens  after  firing  at  Cone 
9  than  was  found  for  Farnley  fireclay.  The 
expansion  of  the  air-c(x>led  test  pieces  was 
intermediate  between  those  of  the  water- 
cooled  and  slowly-cooled  sam|)les.  At  Cone 
14  (1410°)  the  thermal  expansion  of  the  air- 
cooled  and  water-cooled  specimens  were 
nearly  the  same  and  considerably  less  than 
that  of  the  slowly  cooled  test  pieces. 

The  whole  of  the  i)henomena  were  consis- 
tent with  the  explanation  that  solution  of 
free  silica  occurred  at  higher  temperatures, 
and  .separated  out  as  cristobalite  or  tridy- 
nute  on  slow  cooling,  exerting  its  charac- 
teristic influence  on  the  expansion  curve, 
but  that  it  did  not  so  separate  on  rapid 
cooling.  Some,  iiinperfect  separation  was 
possible. 

Glasfthome  Pots— Some  Notes  on  their 
Manufacture  and  Use,  by  Mr.  Pkrcivm. 
.Marsun  (rend  by  Prof.  W.  E.  S.  Turner). 

Aft<^r  suitable    weathering    the    fireclavs 
us<'d  as  pot  clays    were  ready  for    blending 
mixing,    and  grinding.       Part    of  the    new 


378 


tHfi  CHteMICAL  NEWS. 


t)ECEMBER  14,  1923. 


mined  lumps  of  fireclay  were  selected  and 
sent  to  the  kilns  for  burning.  When  burnt, 
these  were  broken  up  and  ground  down  for 
the  grog  used  in  the  pot  clay  mixtures.  It 
should  not  be  burnt  to  less  than  1850°  C, 
and  should  be  free  from  the  faults  of  burn- 
ing, such  as  black  core  and  soft  firing.  The 
grinding  and  grading  should  also  be  kept 
within  prescribed  standards. 

The  methods  of  pot  manufacture  were 
noted,  the  author  observing  that  pots 
which  had  been  stored  for  two  <x  three 
years,  after  drying,  gave  more  regular  and 
reliable  results"  than  new  pots  used  shortly 
after  drying.  Reference  was  made  to  the 
different  practices  in  vogue  in  heating  up 
pots  in  the  pot  arch.  Mention  was  also 
made  of  the  chief  faults  which  pots  de- 
veloped in  the  drying  room,  pot  arch  and 
furnace. 

The  Casting  Process  for  Glasshouse  Re- 
fractories in  German  Glass  Plants,  by  Prof. 
Kurd  Endell,  Dr. Phil,  of  the  Technische 
HocHSCHULE,  Charlottenburg,  Berlin. 

Prof.  Endell  considered  that  the  casting 
process  would  give  satisfactory  results  in 
practice.  He  was  unable  to  present  any 
precise  experimental  results  on  chemical  re- 
sistance to  molten  glass,  but  he  believed 
that  cast  pots  were  chemically  more  resis- 
tant than  hand-made  pots. 


THE  ROYAL  INSITUTION  OF  GREAT 
BRITAIN. 

A  General  Meeting    of  the    members    of 
the  Royal  Institution  was  held  on  December 
3,     Sir  James  Crichton-Browne,     Treasurer 
and  Vice-President,  in  the  chair.       It  was 
announced  that    the  Managers    had  elected 
Mr.     Joseph    Barcroft,     F.R.S.,     Fullerian 
rofessor  of  Physiology,    in  succession  to  Sir 
Arthur  Keith.       The  special  thanks  of  the 
members  were  returned  to  Dr.  Rushton  Par- 
ker for  his    donation  of  one  hundred  pounds 
towards  the  improvement  of  the    Library. 
M.  le  Due  de  Broglie,  Dr.  C.  L.  Guillaume 
and  Professors  Debye,  Einstein,  Groth  and 
von  Laue  were  elected  honorary  members 
of  the  Institution.     Miss  Day,  Mrs.  Grims- 
dale,  Mrs.    King,  Miss    Moller,  Mrs.    Tip- 
pinge.   Sir  George    Beilby,   Colonel  Hippis- 
ley,     Sir    Alfred    Hopkinson,     Sir    Richard 
Paget,  Dr.  J.  H.  Jeans,  F.R.S.,    Professor 
Arthur  Smithells,   F.R.S.,  and    Messrs.  A. 
S.  C.  Ackermann,  F.  H.  Hargrove,  H.  M. 
Hubbard,  F.  L.  Lawson-Johnston,  M.  Man- 
naberg,    E.  B.  Michell,    A.  Muller,    B.  J. 
Orsman,     and     G.     Shearer    were    elected 
members. 


THE  CHEMICAL  SOCIETY . 

Papers  read  at  the  Ordinary  Meeting, 
December  6 :  — 

The  additive  formation  of  four-mem- 
bered  rings.  Part  III.  A  system  of  No- 
menclature for  Heterocyclic  our-meynhercd 
Rings,  and  the  formation  and  properties  of 
some  Derivatives  of  -methylene  di-imine- 
oxide,  by  C.  K.  Ingold. 

Four-membered  ring  formation  by  the 
additive  union  of  double  bonds  is  found  to 
be  general.  The  variety  of  new  heterocyclic 
ring-types  produced  from  the  five  types  of 
double  bond  studied  (C:C,  C:N,  C:0, 
N  :N,  N  :0),  is  such  as  to  call  or  a  definite 
scheme  of  nomenclature.  One  object  of 
these  investigations  was  to  discover  which 
types  of  four-membered  heterocyclic  ring 
were  the  most  stable.  It  has  been  shown 
that  certain  azomethines  tend  to  pass  into 
stable  ring  bimerides.  There  is  also  evi- 
dence that  many  nitroso- com  pounds  pass 
into  stable  ring  bimerides.  Hence,  if  an 
azomethine  and  a  nitroso-compound  of  the 
types  referred  to  be  placed  together,  they 
should  unite,  giving  a  ring  in  which  2  N- 
atoms  are  united  to  a  C-  and  an  0-atom. 
Experiment  shows  that  the  ring  obtained  in 
this  way  has  the  structure 
>C— N— 

I        i 
— N— 0 

It  is  quite  stable  at  ordinary  temperatures. 
Its  constitution  has  been  established  by  al- 
ternative synthesis,  and  by  a  study  of  its 
decomposition  at  a  higher  temperature. 

The  Dependence  of  Polarisation-overvolt- 
age  on  Hydroxyl  and  Hydrogen  Ion  Concen- 
tration. Part  I.  Polarisation-overvoJiage  of 
an  Antimony  CatTwde  in  Aqueous  Alkuliiie 
Solution,  by  H.  J.  S.  Sand  and  E.  J. 
Weeks. 

The  overvoltage,  w,  of  an  antimony  ca- 
thode in  alkaline  solution  is  found  to  obey 
the  empirical  equation :  m  =  a  —  2h  (h  is 
the  potential  difference  between  a  standard 
electrode  and  a  hydrogen  electrode  in  the 
solution  examined,  and  a  is  a  constant  de- 
pending only  on  temperature).  This  result, 
as  well  as  the  sipontaneous  formation  of  gas- 
bubbles,  may  be  explained  by  the  assump- 
tion that  an  ion  H  (OH),"  exists  which  has 
a  definite  supersolubility  limit.  When  a 
sufficient  number  of  these  ions  have  as- 
sembled to  produce  the  energy  necessary  foi' 
the  formation  of  a  gas-buhhie.  thoy  decom- 
pose simultaneously   (explode). 


DECEMBER  14,  1923. 


THE  CHEMICAL  NEWS. 


379 


Stereoisomerism  and  Jjocal  Aruesthetic 
Action  in  the  (B-eueaine  Group.  Resolution 
of  /3-  and  iso-fi-eucaine,  by  Harold  King. 

a-  and  )8-vinyldiacetonalkamines  on  beu- 
zoylation  yield  0-benzoyl  derivatives.  Ben- 
zoyl a-vinyldiacetonalkamine  is  the  local 
anaesthetic  /3-eucaine,  and  it  is  proposed  to 
call  benzoyl  ^-vinyldiacetonalkamine,  iso-^- 
eucaine.  The  two  were  resolved  by  eani- 
phorsul phonic  and  bromocjiiutphorsulphonic 
acid  respectively.  The  resolution  of  /3- 
eucaine  was  effected  within  the  transition 
interval  where  the  partial  racemate  dl-^- 
eucaine  d-caniphorsulphonate  is  the  most 
stable  foiiii,  whilst  in  the  ease  of  iso-/J- 
eucaine,  the  salts  being  of  approximate 
equal  solubility,  separate  .ilternately  from 
the  solution  on  fractional  irystallisation. 

^-Alizarin.  An  Isomeric  Form  of  Ali- 
zarin, by  Albp:iit  Green. 

When  alizarin  is  boiled  with  thionyl 
chloride  to  complete  solution,  and  the  sol- 
vent is  evHiporated,  a  light  brown  solid  is 
formed.  B^crystallisation  from  glacial  ace- 
tic acid  and  then  from  benzene  or  alcohol 
yields  yellow  needles,  m.p.  IHS-T*.  The 
light  brown  solid  fumes  in  air.  owing  to  de- 
composition of  adhering  thionyl  chloride, 
and  yields  alizarin. 

Analyses  and  molecular  weight  determi- 
nations of  the  yellow  substance  indicate  the 
formula  C,^HgO,.  /3-Alizjiiin  us  converted 
into  alizarin  by  boiling  with  alcoholic  solu- 
tions of  hydrogen  chloride,  hydrogen  bro- 
mide, or  hydroxylamine  hydrochloride.  The 
same  result  is  obtained  by  pouring  its  solvi- 
tion  in  concentrated  HjSO,  into  water  or 
ether,  or  by  acidifying  its  solution  in  aque- 
ous sodium  hydroxide.  Bromination  gives 
8.bromo-l  .2.-dihydroxy  anthraquinone. 

Boiling  for  six  hours  with  acetic  anhydride 
^-alizarin  gave  pure  diacetyl  alizarin.  Ali- 
zarin gave  an  impure  product  after  16  hours' 
boiling.  Since  1. hydroxy  anthraquinones 
are  alkylated  only  with  difficulty,  while  the 
ethers  of  2.hydroxyanthraquinone8  are  eas- 
ily prepared,  the  former  may  have  an  o- 
quinonoid  stnicture. 

The  Isomerism  of  the  Oximes.  Part  XV. 
The  supposed  Fourth  BenzHdioximc,  by  0. 
L.  Brady  and  F.  P.  Dunn. 

The  authors  have  failed  to  obtain  any  evi- 
dence of  the  existrcnce  of  a  fourth  benzildi- 
oximo. 

The  AUrnuition  in  the  TTents  of  Crystnlli- 
sation  of  the  Normal  Monobasic  Fatty 
Acids,  by  W.  E.  Garner  and  F.  C.  Randall. 


The  following  values  for  the  Heats  of 
crystallisation  for  fatty  acids  have  been 
obtained: — laurie,  43.78;  undeeoie,  32.20; 
oJNpric,  38.86;  non;;ic,  30.54;  capryhc,  '66 AA 
cal/gm.  The  heat  of  crystallisation  of  an 
odd  acid  is  lower  than  the  mean  for  its 
neighbours  in  the  series,  and  the  heat  of 
crystallisation  curve  resembles  the  melting 
point  curve  for  these  acids.  These  results 
throw  light  on  the  causes  of  alt<'rnation  in 
the  physical  properties  of  organic  substances 
with  long  chains. 

The  odd  acids,  undeeoie  and  nonoic,  crys- 
tallise in  two  enantiotropic  forms,  a  and  fS, 
and  the  heat  of  transition  of  these  have 
been  found  to  be  9.89  and  8.39  cal/gm.  The 
heat  of  crystallisation  of  the  j3-forms  of  the 
odd  acids  lie  slightly  above  the  curve  for 
the  even  acids,  thus  giving  an  example  of 
inverse  alternation.  The  results  are  in 
agreement  with  the  view  that  the  even 
aoids  are  more  closely  related  to  the  ft  than 
to  the  a  forms  of  the  odd  acids.  The  differ- 
ences between  the  heats  of  crystallisation  of 
the  higher  members  of  the  odd  and  even 
acids  may  be  ascribed  to  differences  in  the 
mode  of  attachment  of  the  carboxyl  groups 
in  the  crystal  molecule. 

Ordinary  Scientific  Mebtinu,    Thuhsdav, 
December  20,  1923,  at  8  p.m. 

The  following  pa()ers  will  be  read  :  — 
The  Relation  between   the  Glow  of  Phos- 
phorus and  the  Formation  of  Ozone,  by  W. 

E.  Downey. 

I  The    Origin     of    Mutarotation     and     the 

Mechanism  of  Isomeric  Change.      A  Rejdy 
to  Baker,    Ingold    and  Thorpe,    by    T.    M. 

fiOWRY. 

The  Action  of  Inorganic  Haloids  on  Or- 
gano-Metallic  Compounds,  by  F.  Cuallen- 
OER  and  F.  Pritchard. 

Organo-Derivatives  of  Bismuth.  Part 
VII.  lodo-  and  Nitro-Derivativcs  of  Tri- 
phenylbismuthine ,  by  J.  F.  Wilkinson  and 

F.  Challenger. 


THE  FARADAY  SOCIETY. 

General  Discussion    on    "  Electrodk 
Reactions  and  Equilibria,"  November  26. 

(Continued  from  Page  365.) 

The  Oas  Film  Theory  of  Overvoltage,  by 
N.  V.  S.  Knibbr. 

The  theory  which  attributes  overvoltage 
to  a  film  of  gas  on  the  electrode  affords  an- 


380 


THE  CHEMICAL  NEWS. 


DECEMBER  14.  1923. 


other  instance  of  a  discredited  theory  which 
is  essentiaHy  correct. 

Suppose  a  metal,  the  surface  of  which  is 
free  from  adsorbed  gas,  to  be  made  cathode 
in  dilute  sulphuric  acid,  any  suitable  anode 
being  used.  It  is  known  that  even  with  a 
very  low  cathodic  potential  a  considerable 
current  passes  for  a  very  short  time,  fol- 
lowed by  a  slight  "residual"  current.  This 
pulse  presumably  occurs  because  the  elec- 
trode is  free  from  electromotively  active  hy- 
drogen. Once  current  has  passid  the  elec- 
trode becomes,  in  effect,  a  hydrogen  elec- 
trode, and  only  the  residual  current  (I'eplen- 
ishing  the  hydrogen  which  diffuses  away) 
passes  until  the  cathodic  potential  exceeds 
that  of  the  hydrogen  electrode.  A  point 
that  it  is  here  desired  to  make  is  that  the 
hydrogen  in  some  way  must  cover  the  metal 
surface,  and  it  seems  natural  to  conclude 
that  it  is  adsorbed  to  the  surface.  Now. 
suppose  the  potential  to  be  increased  until 
visible  gas  formation  begins.  What  is  the 
mechanism  by  which  the  ions  are  dis- 
charged and  eolved  as  gas  bubbles? 

liideal  maintains  that  the  hydrogen  ions 
must  be  adsorbed  to  the  electrode  in  ord(  r 
that  they  may  be  discharged.  The  dis- 
charged ions  (atoms)  then  unite  to  form 
molecules  which  are  still  adsorbed  but 
which  evaporate  at  a  definite  rate  into  the 
electrolyte  or  into  any  neighbouring  gas 
bubble.  Except  at  platinised  platinum  mid 
similar  surfaces  this  rate  is  equivalent  to 
only  a  minute  current  density  and  therefore 
at  any  ordinary  current  density  the  ions 
must  perform  the  work  qf  describing  the  hy- 
drogen molecules  before  they  can  discharge. 
The  energy  of  desorption  is  held  to  be  equi- 
valent to  the  overvoltage. 

Some  investigators  maintain  that  the  dis- 
charged ions  form  molecules  which  pass 
into  solution  in  the  electrolyte  forming 
supersaturated  solutions.  Others  assume 
that  the  monatoniic  hydrogen  formed  by 
the  discharge  ol  the  ions  accumulates  on 
the  electrode  owing  to  the  finite  velocity  of 
the  reaction  :  2Hj  =  Hg.  Another  sugges- 
tion is  that  a  compound  of  the  metal  with 
hydrogen  is  formed  either  as  an  interme- 
diate compound  or  as  a  side  reaction. 

Regarding  the  supersaturated  solution 
theory  the  question  arises  as  to  why  such  a 
solution  (which  must  be  of  high  supersatu- 
ration  to  explain  even  the  lowest  overvolt- 
ages)  is  formed  when  the  hydrogen  mole- 
cules could  attach  theinselves  to  the  elec- 
trode or  ipass  into  the  gas  phase  imme- 
diately.       No  adequate  reasons  have   been 


given.  The  monatomic  hydrogen  thory  pos- 
tulates that  the  magnitude  of  the  over- 
voltage  depends  on  the  concentration  of 
monatomic  hydrogen,  but  the  latter  will 
vary  with  the  current  density  in  a  manner 
easily  calculable  and  the  actual  variation 
differs  from  that  calculated.  The  metal  hy- 
dride theory  has  the  disadvantage  that  no 
such  compounds  are  known,  and  there 
seems  no  reason  why  they  should  form. 

There  can  be  little  doubt  that  the  hydro- 
gen atoms  or  molecules  will  be  adsorbed  to 
the  surface,  but  once  all  spaces  are  occupied 
the  nature  of  the  process  becomes  more  open 
to  conjecture.  It  is  not  easy  to  picture  the 
process  of  the  ion  ejecting  the  molecule 
from  the  surface,  as  postulated  by  Rideal. 
One  rather  pictures  the  ions  crowding  on 
top  of  the  molecules  and  tending  to  inhibit 
desorption. 

No  mention  has  yet  been  made  of  anodic 
overvoltages,  and  until  further  measure- 
ments have  been  made  specvilation  is  not 
very  profitable.  Even  the  recent  measure- 
ments of  Knobel,  Caplan,  and  Eiseman  are 
not  of  much  assistance.  Halogen  overvolt- 
ages  seem  to  increase  almost  proportionally 
to  the  current,  and  except  on  graphite  do 
not  reach  high  values  at  the  current  densi- 
ties at  which-  measurements  have  been 
made.  It  is  unlikely  that  the  conditions 
which  obtain  with  gases  of  low  solubility 
such  as  hydrogen  and  oxygen  are  reached  at 
any  reason  irt^le  current  density  with  such  a 
highly  reactive  and  soluble  gas  as  chlorine. 
All  investigators  agree  that  oxygen  over- 
voltages  are  much  more  variable  than  those 
of  hydrogen  and  reproducible  results  are  dif- 
ficult to  obtain.  This  may  be  due  to  the  for- 
mation of  actual  oxide  films,  not  always 
visible,  on  the  anodes.  In  general,  oxygen 
overvoltages  seem  to  be  higher  than  the 
hydrogen  overvoltages  at  the  same  metals, 
due,  perhaps,  to  the  greater  affinity  of  the 
metals  for  the  former  gas. 

The  Influence  of  Obstructive  Films  on 
Anodic  Processes,  by  TJltck  R.  Evans. 

The  anodic  attack  of  a  metal  iproceeds 
readily  when  the  product  is  soluble,  or  even 
when  it  is  insoluble  but  non-adherent ;  but 
an  adherent  insoluble  film  may  interfere 
with  further  attack  of  the  anode,  and  may 
even  (if  non-conducting)  produce  valve- 
action.  The  degree  of  adhesion  of  the  film 
flepends  partly  on  considerations  of  inter- 
facial  energy ;  but  the  substance  is  more 
likely  to  be  adherent  if  it  is  the  direct  pro- 
duct of  anodic  attach,  than  if  it  is  produced 


i 


DECEMBER  14,  1923. 


THE  CHEMICAL  NEWS. 


381 


b\  precipitatiun  at  a  small  distance  from  the 
anuJe  sm'face.  Passivity  is  probably  due  to 
a  la3er  of  attached  oxygen  atoms  (or  half- 
discliargc'd  oxygt-n-rich  ions);  it  may  be  re- 
garded as  an  oxide-filui,  but  is  not  identical 
with  any  oxide  known  in  the  massive  state. 
Any  treatment  which  tends  to  scrape  off, 
reduce,  dissolve  or  loosen  this  oxide  tends  to 
remove  passivity.  The  oxygen  atoms  do 
not  merely  offer  mechanical  obstruction  t<> 
electro<^lic  dissolution,  but  causes  a  perma- 
nent or  temporary  shift  in  the  potential  at 
which  equilibrium  between  the  metal  and 
its  'urns  is  established  after  current  has 
ceased  to  flow;  this  is  Ix'st  explained  by 
supposing  that  the  attachment  of  oxygen 
atoms  reduces  the  "active  mass"  of  the 
metal,  whilst  leaving  that  of  the  ions  un- 
changed. "Degrees  of  passivity"  are  pos- 
sible, and  one  often  meets  with  metallic 
specimens  which  are  "partially  pasisive." 

Most  metals  of  the  "A"  groiiips  of  (he 
PerLolic  Table  appear  to  be  ixrinancnllji 
jtaHHive ;  although  these  elements  cannot — 
in  general — b;'  obtaim-d  by  electrcdep.si- 
tion  f..)m  fupieous  solution,  the  metuJs  have 
a  similated  nobility,  due  to  an  adherent 
oxide-film  (tantalum,  tiuigsten,  etc.);  past 
experiments  which  claim  to  ditermine  the 
reversible  "electnnle  potentials"  of  such 
metals  require— in  some  cases — a  different 
interpretation.  Likewise  in  the  transitL  n 
olementvs  (iron,  nickel,  platinum,  etc.),  there 
seems  to  l)e  a  gap  JH-tween  the  dopositic.n- 
potential  and  the  dissolution-potential,  and 
this  causes  many  apparent  anomalies.  Dis- 
agreement even  still  prevails  as  to  whether 
iron  should  stand  above  ()r  Inflow  cadmium 
in  the  Potential  Series. 

Studieft  in  Hcterogrncnus  Equilibria. 
Part  II. — Thr  Kinetic  Intcrprriation  of  the 
Nrrnst  Thenrtj  of  FAccin^motirc  Force,  by 
F.  A.  V.  RrTLKR.  M.Sc. 

The  Nernst  theory  of  the  electrolytic  P.D. 
of  metals  is  developed  on  kinetic  grounds, 
and  a  kinetic  deduction  of  the  Nernst  equa- 
tion is  given.  Values  of  the  electrode  pr.- 
tentials  calculated  in  accordance  with  the 
equations  are  at  least  of  the  right  order  of 
magnitude.  The  Nernst  conception  there- 
fore gives  an  adequate  and  physically 
acceptable  explanation  of  the  facts. 

Studies  in  Hrtrroqenenus  Equilihria. 
Part  III. — A  Kinetic  fheonj  of  Hei^rsihle 
Oridation  Potentials  at  Inert  Electrodes,  by 
J.  A.  V.  BuTLKR,  M.Sr. 

When  an  inert  electrode  is  dipped  into  a 
solution  containing  two  substances    related 


by  a  simple  oxidation-reduction  process,  it 
usually  acquires  a  perfectly  definite  and  re- 
versible electrode  potential.  Tliermodyna- 
mically  the  electrical  work  done  against 
this  potential  difference  in  the  oxidation  of 
one  equivalent  of  the  reduced  substance  at 
the  electrode  is  a  measure  of  tlie  free  energy 
A  the  process.  Kinetically  it  may  be  sup- 
posed that  the  potential  has  its  origin  in  the 
tendency  of  the  more  highly  oxidised  sub- 
stanci'  to  take  up  electrons  and  that  of  the 
less  iiighly  oxidised  substance  to  lose  elec- 
trons, a  transfer  that  occurs  through  the 
agency  of  the  inert  electrode. 

It  is  pointed  out  that  a  metal  which  ion- 
izes in  tw.>  stages  will  ccmtain  in  the*  solid 
form  atoms  that  have  lost  ekictions  corres- 
ponding to  both  states.  There  will  be  a  de- 
finite equilibrium  between  the  two  kinds  of 
ions  and  electrons.  Th{»  three  processes 
occurring  at  the  surface  can  only  give  rise 
to  the  same  P.D.  if  the  relative  prop.irtions 
of  ions  in  the  adsorbed  layer  are  the  same  as 
in  the  interior  of  the  metal.  The  solution 
which  is  in  equilibrium  with  the  metal  is 
that  which  gives  an  adsorbed  layer  of  ions 
in  this  proportion.  The  adsorbed  layer  is 
n'>w  identical  in  composition  with  the  in- 
teriw  and  there  is  no  P.D.  (E,)  between 
the  two.  That  is,  the  whole  P.D.  is  be- 
t\Veen  the  adsorbed  laj'er  and  the  solution, 
and  this  is  now  the  electrode  potential  for 
all  thn»e  processes  concerned. 

.\  general  expression  was  deduced,  which 
is  in  accordance  with  the  thermodynamic 
equation  and  which  distinguishes  the  fac- 
tors determining  the  normal  potential.  The 
relation  between  the  (Neftist)  metal  poten- 
tial and  the  oxidation  potential  for  a  metal 
in  a  solution  containing  its  ions  in  different 
stages  of  oxidation,  was  discussed. 

Irreversible  Electrode  Phenomena,  by  H. 
J.  T.  Ellinoh.am  and  A.  J,  Allmand. 

The  owmrrence  of  any  process  with  finite 
velocity  necessarily  involves  more  or  less 
irreversibility.  In  the  case  of  an  electro- 
chemical react im  proceeding  at  given  finite 
current  density,  the  extent  of  the  irreversi- 
bility under  given  conditions  is  indicated  by 
the  deviation  of  the  potential  of  the  elec- 
trode at  which  it  is  occurring  from  the  cor- 
responding equilibrium  potential  of  the  re- 
action. Thus  the  degree  of  irreversibility  of 
an  electrochemical  reaction  under  various 
conditions  may  be  conveniently  summarised 
by  curves  showing  the  relation  between  the 
potential  of  the  electrode  and  such  variables 
as  current  density,  time,  temperature,  etc. 
The    polarisation    due     to    concentration 


382 


THE  CHEMICAL  NEWS. 


DECEMBER  14,  1923. 


changes  in  the  surface  layers  of  the  electrode 
generally  cannot  be  estimated.  It  may  vary 
from  ziro  in  a  case  where  the  electrode  nei- 
ther furnishes  reactants  the  removal  of 
which  can  change  its  composition,  nor  dis- 
solves resultants  of  the  reaction  to  any  ap- 
preciable extent;  to  values  which  may  be 
very  large  owing  to  slow  rates  of  diffusion  or 
low  velocity  of  chemical  reactions  in  solid 
solutions.  The  magnitude  of  the  polarisa- 
tion due  to  concentration  changes  in  the 
boundary  layer  of  the  electrolyte,  can,  how- 
ever, generally  be  computed  approximately 
from  the  known  diffusion  coefhcients  of  sub- 
stances in  solution  and  an  estimated  value 
of  the  thickness  of  the  layer  in  which  the 
concentration  gradient  is  established. 
Polarisation  of  this  kind  which  is  usually 
known  simjply  as  "concentration  polarisa- 
tion" is  generally  small  owing  to  the  rela- 
tively high  rates  of  diffusion  of  substances 
in  solution  and  the  relatively  high  velocities 
of  chemical  reactions  under  these  condi- 
tions. Also  conviction  and  ionic  migration 
may  assist  in  keeping  it  low.  Under  some 
circumstances,  however,  this  type  of  polari- 
sation may  attain  a  considerable  magnitude, 
examples  of  this  were  given. 

The  authors  discussed  irreversible  pheno- 
mena at  finite  current  densities,  and  at  very 
small  current  densities.  They  then  gave,a 
theoretical  interpretation  of  the  results. 

Electromotive  Equilihriuw  and  Polarisa- 
tion, by  A.  Smits. 

Though  the  phenomena  of  passivity  and 
polarisation  have  been  known  for  more 
than  a  century,  one  has  not  yet  agreed  on 
their  explanation. 

The  presence  of  a  film  of  oxide  produced 
by  chemical  attack  or  anodic  solution  was 
first  thought  to  be  the  cause  of  the  passive 
state  (Faraday).  It  was  completely  for- 
gotten, however,  that  if  in  the  passive  state 
such  a  film  was  present,  the  phenomenon  of 
the  origin  of  passivity  was  not  in  the  least 
solved.  Take  for  instance  the  case  of  iron 
which,  when  dipped  into  strong  nitric  acid, 
first  dissolves  rapidly  and  then  suddenly 
dissolves  no  more.  In  which  state  is  the 
iron  covered  by  a  film  of  oxide?  Why  does 
iron  dissolve  at  constant  temperature  in  a 
solution  of  ferrous  sulphate  anodically  up 
to  a  certain  current  density,  following  Fara- 
day's law,  and  why  at  a  current  density  but 
a  little  higher  does  the  potential  rise  and 
oxygen  is  evolved,  while  the  iron  nearly 
ceases  to  dissolve?  Further,  we  can  ask, 
why  is  the  potential  of  iron  changed  in  the 
direction  of  that  of  the  noble    metals  when 


it  is  dipped  into  a  solution  of  a  ferric  salt, 
a  chaiioe  which  is  so  large  in  a  solution  of 
ferric  nitrate,  that  the  iron  bcccmes  pas- 
sive ? 

Why  is  this  phenomenon  dependent  to 
so  great  an  extent  on  temperature  that,  for 
instance,  iron  dipped  into  a  solution  of  0.14 
gr.  mol.  Fe(N03)3  per  litre,  remains  active 
above  34°,  but  becomes  passive  imme- 
diately below  31°,  and  why  have  traces  of 
halogen  salts  such  an  enormous  influence 
on  all  these  phenomena? 

From  this  it  follows  that  the  cause  of  the 
phenomenon  cannot  be  a  film  of  oxide,  but 
that  it  lies  deeper. 

Whatever  be  the  final  state  of  the  metal ; 
whether  there  be  a  film  of  oxide  or  some- 
thing else,  the  primary  phenomenon  is  that 
of  passivity  itself.  At  first,  and  indeed, 
even  until  quite  lately,  this  was  not  gener- 
ally understood. 

All  later  theories  have  this  in  common 
that  they  assaime  as  the  cause  of  passivity 
the  retardation  of  some  process  or  other, 
which  goes  on  when  a  metal  is  dissolved  or 
precipitated.  These  theories  can  therefore 
be  called  velocity-theories,  and  they  can  be 
divided  into  the  following  groups: — 

1.  Theories  which  assume  the  formation 
of  oxides  as  a  result  of  a  retardation. 

2.  Theories  in  which  the  cause  of  ipnssiv- 
ity  is  ascribed  to  the  formation  of  an  oxygen- 
charge  or  of  a  metal-alloy. 

3.  Theories  in  which  hydrogen  acts  as  an 
activating  agent  (Grave,  Adler,  Rathert). 

4.  Theories  combining  the  hydrogen-  and 
oxygen-charge  hypothesis  (Foerster). 

5.  Hydration- velocity  theory  (Leblanc). 

6.  Valency  theory  (Finkelstein,  Miiller). 

Evidence,  based  on  the  study  of  the  in- 
fluence on  the  potential  difference  of  small 
quantities  of  mercury  dissolved  in  alu- 
minium, is  brought  forward  in  support  of 
an  explanation  based  upon  catalytic  in- 
fluence . 


COBEESPONDENCE. 
To  the  Editors  of  The  Chemical  News. 

Sirs, — From  time  to  time  the  non-tech- 
nical journalist  supplies,  in  all  good  faith, 
misleading  information,  and  I  fear  that  it  is 
seldom  possible  to  catch  up  with  items  of 
news  which  are  widely  circulated  and  which 
contain  statements  of  dubious  ^accuracy. 

A  paragraph  recently  circulated  and 
quoted  by  the  Technical  Press  refers  to  a 
vio'lent  explosion  which  set  fire  to  and  sank 
the  British  steamer  "  Otterbum."  The 
paragraph    concluded    by    saying  that    the 


DECEMBER  14,  1923. 


THE  CHEMICAL  NEWS. 


888 


disaster  was  thought  to  be  due  to  ihe  exiplo- 
sion  of  barrels  of  chlorate  of  potash.  I  am 
infoniic'd,  ou  what  appears  to  bo  quite  gool 
authority,  that  there  was  no  chlorate  of  2J<jt- 
ash  on  board  the  ship,  but  that  there  was  a 
parct^l  of  chloride  of  potassium. 

The  transport  of  dangerous  substance's  is 
always  a  matter  of  difficulty,  and  it  is  there- 
fore desirous  that  one  should  not  unwit- 
tingly increase  the  difficulties  by  blaming  a 
dangerous  substance  unnewssarily.  To 
weigh  down  the  statistics  of  explosions  due 
to  chlorate  of  potash  by  such  items  of  news 
as  that  to  whTlih  1  refer  would  be  mislead- 
ing and  prejudicial  to  those  firms  who  hav( 
to  send  abroad  such  goods. — Yours,  Ac., 
W.  J,   U.   VVOOLCOCK, 

General  Manager. 
The  Association  of  British  Chemical 

Manufacture:  s. 
166,  Piccadilly,  Ijondon,  W.l. 
December  3,  1923. 


NOTICES  OF  BOOKS. 
The  Electron  in  Chetnixtry,  by  Sir  J. 
J.  Thomson,  O.M.,  F.K.S.  Pp.  V.  +  114 
(with  index).  Messrs.  J.  B.  Lippincott 
Company,  Philadelphia,  Penn.  1923. 
Price  $1.75. 

This  book  embodies  the  five  lectures  Sir 
J.  J.  Thomson  delivered  before  the  Franklin 
Tnsfitiite  'in  April,  1923;  and  it  contains 
uuurh  new  matter  which  Prof.  Thomson  had 
himself  contributed  to  the  subject  of  tin 
electron  in  chemistry,  etc.,  which  had  ap- 
peared in  the  FhiU>80i)hical  Magazine  and 
elsewhere. 

The  main  subjects  dealt  with  are: — Ar- 
rangement of  electrons  in  at-oms;  stability; 
periodic  law;  allotrqpic  form;  atomic  pizf ; 
ionisation  potential ;  specific  inductive 
capacity  of  gases;  molecules;  electron  the- 
ory of  valency  ;  arrangement  of  electrons  in 
octets;  chains;  chlorides,  carbonates,  etc.; 
residual  affinity;  molecular  compounds; 
Werner's  theory;  electrolytic  dissociation; 
mechanism  of  combinations;  condensation 
on  surfaces ;  double  electrical  layers ;  active 
molecules;  Thiele's  thtH)ry;  Keto-enol 
change;  prwluction  of  light;  homologous 
elements;  variable  valency;  paranuignet- 
ism  ;  diamagnetism ;  solids;  crystals;  vibra- 
tion of  electrons  in  crystals;  compressibil- 
ity ;  surface  tension ;  intermetallic  oom- 
poundjs,  Ac. 

Of  particular  value  is  the  bringing  out  of 
certain  atomic  and  molecular  attributes  as 
due  to  the  behaviour  of  electrons  as  re- 
veaUfl  by  positive-ray  exiperiments  and 
other     phenomena,      in     connection     with 


which  Prof.  Thomson  is  a  pioneer  investi- 
gator. The  following  are  a  few  interesting 
features. 

The  proposed  law  of  force  between  a  posi- 
tive charge  and  a  negative  electron  is  shown 
to  lead  to  electrons  in  positions  of  stability 
round  a  nucleus  without  describing  orbits 
round  it. 

The  cubical  theory  of  atoms  and  twisted 
cubes  are  discussed,  but  the  latter  Ls  not 
drawn. 

On  page  3,  Prof.  Thomstm  says :  "  As  up 
to  the  present  nothing  has  been  discovered 
that  cannot  be  n^solved  into  electrons  and 
positively  electrified  particles,  it  is  natural 
to  frame  a  theory  of  the  sti'ucture  of  the 
atom  on  the  supposition  that  it  is  built  up. 
of  these  two  ingredients.  It  should  be 
borne  in  mind,  however,  that  our  means  of 
detecting  the  existence  of  electrioally 
charged  bodies  far  surpass  those  for  detect- 
ing uncharged  ones,  and  if  there  were  any 
uncharged  ctmstituents  of  the  atom,  they 
would  in  any  ca«e  probably  have  escaped 
detection.  We  know,  however,  that  even 
supposing  such  constituents  do  exist,  the'r 
mass  must  be  negligible  compared  with 
that  of  the  positive  parts,  for  these  parts 
account  for  well  within  a  fraction  of  a  per 
cent,  of  the  whole  mass  of  the  atom.  " 

On  page  26  it  is  pointed    out    '*  that    on 
passing  from  one  period    to  the    ne.\t,    the 
volumes    of  all  the  atoms  are    increased  in 
the  same  proporti m,  "  thus :   - 
r  =   1.35  A  «mits  in  diameter. 
("I  =  2.10 
O   =    1.80 
S   =  2.05';  kc. 
Tlien,  by  comparison: 
CI  F  =   1.55. 
SO     =   1.57;  Ac. 

In  the  section  (see  page  89)  dealing  with 
combinations  of  different  elements,  it  is 
noted  that  Thomson  distinguishes  between 
the  molecule  of  carbon  monoxide  (CO)  and 
that  of  the  carbonyl  radicle  (CO).  In  the 
latter  it  is  suggested  that  two  out  of  the 
four  electrons  of  the  carbon  atom  have 
united  with  the  oxygen  to  make  up  the 
(wtet.  while  the  oth<'r  two  are  free  to  join 
up  with  other  electrons.  In  the  same  way 
there  are  two  NO's. 

On  page  105,  Prof.  Thomson  says  of  oxy- 
gen :  "  The  most  fascinating  of  all  mag- 
netic bodies  is,  to  my  mind,  oxygen.  Here 
we  have  one  of  the  simplest  of  atoms;  its 
atom  contains  only  eight  electrons,  it  is  a 
gas,  and  therefore  in  the  simplest  of  all  phy- 
sical st.ates,  and  yet  it  al<«ie  of  all  gases  is 
I)aramagnetic,  and  quite  strongly  so.      An- 


384 


THE  CHEMICAL  NEWS. 


DECEMBER  14,  1923. 


other  remarkable  thing  about  it  is  that  in- 
numerable as  are  the  compounds  of  oxygen, 
there  is  only  one,  NO,  into  which  oxygen 
carries  its  magnetic  properties.  This  Mould 
seem  to  suggest  that  the  magnetic  quality 
does  not  arise  from  some  quality  intrinsic 
to  the  atom,  but  from  some  speciality  in 
the  arrangement  of  the  colligating  electrons 
in  those  molecules  where  it  exhibits  its  mag- 
netic character.  The  oxygen  molecule  it- 
self is  the  most  conspicuous  example ;  the 
arrangement  of  the  electrons  may  be  repre- 
sented symbolically  as  two  cubes  having  a 
face  in  common,  this  face  being  at  right 
angles  to  the  line  joining  the  atoms.  if 
the  system  were  rotating  alyout  this  line 
-there  would  be  an  odd  number  of  square 
faces  in  rotation.  A  rotating  square  with 
its  electrons  would  act  like  a  current  and 
thus  behave  like  a  magneton.  Now,  sup- 
pose that  the  rotation  of  electrons  must  Ix^ 
such  that  adjacent  squares  rotate  in  oppo- 
site directions,  and  it  is  evident  that  if  we 
start  one  from  rest  in  one  direction,  the  ad- 
jacent one  will  start  in  the  opposite 
direction.  Suppose,  then,  that  the  elec- 
trons in  the  planes  of  the  squares  were  ro- 
tating so  that  the  rotation  in  one  plane  is 
opposite  to  that  in  the  adjacent  plane,  then 
two  of  these  planes  will  be  rotating  in  one 
direction  and  the  third  in  the  opposite,  the 
resuling  magnetic  effect  will  be  the  same  as 
if  only  one  plane  rotated,  and  this  will  pro- 
duce a  magnet  of  finite  moment." 

The  above  statement  may  be  clear  to 
some  readers,  but  we  think  that  a  diagram 
showing  the  rotations  would  have  been 
helpful  in  this  case. 

Paying  tribute  to  Prof.  Ric^hards'  work  in 
respect  of  the  compressibility  of  the  ele- 
ments, Prof.  Thomson  gives  some  calcula- 
tions of  the  compressibility  of  metals  based 
on  the  supposition  "that  they  are  made  up 
of  cubical  cells  with  an  atom  and  one-eighth 
of  an  electron  [not,  of  course,  a  fractional 
electron]  at  each  of  its  eight  corners,  each 
cell  corresponding  to  an  atom  with  its  elec- 
tron." This  leads  to  a  formula  for  k,  the 
compressibility  being  Ijk,  which  is — 
1c  =  (n.e,5[9)e-'  (A/M)| 

e  =  charge  of  an  electron ; 

M  =  mass  of  an  atom ; 

N  =  density  of  the  solid ; 

A  =  density. 

For  example,  lithium  is — 

A  =  0.534; 

k  =  0.14  X   1012  calculated  by  above  for- 
mula; 

k  -  0.114  X  KP-  as  observed  by  Richards. 

Developing    the  subject    further,    in  the 


case  of  the  diamond  \\k  —  0.178  x  10- 1^, 
which  agrees  closely  w4th  the  recent  value 
of  Adams  {Washington  Acad.  Sci.,  1921, 
XL,  p.  45),  0.16   X   10-^-. 

Prof.  Thomson's  book  is  rich  in  sugges- 
tive ideas,  and  it  should  be  widely  read. 
There  is  only  one  feature  in  respect  of  its 
get-up  which  we  think  could  have  been  im- 
proved, and  that  is  to  have  introduced  a  re- 
capitulation at  the  end  of  each  section  or 
chapter,  so  that  the  reader  would  know 
where  ho  stood  in  matters  which  may  seem 
rather  confusing,  especially  to  those  not 
steeped  in  the  subject.  The  printing  and 
binding  is  up  to  the  high  standard  of  book 
production  as  set  by  the  most  progressive 
publishing  houses. 


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206229-Chance  &  Hunt,  Ltd.,  Calder,  W.  A.  S.,  and 
and  Palmer,  W.  H. — Process  for  condens- 
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186589 — Hansgirg,  Dr.  F. — Process  and  apparatus 
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29313— Chemische  Fabrik     in     Billwarder     vorm.. 
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206671— Stacey,  F.— Electric  apparatus  for  the 
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Abstract  Published  this   Week. 

204886— Cjiiomium  oxide  and  salts;  chromates; 
barium  chloride.  —  Chemische  Fabrik 
Griesheim-Elektron,  of  51,  Gutleutstrasse, 
Frankfort-on-Main,  Germany. 

Alkali  chromates;  chromium  oxides  and  salts: 
barium,  chromium,  and  iron  chlorides. — Chrome 
iron  ore  is  converted  into  ferrochromium  in  the 
known  manner,  the  ferrochromium  is  dissolved 
in  hydrochloric  aoid,  and  the  chromium  precipi- 
tated as  hydrated  oxide  by  calcium  or  barium 
carbonate.  The  precipitate  is  separated  and  used 
to  produce  alkali  chromate  or  chromium  salts. 
The  filtrate,  if  barium  carbonate  was  used,  is 
evaporated  and  cooled  to  separate  barium  chlor- 
ide, and  the  mother  liquor  may  be  evaporated  to 
obtain  ferrous  chloride.  In  the  precipitation  of 
the  chromium  hydrate  it  is  preferred  to  use  granu- 
lar limestone  or  witherite  and  hot  chloride  solu- 
tion. 

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DECEMBER  21.  1923. 


THE  CHEMICAL  NEWS. 


865 


THE    CHEMICAL  NEWS, 

VOL.  CXXVII.      No.  3323. 


4'  AMINO  1  PHENYL    5  METHYLBEN- 
ZOTHIAZOLE  AND  ITS  BROMIXATION 

IN  GL-\CIAL  ACETIC  ACID,  THE 

DIBHOMO  PRODUCT  OF  GATTERMAN 

AND  THE  FLUORESCENCE  OF  SOME 

BENZOTHIAZOLES. 

By  R.  F.  Hunter,  F.C.S. 

Gattermun,  duiing  his  researches  on  4' 
amino  1  phenyl  5  methyl  benzothia/ole,  oh- 
sorved  that  when  the  base  is  dissolved  m 
glacial  ac<'tic  acid  and  broininated,  it  adds 
two  bromine  atoms  according  to: 

C.JI.^NjS  +  Br,  =  C,,Hj,N,SBr,. 

Ansclmt/  and  Schultz,    while  working    in 
the  same  field,    observed  the    formation    of 
similar  compounrls  in  the  eases  of  the  dehy 
drothioxylidins.     We  should  expect  the  re- 
action observed  by  Gatterman  to  be : 

S 
CH.C.H,   <;    •>    CC.H.NH,  4  2Br  = 

S 
CH,C.H3  ^         ^  CBrC.H.NH,. 
^^NBr^ 

that  is  to  say  to  consist  in  the  normal  split- 
ting of  the  double  bond  and  the  addition  of 
bromine  at  the  nitrogen  and  carbon  atoms. 
The  objection  to  this  which  has  been  raised 
is  that  in  the  above  structure  we  have  a  bro- 
mine atom  attached  to  a  nitrogen  atom  di- 
rectly, and  that  the  compound  should  l)e 
very  unstable  and  therefore  tend  to  re- 
semble nitrogen  bromide  in  .properties  antl 
stability  to  a  certain  extent.  Whereas  the 
compound  is  known  to  be  quite  stable  at 
ordinary  temperatures.  It  was  therefore 
decided  to  prepare  this  compoimd  and  ex- 
amine it.  A  further  point  to  be  obsen'cd  is 
that  if  the  interpretation  given  to  the  jv- 
action  is  correct,  then  this  reaction  shouM 
be  a  general  one  and  ajpply  to  all  substituted 
benzothiazoles  of  this  class.  The  recent  re- 
searches which  have  been  canied  out  on  the 
derivatives  of  the  base  show  that  these 
brown  products  are  formed  whenever  the 
thiazole  is  dissolved  in  glacial  acetic  acid 
and  brominated  in  the  manner  described  in 
the  experimental  part  of  this  paper,  some  of 
the  result*  have  been  commimicated  to  the 


transactions  of  the  Society  of  Chemical  In- 
dustry, and  a  good  many  are  as  yet  unpub- 
lished. Another  point  which  was  noticed 
during  the  investigation  of  these  com- 
pounds was  the  remarkably  fine  fluorescence 
which  some  of  them  display  in  solution. 
This  has  been  noticed  previously  by  various 
workers.  The  effect  is  remarkably  good 
when  the  substances  are  f)laced  under  the 
action  of  the  ultra  violet  rays  of  a  mercury 
lamp.  Three  derivatives  were  examined  in 
this  manner :  the  base  itself  in  alcoholic  so- 
lution, the  acetyl  derivative,  and  the  di- 
bromo  product.  The  last  two  were  used  in 
the  form  of  their  solutions  in  acetic  anhy- 
dride and  glacial  acetic  acid  respectively. 

Experimental. 

The  4'  amino  1  phenyl  5  methylbenzo- 
thiazole  used  in  the  experiments  was  pre- 
pared by  the  method  described  some  time 
ago  {Trans.  Soc.  Chem.  Ind.,  1923,  XLII.. 
302).  The  product  was  recrystallised  from 
alcohol  in  the  manner  described  in  the  ori- 
ginal paper. 

Dehydrothioparatoluidine  Dibromide. — 1 
gm.  of  pure  base  is  dissolved  in  20  to  30  ccs. 
of  pure  glacial  acetic  acid  in  a  140  cc. 
beaker.  Excess  of  bromine,  according  to 
the  theoretical  equation  given  alx)ve,  is 
then  added  drop  by  drop  from  the  burette 
cMitaining  bromine;  the  .solution  in  the 
beaker  is  kept  well  stirred  durinj,'  the  bro- 
mine addition;  about  2  ccs.  of  bromine  are 
added  altogether.  The  first  drop  of  bro- 
mine produces  an  immediate  iprecipilati , 
which  is  of  a  dark  red-bmwn  in  colour.  The 
solution  is  then  allowed  to  stand  for  twenty 
minutes,  and  then  drowned  in  water  (about 
100  ccs.  of  cold  water  being  added  for  com- 
plete precipitation).  The  precipitat<»  is  al- 
lowed to  stand  for  a  minute  or  two  and  then 
filtered,  washed  for  some  time  with  hot 
water  and  then  with  alcohol,  dried,  and  then 
weighed.     Yield.  L3  gm. 

The  product,  when  dry,  is  a  chocolate 
powder,  as  prepared  above.  It  is  soluble, 
as  most  of  these  compounds  are.  in  xylene 
and  in  acetic  acid.  It  was  thought  that  it 
might  be  possible  to  diazotise  the  dibromo 
compound,  and  couple  this  with  suitable 
couplers  to  form  azo  dyes,  though  such  dyes 
would  be  rather  unstable.  Some  of  the 
compound  was  therefore  dissolved  in  acid, 
and  sodium,  nitrite,  nitrous  acid,  however, 
was  found  to  split  off  bromine,  the  odour  of 
bromine  being  quite  distinct.  Nitrous  acid 
was  also  found  to  have  a  similar  efTect  on 
the  dibromo   compound    of    benzaldehydro- 


386 


THE  CHEMICAL  NEWS. 


DECEMBER  21,  1923. 


thioparatoluidine,  which  was  also  examined. 
4'  amino  1  phenyl  5  methyl  henzothiazole. 
A  solution  of  the  base  in  alcohol  was  exposed 
to  a  mercury  lamp;  the  solution  exhibits  a 
beautiful  green  fluorescence. 

The  Dibromo  product. — This  was  ex- 
amined in  a  similar  manner,  using  a  solu- 
tion of  the  substance  in  glacial  acetic  acid. 
The     fluorescence    was    a    beautiful     blue 


colour.  The  introduction  of  the  bromine 
atoms  shifts  the  colour  from  the  red  end  of 
the  sipectrum  to  the  violet  end. 

4'  Acctylamino  1  phenyl  5  meihylbenzo- 
thiazole. — A  solution  of  this  in  acetic  anhy- 
dride gave  a  bright,  strong  fluorescence. 

The  h)i-perial  College  of  Science 
and  Technology. 

September,  1923. 


ARE  THE  NATURAL    GROUPINGS  OF 

THE  ELEMENTS  AND  THE  SPECTRAL 

LINES  OF  HYDROGEN  RELATED? 

Part  VII. 

By  F.  H.  LoRiNG. 

In  further  development  of  this  study — 
see  The  Chemical  News,  1923,  CXXVII., 
pp.  225,  257,  273,  290,  337,  355,  369— at- 
tention is  here  drawn  to  an  extension  of  the 
direct  relations  between  the  group  numbers 
derived  from  the  five  Balmer  lines  and  the 
distances  of  the  various  satellites  from  their 
respective  planets. 

In  the  main  part  of  this  investigation  the 
planets  Uranus,  Jupiter,  and  Saturn  will  be 
dealt  with,  as  these  planets  are  particularly 
rich  in  satellites;  and  they  consequently 
afford  a  range  of  values  with  which  to  test 
further  the  significance  of  the  relationships 
thus  far  revealed  for  the  first  time,  so  far  as 
the  writer  is  aware. 


The  accompanying  tabulations  show  the 
results  of  these  findings,  and  they  need  no 
special  explanation,  except  to  stale  that 
the  values  under  the  letter  C  were  obtained 
from  a  drawing  given  in  the  Encyclopcedia 
Britannica  (Planets),  which  gives  the  rela- 
tive distances  in  an  arbitrary  scale.  This 
was  a  desirable  precaution  to  take  at  the 
outset,  partly  as  a  rough  check  against 
the  other  values  obtained  from  Chambers' 
"Handbook  of  Astronoiiiy"  (1889),  Vol.  I., 
which  are  used  here.  Of  course,  the  values 
(C)  are  only  approximate. 

It  is  important  to  specify  all  distances  in 
terms  of  u  common  unit,  in  this  case  miles, 
M,  so  that  the  same  reducing  constant  (K) 
can  be  used  for  each  planetary  system.  S- 
is  the  name  of  the  satellite.  N  is  the  result 
of  dividing  M  by  K,  while  the  correspond- 
in  group  numbers  derived  from  the  Balmer 
lines  are  indicated  by  the  letter  B.  D  is 
the  difference. 


1st 
2nd 


S 
Ariel 
Umbrit 


C 

(6.4) 

(8.9) 

3rd    Titania       (14.3) 

4th    Oberon       (18.5) 

(+0.54)  +  (  +  1.24) 


Uranus. 
M  K 

124,700/19,310 
173,900 
285,300 
381,600 


N 

6.46 

9.00 

14.77 

19.76 


(+1.78),   which  balances  (-1.77). 


B 

7 

9 

13 

21 


D 

+0.54 

0.00 

-1.77 

+1.24 


It  will  be  seen  that  in  the  case  of  this 
planet,  the  satellite  distances  agree  very 
closely  indeed  with  the  B  values. 

With  regard  to  the  derivation  of  the  con- 
stant (K),  if  XM.  represents  the  sum  of  the 
satellite  mean  distances,  and  2)B  represents 
the  sum  of  the  group  numbers  (B),  then 
SM/n  (n  being  the  number  of  satellites,  in 
this  case  4)  divided  by  SB/n.  {n  being  the 
number  of  group  numbers,  also  4),  gives  the 
constant  K  here  employed  for  systematic- 
ally reducing  all  satellite  distances  to  a  set 
of  oomip arable  figures.  This  calculation, 
based  upon  the    Uranug  values,    gives    the 


constant  (K),  which  is  applicable  also  to  the 
satellites  of-  Jupiter  and  Saturn,  though  in 
the  latter  case  there  appears  to  be  a  sys- 
tematic error  in  respect  of  Rhea  and  Titan ; 
but  this  may  be  due  to  the  attempt  to  ex- 
tend the  Balmer  values  rather  than  develop 
the  Paschen,  or  even  the  Lyman  or 
Brackett,  series  (see  Note  4  in  Part  VI.  of 
this  paper).  In  the  instance  of  satellites 
much  nearer  to  their  planet  (Mars)  than 
any  here  shown,  the  Lyman  series  may  give 
the  proper  values,  but  the  examples  are  not 
numerous  enough  to  afford  a  test  that  is  so 
convincing  as  those  being  dealt  with  here. 


DECEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


381 


S  C 

1st     lo       (13.5) 

2nd  Europa       (21.0) 

3rd    Ganvmede       ....  (34.1) 


JUPITEB. 

M                K 

N 

B 

D 

267,300;  10,310 

=     13.84 

13 

-0.84 

425,100 

=     22.01 

21 

-1.01 

678,300 

=     35.12) 

48 


61.72) 


4th    Callisto       (57.2)        1,192,800 

*  Mean  =  48.42,  giving  D  =  (-0.42).   A  mean  error  for  all  the  values  is  (-0.76), 
which  is  very  satisfactory. 


It  should  be  noted  that  the  first  two 
terms  of  the  series  are  absent  in  this  case, 
IS  the  relations  do  not  indicate  whether  the 


lacunae,  so  to  speak,  will  or  will  not  contain 
satellites,  very  much  as  with  elements  in 
the  case  of  the  periodic  table. 


S  C 

1st     Mimas       (6.0) 

2nd  P^uceladus       (8.0) 

3rd     Tethvs        (  ID.O) 

4tli    Dione      (13.3) 

r)th     Khea       (1H.6) 

6th    Titan       (42.5) 

7th     Hyperion       (54.0) 

8th    lapetus       (124.5) 

See  remarks  above  re  Rhea  and  Tit  ui. 


Saturn. 

M           K  N  B  D 

115,100/19,310  =  5.95  —                  — 

147.750  =  7.65  7  -0.65 

183,000  =  9.46  0  -0.46 

234.400  =  12.14  13  +0.86 

327,300  =  16.95  21  +4.06 

758,700  =  39.30  —                  — 

916.700  =  47.48  48  +0.52 

2,221,100  =  115.02  —                  — 


If.  now,  all  the  foregoing  values  corres- 
poufling  properly  to  numbers  7,  9,  18,  21. 
IH,  he  grouped  and  averaged,  the  following 
lesults  are  obtained:  — 


(6.40 

(9.00 

(14.77 

(19.76 

(48.42 


7. 65)/ 2 

0.40)/ 2 

13.84  + 

22.01) /2 

47.48)/2 


12.14)/3      = 


7.05 

9.23 

18.58* 

20.88 

47.95 


*  The  moon's  distance  from  the  earth 
when  reduced  by  the  constant.  K,  gives  the 
value  12.37.  Averaging  this  value  with 
13.r)8  gives  12.97.  which  is  practically  13. 
Then  :£X  =  SB. 

Considering  the  wide  range  of  phenomena 
represented,  there  seems  to  be  no  doubt 
whati'ver  that  the  relations  thus  indicated 
in  tliis  series  of  papers  are  significant  of 
some  important  law  of  far-nacliing  eonse- 
(pu'iu'es;  but  it  must  be  remembered  that 
thesi'  studies  are  only  first  eff''*«  in  m  nmv 
line  of  invt^tigation. 

Summary. 

1m  this  paper  it  is  shown  that  tlu-  ilis- 
tances  from  the  sat<'llites  of  Ihanus,  Jupi- 
ter, Saturn  and  the  Earth-  follow  a 
planetary  disiplaeement  law  represented 
by  the  numbers  7,  9,  13,  21,  48, 
which  arc  derivable  directly  from  5 
Balmer  lines  of  the  hydrogen  atom  spec- 
trum, or  from  the  5  groupings  of  the  periodic 


table  of  the  chemical  elements.  These 
numbers  also  agree  with  the  radial  dis- 
tances of  5  consecutive  planets,  measuring 
from  the  sun,  counting  the  asteroids  collec- 
tively as  one  member  of  the  system.  The 
<luestion  is  raised  as  to  whether  one  of  the 
«)ther  line-series  will  likewise  afford  other 
values  for  the  satellites  much  nearer  their 
planets  than  those  harmonised  by  this 
study,  and  also  incidentally  harmonise  the 
irregularity  in  the  case  of  Rhea  and  Titan. 
It  is  to  he  noted  that  there  are  9  planets  in 
the  solar  system,  counting  the  asteroids  col- 
lectively as  one,  so  that  some  further  de- 
velopment of  one  or  the  other  of  these  series 
is  to  be  expected,  as  the  Balmer  series  only 
agrees  with  5  members.  The  point  to  be 
made,  however,  is  that  the  values  above 
(fiven  agree  in  wany  consecutive  instances 
over  a  range  of  natural  phenomena  of  al- 
most incredible  magnitude. 

Notes, 

Other  Satellites : 
Earth— 

1  only.  Moon.    238,900/19.310  =    12.37* 

*  Near  to  the  value  18. 
Neptune — 

1  only.  Lassell.  223.000/19.310  =   11.54* 

*  Mean  between  0  and  13;  but  may  be- 
long to  another  series.  Chambers  men- 
tions that  this  satellite  is  peculiar  in  its 
movement.  It,  of  course,  belongs  to  the 
most  distant  planet. 


388 


THE  CHEMICAL  NEWS. 


DECEMBEK  21,  1923. 


Mars-- 
1st     Phobos     6,000)     See  remarks  above 
2nd  Deimos  15,000)     re  other  series. 

Saturn — 

The  Balmer  ^  line,  by  the  iormula,  p. 
291,  gives  5.6,  which  is  near  to  the  value 
above  for  Mimas:  5.95.  62.5  may  be  used 
as  a  dividing  constant  instead  of  61.5  for  the 
whole  series.  A  more  recently-discovered 
satellite  of  this  planet  (Phoebe)  has  the  prob- 
able comparative  values  as  follows:  — 
7,798,300/19,310  =  403.83* 

*  This  is  outside  the  present  range  of  cal- 
culations, and  it  would  seem  to  involve  an- 
other series  as  indicated  above. 

Jupiter — 

A  naore  recently -discovered  satellite  of 
this  planet  has  the  probable  comparative 
values  as  follows  :  — 

109,160/19,310  =  5.65* 

*  Averaging  this  figure  with  that  of 
Mimas,  5.95,  gives  5.80,  the  theoretical 
value  being  about  5.6. 

These  distances  here  are  also  in  miles,  as, 
given  above  in  the  case  of  Uranus,  &c. 

DYESTUFFS    (IMPORT  REGULATION) 

ACT,  1920. 

Applications  for  Licences  in  November, 

1923. 

The  following  statement  relating  to  app.i- 
cations  for  licences  under  the  J^yestuffs 
(Import  Regulation)  Act,  1920,  made  dur- 
ing November,  has  been  furnished  to  the 
Board  of  Trade  by  the  Dyestuffs  Advisory 
Licensing  Committee. 

The  total  number  of  applications  received 
during  the  month  was  612,  of  which  485 
were  from  merchants  or  importers.  To 
these  should  be  added  8  cases  outstanding 
on  November  1,  making  a  total  for  the 
month  of  620.  These  were  dealt  with  as 
follows  :  — 

Granted — 433  (of  which  413  were  dealt 

with  within  7  days  of  receipt). 

Referred  to  British    makers  of  similar 

products — 119    (of  which  105    were  dealt 

with  within  7  days  of  receipt). 

Referred  to  Reparation  supplies  avail- 
able— 40    (all  dealt  with  within  2  days  of 

receipt). 

Outstanding  on   November  30,    1923 — 

28. 

Of  the  total  of  620  applications  received, 
558,  or  90  per  cent.,  were  dealt  with  within 
7  days  of  receipt. 


GENERAL    NOTES. 


ATMOSPHERIC  CORROSION  OF 
METALS. 

Future  generations  will  express  astonish- 
ment that  right  into  the  twentieth  century 
we  have  been  content  to  extend  the  use  of 
constructional  materials,  without  appar- 
ently giving  any  consideration  to  their  rela- 
tive corrodibility. 

A  small  committee  which  could  marshall 
the  available  scientific  knowledge  smd  apply 
the  simplest  of  business  costing  principles, 
would  almost  certainly  effect  extraordinary 
changes  in  the  choice  of  materials  for 
building,  public  works,  and  innumerable 
engineering  purposes.  Much  too  little 
attention  is  usually  paid  to  upkeep  expenses 
in  relation  to  initial  cost  of  installation. 

Comparing  two  metals,  for  instance;  in 
the  one  case  the  initial  cost  may  be  less, 
but  after  the  ipainting,  repainting,  repairing 
and  perhaps  even  replacement  are  added,  it 
may  frequently  prove  much  less  economical 
than  a  second  metal  which  can  be  used 
without  any  protective  coating  whatever. 

The  real  problems  of  corrosion  and  their 
solution  cannot,  of  course,  be  solved  in  this 
way,  since  much  more  fundamental  know- 
ledge of  the  causes  and  sequence  of  effects 
is  required. 

There  seems  to  be  no  doubt  that  still 
greater  advances  in  the  choice,  treatment, 
and  use  of  materials,  from  the  point  of  view 
of  their  resistance  to  corrosion,  will  result 
from  systematic  observation  and  experi- 
ments. 

One  of  the  most  important  researches  on 
the  subject  is  that  being  carried  out  by  the 
Atmospheric  Corrosion  Committee  of  the 
British  Non-Ferrous  Metals  Research  As- 
sociation. Mr.  W.  H.  J.  Vernon,  B.Sc, 
the  investigator,  has  just  submitted  his 
first  experimental  report,  which  was 
read  before  the  Faraday  Society  in  London 
on  Monday,  December  17.  The  work  de- 
scribed has  been  carried  out  under  the 
supervision  of  Professor  H.  C.  H.  Carpen- 
ter, F.R.S.,  at  the  Royal  School  of  Mines, 
and  dealt  chiefly  with  the  initial  stages  of 
corrosion — the  tarnishing  of  metals.  Quan- 
titative measurements  have  been  made  on 
the  relative'  behaviour  of  different  metals 
and  alloys,  both  indoors  and  outdoors.  The 
subj'ect  is  of  immense  importance,  not  only 
to  those  who  are  concerned  in  the  manufac- 
ture of  metal  fittings  and  articles,  but  in  its 
direct  relation  to  labour-saving  in  daily 
housework. 


December  21,  i92S. 


THE  CHEMICAL  NEWS. 


889 


The  investigation  was  by  no  means  con- 
fined to  tarnishing,  which  formed  the  out- 
standing feature  of  the  first  report,  merely 
because  it  represented  the  initial  stage  of 
corrosion.  Exposure  tests  to  outside  atmos- 
pheric influences  have  been  progressing 
-ince  the  commencement  of  the  research, 
lud  will  doubtless  yield  their  quota  of  evi- 
dence in  due  course. 

The  extension  of  this  work  dcipends  to  a 
large  extent  on  the  support  given  to  the 
British  Non-Ferrous  Metals  Research  Asso- 
ciation for  this  specific  purpose;  the  inves- 
tigation already  has  the  backing  of  the 
Itoyal  Institute  of  British  Architects,  the 
Department  of  Scientific  and  Industrial  Re- 
search, and  many  of  the  leading  firms  and 
associations  in  the  metal  industry. 


THE  WORLD'S  WHEAT  SUPPLIES 
AND  REQUIREMENTS. 

According  to  an  estimate  made  by  the  In- 
ternational Institute  of  Agriculture,  at 
Rome,  the  wheat-exporting  countries  are 
thef)reticnlly  in  u  position  to  furnish  to  th<' 
importing  countries  during  the  cereal  season 
from  August  1,  1923,  to  July  81,  1024. 
about  570  million  centals  of  wheat.  To  this 
quantity  Canada  could  contribute  about  221 
million  centals,  the  United  States  a  little 
over  112  million,  India  12  million,  Argen- 
tina 122  million,  Australia  .'jS  milk»,  while 
the  Balkans,  Hungary,  Hussia,  and  the 
French  colonies  in  North  Africa  oould  fur- 
nish altogether  about  45  million  centals. 

Estimates  of  probable  requirements  in 
the  importing  countries  are  not  at  all  easy 
to  prepare  for  the  current  season,  owing  to 
recurring  difficulties  presented  by  the  finan- 
cial and  economic  conditions  existing  in 
sundry  European  States  and  by  the  efforts 
of  some  Governments  to  limit  imports  of 
foreign  wheat.  In  pre-war  times  it  might 
generally  be  assumed  that  individual  con- 
sumption in  a  given  country  would  not  vary 
much  from  year  to  year.  Having  ascer- 
tained the  quantity  produced  in  a  certain 
counti7  (lining  a  staticd  season,  it  was  pos- 
sible to  define  with  fairly  close  approxima- 
tion the  quantity  of  wheat  required  to  sup- 
plement home  production  during  the  twelve- 
month. 

Now,  however,  the  basis  for  such  an  esti- 
mate has  l>ecome  imich  less  secure,  and  it 
by  no  means  follows  that  a  short  crop  en- 
tails a  correspondingly  larger  import,  or 
vice  versa.    There  is  proof  of  this  in  effect- 


ing comparison  between  data  of  production 
and  imports,  for  the  two  seasons  1921-22 
and  1922-23  respectively. 

Although  the  1922  crops  in  importing 
countries  were  110  million  centals  less  than 
in  1921,  these  countries  took,  between  Aug- 
ust 1,  1922  and  July  31,  1923,  much  the 
same  quantity  of  foreign  wheat.  For  the 
most  part  the  causes  leading  to  such  a  de- 
cline in  consuniiption  are  still  in  operation. 
Even  if  the  plentiful  yields  so  general  in 
1923  should  result,  for  some  countries,  in  a 
larger  consumption  than  lust  year's,  it 
seems  probable  that  import  requirements 
between  August  1,  1923,  and  July  31,  1924, 
will  be  on  a  more  restricted  scale  than  those 
of  last  seascHi.  In  any  event,  these  im- 
ports are  unlikely  to  exceed  last  year's  total 
of  430  million  centals. 

To  sum  up  :  — 

(1)  The  quantity  of  wheat  that  theoretic- 
ally might  be  despatched  by  the  exporting 
countries  to  the  importing  States  between 
August  1,  1923  and  July  31,  1924,  is  about 
570  million  centals. 

(2)  The  quantities  required  for  the  same 
period  by  importing  countries  to  8U»pple- 
ment  their  home  production  may  reach  480 
million  centals  at  most,  but  it  is  improbable 
that  this  figiue  will  be  attained. 

(3)  The  quantity  available  in  exporting 
oountrie«  will  therefore  suffice  to  ni«'et  the 
requirements  of  the  importing  countries 
until  the  next  harvest  in  the  northern  hemi- 
sphere, and  to  leave  a  surplus  on  hand  at 
August  L  1924.  This  surplus  nuiy  be  esti- 
mated at  not  loss  than  140  million  centals. 


DRUGS,  CHEMICALS,  ETC.,  FOR 
EGYPT. 

The  British  Commercial  Agent  for  Egypt 
has  forwarded  to  the  Department  of  Over- 
seas Trade  copies  of  documiiuts  issued  by 
the  Egyptian  Ministry  of  the  Interior  in 
connection  with  a  call  for  tenders  for  the 
supply  of  miscellaneous  dru^s,  chemicals, 
<'tc.,  required  by  the  Department  of  Public 
Health  during  1924-25.  The  schedule  of 
stores  re(]uired  includes:  — 

(1)  Proprietary  articles; 

(2)  Druggists'  sundries; 

(3)  Surgical  dressings; 

(4)  Crude  drugs  and  heavy  chemicals; 

(5)  Fine  chemical  iproducts;  and 
(())  Galenicals  and  packed  articles. 
Tenders  will  be  received    by  the  Director 

of  Stores.  Department    of    Public    Health, 


3§6 


TSB  CHJBMiCAL  NEWS. 


December  21,  192s. 


Cairo,  up  to  noon  on  January  14,  1924. 
Article  5  of  the  conditions  of  tender  states 
that  "the  articles  supplied  must  be  exactly 
similar  to  the  standard  sealed  pattern,  kept 
at  the  Central  Stores,  Department  of  Pub- 
lic Health,  Cairo,  and  in  number,  weight, 
and  measurements  in  accordance  with  the 
written  schedule  or  size  roll  given  to  the 
contractor  by  the  Director  of  Stores.  The 
standard  pattern  will  be  sealed  by  the  De- 
partment and  by  the  contractor."  It  is 
also  stipulated  that  the  tenderer  must  be  a 
person  residing  in  Egypt,  or  must  have  a  re- 
presentative there,  and  will  give  in  his  offer 
an  address  at  which  notices  may  be  served 
upon  him.  The  Department  of  Overseas 
Trade  will  furnish  U.K.  firms  desirous  of 
tendering  and  not  represented  locally  with 
the  names  and  addresses  of  United  King- 
dom merchant  firms  established  in  Egypt, 
who  would  be  prepared  to  handle  tenders  on 
their  behalf. 

A  copy  of  the  schedule  of  stores  required, 
conditions  and  form  of  tender,  may  be  seen 
on  application,  while  a  further  set  of  these 
documents  is  available  for  loan  to  firms  in 
the  provinces  who  may  be  unable  to  arrange 
for  a  London  i*eipresentative  to  call  here. 


GERMANY'S  COMMERCE  AND 
INDUSTRY  DURING  NOVEMBER. 

Mr.  J.  W.  F.  Thelwall,  H.M.  Commer- 
cial Secretary  at  Berlin,  has  forwarded  to 
the  Department  of  Overseas  Trade  a  review 
on  the  state  of  Germany's  trade  and  indus- 
try during  November. 

No  improvement  occurred  in  the  econo- 
mic situation  in  November.  The  position  in 
occupied  territory  continued  hopeless. 
Its  economic  life,  with  a  few  excetptions, 
remained  stagnant.  There  the  possibilities 
of  export  diminished  more  and  more,  while 
imports  of  such  raw  materials  as  were  for- 
merly produced  in  the  country  increased. 
Unproductive  work  became  more  extensive, 
an  exceptional  rise  in  the  costs  of  produc- 
tion occurred,  and  the  level  of  prices  for 
goods  was  generally  very  high. 
Mining. 

The  pit-coal  production  in  Upper  Silesia 
was  again  interrupted.  The  small  output  of 
the  preceding  month  was,  therefore, 
scarcely  exceeded.  There  was  no  complaint 
as  to  the  supply  of  trucks.  In  spite  of  a  re- 
duction of  advance  freights  by  the  railway 
and  of  reduced  shipping  rates,    there  were 


practically  no  consignments  to  places  of 
transhipment.  The  demand  revived  as 
compared  with  last  month  owing  to  the 
more  pressing  requirements  at  this  time  of 
the  year  of  agriculture,  household  coal  con- 
sumers and  gasworks.  As  before,  however, 
the  orders  for  dust  coal  were  not  extensive. 

In  the  Central  German  brown  coal  dis- 
trict the  market  conditions  continued  un- 
favourable, so  that  shifts  had  to  be  dropped 
in  many  mines,  althous;h  after  the  last 
strike  a  fairly  considerable  number  of 
workers  were  not  reinstated.  In  some  works 
the  number  had  been  reduced  by  15-45  per 
cent.  Other  works  had  not  yet  started 
operations  again  after  the  strike. 

In  the  Ruhr  coal  district  all  the  miners 
and  employees  were  given  notice  of  termi- 
nation of  work  on  November  30  and  Decem- 
ber 31  resipectively. 

Potash. 

In  the  potash  industry,  with  the  excep- 
tion of  a  somewhat  more  lively  export  of 
sulphates  to  North  America,  the  market 
was  very  unfavourable.  Further  shifts  had 
consequently  to  be  dropped  in  all  the  works, 
and  dismissals  had  partly  to  be  resorted  to. 
Inland  business  became  more  and  more 
paralysed.  It  is  hoped,  however,  that  after 
the  introduction  of  a  sufficient  quantity  of 
stable  media  of  payment,  the  main  difficulty 
in  the  jMuchase  of  potash  salts  will  be  over- 
come. The  demand,  particularly  from 
abroad,  for  chemical  by-products,  was  still 
satisfactory.  In  order  to  offer  an  incentive 
to  the  immediate  placing  of  orders  for  pot- 
ash, the  Potash  Syndicate,  in  agreement 
with  agricultural  and  trade  organisations, 
granted  a  goods  discount  to  consumers.  In 
spite  of  this,  however,  only  small  orders 
were  placed  on  behalf  of  agriculture,  so 
that,  next  to  April,  November  was  the  most 
unfavourable  month  of  this  year  as  far  as 
sales  were  concerned. 

Metals. 

The. metal  trade  was  at  times  brought  to 
a  standstill,  as  the  position  on  the  metal 
market  grew  continually  worse.  The  decree, 
issued  at  the  end  of  October,  again  pro- 
hibiting free  transactions  in  foreign  values 
and  the  action  taken  at  the  same  time  by 
the  Reichsbank  to  support  the  mark,  re- 
sulted in  a  very  important  difference  be- 
tween the  inland  and  foreign  mark  rates. 
The  metal  trade  was  thereby  greatly  ham- 
pered, and  the  fixing  of  uniform  metal 
prices  was  impossible.  For  this  I'eason  the 
Berlin  Metal  Exchange  again  ceased  to 
issue  quotations. 


DECEMBER  21,  1923. 


THE  CHEMICAL  NEW 


891 


Chemical  Industry. 
The  general  economic  situation  necessi- 
tated further  restrictions  of  work  in  the 
chemical  industry  in  occupied  territory.  If 
unintei  rupted  communication  with  unoccu- 
pied Germany  is  not  madt-  possible,  the 
works  must  come  to  a  total  standstill.  In 
the  chemical  pretparations  industry  the  de- 
mand for  laboratory  chemicals  was  very 
small,  and  that  for  glass  chemicals 
diminished  in  the  degree  in  which  the  glas;;- 
works  were  compelled  to  restrict  work  or 
close  down.  The  demand  tr(;m  abroad  also 
fell  off  as  sale  prices  approached  the  world's 
market  level.  It  is  felt  to  be  a  particular 
burden  that  just  at  the  present  time  the  re- 
funding of  the  British  ll<paration  Ix'vy 
should  have  been  discontinued,  and  thus  all 
possibility  of  selling  German  products  to 
Kngland  removed.  It  is  all  the  more  to  be 
regretted,  as  tYench  competition  is  greatly 
felt  in  England,  and  will  now  secure  the 
whole  trad<'  without  effort.  A  alight  revival 
of  both  inland  and  foreign  trade  in  the  re- 
maining chemical  preparations  was  re- 
ported. 

Qlass  Induniry. 
In  the  sheet  glass  industry  there  was  no 
improvement  on  the  inland  market.  Thi- 
demand  from  abroad  increa.sid  somewhat, 
but  prices  were  so  depressed  owing  to 
Czech o-Slovaki an  and  Jiel^'ian  competition 
that  they  scarcely  covered  much  more  Ih  in 
half  the  costs  of  production.  Wage  strikes 
interfered  with  pnxluction  in  the  hollow- 
glass  industiy.  The  advanc*-  in  iho  costs  of 
production,  which  made  competition  abroad 
impossible,  led  to  further  restrictions  of 
work  and  the  closing  down, of  factories. 
Ceramic  Induslry. 
The  position  of  the  porcelain  industry  b«- 
came  considerably  worse,  and  was  charac- 
terised by  a  complete  stagnation  in  inland 
sales,  numerous  cancellations  of  orders,  and 
restriction  of  oi)erations.  K<  stricted  opera- 
tions were  reported  from  the  Palatinate, 
Wurtteml)€rg,  Thuringia.  S:ixony,  Silesia, 
and  Brandenburg.  The  electro-technical 
porcelain  industry  suffen-d  from  a  great 
lack  of  orders  and  from  short-time  work. 
Only  the  glazed  wall-tile  facti  rip>;  \vi>v  in 
part,  well  employed. 

Paper  Industry. 
The  degree  of  employment  in  the  paper 
industry  was,  in  general,  not  unfavourable 
as  compared  with  other  branches  of  indus- 
try. By  the  middle  of  October,  however, 
the  number  of  unsatisfactoiily  employed 
works  which  hatl  to  curtail  working  hours  or 


work  fw  stock  preponderated.  Since  then 
the  position  has  grown  considerably  worse. 
The  financial  difficulties  (growing  costs  of 
production,  diminishing  receipts  owing  to 
falling  off  of  sales,  restriction  of  credit  and 
the  ditiiculty  of  obtaining  the  latter  from 
the  banks)  increased  continually,  and  the 
stock  of  orders  was  reduced.  According  to 
one  report  from  an  industiial  association,  in 
land  trade  was  pxactlcally  at  a  standstill. 
The  raising  of  even  the  most  necessary 
funds  for  raw  mateiials,  wages  and  salaries, 
etc.,  met  with  the  greatest  difficulties.  In 
order  to  maintain  the  factories,  the  industry 
is  more  than  ever  despondent  on  exports.  In 
the  paper  producing  and  working  up  indus- 
try, the  possibilities  of  export  in  general  de- 
clined more  and  more,  owing  to  excessively 
high  prices.  For  the  rest,  the  conditions  as 
regards  production  were  not  unfavt)urable, 
especially  for  the  paper  raw  material  indus- 
try. The  wat^r  conditions  imiproved,  and 
sufficient  German  coal  was  obtainable  (the 
demand  having  fallen  off  in  view  of  restric- 
tions of  work),  though  it  was,  in  part,  more 
expensive  than  British  coal.  The  supply  of 
auxiliary  materials,  with  the  exception  of 
dyes,  was  adequate.  The  production  of 
wood-pulp  increased,  but  the  demand  was 
generally  small. 

Leather  Industry. 
ITie  prices  of  hides  and  skins  rose  con- 
siderably, owing  to  the  further  depreciation 
of  the  mark.  With  a  few  exceptions,  the 
pre-war  prices  have  not  only  been  reached, 
but  exceeded.  A  more  wholesome  demand 
on  the  part  of  manufacturers  was  recorded. 
The  turnover  would  have  been  greater,  had 
it  not  been  for  money  difficulties.  In  the 
leather  trade  business  was  almost  stagnant 
in  the  first  part  of  the  month,  owing  to  the 
lack  of  money ;  but  here  also  a  more  whole- 
some demand  set  in  subsequently,  although 
an  important  turnover  could  not  be  achieved 
in  consequence  of  the  difficult  position  as 
regards  currency.  As  before,  complaint  was 
made  in  the  boot  and  shoe  industry  as  to  the 
lack  of  purchasing  power  on  the  part  of  the 
public.  A  better  turnover  was,  however, 
obtained  in  the  retail  trade. 

Sugar  Industry. 
Lively  business  in  sugar  (for  consump- 
tion) from  the  new  harvest  developed  in  the 
course  of  the  month.  The  reip<wt8  regard- 
ing the  proposed  export  by  the  Government 
of  sugar  and  regarding  tne  estimated  har- 
vest yield  (the  latter  is  estinuit(>d  to  be 
about  20  per  cent,  smaller  than  last  year) 
called  forth  a  brisk  demand  for  sugar.  The 


392 


d?HE  CHEMICAL  T^fiWS. 


DfiCEMBEK  21,  1928. 


factories,  however,  placed  only  compara- 
tively small  quantities  on  the  market.  The 
result  was  an  increase  in  prices,  so  that  in- 
land prices  habe  now  exceeded  the  world's 
market  level,  although  the  latter  has  also 
advanced  considerably.  The  sugar  working 
up  industry  continued  to  complain  of  a 
strong  decline  in  business  owing  to  too  high 
prices,  and  also,  in  particular,  of  a  great 
shortage  of  sugar,  so  that  short  time  work 
and  dismissals  frequently  became  neces- 
sary. 


PROCEEDINGS    AND  NOTICES  OF 
SOCIETIES. 

THE  ROYAL  SOCIETY  OF  ARTS. 

On  Monday,  December  10,  the  Cantor 
Lecture  (IL),  entitled  Recent  Progress  in 
the  Wool  Industries,  was  read  by  Aldred  F. 
Barker,  M.Sc,  Professor  of  Textile  Indus- 
tries, the  University,  Leeds. 

On  Wednesday,  December  12,  at  the  Or- 
dinary Meeting,  a  paper  entitled  The  Preser- 
vation of  Historic  Buildings  and  Ancient 
Monuments  was  read  by  Sir  Frank  Baines, 
C.B.O.,  C.B.E.,  Director  of  Works,  H.M. 
Office  of  Works.  Sir  Aston  Webb,  K.C.V.O.. 
C.B.,  C.R.A.,  Vice-President  of  the  Society, 
presided. 

The  Dominions  j>nd  Colonies  Section  held 
a  meeting  on  Monday,  December  17.  A 
lecture  entitled  Empire  Settlement  was  de- 
livered by  William  C.  Noxon,  Esq.,  Agent- 
General  for  Ontario.  The  Right  Hon.  the 
Earl  of  Airlie,  M.C.,  presided. 


SOCIETY  OF  PUBLIC  ANALYSTS  ANI^ 

OTHER  ANALYTICAL  CHEMISTS. 

Ordinary  Meeting. 

Held  at  the  Chemical  Society's  Rooms, 
Burlington  House,  on  Wednesday,  Decem- 
ber 5,  1923,  Mr.  P.  A.  Ellis  Richards  (Pre- 
sident) in  the  chair. 

Certificates  were  read  for  the  first  time  in 
favour  of: — Messrs.  Frank  Knowles.  Archi- 
bald Knox,  A. I.e.,  Charles  Roger  Middle- 
ton,  B.Sc,  A.R.C.S.,  D.I.C.,  A.I.C.,  Har- 
old Richard  Read,  A.I.C.,  George  Hogan, 
F.I.C.,  Thomaw  Fi'ancis  Doyle. 

Certificates  were  read  for  the  second 
time  in  favour  of: — Messrs.  Robert  Charles 
Frederick,  Hubert  Thomas  Stanley  Britton, 
M.Sc.  (Lond.),  F.I.C. 


The  following  were  elected  members  of 
the  Society:  — 

Messrs.  Laurence  Eversley  Campbell, 
M.Sc.  (Lond.),  F.I.C,  John  Troubridge 
Hannen,  B.A.  (Cantab.),  A.R.C.Sc., 
A. I.e.,  Cyril  Langley  Hinton,  F.I.C, 
Douglas  William  Kent- Jones,  M.Sc. 
(Lond.),  F.I.C,  Thomas  William  Alan 
Shaw,  M.Sc.  (Liv.),  William  Hall  Sim- 
mons, A. I.e.,  Kenneth  Edward  Nethercoate 
Williams,  Percy  Noel  Williams,  M.Sc. 
(Liv.),  A. I.e. 

The  followng  patpers  were  read  :  — 

The  Crystalline  Bromif^es  of  Linseed  Oil, 
by  Harold  Toms,  M.Sc,  A.I.C 

The  "insoluble  bromide"  of  linseed  oil, 
first  described  by  Hehner  and  Mitchell,  ap- 
pears to  consist  of  mixtures  in  varying  pro- 
portions of  two  crystalline  bromides,   viz.  : 

(1)  a  linolic-dilinolenic  bromo-glyceride,  and 

(2)  the  trilinolic  bromo-glyceride  of  the 
oleic-linolic-linolenic  bromo-glyceride.  These 
two  bromo-glycerides  have  been  obtained  in 
pure  condition  by  crystallisation  froni  ethyl 
acetate.  They  melt  at  153°  C  (corr.)  and 
117°  C  (corr.),  respectively.  The  solubility 
of  the  more  insoluble  bromide  in  ethyl  ace- 
tate lies  between  0.15  and  0.20  grm.  per  100 
cc.  at  15  to  20°  C  The  methods  of  estimat- 
ing the  bromine  in  these  compounds  have 
been  studied,  and  it  is  shown  that  theoreti- 
cal results  can  be  obtained  by  the  method  of 
Carius  and  by  a  modification  of  the  method 
of  Stephanow,  but  not  by  the  lime  method. 
Vai'ious  methods  of  estimating  the  more  in- 
soluble crystalline  bromides  are  described, 
the  yields  of  th^'  purest  product  varying 
from  9.39  to  11.6  per  cent,  in  the  case  of 
different  oils.  The  results  obtained  suggest 
that  there  is  some  relationship  between  the 
yield  of  this  crystalline  bronjide  and  the 
iodine  value  of  the  original  oil. 

The  Plea  for  Standardisation,  by  M.  S. 
Salmon,  B.Sc. 

The  author  emphasises  the  fact  that  in 
every  field  of  analytical  chemistry  instances 
are  continually  occurring  where  different, 
although  well  recognised  methods  of  analy- 
sis yield  varying  results.  He  refers  in  par- 
ticular to  the  case  of  dried  milks,  and  in- 
stances one  example  where  one  sample  of 
dried  milk  was  sent  to  fom-  w<.'ll -known 
analysts,  and  a  considerable  divergence  of 
figures  resulted  according  to  the  methods 
used,  particularly  in  the  case  of  the  fat  and 
lactose  estimations. 


DECEMBER  21,  1023. 


VHB  CHEMICAL  NEWS 


Referring  next  to  essential  oils,  the  need 
for  standardisation  is  seen  to  be  urgent,  lor 
in  nianv  cases  minute  modifications  m  de- 
tail cause  substantial  differences  in  results. 
The  same  remarks  apply  to  the  case  of  in- 
organic materials  of  sinnpler  composition, 
and  the  author  sees  a  recognition  of  the  dit- 
ficulties  in  the  details  laid  down  for  analyses 
under  the  Fertiliser  and  Feeding  Stufis  Act 
and  he  strongly  advocates  the  formation  of 
a  Committee  to  consider  the  whole  question. 

A  Note  on  the  Estimation  of  Chromium, 
by  Hubert  T.  S.  Britton,  M.Sc,  F.I.C. 

"^The  gravimetric  methcxls  of  estimating 
chromium  as  oxide  are  discussed.  What- 
ever precautions  are  taken  to  use  only  tnc 
purest  reagents  and  salts,  and  platinum  cru- 
cibles ,the  ignited  oxide  is  always  found  to 
contain  some  chromate.  This  may  be 
sho^u  by  extracting  witb  water  Hence, 
such  methods  lead  to  high  results  It  has 
been  found  that  chromium  can  be  quickly 
and  accurately  estimated  volumetrically. 
The  procedure  is  to  add  to  an  approximately 
neutral  solution  of  a  chromium  salt  an  ex- 
cess of  sodium  peroxide— about  a  gram— 
and  boil  for  ten  minutes  to  complete  the 
oxidation  to  chromate  and  to  d^ompoee 
the  unused  peroxide.  After  acidificatio-n 
with  either  sulphuric  or  hydrochloric  acid, 
excess  of  potassium  iodide  is  added,  and  the 
liberated  iodine  titrated  in  the  usual  way. 

The  Colorimeiric  Estimation  of  Lead  in 
Cream  of  Tartar,  by  R.  L.  Andbbw. 

During  1921-22  all  importations  of  cream 
of  tartar  to  New  Zealand  were  exammed  for 
lead,  and  the  following  method  was  found 
to  give  simihu-  results  and  to  be  less  cum- 
bersome than  the  B.P.  n.ethod.  One  cc.  of 
5  per  cent,  potassium  cyanide  solution.  1  oc. 
of  ammonia  solution,  and  40  oc.  of  water 
are  added  to  two  grams  of  cream  <>«  ^af^a^' 
and  soultion  effected  by  warming  and  shak- 
ing. After  ooling  and  filtering,  any  tint  is 
matched  in  the  standards  by  the  addition  of 
verv  dilute  caramel.  These  standards  aiv 
prepared  in  a  similar  way  from  2  grains  of 
iVad.  free  from  cream  of  tartar  with  the 
a.Idition  of  requisite  amounts  of  lead  nitrate 
solution  containing  0.01  per  «nt.  of  lead^ 
A  few  drops  of  10  per  cent  sodium  sulphide 
foh^ion  a?e  added,  ami  the  solutions  anj 
all  made  up  to  the  mark  and  the  an'^mnt^of 

Lrd^w^atr  sohiion  oHeRdTs  used,  a  serious 
'rroi  rintro^iucvd,    as  the  colour    is    only 


about  half  the  depth  of  that  produced  with 
a  tartrate  solution,  and  the  effect  of  ferric 
and  ferrous  iron  is  investigated. 


THE    SOCIETY    OF    GLASS 
TECHNOLOGY. 
A  meetmg  of  the  Society  of  Glass  Tech- 
nology   was    held     in    University    College, 
Gower  Street,  W.C.I,  on  December  12. 

The  following  papers  were  received  and 
discussed:  — 

An  Apparatus  for  the  Calibration  of  Bu- 
rette Tubes,  by  Verney  Stott,  B.A., 
F.Inst.P. 

Some  Factors  Affecting  Efficiency  in  the 
Glass  Trade,  by  Eric  Farmer,  M.A.  (In- 
dustrial Fatigue  liesearch  Board). 

Specifications  in  the  Glass  Industry,  ivith 
Special  Reference  to  Soda-Lime  Glasses  for 
Containers,  by  Trofessor  W.  E.  S.  Tur- 
ner, D.Sc. 


THE  PHYSICAL  SOCIETY  OF  LONDON. 

A  meeting  of  the  Society  was  held  on  Fri- 
day, December  14,  at  the  Imperial  College 
of  Science,  South  Kensington,  S.W. 

The  following  papers  were  read:  — 

The  Aerodynamic  Resistance    of  Spheres 

Shot  Upward  to  Measure  the  Wind,    by  L. 

F.  Richardson,  F.Inst.P.,  F.R.Met.Soc. 

X-Ray  Analysis  of  Zinc-Copper  Alloys,  by 
E.  A.  Owen,  M..\.,  D.Sc,  and  G.  D.  Pres- 
ton, B.A. 

bivestigations  of  Pic zo- Electric  Effects 
with  Dielectrics,  by  K.  R.  Brain,  B.Sc. 

A  Demonstration  of  "  The  Neon  Tube 
Oscillograph  "  was  given  by  H.  St.  G. 
.Vnsou. 


J 


THE  OPTICAL  SOCIETY. 
A  meeiing  was  held  at  the.  Imperial  Col- 
\oav    S:)uth  Kensington,  on  Thursday,  Dec. 
13.       The  following  pai>ers  were  presented 
and  discussed:  — 


a94 


THE  CHEMICAL  NEWS. 


DECEMBER  21,  1923. 


The  Primary  and  Seeondary  Constant 
Magnification  Surfaces  of  Thin  Lenses,  by 
T.  Smith,  M.A.,  F.Inst. P. 

A  Suggested  Standard  Trial  Case  and 
Simplification  in  Ophthalmic  Policy,  by  W. 
SWAINE,  B.Sc. 

"  An  optical  revolution  counter  "  was 
exhibited  and  described  by  B.  K.  Johnson. 


PROGEEDINOS  OF  THE  GEOLOGICAL 
SOCIETY  OF  LONDON. 

December  5. 

Prof.  A.  C.  Seward,  Sc.D.,  F.R.S.,  Pre- 
sident; and,  afterwards,  Dr.  G.  T.  Prior, 
F.R.S.,  F.G.S.,  in  the  chair. 

Dr.  F.  A.  Bather  exhibited,  on  behalf  of 
Mr.  A.  S.  Hirst,  F.Z.S.,  specimens,  micro- 
scQpe-slides,  and  lantern- slides  of  Arachnid 
Remains  from  the  Rhynie  Chert,  and  de- 
scribed their  structure  and  affinities. 

The  following  communications  were  read 
and  discussed  :  — 

The  Geology  of  the  Northern  Border  of 
Darlmoor,  between  Whiddon  Down  and 
B^itterdon  Down,  by  Charles  William  Os- 
MAN,  M.Inst.C.E.,  F.G.S. 

The  Geology  of  Southern  Guernsey,  by 
Donald  John  Farquharson,  M.Sc,  F.G.S. 

Rock-specimens  and  microscope-sections 
were  exhibited  by  Mr.  C.  W.  Osman,  and 
microscope-sections  were  exhibited  by  Mr. 
D.  J.  Farquharson,  in  illustration  of  their 
respective  papers. 

A  meeting  of  the  Society  was  held  on 
Wednesday,  December  19. 

Prof.  W.  J.  Sollas,  F.R.S.,  F.G.S..  de- 
monstrated the  Method  of  Investigating 
Fossils  by  means  of  Serial  Sections,  and 
exhibited  some  of  the  results  obtained. 

Mr.  John  Walton.  M.A.,  dealt  with  the 
Investigation  of  the  Nature  of  Fossil 
Plants,  illustrating  his  remarks  by  lantern- 
slides. 


THE  ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

Lectures  Before  Easter,  1924. 

Friday  Evening  Discourses,  addressed  to 
members  and  their  friends,  at  9  p.m.  :  — 

Jan.  18:  Prof.  Henry  E.  Armstrong, 
LL.D.,  F.R.S.,  M.R.I. ,  The  Scientific 
Work  of  Prof.  Sir  James  Deivar,  LL.D., 
D.Sc,  F.R.S.,  Fullerian  Prof,  of  Chemistry 
(1877-1923). 

Jan.  25:  Sir  Aston  Webb,  K.C.V.O., 
C.B.,  President  of  the  Royal  Academy, 
The  Future  Developm^^nt  of  London. 

Feb.  1:  Sir  William  Bragg,  K.B.E., 
D.Sc,  F.R.S.,  M.R.I. ,  Fullerian  Prof,  of 
Chemistry,  Recent  Research  on  Crystalline 
Stinicture. 

Feb.  8:  Sir  Arthur  Evans,  D.Litt., 
LL.D.,  F.R.S.,  F.S.A.,  Prof,  of  Prehis- 
toric ArchEeology,  University  of  Oxford,  Re- 
cent Lights  on  the  Minoan  Art  of  Crete. 

Feb.  15:  J.  H.  Jeans,  LL.D.,  D.Sc, 
F.R.S..  M.R.I.,  Secretary  of  the  Royal  So- 
ciety, The  Origin  of  the  Solar  Sy stern. 

Feb.  22:  G.  Elliot  Smith,  M.D.,  F.R.S., 
F.R.C.P.,  M.R.I..  Prof,  (f  Anatomy,  Uni- 
versity of  London,  The  Liu  in  an  Brain. 

March  7:  Walter  Rosenuaix,  D.Sc, 
F.R.S.,  Superintendent  of  Metallurgy  De- 
partment, National  Physical  l^aboratory. 
The  hiner  Structure  of  Alloys. 

March  14:  J.  W.  Mackail,  LL.D., 
F.B.A.,  Hon.  Fellow  of  Balliol  College, 
Oxford,     "  The  Pilgrim's  Progress." 

Mai'ch  21 :  Sir  Frederick  Keeble. 
C.B.E.,  Sc.D.,  F.R.S.,  Sheradian  Prof,  of 
Botany  and  Fellow  of  Magdalen  College, 
Oxford.  The  Plant  Commonwealth  and  its 
Government. 

March  28:  Hugh  Maclean,  M.D.,  D.Sc, 
Prof,  of  Medicine,  University  of  London, 
Insulin. 

April  4  :  Sir  Ernest  Rutherford,  LL.D., 
D.Sc,  F.R.S.,  M.R.I. ,  Prof,  of  Natural 
Philosophy  and  Cavendish  Prof,  of  Experi- 
mental Physics,  University  of  Cambridge, 
The  Nucleus  of' the  Atom. 

April  11:  Jocelyn  Thorpe,  C.B.E., 
D.Sc,  F.R.S.,  Prof,  of  Organic  Chemistry, 
Imperial  College  of  Science  and  Techno- 
logy, Colours,  Stains  and  Dyes. 


Juvenile  Christmas  Lectures- 
O'clock,  Afternoon. 


-Three 


Concerning  the  Nature  of  Things,  by  Sir 
William  Bragg,  K.B.E..  D.Sc,  F.R.S., 
M.R.I.,    Fullerian    Prof,    of    Chemistry. — 


DECEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


895 


Ninety-Eighth  Course,  adapted  to  a  Juven- 
ile Auditory  (Illustrated) : — ■ 

(I.)  The  Atotns  of  which  Things  are 
Made;  (II.)  The  Nature  of  Gases;  (III.) 
The  Nature  of  Liquids;  (IV.)  The  Nature  of 
Crystals:  The  Diamond;  (V.)  The  Nature  of 
Crystals:  Ice  and  Snoiv;  (VI)  The  Nature 
of  Crystals :  Metals. 

(I.)  Thursday,  Dec.  27;  (II.)  Saturday. 
Dec.  29;  (III.)  Tuesday,  Jan.  1;  (IV.) 
Thursday,  Jan.  3;  (V.)  Saturday,  Jan.  5; 
(VI.)  Tuesday,  Jan.  8. 

General  Courses  of    Lectures  Before 
Easter,  1924. 

Tuesdays  and  Thursdays  at  o.lu  p.m. ; 
Saturdays  at  3  p.m. :  — 

Tuesdays,  Jan.  15,  22 :  Drug  Addictions, 
by  Walter  E.  Dixon,  M.D.,  F.li.S.,  Prof, 
of  Pharmacol f>gv,   King's  College,   London. 

Tuesdays,  Jan.  29,  Feb.  5:  What  is 
Heredity?  by  Arthur  DBiroy,  D.Sc, 
F.R.S.,  Prof,  of  Zoolo^'v.  University  of 
London  (King's  College). 

Tuesdays.  Feb.  12,  19.  26,  Man-h  4  :  Thr 
Respiratory  Pigments  in  Animal  Life  and 
Their  Significance,  by  .Joseph  Bancroft. 
C.B.E.,  F.U.S.,  Fellow  of  King's  College, 
Fullerian  Prof,  of  Physiology. 

Tuesdays,  March  11,  18:  Recent  investi- 
gation Concerning  the    Safety  of    Railway 
Bridges,  by  Major  C.  E.  Ixoub,    O.B.E.'. 
M.A.,    A.M.lNST.C.E.,     I'rof.  of  Engineer 
ing.  University  of  Cambridge. 

Tuesdays,  March  25,  April  1,  8:  Ballads. 
by  CtEorok  Gordon,  Mtrtmi  Prof,  of  Eng- 
lish Literature,  University  of  Oxford. 

Thursdays,  Jnn.  17.  24.  'M  :  Straws  from 
Cumberland  Market,  by  Walter  Sickkrt. 

Thursdays,  Feb.  7.  14,  21,  28:  The  Cnjs- 
talline  Structure  of  Ornanic  Substances,  by 
Sir  William  Bragg.  K.B.E.,  D.Sc. 
F.R.S.,  M.R.I. ,  Fulleriaii  Prof,  of  Cheniis- 
try. 

Thursdays.  March  6,  13:  I.,  Modes  of 
Volcanic  Action;  II.,  Types  of  Volcanic 
Structures,  bv  John  S.  Flett,  D.Sc. 
LL.D.,  F.R.S"..  Director  of  H.M.  Geologi- 
cal Survey  and  Museum  of  Practical  Geo- 
logy- 

Thursdavs.  March  20,  27:  Evolution  To- 
Day,  by  I).  S.  M.  Watson,  M.Sc.  Jfxlrell 
Prof,  of  Zoology  and  Comparative  Ana- 
tomy.  University  of  Ivondon. 

Thursdays.  April  3,  10:  Scientific  Re- 
search on  Sea  Fisheries.  h<-  E.  J.  Allen. 
D.Sc,  F.R.S.,  Secretary  of  the  Marine 
Biological  .Association  and  Director  of  the 
Plymouth  Laboratory. 


Saturdays,  Jan.  19,  26,  Feb.  2:  I.,  The 
Mechanical  Reproduction  of  Music,  by 
Reginald  Reynolds,  A.G.S.M.  (with 
musical  illustrations);  II.,  I^ie  Couperin 
Dynasty;  III.,  The  Influence  upon  Compo- 
sition of  Improvements  in  Musical  Instru- 
ments, by  W  illiam  Wallace  (with  musical 
illustrations). 

Saturdays,  Feb.  9,  16 :  The  Last  Years  of 
the  Scottish  Parliament,  by  Robert  S. 
Kait,  C.B.E.,  LL.D.,  Historiographer 
Royal  for  Scotland. 

Saturdays,  Feb.  28,  March  1 :  1., I  magi- 
native  Prose;  II.,  Character  in  Fiction,  by 
Walter  de  la  Mare. 

Saturdays.  March  8,  15,  22,  29 :  Proper- 
lies  of  Gases  in  High  and  Low  Vacua,  by 
Sir  Ernest  Rutherford,  LL.D.,  D.Sc. 
F.R.S.,  M.R.I. ,  Prof,  of  Natural  Philoso- 
phy, R.I.,  and  Cavendish  Prof,  of  Experi- 
mental Physics,   University  of  Cambridge. 

Saturdays,  April  5,  12:  I.,  Aristotle  as  a 
Biologist;  II.,  Leonardo  da  Vinci  as  a  Man 
of  Science,  by  Charles  Singer,  D.Litt., 
M.D.,  F.R.C.P..  Lecturer  on  the  History 
of  Medicine,  University  of  London,  Univer- 
sity College. 


THE  FAIIADAY  SOCIETY. 

First  {Experimental)  Report  to  the  At- 
mospheric Corrosion  Research  Committee 
[of  the  British  Non-Ferrous  Metals  Re- 
search Association),  by  W.  H.  J.  Vernon, 
B.Sc,  read  on  Monday,  December  17. 

The  research  has  proceeded  mainly  along 
two  lines.  "Field  Tests"  have  boon  car- 
ried out  with  relatively  large  specimens  ex- 
[xjsed  to  repilsentative  atmospheres,  with 
the  primarv  objects  of  (a)  comparing  the 
effects  of  these  atmospheres  upon  typical 
metals  and  alloys,  and  (b)  correlating  the 
l)ehabiour,  among  themselves,  of  as  wide  a 
range  of  materials  as  possible.  Laboratory 
experiments,  on  the  other  hand,  were  con- 
ducted uf)on  relatively  small  specimens, 
with  the  object  of  obtaining  information 
concerning  the  mechanism  of  atmospheric 
corrosion. 

The  work  was  divided  into  two  parts,  de- 
voted respectively  to  these  main  branches 
of  the  work.  Although  much  the  greater 
amount  of  time  has  been  expended  in  the 
former  direction,  actually  the  results  so  ob- 
tained have  contributed  largely  to  the  ob- 
ject envisaged  by  the  latter;  for  this  reason 
the  distinction  Ix 'tween  the  two  parts  has 
not  been  retained    in  summarising    the  r«- 


396 


THE  CHEMICAL  NEWS. 


DUCBMBER  21,  1926. 


suits.  It  should  be  stated  that  in  conse- 
quence of  the  comparatively  early  stage 
which  it  represents,  the  present  report  is 
occupied,  in  the  main,  only  with  the  pheno- 
menon of  tarnishing,  as  distinct  from  corro- 
sion in  the  ordinary  sense. 

The  types  of  atmosphere  investigated  in- 
cluded (1)  an  indoor  atmosphere  main- 
tained continuously  in  the  unsaturated  con- 
dition with  respect  to  water  vapour.  (2)  An 
indoor  atmosphere  of  variable  (but  rela- 
tively high)  humidity,  occasionally  reaching 
saturation.  (3)  An  ordinary  domestic  kit- 
chen. (4)  Open-air  exposure  (at  South 
Kensington). 

The  methods  of  examining  and  estimat- 
ing tarnish  films  were  :  (1)  Visual  (supple- 
mented, as  occasion  required,  by  the  micro- 
scope). (2)  Optical.  After  suitable  pre- 
paration, the  reflectivities  of  metal  surfaces 
have  been  determined,  (c)  in  the  freshly- 
cleaned  condition,  (b)  during  the  course  of 
exposure.  The  loss  of  reflectivity  affords  a 
very  sensitive  means  of  estimating  the 
changes  taking  place  at  the  surface,  appli- 
cable more  particularly  to  the  earliest 
stages  of  tarnishing.  (3)  Gravimetric.  Ac- 
curate determinntions  have  been  made  of 
the  increase  in  weight  of  the  test-plates,  at 
intervals  during  the  wjiole  period  of  indoor 
exposure,  and  also  in  the  very  early  stages 
of  open-air  exposure.  In  the  case  of  indoor 
conditions,  interesting  relationships  have 
been  found  to  obtain  between  weight- 
increment  and  iperiod  of  exposure. 

The  significance  of  the  shape  of  the  curve 
obtained  by  plotting  weight-increment 
against  time  was  discussed  in  relation  to  the 
function  of  the  corrosion  product  or 
"scale,"  and  the  principle  involved  ap- 
pears to  be  of  much  importance.  Three 
types  of  curve  have  been  distinguished  : 

(1)  A  porahola  whose  axis  coincides  with 
the  time-axis  of  co-ordinates.  Weight-incre- 
ment is  thus  proportional  to  the  square 
root  of  time,  i.e.,  the  rate  of  attack  is  re- 
tarded as  the  period  of  exposure  increases. 
The  scale  forms  a  continuous  envelope,  the 
rate  of  diffusion  of  the  corroding  atmos- 
phere through  which  regulates  the  attack 
upon  the  underlying  metal.  Example: 
Copper,  within  a  wide  range  of  humidity 
conditions. 

(2)  A  straight  line  passing  through  the 
origin.  Weight-increment  is  directly  pro- 
portional to  time,  i.e.,  the  rate  of  attack  re- 
mains constant  as  the  period  of  exposure 
increases.  The  scale  is  completely  perme- 
able, allowing  free  access  of  atmosphere  to 


the  metal,  and  itself  playing  a  neutral  part. 
Example  :  Zinc,  in  an  unsaturated  atmos- 
phere. 

(3)  A  parabola  whose  axis  coincides  with 
the  weight-axis  of  co-ordinates.  Weight- 
increment  is  proportional  to  the  square  of 
time,  i.e.,  the  rate  of  attack  is  accelerated 
as  the  period  of  exposure  increases.  The 
scale  is  discontinuous,  and  accelerates  the 
attack  upon  the  remaining  metal  in  propor- 
tion to  the  amount  which  is  already  present. 
Example  :  Iron  in  an  atmosphere  of  rela- 
tively high  humidity,  intermittently  reach- 
ing saturation. 

Whilst  no  appreciable  difference  has  usu- 
ally been  observed  by  ordinary  visual  ex- 
amination between  the  behaviour  of 
emeried  and  brightly-polished  surfaces  re- 
spectively, the  optical  and  gravimetric 
methods  have  shown  under  certain  condi- 
tions a  greater  degree  of  tarnishing  on  the 
rougher  surface.  Under  "inside"  condi- 
tions the  maximum  differences  have  been 
observed  in  the  atmosphere  of  low  relative 
humidity.  In  the  more  humid  atmosphere, 
"dull"  and  "bright"  surfaces  have  given 
practically  identical  results  (both  as  regards 
weight-increment  and  percentage  less  of  re- 
flectivity). 

In  the  atmosphere  of  the  kitchen,  ano- 
malous results  have  been  observed,  parti- 
cularly with  silver  and  silver-copper  alloys, 
fine  silver  then  showing,  by  all  methods  of 
examination,  a  greater  degree  of  tarnish  on 
the  polished  surface;  on  the  other  hand,  in 
the  case  of  the  standard  alloy,  the  normal 
result  obtains  but  to  an  exceptional  and  ex- 
cessive degree,  the  brightly-polished  sur- 
face then  being  relatively  immune  from  at- 
tack. 

In  all  instances  investigated  the  differ- 
ence in  behaviour  between  materials  having 
the  maximum  degree  of  hardness  and  of 
softness  respectively  has  been  exceedingly 
small — always  below  the  limits  of  visual  de- 
tection, and  fi-equently  incapable  of  estima- 
tion even  by  the  optical  method.  Wherever 
an  appreciable  difference  has  been  recorded, 
however,  the  harder  material  has  always 
been  found  to  have  undergone  the  greater 
amount  of  change ;  the  difference  is  more 
readily  detected  with  dull-polished 
(emeried) 'than  with  brightly-polished  speci- 
mens. 

A  considerably  greater  degree  of  tarnish- 
ing obtains  during  the  winter  than  during 
the  summer  months,  even  in  an  indoor  at- 
mosphere in  which  no  combustion  processes 
are  carried  on,  the  difference  being  due,  ipre- 


DECEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


397 


stHiutbly,  to  the  greater  pollution  of  tlie  at- 
mosphere during  the  former  period.  More- 
over, the  incidence  of  cold  spells  of  weather 
is  also  accompanied  by  an  increase  in  the 
rate  of  tarnishing,  due  doubtless  to  the 
same  cause.  It  is  important  to  note,  how- 
ever, that  these  remarks  refer  to  initially- 
clean  surfaces  exposed  during  the  periods 
concerned.  With  copper,  and  copper-rich 
alloys,  the  rate  of  tarnishing  is  controlled 
(within  a  wide  range  of  atmospheric  condi- 
tions) by  the  nature  of  the  tarnish  film 
which  is  initially  fcwmed. 


THE  INSTITUTION  OF  PETROLEUM 
TECHNOLOGISTS. 

Paper  read  at  the  Royal  Society  of  Arts, 
on  December  11 : 

The  Modem  Rotary  Drilling  System,  by 

L.  R.   McCOLLUM. 

The  percussion,  or  cable  tool  method  of 
drilling,  which  Col.  Drake  first  used  in 
1859,  has  changed  but  little  in  principle. 

It  has  proved  a  reliable  method  for  drill- 
ing in  most  fields,  and  its  use  has  been 
widespread  throughout  the  United  States, 
and  in  many  foreign  fields. 

Later,  exiploitation  work  in  the  Gulf 
Coast  regions  of  Texas  and  Louisiana  en- 
countered unconsolidated,  soft,  and  caving 
formations,  which  gave  the  cable  tools  a 
bad  time.  To  combat  these  conditions  the 
Rotary  system  was  invented,  or  rnthiT  (!«•- 
veloped,  upon- the  Fauck  system,  which 
had  been  in  use  in  Europe  since  184.5. 

By  this  method  a  rigid  stem  of  pipr  ro- 
tates a  fish  tail— or  other  type  of  bit-  at  the 
bottom  of  the  hole,  being  assisted  by  the 
action  of  clay  mud  in  the  fluid  state, 
pumped  under  hydraulic  pressure,  through 
the  drill  pipe.  The  circulating  mud  also 
removes  the  cuttings  from  the  nolo. 

So  great  were  its  virtues  of  speed  and 
economy  that  modifications  and  improve- 
ments were  soon  added  which  enabled  it  to 
penetrate  thick  strata  of  extremely  hard 
rock  at  great  depths.  This  capacity  has 
now  been  probed  beyond  the  questioning  of 
intelligent  operators. 

The  extreme  speed  attained  with  this 
type  of  equipment,  and  the  few  strings  of 
casing  necessary,  are  its  chi»f  assets. 

One  of  the  objections  which  is  raised 
against  the  Rotary  system  by  operators  un- 
familiar with  its  working,  is  that  there  is 
the  danger  of  mudding  off  unknown  oil 
sands,  but  it  was  pointed  out  that  this  risk 
was  very  small  and  could  be  overcome.       i 


j  The  author  went  on  to  describe  the  prin- 

j  ciple  and  accessories  of  the  system,  and 
I  deatl  with  such  matters  as  mud  storage, 
i       power,    pumps,    the    actual  operation    and 

speed  attainments.     The  advantages  of  the 

method  were  well  brought  out. 


The  Library  of  the  Chemical  Society  will 
be  closed  for  the  Christmas  holidays  from 
Monday,  December  24,  to  Thursday,  De- 
cember 27,  inclusive. 


NOTICES  OF  BOOKS. 

Valence  and  the    Structure    of    Atoms 
and    Molecules,    by    Professor    G.     N. 
Lewis.     Pp.  172.     1923.     The  Chemical 
Catalog  Company,  19,  East  24th  Street, 
New  lork,   U.S.A.     (American  Chemical 
Society  Monograph  Series).     Price  $3.00. 
Prof.  G.  N.  i^ewis,    the  pioneer    in    the 
structure  of  atoms  and  molecules  as  based 
upon  electrons  arranged    at  the  corners    of 
cubes,  has  written  a  monograph  of  consitler- 
able  value.  Of  particular  historical  interest  in 
this  connection  is  a  reproduction  of  his  ori- 
ginal sketches  of  atoms,  as  made  in  11K>2. 

This  book  is  in  the  nature  of  a  survey,  in 
which  some  of  the  present-day  theories  of 
the  atom  are  clearly  expounded.  It  seems 
a  little  extraordinary  that  so  much  space 
should  be  given  up  to  the  Bohr  atom,  st^-eing 
that  Prof.  Lewis  was  the  originator  of  a 
theory  quite  as  interesting  and  valuable; 
but  this  is  no  doubt  done  in  a  spirit  of  fair- 
ness, though  one  might  have  expected  the 
pioneer  of  the  octet  theory  to  have  given  his 
whole  attention  to  its  elucidation  and  ex- 
pansion as  developed  by  other  workers. 

Referring  to  the  attempt  to  co-ordinat<' 
the  static  theory  with  the  dynamic,  this,  as 
far  as  expounded  by  Prof,  l^ewis,  cannot  be 
said  to  be  at  all  successful,  but  this  com- 
ment is  not  in  the  nature  of  an  adverse  cri- 
ticism, since  one  is  compelled  to  make  the 
most  of  co-ordination  ideas  in  lK>oks  of  this 
type. 

Many  of  the  more  or  less  usual  intrfnluc- 
tory  statements  appear,  but  the  implication 
that  Helmholtz,  in  1881,  was  the  first  to 
make  important  observations  that  electri- 
city was  atomic  in  character  is  not  historic- 
ally true.  Wilhelm  Weber,  in  1871,  intro- 
duced in  his  theoretical  work  the  idea  of 
particles  of  positive  and  negative  electri- 
city, and  went  so  far  as  to  postulate  that  the 
+  particle  described  an  orbit  round  the  - 
particle,  thus    indicating    the    "  Amperian 


398 


THE  CHEMICAL  NEWS. 


DECEMBEE  21,  1923. 


luolecular "current,"  to  quote  his  words.  In 
1874,  G.  Johnstone  Stoney,  at  Belfast, 
read  a  paiper  (printed  later),  in  which  the 
elementary  electrical  charge  was  clearly 
enunciated,  and  an  attempt  was  made  to 
evaluate  its  magnitude  which  approximated 
to  the  truth;  and,  moreover,  Prof.  Stoney, 
in  1891,  designated  this  charge  by  the  name 
electron.  The  later  work  of  H.  A.  Lorentz 
is  not  mentioned.  The  reviewer  does  not 
presuppose  that  Prof.  Lewis  was  unaware 
of  these  matters,  but  the  omissions  are, 
nevertheless,  apparent :  an  oversight,  no 
doubt. 

On  page  33,  the  Lewis  and  Kossel  models 
are  depicted  side  by  side,  the  former  being 
cubic  and  the  latter  an  arrangement  of  the 
electrons  in  one  plane,  the  outer  number  in 
these  examples  being  8,  the  octets  being 
completed  ones.  On  the  same  page  Lewis 
says: — "  In  this  connection  I  emphasise! 
the  peculiarity  of  hydrogen  which,  by  giv- 
ing off  an  electron,  can  become  the  simplest 
of  positive  ions,  consisting  solely  of  an 
atomic  nucleus,  while  by  taking  on  one 
electron  it  can  complete  the  group  of  two, 
characteristic  of  the  helium  atom.  This 
process  seemed  so  nearly  like  the  taking  on 
of  one  electron  by  fluorine  or  by  chlorine  to 
form  F-  or  CI-,  with  structures  corres- 
ponding to  neon  and  argon,  that  I  felt  justi- 
fied in  regarding  hydrogen  as  belonging,  in 
this  resipect  at  least,  to  the  halogens;  and 
therefore  predicted  that  metallic  hydrides 
would  prove  to  have  the  character  of  salts, 
consisting  of  metal  ion  and  hydride  ion,  and 
further  that  electrolysis  of  a  hydride  should 
produce  hydrogen  at  the  anode.  This  pre- 
diction has  been  entirely  verified  in  the  work 
of  Bardwell  (1922),  who  succeeded  in  elec- 
trolysing a  melt  containing  calcium  hydride, 
and  obtaining  hydrogen  at  the  anode  in 
amount  corresponding  to  Faraday's  law." 

In  Chapter  III.  the  spectral  lines  are  well 
illustrated  and  the  "physicist's  view  of  the 
atom"  given.  The  Ijyman,  Balmer,  Pas- 
chen  and  Brackett  series  formulae  are  stated 
on  page  38,  together  with  diagrams  illus- 
trating the  principal  lines  and  the  "basic 
frequencies  of  hydrogen."  The  quantum 
theory  is  dealt  with  at  some  length,  and  the 
energy  levels  in  the  H  atom  diagrammetric- 
ally  given  on  ip.  43.  X-ray  spectra,  ionisa- 
tion,  and  resonance  potentials  are  treated 
briefly. 

On  page  '50  the  following  appears: — "  It 
was  predicted  from  the  classical  electro- 
magnetic theory  that  any  accelerated  charge 
would  enait  radiant  energy,  but  the  electron 


in  one  of  the  stable  orbits  of  the  Bohr 
theory  is  subject  to  constant  aoceleration 
toward  the  centre  of  the  atom,  and  yet  it  is 
supposed  to  emit  no  radiation.  However, 
such  emission  of  energy  from  an  accelerated 
charge  does  not  seem  to  be  an  entirely  in- 
evitable consequence,  even  of  classical 
theory,  and  for  this  reason  we  may  turn  our 
attention  to  a  still  more  elementary  way  in 
which  I  have  attempted  to  show  (1917)  the 
divergence  between  the  properties  of  the 
Bohr  atom  and  the  properties  that  would 
formerly  have  been  assumed  for  a  system 
containing  an  electron  in  motion."  The 
argument  that  follows  here  is  interesting 
and  should  be  studied  in  the  original. 

On  page  58  Lewis  records  that  "  in  a  re- 
cent investigation  of  extraordinary  interest. 
Stern  and  Gerlach  (1921)  have  succeeded  in 
studying  in  a  most  direct  manner  the  mag- 
netic properties  of  the  silver  atom,  which, 
like  the  hydrogen  atom,  we  suppose  to  have 
one  electron  in  its  outer  shell.  They  find 
that  its  behaviour  is  similar  to  that  which 
would  be  predicted  for  the  hydrogen  atom 
by  the  Bohr  theory."  Further,  on  page  66, 
we  find  the  following: — "  In  the  mean- 
time it  must  be  admitted  that  the  problem 
is  by  no  means  completely  solved.  Both 
Bohr  and  Bury  assume  that  the  last  frag- 
mentary period  of  the  Mendel^eff  table  is  a 
period  of  thirty-two  elements;  but  I  have 
pointed  out  in  a  previous  chapter  that  the 
properties  of  thorium  and  uranium  indicate 
a  far  less  resemblance  to  the  preceding 
period  of  thirty-two  than  to  the  "next  pre- 
ceding period  of  eighteen."  We  may  re- 
mark here  that  Loring's  wedge  table  ac- 
cords with  Lewis  in  this  respect. 

Of  particular  interest,  the  part  from 
Chapter  V.  onwards  may  be  noted.  Here 
we  find  discussions  of  the  union  of  atoms, 
the  chemical  bond,  pairing  of  electrons, 
double  and  triple  bond,  limitation  of  mul- 
tiple bonds,  exceptions  to  the  rule  of  eight, 
valence  and  co-ordination  number,  quadri- 
valence  of  nitrogen,  valencies  higher  than 
four,  valence  and  condensed- systems,  com- 
pounds of  elements  with  small  kernels,  ele- 
ments in  positive  and  negative  states, 
electromers,  &c. 

Finally,  we  may  quote  from  page  142,  as 
follows: — "  We  are  inclined  to  think  of 
substances  as  possessing  acid  or  basic  pro- 
perties, without  having  a  particular  sol- 
vent in  mind.  It  seems  to  me  that  with 
complete  generality  we  may  say  that  a 
basic  substance  is  one  which  has  a  lone  pair 
of  electrons  irhirh  may  be  used  to  com/plete 


DECEMBER  21,  1923. 


THE  CHEMICAL  NEWS. 


399 


the  stable  yruup  of  another  atom,  aud  that 
an  acid  substance  is  one  which  can  employ 
a  lone  pair  from  aywther  molecule  in  coni- 
pJeting  the  stable  group  ot  one  of  its  own 
atoms,  lu  other  words,  the  basic  substauce 
furnishes  a  pair  of  electrons  for  a  chemical 
bond;  the  axiid  substance  accepts  such  a 
pair."  Prof.  Lewis  (page  148)  regards  the 
pairing  of  electrons  "as  the  most  funda- 
mental phenomenon  in  all  chemistry." 

A  list  of  references  is  given  at  the  conclu- 
sion of  the  book.  The  book  is  indexed  (but 
this  might  \>e  slightly  improved — a  stat<'- 
ment  which  applies  to  most  books),  and  the 
printing  and  binding  is,  of  course,  up  to  the 
best  standard. 


Kolloide  in  der  Technik,  von  Db.  K.  E. 

LiESEG.\NG.     Pp.   157.     Dresden  &  Lei,|)- 

zig.        Verlag    von    ThtXKjM"    Steinkopff. 

1923.     Price  3s.  6d. 

The  importance  of  a  thorough  knowledge 
of  the  principal  phenomena  exhibited  by 
substances  in  the  colloidal  condition  is  now 
becoming  recognised  by  tochnolocists. 

Prof,  liiesegang  has  presented,  in  tliis 
volume,  a  very  interesting  aooount  of  tbi 
application  of  these  principles  to  various 
technical  and  industrial  prooeases.  He 
gives  M  very  good  resume  of  the  recent 
tlu'oretical  and  practical  advaaceB  that  h.iv.' 
bcH'n  made. 

From  ft  description  of  the  behaviour  c; 
Ixxlies  in  the  colloidal  state  as  exemplified 
by  gelatin  and  similar  bodies,  and  the  pro 
tective  colloids,  he  passes  to  their  connec- 
tion with  such  processes  as  that  of  tanning 
and  those,  for  instance,  of  the  textile  indus- 
industrie>J. 

Soa4ps,  oils,  resins,  rubber,  the  metals, 
ceramics  and  foodstuffs  are  all  discusseij 
from  the  point  of  view  f>f  colloids. 

The  final  chapter  on  I'hotography  has 
been  very  al)ly  written,  and  coatains  an  ex- 
cellent jujoount  of  the  latest  work  and 
theories  in  all  the  processes  enoountered  in 
this  field. 

The  references  to  British  and  American 
workers  and  their  researches  are  surpris- 
ingly good  when  it  is  remembered  that  Ger- 
man scientists  encounter  great  difficulties 
in  obtaining  inomiation  concerning  scienti- 
fic work  carried  on  outside  their  country. 


Uses  of  Waste  Materials,  by  Prof.  Ar- 
TURO  Bruttini.  Pp.  X\.  +  367.  1928. 
Messrs.  P.  S.  King  Si  Son,  Ltd.,  Orchard 
House,  2  &  4,  Great  Smith  Street,  West- 
minster. 12r.  net. 
The  aut/hor  has  coUeoted  muoh  useful  in- 


formation on  the  utilisation  of  waste 
materials  during  the  years  1914-22,  for  mak- 
ing human  and  animal  foods,  and  for  agri- 
cultural fertilisers. 

For  many  of  these  products,  it  may  be 
noted  that  no  essentially  new  process  was 
involved,  but  instances  are  given  where  new 
and  often  ingenious  methods  were  adopted. 

Attention  is  drawn  to  the  importance  of 
profiting  by  these  experiences.  Processes 
of  proved  economic  value  should  be  re- 
tained and  developed  in  the  future.  It  will 
be  realise<l  that  many  of  the  substitutes 
manufactured  during  the  war  in  the  belli- 
gerent nations  were  of  no  permanent  im- 
portance, since  they  were  introduced  to 
meet  exceptional  and  temporary  needs. 

In  Part  I.  the  author  gives  the  legislative 
measures  adopted  for  the  utilisation  of 
waste  pr<HJucts  as  foods,  etc. 

Part  II.  contains  a  detailed  account  of  the 
collection  and  treatment  of  various  types 
of  waste.  The  limits  to  which  Germany 
was  driven  by  the  war  in  her  efforts  to  pro- 
vide substitutes  for  almost  every  item  of 
food  are  fully  realised  by  a  perusal  of  Prof. 
Bruttini 's  compilation.  Yeast,  blood,  pota- 
toes, straw,  meal,  etc.,  were  all  used  in  eke- 
ing  .Hit  flour  in  bread-making.  Various 
plant  products  were  employed  for  making 
something  to  res<iuble  coffee,  and  a  valu- 
able list  of  wild  plants  fit  for  human  con- 
sumption ]s  given.  The  substitutes  for  meat 
and  table  oils  in  the  Central  Empires  were 
naturally  far  removed  from  the  articles  they 
were  intended  to  replace. 

Great  ingenuity  was  disiplayed  by  agricul- 
turists in  all  countries  during  the  period 
under  review,  in  (opening  up  new  sources  of 
fodder.  Matter  of  more  permanent  value 
is,  however,  to  be  found  in  the  section  on 
fertilisers.  Residues  from  many  industries 
could  well  be  utilised  as  fertilisers  to  a  far 
greater  extent  than  is  at  present  realised. 
Undoubtedly  a  more  scientific  and  intensive 
use  of  waste  can  be  achieved,  involving  a 
saving  of  much  wealth  at  present  lost.  This 
monograph  very  cTearly  shows  the  lines  on 
which  the  problem  should  be  attacked. 

A  number  of  misprints  have  crept  into 
this  excellent  work.  These  should  be  cor- 
i-ected  in  future  editions,  which  may  be  con- 
fidently exipected. 


Industrial  Filtration,  by  Arthur 
Wright,  M.E.  Pp.  X.  +  336.  Vol.  1.. 
1923.  The  Chemical  Catalog  Co.  Inc., 
19.  East  24th  Street,  New  York,  U.S.A. 
$5.00. 
There  are  so  few  books  on  specific   indus- 


400 


THE  CHEMICAL  NEWS. 


DECEMBER  21,  1923. 


trial  processes,  and  it  is  noteworthy  that 
this  is  the  first  of  a  new  series,  each  volume 
of  which  is  to  be  devoted  to  one  particular 
process.  Among  those  to  follow  are 
volumes  on  Heat  Transfer  and  Evaporation ; 
Theory  and  Practice  of  Evaporation;  and 
Fractional  Distillation. 

The  present  volume  is  divided  into  three 
parts.  In  the  first  part,  the  author  dis- 
cusses such  matters  as  clarification,  cake 
building,  washing,  drying,  and  discharging ; 
filter  media,  and  auxiliary  equipment.  This 
section  is  entitled  Theory  of  Filtration, 
which  is  somewhat  misleading  to  an  Eng- 
lish reader  (this  is  an  American  publica- 
tion). 

Part  two,  the  Mechanics,  of  Filtration, 
gives  a  useful  account  of  certain  types  of 
filters  and  presses  now  used,  although  there 
is  no  mention  of  centrifugal  apparatus. 

Part  three  is  concerned  with  the  applica- 
tions of  the  various  types  of  plants  de- 
scribed, and  the  general  works  practice. 

The  author's  aim  has  been  to  emiphasise 
the  importance  of  the  fundamental  prin- 
ciples, and  to  discuss  the  merits  of  certain 
types  of  American  machines.  This  latter 
has  unfortunately  given  the  book  somewhat 
the  aspect  of  a  commercial  catalogue. 

The  book  will  be  helpful  to  many 
technical  chemists  who  have  filtration 
problems  to  contend  with. 


The  Department  of  Overseas  Trade  has 
published  (through  H.M.  Stationery  Office) 
a  Report  on  the  Economic  Conditions  in 
South  Africa,  by  Mr.  W.  G.  Wickham, 
H.M.  Senior  Trade  Commissioner  in  South 
Africa;  July,  1923,  price  Is.  6d.  net. 

Among  industrial  raw  materials,  soda 
ash,  caustic  soda  and  potash  show  consider- 
ably increaesd  importation  at  lower  price 
levels.  On  the  other  hand,  in  spite  of  the 
lower  price,  we  find  actually  a  reduction  in 
the  quantity  imported  of  nitrates,  glycerine, 
suliphur,  and  cyanides.  The  dislocation  in 
gold  mining  and  cessation  of  diamond  min- 
ing are  no  doubt  responsibe  1  directly  and 
indirectly  by  reducing  the  demand  for  the 
locally  manufactured  explosives. 

Paraffin  wax  shows  an  importation 
doubled  in  quantity,  but  at  a  much  reduced 
price.  Vegetable  and  mineral  oils  are  also 
lower  in  price,  but  demand  has  not  fully  re- 
sponded to  this  stimulus. 

BOOKS  EECEIVED. 

The  Life  of  Sir  William  Croohes,  .M., 
F.li.S.,  by  E.  E.  Fournter,  D.Albe., 
D.Sc,  F.Inst. P.,  with  a  foreword  by    Sir 


Oliver  Lodge.  Pp.  XVII.  +  409.  1923. 
Messrs.  T.  Fisher  Unwin,  Ltd.,  Adelphi 
Terrace,  W.C.2.     25s.  nut. 

The  British  Journal  Fhotoyraphic  Alma- 
nac for  1924,  Edited  by  CtEorge  E.  Brown, 
F.I.C.  Pp.  812.  Henry  Greenwood  &  Co., 
24,  Wellington  Street,  .  Strand,  W.C.2. 
Paper,  2s.  net. ;  cloth,  3s.  net. 

Molekulargrossen  von  Elektrolyfen,  von 
Dr.  Phil.  Et  Chem.  Paul  Walden.  Pp. 
XI.  +  350.  1923.  Verlag  von  Theodor 
Steinkopff,  Residenzstr.  12b,  Dresden  und 
Leipzig,     lis.  6d. 

The  Principal  of  Relativity,  by  Albert 
Einstein,  H.  A.  Lorentz,  H.  Minkowski, 
A.  Sommerfeld,  H.  Wcyl;  Translated  by 
G.  B.  Jeffery,  D.Sc,  and  W.  Perrett. 
Ph.D.  Pp.  VIII.  +  216.  1923.  Messrs. 
Methuen  &  Co.,  Ltd.,  36,  Essex  St.,  W.C.2. 
12s.  6d.  net. 


This  list  is  specially  compiled  for     The    Chemical 

News  by  Messrs.  Rayner  &  Co.,  Registered  Patent 

Agents,  of  5,  Chancery  Lane,  London,  from  whom 

all  information  relating  to  Patents,  Trade  Marks, 

and  Designs  can  be  obtained  gratuitously. 

Latest   Patent   Applications. 

30305— Bredig,   G.— Production     of     cyanide     com- 

ix)unds.     Dec.  1. 

Abstract  Published  this  Week. 
205288— Nitrogen   oxides.— Goodwin,     C,   J.,     of   7, 
Idol  Lane,   London. 

In  the  production  of  nitrogen  oxides  by  explod- 
ing a  mixture  of  combustible  gas  and  air  of  oxy- 
gen .  in  a  bomb  or  engine,  the  combustible  gas, 
such  as  coke  oven  gas,  coal  gas,  water-gas,  or  pro- 
ducer gas,  is  treated  to  increase  its  nett  calorific 
value  by  removing  some  or  all  of  its  free  hydro- 
gen. 

The  invention  is  described  with  particular  re- 
ference to  coke  oven  gas,  and  the  hydrogen  alone, 
or  the  hydrogen  and  carbonic  acid  are  removed. 
The  removal  of  the  hydrogen  may  be  effected  in 
any  suitable  manner,  either  physical,  such  as 
liquefaction  or  low-temperature  separation,  or 
chemical,  as  by  adding  carbon  monoxide  and  us- 
ing the  mixture  to  synthesise  methyl  or  ethyl  al- 
cohol under  pressure  by  catalytic  or  other  means, 
the  remaining  gas  in  this  last  case  being  mainly 
methane.  When  the  hydrogen  is  removed  as  such 
it  may  be  converted  into  ammonia  by  the  known 
synthesis. 

Messrs.  Rayner  &  Co.  will  obtain  printed  copies 
of  the  published  specifications  and  abstract  only, 
and  forward  on  post  free  for  the  price  of  Is.  6d. 
each. 


Mr.  Edward  C.  Davies,  M.Sc,  a  distin- 
guished student  of  Prof.  Robert  M.  Wild  at 
Manchester  University,  ha«  been  appointed 
as  Assistant  Ijecturer  in  Chemistry  at  the 
Natal  Technical  College,  Durban,  S  .Africa. 


DECEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


401 


THE    CHEMICAL  NEWS, 

VOL.  GXXVII.      No.  3324. 


4'  HYDROXY  1  PHENYL  5  METHYL- 

BENZOTHIAZOLE  AND  ITS 

BROMINATION. 

By  R.  F.  Hunter. 

If  the  considerations  which  have  already 
been  put  forward  by  the  author  as  to  the 
structure  of  the  dibroniination  products  of 
dehydrothiotoluidin  and  its  derivatives  are 
correct,  then,  since  the  phenollic  derivative 
of  this  benzothiazole  contains  the  usual 
thiazole  ring  containing  the  double  bonded 
nitrogen  and  carbon  atoms,  the  4'  hydroxy 
1  phenyl  5  rnethyiben/.othiazole  should  add 
bromine  according  to  the  equation:  — 

S 
CH,CeH3  <    >^CC,H,OH  +  2Br  = 

N  • 


CH^C.H,   <■         •>    CBrC.H.GH. 
^  NBr*^ 

when  dissolved  in  glacial  acetic  acid.  A 
point,  however,  arises,  and  that  is  whether 
the  presence  of  the  hydroxyl  group  in  the 
benzene  part  of  the  molecule  might  not 
produce  a  tendency  towards  substitution  in 
addition  to  the  bromine  addition  to  the  thia- 
zole ring.  If  such  a  tendency  does  exist, 
then  clearly  we  should  expect  that  a  pre- 
oif)itate  would  be  formed  when  bromine  i« 
added  to  the  aqueous  solution  of  the  phenol 
in  a  manner  analogous  to  the  precipitation 
of  tribromoiphenoi  from  aqueous  solutions 
by  means  of  bromine  water.  The  4'  hy- 
droxy 1  phenyl  5  methyl  benzothiazole  was 
therefore  prepared  and  examined  by  the 
method  given  in  the  experimental  portion  of 
this  paper.  Addition  of  bromine  to  a  solu- 
tion of  the  compound  in  glacial  acetic  acid 
produced  the  expect<^d  precipitate  of  the 
usual  type.  Addition  of  l)romine  water  to 
an  aqueous  solution  of  the  compound  ap- 
parently had  no  action.  This  evidence 
cannof.  he  considered  of  very  great  impor- 
tance, since  the  solubility  of  the  phenol  of 
dehydrothiotoluidin  is  very  low.  On  the 
other  hand  addition  of  bromine  water  to  an 
alcoholic  solution  of  the  compound  pro- 
duced a  grey  flocculent  pii cipitnte.  which 
quite  possibly    was    unchanged,    the    base 


settling  out  owing  to  the  diminished  solu- 
bility in  the  solvent.  The  quantity  was,  of 
course,  too  small  for  investigation. 

Experimental. 

1.5  gm.  of  pure  dehydrothiotoluidin  from 
alcohol  is  dissolved  in  the  minimum  of 
fairly  strong  sulphuric  acid  in  a  250  cc. 
flask.  The  solution  is  cooled  under  the  tap. 
0.5  gm.  of  sodium  nitrite  dissolved  in  3  ccs. 
of  water  is  then  added  to  the  cooled  solu- 
tion. The  resulting  solution  is  then  heated 
on  a  boiling  water  bath  till  the  evolution  of 
nitrogen  ceases,  a  red  brown  tarry  solid  re- 
maining, which  floats  on  the  surface  of  a 
-similarly  coloured  liquid.  It  was  wrongly 
thought  that  the  compound  might  be  vola- 
tile in  steam,  so  that  the  flask  and  its  con- 
tents were  therefore  steam  distilled  for 
three  hours,  and  the  distillate  searched  for 
a  substance  with  phenolic  properties  in 
vain.  The  solid  remained  quite  unaffected 
in  the  flask  during  the  distillation.  The 
acid  present  was  neutralised  with  strong 
caustic  soda  solution.  Further  addition 
caused  sudden  and  nearly  complete  solu- 
tion as  a  deep  brown  liquid.  This  was  fil- 
tered from  a  small  black  residue  to  a  deep 
l)rown  clear  liquid,  to  which  hydrochloric 
acid  was  added  drop  by  drop,  with  the  im- 
mediate' formation  of  a  yellow  brown  pre- 
cipitate. The  addition  of  acid  was  continued 
imtil  nothing  more  was  precipitated.  The 
liquid  was  then  filtered,  and  the  precipitate 
V. ashed  and  dried.  The  phenol  remained  on 
the  filter  paper  as  a  pale  brown  solid. 

.\  portion  was  dissolved  in  glacial  acetic 
acid,  and  bromine  was  added  drop  by  drop 
from  a  burette.  A  brown  precipitate 
fonned  at  once.  The  precipitation  was  c(  m- 
pleted  by  drowning  with  cold  water,  after 
allowing  the  bealcer  containing  the  bromi- 
nation  product  and  excess  bromine  to  stand 
for  a  few  minutes. 

A  small  amount  of  the  phenol  was  dis- 
solved as  completely  as  possible  in  hot 
water,  the  solution  filtered,  and  bromine 
water  added  to  the  filtrate.  There  was  no 
precipitate. 

A  small  amount  of  the  substance  was  dis- 
solved in  alcohol  in  the  same  way,  and  bro- 
mine water  was  added.  A  grey  flocculent 
precipitate  resulted. 

(  The  Imperial  College  of  Science  and 

Technology,  S'.W.l. 

September.  1023. 


402 


THE  CHEMICAL  NEWS. 


DEGEMBEH  28,  1923. 


"  DRY-EOT  '\   DISEASE    OF  TIMBEE. 
By  E.  H.  Ellis. 

Amongst  other  non-chemical  problems 
upon  which  industrial  chemists  are  required 
to  give  advice,  the  control  of  "drj-rot"  of 
timber  is  one  of  annoying  persistence. 

"Dry-rot"  is  caused  principally  by  the 
fungus  Merulius  lacrymans.  It  is  a  disease 
of  civilisation.  Indeed,  quite  apart  from 
the  fact  that  the  actual  dry-rot  fungus 
grows  only  upon  worked  wood  and  is  rarely, 
if  ever  found  on  living  trees,  the  term  "dry- 
rot"  has  been  restrict-ed  by  architects  and 
timber-merchants  to  the  '  rot  of  worked 
wood;  many  fungus  diseases  produced  in 
the  standing  timber  being  known  collec- 
tively   as    "  wet-rot." 

Infection  of  wood  often  occurs  during 
storage  in  a  timber  yard.  The  spores  of 
dry-rot,  although  capable  of  remaining  vi- 
able for  a  period  of  years,  aipparently  infect 
sound  wood  with  difficulty.  Hence  infec- 
tion is  rarely  caused  by  the  spores,  being 
commonly  due  to  the  spread  of  the  myce- 
lium. Also,  during  periods  of  drought,  the 
protoplasmic  contents  of  the  mycelium  be- 
come agglomerated,  the  cell-walls  break  up 
into  small  resting  bodies  (oidia),  which  are 
easily  scattered,  and  which  germinate 
readily,  causing  re-infection. 

In  spite  of  its  name,  the  "dry-rot"  fun- 
gus, like  all  fungi,  must  have  moisture  to 
enable  it  to  grow;  the  term  "dry-rot"  re- 
ferring rather  to  the  condition  of  wood  at- 
tacked by  the  fungus  than  to  the  fungus  it- 
self. 

When  a  piece  of  constructional  timber  is 
attacked  by  dry-rot,  two  distinct  types  of 
growth  -may  be  seen.  The  first  consists  of 
a  fine  network  actually  inside  the  wood, 
which  supplies  the  proteins  essential  to 
fungus  growth.  The  threads  composing  the 
network  .secrete  various  enzymes  as  hadro- 
mase,  cytase  and  emulsin,  by  which  the 
coniferin  (constrvictional  timber  is  usually 
coniferous),  and  cellulose  of  the  cell-walls 
are  dissolved,  and  a  residue  of  lignin,  tannin 
and  calcium  oxalate  i,s  left  behind.  So  long 
as  sufficient  moisture  is  present  the  wood 
retains  its  original  volume,  but  with  the 
gradual  withdrawal  of  water  numerous 
right-angled  cracks  appear.  Under  certain 
conditions  of  moisture  a  skin-like  growth  or 
balled  pads  of  the  fungus  may  invest  a  tim- 
ber balk.  Sometimes,  principally  through 
either  a  lack  of  food  material  or  moisture, 
the  filaments  of  the  fungus  grow  together, 


forming  white  cords,  which  later  become  a 
slaty-gi-ey  colour  and  may  become  about  a 
quarter  of  an  inch  thick.  The  cords  have  a 
characteristic  structure,  and  examination 
vA'ith  a  microscope  reveals  three  kinds  of 
threads  that  can  be  distinguished  according 
to  their  size  and  the  thickness  of  their  cell- 
walls.  There  are  thin-walled  threads  of 
normal  width;  long  and  wide,  water- 
conducting-threads ;  and  fibrous  threads, 
whose  thickened  walls  serve  for  mechanical 
support.  The  whole  fungus  may  glisten 
with  droips  of  extruded  water,  possibly  for 
ultimate  conduction  to  the  point  of  attack 
upon  the  drier  parts  of  the  wood.  These 
tear-drops  are  n  ,t  crmducted  from  the 
source  of  water-supply,  but  are  formed  by 
the  respiration  of  the  fungus.  The  principle 
involved  is  mainly  one  of  oxidation  of  the 
host  wood.  Oxygen  from  the  air  is  essen- 
tial for  respiration.  Adopting  an  eniipirieni 
formula  for  wood,  the  dry-rot  fungus  has 
been  shown  to  be  able  to  produce  water  to 
about  half  the  weight  of  I'le  original  wood. 


^42^6600 

(1018) 
(Wood) 


+    89  0 


SSH/) 

(594) 


4200, 


Thus  the  dry-rot  fungus  can  actually  pro- 
duce the  moisture  necessary  for  its  own 
existence.  The  formation  of  oidia,  or  the 
variously  coloured  fruit  bodies,  is  more  or 
less  an  indication  of  local  failure  of  water 
supply  or  food  material.  The  superficial 
growth  can  also  be  related  to  local  shortage 
of  water  supply,  and  by  means  of  it  the 
fungus  can  spread  over  such  unpromising 
material  as  brickwork  and  tiles,  and  can 
penetrate  mortar  and  thus  attack  distant 
wood. 

"Dry-rot"  has  been  the  reputed  cause  of 
various  human  diseases,  but  this  is  impos- 
sible, as  blood  heat  is  fatal  to  the  fungus. 

In  questions  of  control  a  distinction  must 
be  drawn  between  prevention  of  infection, 
and  dealing  with  existing  infection.  In  the 
first  case,  c<3ntact  with  infectious  material 
must  be  guarded  against,  only  well- 
seasoned  wood  should  be  selected,  and 
samn  wood  should  be  stored  in  the  dry  and 
be  well  ventilated.  Buildings  in  which  the 
timber  is  afterwards  used  should  also  be 
well  ventilated. 

Timber  can  be  treated  with  antiseptics, 
but  this  method  is  very  costly,  as  for  per- 
fect success  tlie  wood  must  be  impregnated. 
Copper  sulphate,  iron  sulphate,  zinc  chlor- 
ide and  mercuric  chloride  have  been  reoom- 


DECEMBER  28.  1923. 


THE  CHEMICAL  NEWS. 


403 


mended,  but  are  impracticable.  Sodium 
fluoride,  boric  acid,  and  above  all,  magne- 
sium silicofluoride,  have  been  found  to  be 
the  best  inorganic  .preservatives.  Amongst 
organic  preservatives  creosote  and  tar.  but 
their  colour  and  smell  restrict  their  use. 

Dinitrophenates  and  dlnitrocresates  of 
potassium  and  sodium  are  effective,  parti- 
cularly the  sodium  salt  of  dinitrophenol, 
which,  however,  is  decomposed  by  liglit. 
and,  being  explosive,  must  be  mixed  with 
an  inert  substance.  Kiln  drying  of  woml 
has  also  been  recommended. 

When  dealing  with  an  existing  attack  of 
"  dry-rot,"  infected  wood  must  be  re- 
moved, surrounding  woodwork  examined, 
and  exposed  surfaces  disinfected.  Walls 
and  woodwork  may  be  washed  with  forma- 
lin, and  finally  coated  with  an  antiseptic. 
Care  should  be  taken  to  obviate  futun- 
damp. 

[An  excellent  critical  account  of  "dru- 
rot"  and  aho  of  many  other  fungu»  disease  ft 
of  timber  may  be  found  in  the  "  Handbooh 
of  the  Laryer  British  Fungi,"  by  Mr.  J. 
Ranisbottom,  the  well-known  authority  on 
these  mailers,  recently  published  by  the 
British  Museum  (Natural  History.)] 


W^HAT  IS  A  CHEMICAL?* 

By  J.  N.  Taylor,  M.S.* 

There  has  recently  come  about  a  most 
interesting  discussion  regarding  the  defini- 
tion of  a  synthetic  organic  chemical. 
According  to  Chemical  Age  (New  York)  for 
Ai)ril,  1923,  the  lioard  of  Governors  of  the 
Synthetic  Organic  Chemical  Manufn< - 
tiirers'  Association  has  adopted  the  follow- 
ing definition:  "  Synthetic  Organic  Chemi- 
cal— An  organic  chemical  which  has  been 
produced  by  a  controlled  process  involving 
change  in  chemical  identity."  A  "chemi- 
cal" is  defined  as  "a  material  containing  a 
preponderating  proportion  of  an  individual 
substance  of  definite  elementary  compo<si- 
tif.n."  Attt^ntion  was  called  to  trhese  defini- 
tions in  an  editorial  appearing  in  Chemisfry 
and  Industry  for  May  18.  1023,  and  further 

*  Reprinted  from  "The  American  Journal 
of  Pharmacy,"  Philadelphia.,  Pa.,  October. 
1923. 

'  Instructor  in  Chemistry  at  the  Wash- 
ingion  Preparatory  School  and  at  George 
Washington  University. 


reference  was  made  to  the  definition  of 
"synthetic  organic  chemical"  by  Mr.  E. 
Parry  in  giving  testimony  at  the  liearing 
(June  15,  1923),  on  "Formaldehyde," 
under  the  Safeguarding  of  Industries  Act 
(England),  as  to  whether  or  not  formalde- 
h3'dc  is  a  synthetic  organic  chemical.  He 
observed-  "that  the  difficulties  of  definition 
had  become  so  great  in  the  United  States 
that  only  this  month  the  Synthetic  Organic 
ChemicaJ  Manufacturers'  Association  of  the 
United  States  had  attempted  to  define  a 
synthetic  organic  chemical,  but  the  defini- 
tion arrived  at  was  meaningless." 

The  subject  of  chemical  nomenclature  is 
one  of  general  interest,  engaging  the  atten- 
tion of  educators  in  the  science  as  well  as 
the  various  chemical  societies  and  other 
associations  having  for  their  object  the  ad- 
vancement of  science.  Some  time  ago  the 
present  writer  took  occasion  to  direct  atten- 
tion to  the  desirability  of  greater  uniformity 
in  chemical  terminology,'  especially  in  our 
schools  and  colleges.  A  number  of  wel- 
come and  helpful  criticisms  of  the  paper 
were  received  pointing  out  that  the  Eng- 
lish language  is  a  growing  one,  that  it  is  yet 
in  iprocess  of  evolution,  and  that  growth 
and  change  in  our  language  demand  simpler 
and  more  concise  forms  for  conveying 
chemical  ideas.  This  is  indeed  tnie.  In 
any  live,  growing  language,  words  change 
in  meaning  in  the  course  of  time.  Couch. 
in  his  admirable  series  of  articles  now  ap- 
pearing in  the  American  Journal  of  Phar- 
macy, entitled  "The  Evolution  of  Chemical 
Terminology,"  traces  this  very  interesting 
development  of  our  science.  Divergences 
in  the  connotation  of  a  word  or  term,  recog- 
nisably  depend  in  great  measure  upon  the 
aspect  which  the  word  or  term  assumes. 
Such  terms  as  "chemical"  and  "synthetic 
organic  chemical,"  for  example,  might  each 
convey  different  meanings  from  the  point 
of  view  of  a  manufacturer,  a  dealer,  a  tea- 
cher, or  an  analyst,  or  when  viewed  from 
the  standpoint  of  the  tariff  or  the  census, 
or  when  thought  of  as  entering  into  int<^r- 
state  commerce. 

"  "Chemistry  and  Industry."  (Jour.  Soc 
Chem.  Ind.)    Vol.  XLIL,  No.  26,  p.  643. 

'  Taylor,  J.  Normati:  "Chemical  Nomen- 
clature and  Pronunciation,"  School  Science 
and  Mathematics,  Chicago,  Vol.  XX.,  No. 
9  (1920).  Reprinted  in  Jour.  American 
Pharm.  Assoc,  Philadelphia,  Vol.  X.,  10- 
11  (1921),  and  in  Chem.  News,  London, 
Voi;  CXXII.,  7  (1921). 


404 


THE  CHEMICAL  NEWS. 


DECEMBER  28,  1923. 


Certain  words,  when  used  in  a  legal 
sense,  are  specifically  defined,  and  the  ex- 
tent to  which  an  adjective  niay  ipartake  of 
the  attributes  of  the  noun  are,  therefore, 
limited  by  definition.  Certain  Acts  of  Con- 
gress specify  for  the  purposes  of  the  Acts 
the  limits  in  meanings  of  certain  words. 
For  example,  the  Food  and  Drugs  Act, 
June  30,  1906,  defines  the  term  "drug"  as 
used  in  the  Act  as  "all  medicines  and  pre- 
parations recognised  in  the  U.S.  Pharmaco- 
poea  or  National  Formulary  for  internal  or 
external  use,  and  any  substance  or  mixture 
of  substances  intended  to  be  used  for  the 
cure,  mitigation  or  prevention  of  disease  of 
either  man  or  other  animal."  The  noun 
"drug"  and  terms  derived  from  it  are, 
therefore,  circumscribed  in  meaning  when 
employed  under  the  provisions  of  the  Act. 
As  anothe  rexample  may  be  mentioned  the 
word  "  insecticide."  The  Insecticide  Act 
of  1910  defines  "insecticide"  as  follows:  — 
"  The  term  'insecticide'  as  used  in  this  Act 
shall  include  any  substance  or  mixture  of 
substances  intended  to  be  used  for  prevent- 
ing, destroying,  repelling  or  mitigating  any 
insects  which  may  infest  vegetation,  man 
or  any  animals  or  households,  or  be  present 
in  any  environment  whatsoever."  Natur- 
ally, the  adjective  "insecticidal"  is  limited 
in  meaning  for  the  purpose  of  the  Insecti- 
cide Act,  because  of  the  meaning  given  the 
word  "insecticide"  by  the  framers  of  the 
Act.  On  the  other  hand,  the  popular 
meaning  of  words  such  as  are  noted  above 
may  extend  beyond  the  limitations  set  down 
for  them  ex  cathedra. 

As  an  adjective,  there  appears  to  exist 
little,  if  any,  confusion  regarding  the  use 
of  the  term  "  chemical."  We  are  accus- 
tomed to  speak  of  "  chemical  reactions." 
"  chemical  compounds,"  "  chemical  pro- 
ducts," etc.,  and,  through  custom  and 
usage,  their  meanings  carry  no  ambiguity. 
To  what  extent,  however,  may  the  popular 
concept  of  the  meaning  of  the  adjective  be 
applied  to  the  noun?  When  an  attempt  is 
made  to  distinguish  between  "chemical" 
and  "  chemical  compound,"  between 
"chemical"  and  "  drug,"  or  between  a 
chemical  and  the  result  of  a  chemical  pro- 
cess, there  appears  to  be  a  misunderstand- 
ing as  to  just  what  is  conveyed  when  the 
word,  "  chemical,"  is  employed  as  a 
noun. 

It  would  seem  apropos,  therefore,  in 
view  of  the  present  discussion  of  the  mean- 
ing of  the  noun  "  chemical,"  to  reaffirm 
the  province  of  chemistry,    hoping  thereby 


to  establish  a  position  from  w-hioh  we  can 
survey  this  question  in  the  light  of  both 
theory  and  practice. 

Chemistry  investigates  the  composition 
and  properties  of  substances  and  the 
changes  which  they  undergo.  It  deals  with 
the  en-^rgy  changes  within  and  between  or 
among  molecules  and  atoms  of  substances. 
Hence,  in  its  application,  it  includes  all 
material  things  which  are  the  result  of 
energy  transf urinations.  To  the  chemist, 
therefore — and  who  should  be  better  quali- 
fied to  speak  on  chemical  topics  than  the 
chemist? — all  substances  which  enter  into 
and  result  from  such  energy  transforma- 
tions are  chemicals. 

There  is  nothing  original  in  this  state- 
ment, however.  Munroe,*  as  long  ago  as 
1905,  in  his  monograph,  "  Chemicals  and 
Allied  Products,"  in  discussing  the  classi- 
fication of  materials  coming  within  the 
scope  of  the  investigation  for  the  Bureau  of 
the  Census,  declared  that,  "in  the  strictest 
technical  sense  every  material  thing  is  a 
chemical." 

Obviously,  until  some  such  fundamental 
definition  of  a  chemical  is  agreed  upon  and 
the  start  is  made  from  this  base,  the  efforts 
to  obtain  divisional  definitions  that  will  be 
generally  accepted  will  be  unavailing.  With 
this  in  mind  the  foregoing  definition  is  pre- 
sented for  oonsderaton. 


THE  SITUATION  IN  THE  COAIi 

INDUSTRY. 
Attitude  of  the  Colliery  Owners. 
In  view  of  the  unauthorised  and  contra- 
dictory statements  that  have  appeared  in 
the  press  with  referenct^  to  the  rneeting  on 
December  18  of  the  sub-comrhittee  ap- 
pointed to  review  the  Wages  Agreement  in 
the  coal  mining  industry,  the  Mining  Asso- 
ciation is  of  opinion  that  an  authoritative 
announcement  should  be  made  with  refer- 
ence to  the  attitude  taken  up  by  the  repre- 
sentatives of  the  owners    on  that  conurut- 

It  will  be  remembered  that  the  demands 
put  forward  by  the  Miners'  Federation  were 
as  follows  :  — 

"  Munroe,  Charles  E.:  "  Chewcah  and 
Allied  Products,"  Census  of  Manvfactures  : 
1005,  Bulletin  92,  Bureau  of  the  Census, 
Department  of  Coinvierce  and  Labour, 
Government  Printing  Office,  Washmgton, 
1908. 


DECEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


405 


1. — That  the  ratio  of  profits  to  v.'ages 
should  be  altered  from  17  to  100  below  the 
standard  and  17  to  83  above  the  standard  to 
■d  constant  ratio  of  13  to  100  both  above  and 
below. 

2.  That  the  minimum  wage  should  be 
raised  from  20  per  cent,  to  40  per  cent, 
agove  the  standard. 

3. — -That  further  information  should  be 
iiccorded  to  the  miners  on  costs  other  than 
wages. 

In  the  course  of  the  discussions  on 
Tiuirsdaj-  last,  it  was  stated  by  Mr.  Evan 
WilHams  on  behalf  of  the  owners  that  on 
certain  points  the  members  of  the  sub- 
committee had  an  ope  nmind,  and  would  be 
prepared  to  recommend  to  the  members  of 
the  Mining  Association  certain  alterations 
in  the  Wages  Agreement  which  would  oper- 
ate to  the  advantage  of  the  men,  provided 
that  certain  concessions  were  made  by  the 
Miners'  Federation  in  regard  to  clauses  that 
inflicted  undue  hardship  upon  the  owners 
in  the  less  pros{)orous  districts. 

As  regards  the  first  claim,  for  the  altera- 
tion in  the  ratio  between  profits  and  wages, 
the  owners*  representatives  on  the  sub- 
committee were  prepared  to  consider  put- 
ting forward  a  recommendation  that  the 
ratio  should  be  constant  both  above  and 
l>el(>w  the  standard,  and  that  the  proportion 
allotted  to  profits  should  be  something  less 
tha  nl7.  No  precise  figure  was  mentioned, 
but  it  was  indicated  that  it  would  have  to 
he  considerably  higher  than  the  18  de- 
manded by  the  Federation. 

As  regards  the  second  demand,  the 
owners  found  themselves  unable  to  make 
my  concession,  and  it  was  pointed  out  by 
.Mr.  Evan  Williams  that  the  proposed  al- 
teration in  the  miniminn  from  20  (per  cent. 
to  40  per  cent,  above  the  standard  woul<l 
not  ameliorate  the  position  of  the  lower 
paid  men,  on  whose  behalf  the  miners' 
leaders  were  putting  forward  the  demand, 
since  these  men  were  already  protected  by 
the  subsistence  wage.  For  instance,  in 
South  Wales  the  standard  wage  for  surface 
labourers  is  5s.  3.0d.  per  shift,  and  the 
minimum  wage  therefore  is  6s.  4.8d.  If 
the  minimum  were  raised  to  40  per  cent, 
above  standard,  the  figure  would  be  7s. 
n.^d.,  whereas  under  the  subsistence  wage 
it  is  actually  7s.  6d. 

The  suggestirm  was,  however,  put  for- 
ward by  Mr.  Evan  Williams  that  the  lot  of 
the  lower  paid  men  might  be  sensibly  im- 
proved by  a  rerlistribiition  of  wages  as  be- 
tween them  and  the  higher  paid  ipiece 
workers.      T{&  instanced  the  14.2  per  cent. 


advance  which  was  awarded  to  the  piece 
workers  to  make  up  for  loss  of  earnings 
consequent  upon  a  reduction  of  the  hours 
from  8  to  7,  and  suggested  that  this  might 
be  more  equitably  allocated  to  the  lower 
paid  men. 

As  a  result  of  this  advance  of  14.2  per 
cent.,  the  earnings  of  the  piece  workers 
showed  a  greater  relative  increase  over  their 
pre-war  earnings  than  did  those  of  the  lo\\  er 
paid  men,  whose  need  was  actually  the 
greater.  For  the  whole  of  the  United  King- 
dom, except  Northumberland  and  Dur- 
ham, which  were  unaffected  by  the  altera- 
tion in  houi-s,  the  percentage  increase  for 
the  higher  paid  piece  workers  was  73,  as 
against  59  for  the  lower  paid  men. 

As  regards  costs  other  than  wages,  Mr. 
Evan  Williams  emphasised  that  the  items 
ff>r  which  the  miners  were  asking  for  fur- 
ther infonnation  were  such  as  could  not  be 
influenced  in  any  way  by  them  (the  miners). 
At  the  same  time,  he  said,  the  representa- 
tives of  the  owners  had  been  favourably 
considering  this  demand,  and  were  prepared 
to  recommend  that  a  considerable  volume 
of  further  information  should  be  given. 

The  principal  counter  proposal  put  for- 
ward by  the  representatives  of  the  owners 
was  in  connection  with  the  recoupment  of 
standard  profits  sacrificed  in  order  to  pay 
the  minimum  wage  which,  under  the  award 
of  the  independent  chairman,  are  practi- 
cally irrecoverable  out  of  any  future  sur- 
plus. The  reprpsentatives  of  the  miners 
were  remmded  that  this  was  not  the  inten- 
tion of  those  who  originally  drafted  the 
Agreement,  and  it  was  indicated  that  the 
owners  would  certainly  require  the  revision 
of  this  restrictive  interpretation  as  a  quid 
pro  quo  for  any  concession  that  they  might 
be  prepared  to  make.  At  the  same  time 
they  realised  that  to  recover  out  of  any  im- 
mediately ensuing  surplus  an  accumulated 
deficit  might  impose  considerable  hardship 
on  the  miners,  and  they  would  therefore  be 
prepared  to  consider  proposals  for  stpreading 
such  recoupment  over  a  period  occupied  by 
several  ascertainments. 

In  conclusion,  the  Mining  Association 
wishes  to  emphasise  the  point  that  mem- 
bers of  the  sub-oommittee, .  in  putting  for- 
ward the  above-mentioned  suggestions  for 
further  discussion,  were  animated  by  the 
sincere  conviction  that  tKe  termination  of 
the  Wages  Agreement  at  the  present  time 
would  he  a  national  disaster.  It  is  realised 
that  this  Agreement  is  a  far  from  perfect 
instniment.  but  at  the  same  time  it  is  held 
to  be  the  greatest  step  forward  yet  made  in 


406 


TfiE  CHEMICAL  NEWS. 


DECEMBER  28.  1923. 


the  history  of  British  industry  towards 
settling  differences  and  apportioning  the 
proceeds  of  an  industry  between  labour, 
capital,  and  management.  It  was  these 
considerations,  and  not  any  conviction  that 
the  agreement  had  hitherto  operated  too 
much  to  the  advantage  of  the  owners — who 
indeed  have  received  far  less  under  it  than 
they  were  entitled  to  expect  —that  led  the 
representatives  of  the  owners  to  make  tliis 
further  attempt  to  secure  for  the  coal  min- 
ing industry  that  peace  which  is  so  essen- 
tial to  national  recovery. 

It  is  upon  the  ability  of  the  industry  to 
ipa  ythat  the  owners  take  their  stan.d  The 
demand  for  an  increase  in  the  minimum  to 
40  per  cent,  above  the  standai'd  destroys 
the  whole  spirit  of  the  Wages  Agreement, 
which  was  based  fundamentally  upon  the 
conception  that  the  industry  must  hence- 
forward be  self-supporting  and  must  pay  its 
own  way.  If  the  demand  were  conceded, 
the  wages  in  the  poorer  districts  would  no 
longer  rest  upon  the  ability  to  pay,  and  this 
would  render  impossible  any  form  of  nation- 
al agreement.  Any  artificial  increase  in  the 
iprice  of  coal  would  be  merely  an  effort  to 
bolster  up  an  uneconomic  situation,  and 
woul  dbreak  down  in  practice  after  having 
caused  a  great  increase  in  the  volume  of 
unemployment. 

It  was  pointed  out  to  the  representatives 
of  the  miners  that  in  the  poorer  districts  the 
rate  of  output  showed  a  greater  reduction 
per  person  employed  than  in  the  more  pros- 
perous areas.  The  solution  of  the  prob- 
lems facing  the  coal  industry  can  only  be 
found  gy  an  increase  in  output  per  person, 
and  it  is  extremely  doubtful  whether  such 
increase  can  be  achieved,  at  any  rate  in  the 
pooreV  districts,  under  the  present  restfic- 
tions— embodied  in  an  Act  of  Parliament— 
on  the  number  of  hours  worked  under- 
ground. 


FEDERATION    OF   BRITISH 

INDUSTRIES. 
(Incorporated  hy  Royal  Charter.) 

Report  of  the  Committee  on  Central  ant- 
Local  Taxation. 
The  Committee  was  appointed  by  thr 
Executive  Committee  in  February,  1923, 
with. wide  terms  of  reference,  to  consider 
the  whole  question  of  central  and  local 
taxation  and  administration,  particularly  m 


regard  to  the  desirability  of  decentralisa- 
tion of  control  and  of  greater  industrial  re- 
presentation on  local  authortiies.  The  fol- 
lowing Report  of  the  Committee  was 
adopted  by  the  Executive  Committee  of 
the  Federation  on  December  12,  1923:  — 
Burden  of  Taxation  upon  Industry. 

The  Committee  feel  that  there  is  no  need 
for  them  to  dwell  upon  the  burden  which  is 
being  borne  by  industry  in  the  form  of  taxa- 
tion at  the  present  time.  Of  the  huge 
amount  levied  annually  for  the  national  ex- 
chequer, by  far  the  largest  portion  is  de- 
rived in  one  form  or  another  from  industrial 
sources.  To  this  burden  must  be  added 
the  further  contribution  which  has  to  be 
made  by  industry  in  the  form  of  rates.  The 
growth  of  municipal  expenditure  in  the 
course  of  the  last  twenty  years  has  been  ex- 
traordinary, and  although  the  most  recently 
published  figures  show  that  some  reduc- 
tion is  now  beginning  to  be  effected,  the 
total  still  remains  at  a  very  high  figure. 

A  further  fact  which  intensifies  the  bur- 
den is  the  unfair  inclusion  of  machinery  for 
rating  purposes.  This  accentuates  the  in- 
equalities as  between  industrialists  and 
other  ratepayers.  The  Committee  under- 
stand that  the  Government  has  appointed 
a  Committee  to  investigate  this  question, 
and  the  publication  of  a  Draft  Rating  and 
Valuation  Bill  is  evidence  that  the  whole 
question  of  assessments  is  receiving  con- 
sideration. The  Committee  consider  that 
legislation  on  the  question  of  machinery 
rating  in  England  is  urgently  required,  and 
strongly  recommend  that  the  Federation 
should  carefully  examine  the  question  by 
means  of  an  expert  Committee,  with  a  view 
to  giving  evidence  before  the  Dt^partinontal 
Committee. 

Increase  in  Rates  Since  1918. 

The  Committee  have  secently  made  (in- 
quiries from  firms  in  a  great  variety  of  in- 
dustries and  scattered  throughout  the  coun- 
try, with  a  view  to  comparing  the  amounts 
paid  by  such  firms  to  local  rates  in  1913  and 
1922.  The  result  of  their  enquiry  shows 
that  the  payments  to  rates  increased  on  an 
average  no  less  than  295  per  cent,  in  the 
period  mentioned,  in  spite  of  the  fact  that 
contributions  to  health  and  unemployment 
insurance,  which  might  have  been  expected 
to  reduce  the  contribution  to  poor  relief, 
have  actually  increased  328  ipor  cent.  Mak- 
ing all  allowances  for  the  difference  in  con- 
ditions l)etween-  the  two  years  mentioned, 
and  in  certain  cases  the  increase    in  assess- 


Z)EC£1MBER  28,  1923. 


THE  CHEMICAL  NEWS. 


407 


mentis  due  to  extensions  of  works,  the  Com- 
mittee still  feel  that  so  large  an  increase  is 
unjustifiable.  When  these  percentage  in- 
creases are  compared  with  the  increase  in 
the  cost  of  living,  whicli,  according  to  the 
index  figures,  rose  from  100  in  1914  to  an 
average  of  181.5  in  1922,  or  the  increase  in 
the  index  of  wholesale  commodity  prices 
from  100  in  1923  to  an  average  of  159  in 
1922,  it  is  clear  that  prhmi  facie  evidence  of 
the  necessity  for  aa  enquiry  into  the  whole 
system  is  afforded. 

Increased  Cost  of  Local  Government 
Since  1913. 

The  Committee  are  aware  that  the  cost 
of  local  government  must  he  higher  at  tlu' 
present  time  than  before  the  war.  The  in- 
creased cost  of  living  is  reflected  in  higher 
wages  and  greater  cost  of  materials,  while 
the  trade  depressioi  has  been  responsible  for 
a  large  increase  in  the  cost  of  relieving  dis- 
tress. Many  expenses  which  normally 
would  have  been  carried  out  during  the  war 
years  have  been  poetponed,  and,  in  addi- 
tion, new  services  have  been  imposed  uipon 
local  authorities  as  the  result  of  legislation 
passed  since  1913.  Tuberculosis,  venereal 
diseases,  maternity  and  child  welfare,  and 
mental  deficiency  services  have  all  been 
added  to  the  duties  of  local  authorities  since 
that  date.  There  are  also  increased  charges 
in  connection  with  housing  and  with  the 
registration  of  electors  under  the  Represen- 
tation of  the  People  Act. 

The  CoTumittee  do  not  wish  for  a  moment 
to  suggest  that  the  objects  of  this  expendi- 
ture are  not  from  a  social  point  of  view  emi- 
nently desirable.  They  believe,  however, 
that  largely  owing  |;o  the  unsatisfactory  de- 
marcation of  functions  between  the  central 
and  local  authorities,  the  administration 
has  not  been  upon  the  most  economical 
basis,  and  that  the  results  obtained  have 
hardly  been  commonsnrnto  with  tlic  cxDcn- 
diture  involved. 
Local  Expenditure  ano  lk.mkal  i  (i.ntkol. 

Many  of  these  services  are  financed 
partly  by  contributions  from  State  Funds, 
and  the  Centra!  Government  Department 
dictates  to  the  local  authority  the  expendi- 
ture which  must  be  incurred.  In  all  eases, 
although  the  administration  is  carried  out 
locally,  a  greater  or  lesser  degree  of  control 
is  retained  in  the  hands  of  the  Central  Gov- 
ernment Department.  The  Committee  are 
convinced  that  this  must  inevitbaly,  and  in 
practice  does,  result  in  overlapping  and  <'x- 
travagance  of  administration.  This  arises 
not  merely    from  the  duplication  of  inspec- 


tion, which  takes  place  notably  in  connec- 
tion with  the  administration  of  the  Educa- 
tion Acts,  but  also  from  the  fact  that  Par- 
liament and  the  Treasury  are  less  well 
placed  to  exercise  detailed  control  over  the 
minutias  of  local  erpenditure  than  the  local 
ratepayers,  to  whom  the  members  of  the 
administrative  committees  are  directly  re- 
sponsible, 

Reliee  of  Distress. 

A  very  striking  examide  where  there  is 
iprobably  overlappmg  in  expendituic  as  well 
as  in  administration  is  afforded  by  the  pay- 
ments for  relief  of  distress  and  unemploy- 
ment. It  is  particularly  unfortunate  that 
these  result  in  swollen  rates  at  a  time  when 
industry  is  least  able  to  bear  an  additional 
burden.  The  effect  of  this  was  shown  in 
1<.)22  in  the  case  of  one  distressed  arya  where 
the  poor  rate  per  ton  of  steel  manufactured 
(comparing  the  output  for  the  respective 
years)  had  increased  no  less  than  2,396  per 
cent,  since  before  the  war,  an  increase  in 
the  cost  of  production  which,  of  itself, 
would  have  no  small  effect  in  restricting  the 
flow  of  orders  and  thus  indirectly  causing 
unemployment. 

While  it  is  diflBcult  to  form  any  estimate 
of  the  extent  to  which  there  is  overlaipping 
of  relief  from  the  different  sources,  the 
Committee  would  call  attention  to  the  lack 
of  co-ordination  at  present  existing  in  the 
administration.  Unemployment  payments, 
poor  law  relief,*  feeding  of  school  children, 
are  all  directed  towards  the  assistance  of 
the  same  class  of  beneficiaries,  and  the  fact 
that  the  administration  of  these  services  has 
not  been  co-ordinated  cannot  fail  to  have 
resulted  in  extravagance.  This  matter  was 
dealt  with  at  some  length  in  the  report 
which  was  presented  to  the  Grand  Council 
a  year  ago  by  the  Unemployment  Insurance 
Committee. 


*  NOTE.— A  further  point  with  regard  to 
poor  relief  is  that  in  recent  years  the  Minis- 
try of  Health  has  given  permission  to 
Boards  of  Guardians  to  raise  short-term 
loans  from  private  lenders,  amounting  in 
some  rases  to  very  large  sums.  While  it 
may  have  been  inevitable  that  extraordi- 
nary additional  sums  should  be  raised  for 
the  relief  of  distress,  it  is,  in  the  opinion  of 
the  Committee,  most  undesirable  that  the 
money  should  he  raised  in  this  way  to  meet 
current  ea-penditure,  and  that  borrou-ing 
powrrs  of  this  nature  should  be  conferred 
upon  Boards  of  Ouardians. 


406 


THE  CHEMICAL  NEWS. 


DECEMBEK  28,  1923. 


The  Committee  would  call  attention  to 
the  valuable  suggestions  which  have  been 
made  on  this  subject  by  the  Denison  House 
Committee  on  Public  Assistance.  That 
Committee  has  advocated  the  publication 
of  a  complete  and  Uip-to-date  annual  return 
of  all  expenditure  from  rates  and  taxes  on 
direct  public  assistance,  with  details  as  to 
administrative  cost,  and,  further,  of  a  regis- 
ter of  beneficiaries,  which  they  maintain 
must  be  the  basis  of  all  reform.  The  Com- 
mittee strongly  commend  these  proposals, 
and  further  support  the  adoption  of  the 
Denison  House  Committee's  reoommenda- 
tion  of  an  annual  estimate  of  future  public 
expenditure  on  direct  public  assistance,  as 
soon  as  general  conditions  become  suffi- 
ciently normal  to  make  this  practicable. 
The  Committee  are  convinced  of  the  econo- 
mies which  can  be  efEected  by  a  greater  co- 
ordination of  public  assistance. 

Need  for  Keconsideration  of  Duties  of 
Local  Authorities. 
In  view  of  what  is  said  above,  the  Com- 
mittee feel  that  the  time  has  come  to  re- 
consider the  duties  of  local  authorities  and 
the  scope  of  the  functions  which  should  be 
delegated  to  them.  Not  only  should  the 
Central  Government  take  as  much  advan- 
tage as  possible  of  local  patriotism  and  local 
talent ;  it  should  also  allow  greater  auto- 
nomy in  administration  to  local  authorities 
within  the  zone  of  approved  expenditure, 
and  although  the  need  will  remain  foi- 
financial  assistance  to  be  afforded  by  the 
national  exchequer,  this,  when  approved, 
should  not  be  accompanied  by  the  detailed 
control  at  j^resent  exercised  by  the  Central 
Departments.  The  Committee  agree  that 
some  safeguards  will  be  necessary,  and  they 
would  suggest  for  consideration  that  where, 
after  a  public  enquiry  held  by  the  Ministry 
of  Health,  it  is  shown  that  a  local  admini- 
stration has  been  guilty  of  extravagance  and 
abuse  of  the  powers  vested  in  it,  the  Minis- 
try of  Health  should  bo  emtpowered  to  sus- 
pend the  local  authority  concerned,  and  to 
appoint  directly  stipendiary  administrators 
to  carry  out  its  duties. 

"Onerous"  and  "Beneficial"  Services. 
The  Committee  wish  to  qualify  their  sug- 
gestions for  a  reconsideration  of  the  func- 
tions of  local  authorities  by  referring  to  the 
distinction  which  has  been  drawn  by  the 
Royal  Commission  on  ]jocal  Government  in 
1896  and  the  Departmental  Committee, 
which  reported  in  1914,  between  "oneious" 
and  "beneficial"  services.  "  Onerous 
services  are  defined  as  those  which  a  local 


authority  is  called  upon  to  perform  for  the 
benefit  of  a  greater  area  than  its  own 
locality,  while  "beneficial"  services  ure 
those  which  confer  a  merely  local  advan- 
tage. They  consider  that  this  distinction 
should  be  kept  in  mind,  although  conditions 
have  changed  so  much  since  the  Report  of 
the  Departmental  Committee  was  Issued 
that  the  conclusions  now  reached  would 
probably  differ  in  some  respects  from  those 
of  tliat  Committee. 

Need  for  Committee  or  Commission  on 
Incidence  of  Taxation. 

Before,  however,  any  final  recommenda- 
tions can  be  made  on  this  subject,  a  strong 
Committee  or  Commission  should  be  ap- 
pointed to  examine  the  incidence  or  taxa- 
tion. At  the  present  time  the  exact  inci- 
dence of  contributions  to  national  or  muni- 
cipal exchequers  is  to  a  great  extent  a  mat- 
ter of  guesswork,  though  both  classes  of 
taxation  undoubtedly  add  to  the  cost  of  pro- 
duction. The  Committee  feel  that  it  is  a 
matter  of  the  greatest  importance  that  an 
enquiry  into  this  subject  shoul  dbe  initiated 
without  delay. 

The  Committee  have  already  called  at- 
tention to  the  Draft  Rating  and  Valuation 
Bill  which  is  now  receiving  the  attention  of 
authorities  interested  throughout  the  coun- 
try. They  understand  that  detailed  recom- 
mendations in  regard  to  this  Bill  are  being 
considered  by  the  Taxation  Committee  of 
the  Federation,  and  they  therefore  do  not 
propose  to  go  into  its  provisions.  They  re- 
gret, however,  that  the  Government  have 
decided  to  bring  forward  this  Bill  before 
they  have  initiated  an  enquiry  into  the  inci- 
dence of  taxation.  For  the  same  reason 
they  are  not  satisfied  that  the  investigations 
at  present  being  carried  out  by  a  Royal 
Commission  into  the  question  of  the  areas 
of  local  government  and  by  a  Departmental 
Committee  into  the  percentage  grant  sys- 
tem can  adequately  meet  the  difficulties  of 
the  situation,  and  while  they  do  not  doubt 
that  both  these  enquiries  will  result  in  use- 
ful information  being  obtained,  they  feel 
that  the  problem  has  more  fundamental  as- 
pects than  can  be  dealt  with  under  the 
terms  of  reference  of  either  body.  For  these 
reasons  they  recommend  that  a  Committee 
or  Commission  should  be  appointed,  with 
the  terms  of  reference  which  they  have  in- 
dicated. 

Tradinox  Services. 
Before  concluding  their  Report,  the  Com- 
mittee desire  to  record    that  they  are    not 
able  to  suggest  any  fresh    resources  which 


DEGEMBEK  28,  1923. 


I'Hfi  CHBMICAL  NBWS. 


409 


can  be  drawn  upon    to  meet  local  expendi- 
ture.    In  more  prosperous  times  the  trading 
services  carried  out  by  municipalities  could 
be  ranked  as  assets,    since  their  operations 
resulted  in  profits  which  went  to  relieve  the 
rates.     Now,    however,     this    position    has 
been  reversed,   and  these    services    are    in 
many  cases  a  definite    hability  leading    k) 
substantial  increases  in  already  heavy  rates. 
Thus,    in  the    case  of  one  local    authwit\ , 
whose  budget  they  have  had  an  opportunity 
of  considering,  the  Committee  note  that  for 
the  year  1913-14  trading  services  showed    a 
credit    balance  of  £91,60<).       In    the    year 
1922-23  this  has  been  converted  into  a  debit 
balance  of  4:118,323.      This    new    situation 
requires  a  complete  review  of  the  principle 
of  municipal    trading  services.      The  Com- 
mittee   are    convinced    that    the    principle 
should    be  generally    adopted  that    trading 
services  must    be  self-supiporting,    and,     if 
not,  should  be    discontinued    in  favour    of 
private    enterprise.      By    this  they    do  not 
mean  that  each  year's  working  must  show  m 
profit,    but    they    consider    that    if  over    ;i 
period    of  years  a  trading    servioe    shows  m 
loss,  power  should    be  taken  to  close  down 
that    particular  trading  activity,    and  thus 
relieve  the  rates  from  the  necessity  of  sub- 
sidising it.     Moreover,  the  Committee  con- 
sider it  wrong  in  principle  that  profit  should 
be  the  primary    object  for  which  municiipal 
enterprises    are    instituted.        Such     enter- 
prises should    be    judged    entirely    on    the 
ground    of    public    policy     involving    such 
questions  as  the    anticipated  service  to  the 
community,    the  dangerous  effect  of  politi- 
cal pressure  on  coets  and  charges,    and  the 
probable    influence    upon    the    competitive 
and  other  industries.      As  to  o^er  possible 
bases  of  taxation  besides  tlmi  which  at  pre- 
sent supports  the  rating  sy-tem,    the  Com- 
mittee find    themselves  in  agreement    with 
the  Royal    Commission    on  Local    Govern 
ment    and    the     Departmental    Conmiiltee 
that  no  suitable  further  local    taxes  can  be 
imposed. 

Kkpreskntation  on  Local  Autikuitiks. 

The  Committee  regret  to  record  the  gen(>- 
ral  apathy  of  industrialists,  which  has  |»r('- 
vented  them  from  serving  on  kxsn  lauthuri- 
ties  or  encouraging  tiieir  slaffs  to  do  s<>. 
They  are  glarl  to  note  that  in  certain  partes 
of  the  Cf)untry  a  greater  interest  in  munici- 
pal affairs  is  being  taken  by  industrialists, 
and  trust  that  tliis  mov»'mcnt  will  sprejui. 
They  cannot  but  feel  that  the  ex|)eri»'nce  of 
business  men  should  be  of  Ihe  greatest  ad- 
vantage in  iimnici(pal  work,  and  that  much 


extravagance  in  the  past  can  be  traced  to 
the  ignorance  of  business  principles  shoun 
by  the  administrators.  The  Committee  do 
not  wish  to  suggest  that  industrialists  or 
tlie  staffs  of  industrial  firms  should  serve 
upon  local  authorities  as  delegates  of  m- 
dustrial  interests  or  in  any  other  capacity 
than  as  citizens,  but  they  desire  to  record 
their  conviction  that  heads  of  firms  who 
wiil  themselves  serve  upon  municipal  coun- 
cils or  will  encourage  suitable  members  of 
their  staffs*  to  do  so  will  be  performing  a 
public  service  of  the  greatest  importance. 


ARGENTINA— EXHIBITION  OF 
EDUCATIONAL    MATERIALS. 

The  Department  of  Overseas  Trade  is  in- 
formed by  the  British  Legation  at  Buenos 
Aires  that  the  American  Academy  of  His- 
tory (President,  N.  Sarmientoj  is  organising 
an  International  Congress  oi  History  and 
Gtography  of  America  and  Exhibition  of 
Educational  Materials,  to  be  held  in  Buenos 
Aires  in  1924. 

The  Academy  invites  all  scientific  and 
geographical  institutions  to  participate,  as 
well  as  manufacturers  of  and  dealers  in 
materials  concerned  in  the  supply  of  educa- 
tional institutions,  libraries,  science  labora- 
tories, etc. 

If  the  project  is  of  interest  to  United 
Kingdom  institutions  or  firms,  further  parti- 
culars of  the  scheme  may  be  obtained  from 
the  Secretary  of  the  Academy,  Dr.  A.  E. 
lie  la  Guardia,  Academia  Americana  de  la 
llistoria,  BuenoH  Aires. 


I'liOCEEDINOS  AND  NOT  ICES  OF 
SOCIETIES. 


THE  CHEMICAL  SOCIETY. 

I'apers  read  at  the  Ordinary  Meeting  on 
Deot'mbcr  2t):  — 

The  Relation  between  the  Qlow  of  Phos- 
I>hnru8  and  the  Formation  of  Ozone,  by  W, 

10.    I)UWXEY. 

The  amount  of  ozone  pro<luced  in  the 
slow  oxidation  of  phosphorus  was  shown  to 
be  proportional  to  the  intensity  of  the  glow. 
Oxygen  was  led  at  varying  pressures  over 
phosphorus,  the  oxiaes  of  phosphwus 
iorme(l  wer(!  frozen  out,  and  the  ozone  was 
absorbed  in  a  s(>hition  of  potassium  iodide. 
The   intensity    of  the  glow  was    measured 


410 


THE  CHEMICAL  NEWS. 


DECEMBER  28,  1923. 


pliotographicallj.  The  light  of  the  glow, 
after  passing  through  a  quartz  or  fluorite 
window,  was  shown  to  ozonise  oxygen.  The 
oxidation  of  phosphorus  trioxide  was  ac- 
companied hy  the  formation  of  ozone;  and 
the  glow  was  also  capable  of  ozonising  oxy- 
gen. The  glow  was  shown  to  be  capable  of 
ionising  air,  and  must  therefore  contain 
light  of  the  region  A  =  1200- 18a)  A. U. 
The  fact  that  the  glow  extends  into  rhis 
region  gives  a  possible  explanation  of  the 
formation  of  ozone  and  ions  found  in  the 
presence  of  glowing  phosphorus. 

The  Origin  of  Mutarotation  and  the 
Mechanism  of  Isomeric  Change.  A  Reply 
to  Baker,  Ingold,  and  Thorpe,    by    T.    M. 

LOWRY. 

The  view  that  water  does  not  intervene 
in  the  mutarotation  of  sugars  was  criticisad 
on  the  grounds  that  it  is  not  in  accordance 
with  experimental  data,  and  that  the 
method  of  proof  based  upon  the  form  of 
the  mutarotation  curves  was  not  valid. 

The  Action  of  Inorganic  Haloids  on 
Organo-MetalUc  Compounds,  by  F.  Chal- 
lenger and  F.  Pritchard. 

The  interaction  of  the  triphenyl  deriva- 
t'ves  of  phosphorus,  arsenic,  antimony  and 
bismuth  with  the  corresponding  trihaloids 
in  ethereal  solution  has  been  studied  at 
ordinary  or  slightly  elevated  temiperatures, 
to  determine  whether  the  reactions  largely 
depended  on  solubility  factors,  or  if  definite 
rules  could  be  discovered  which  govern  the 
migration  of  phenyl  groups  from  one  ele- 
ment to  another. 

With  triphenylbismuthine  and  various 
haloids,  sparingly  soluble  diphenylchloro 
bismuthine,  PhjBi  CI,  is  produced: 

PhjEi  +  P  CI3  =  Ph.Bi  CT  +  PhPClj. 

Similar  results  were  observed  by  Goddard 
and  others,  with  the  tetraphenyl  derivatives 
of  tin  and  lead. 

A  similar,  though  weaker,  tendency  is  ob- 
served with  ti'iphenylarsine,  though  partly 
obscured  by  the  formation  of  additive  pro- 
ducts. Thus,  with  antimony  trichloride, 
some  iphenyldichloroarsine,  Ph  As  CI,,  is 
produced,  and  also  an  additive  product  giv- 
ing the  arsine  and  antimony  oxychloride 
with  water. 

With  triphenylphosphine  the  tendency 
for  migration  of  the  phenyl  group  has  al- 
most disappeared,  additive  products  al- 
ways resultinfT.  These  undergo  an  inter- 
esting decomposition  on  heating,  giving  rise 


to  the  free  metal,  and  presumably,  to 
PhaPClg,  which,  with  water,  gives  triphenyl- 
phosphina  oxide,  PhgPO.  This  holds  for 
the  haloids  of  phosphorus,  arsenic,  and  bis- 
muth, and,  to  a  much  smaller  extent,  of 
antimony,  no  phosphine  oxide  being  iso- 
lated in  this  case.  Phosiphorus  trichloride 
.is  only  reduced  to  a  subchloride.  When 
tiiphenylstibine  interacts  with  metallic 
haloids  these  are  also  reduced  and  tri- 
phenylstibine  dichloride  formed.  Migra- 
tion of  the  phenyl  group  occurs  but  rarely. 

The  difference  in  the  behaviour  of  the 
phosphine  and  stibine  from  that  of  tri- 
phenylbismuthine may  possibly  be  ex- 
plained on  the  assumption  that  the  last- 
named  compound  is  slightly  ionised  in 
ether,  whereas  the  others  are  much  less 
ionised.  However,  the  work  of  Hevesy 
and  Zechmeister  {Ber.,  1920,  LIII.,  410) 
a<ppears  to  show  that  tetraphenyl  plum- 
bane,  PbPh^,  is  not  ionised  in  pyridine  or 
amyl  alcohol. 

Organo-Derivatives  of  Bismuth.  Part 
VII.  :  lodo-  and  Nitro-Derivatives  of  Tri- 
phenyJbismiithine,  by  J.  V.  Wilkinson  and 
F.  Challenger. 

Interactions  between  tiiplienylbisiuuthiue 
and  iodine  and  cyanogen  haloids  have  been 
further  investigated.  It  has  been  shown 
that  triphenylbismuthine  di-iodide,  (CgH5)3- 
Bilj,  exists  nt  low  temperatures,  but  im- 
mediately decomposes  in  ethereal  solution 
at  room  temperature.  At  ordinary  tem- 
peratures, triphenylbismuthine  and  iodine 
yield  diphenyliodobismuthine  and  phenyl- 
di-iodobisiuuthine  in  varying  proportions. 
Additive  compounds  of  triphenylbismuthine 
and  cyanogen  haloids  were  not  formed,  the 
products  being  diphenylehloro-bismuthine, 
diphenylbromo-bismuthine,  and  benzoni- 
trile  with  cyanogen  chloride  and  bromide 
respectively,  whilst  cyanogen  iodide  yielded 
diphenylcyanobismuthine  and  iodobenzene. 
Cyanogen  iodide  reacts  readily  in  dry  ether 
with  the  triphenyl-derivatives  of  phos- 
phorus, arsenic,  and  antimony,  forming  pri- 
marily the  i(xlocyanides,  which  immediately 
decompose  with  traces  of  moisture,  jdeld- 
ing  hydrogen  cyanide  and  the  oxide  (of  tri- 
phenylphosphine) and  hydroxyiodides  (of 
the  triphenyl-derivatives  of  arsenic  and  an- 
timony) respectively.  Attempts  to  nitrate 
triarylhismuthines,  with  the  object  of  de- 
termining the  directing  influence  of  the  bis- 
muth atom  towards  suhstituents,  have 
failed,  benzoyl  nitrate  giving  only  the  re- 
spective bismuthine  dinitrates,    whilst  acid 


DECEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


411 


reageuts  completely  disrupt  the  molecule 
with  the  production  of  ?/i-dinitrobeiizene. 
Derivatives  of  quinquevalent  bismuth, 
however,  are  readily  nitrated,  giving  more 
or  less  stable  meta-nitro-triiphenylbismu- 
thine  dinitrates,  which  yield  crystalline  di- 
haloids.  Of  these  compounds,  the  tetra- 
nitrated  derivatives  appear  the  most  stable. 
The  diehloride  yields  the  corresponding  di- 
hydroxide,  a  stable  compound  of  a  t3pc 
which  hitherto  has  not  been  prepared : 
treatment  of  this  with  hot  alcohol  furnishes 
a  trinitrotriphenylbismuthiDe. 


THE  ROYAL  INSTITUTION  OF  GREAT 
BRITAIN. 

The  subsequent  Christmas  Juvenile  Lec- 
tures arranged  by  the  lioyal  Institution,  on- 
titled  Concerning  the  Nature  of  Things,  by 
Sir  William  Bragg,  are  as  follows:  — 

II. — Saturday,  Dec.  29:  The  Xalure  of 
Gases. 

III.— Tuesday,  Jan.  1 :  The  Nature  of 
Liquids. 

IV.— Thursday,  Jan.  3:  The  Nature  of 
Crystals  :   Diamond. 

V. — Saturday,  Jan.  5 :  The  Nature  of 
Crystals  :  Ice  and  Snow. 

VL— Tuesday,  Jan.  8:  The  Nature  of 
Crystals :  Metals. 

Lecture  hour:  3  o'clock. 


THE  INSTITUTION  OF  ELECTHICAF 
ENGINEERS. 
The  Wireless  Section  will  hold  a  meeting 
on  Wednesday,  January  2,  at  6  p.m.  when 
a  paipor  entitled  Some  Experiments  on  the 
Screening  of  Radio  Receiving  Apparatus 
will  l>o  read  by  II.  H.  Barpikld.  M.Sc. 
student. 


THE    ROYAL    AORICULTT'KAL 
SOCIETY    OF    ENGLAND. 

Th(^  nroceenings  at  the  Monthly  Couneil. 
on  Wednesdav,  December  12  (T. lent. -Col. 
E.  W.  Slanyforth,  President,  in  the  chair), 
included,  amonfr  other  matters,  the  presen- 
tation of  the  followinpj  report  of  th<>  Cheini- 
cal  Conunittoe :  — 

CnFMICM  . 

Mr.  J.  L.  Tiii(Minji;ton  (Chnirmnn)  re- 
ported that  Dr.  Voolcker  had  presented  the 


list  of  samples  analysed  by  him  during  the 
month  of  November.  The  Annual  Report 
of  the  Consulting  Chemist  had  been  con- 
sidered by  the  Committee  and  passed  for 
publication  in  the  next  volume  of  the  Jour- 
ral.  The  Chairman  had  reported  that  he 
had  attended  and  given  evidence  before  the 
Departmental  Committee  o~a  the  Fertilisers 
and  Feeding  Stuffs  Act.  Dr.  Voelcker  had 
leported  on  sG\eral  matters  arising  out  of 
his  correspondence.  l"hese  dealt  with  in- 
ferior cotton  cake,  basic  slag  which  was 
adulterated  with  ground  phosphate,  and 
African  phosphate  which  was  insufficiently 
ground  and  consequently  practically  use- 
less. The  Leaflet  giving  particulars  of  the 
cases  reported  at  the  November  meeting  of 
the  Committee  had  been  circulated  to  all 
the  Governors  and  Members  with  the  re- 
(port  of  the  Council  to  the  annual  general 
meeting. 

The  Committee  estimated  that  for  the 
ensuing  year  their  expenditure  would 
amount  to  £400,  plus  the  amount  of  the 
Fiaboratory  petty  cash. 

The  Committee  had  met  eight  times  and 
had  made  eight  reports  during  the  year. 


ELECTROLYTIC  PRODUCTION  OF 
ACTIVE  HYDROGEN. 

By  Y.  Venkatakamaiah  and  Bh.  S.  V. 
Raohava  Rao. 

[From  the  "Journal  of  the  Science  Asso- 
ciation, Maharajah's  College, 
Vizianagaram.] 

Attempts  at  the  preparation  of  "active 
hydrogen" — 

(i)  by  the  electrolysis  of  solutions  of 
electeoly  tes ; 

(ii)  by  the  action  of  acids  on  metals,  by 
Y.  Venkataramaiah  (Proc.  Sci.  Assoc, 
Maharajah's  College,  Vizianagaram,  July 
10,  1921,  p.  2),  Wendt  and  Landauer  (J.  A. 
C.  S.,  Vol.  XLIV.,  No.  3,  p.  ol3),  ended  in 
a  failure.  Wendt  and  Landnuor  describe 
reasons  for  their  failure  thus  : 

"We  are  here  between  two  experimental 
(lirticulties.  The  hydrogen  must  be 
evolved  so  rapidly  that  it  roaches  the  sul- 
phur within  a  minute,  to  avoid  the  decom- 
pf>sition  of  the  active  form  into  the  ordi- 
n.'iry.  On  the  other  hand  if  ovoliilion  is 
made  rapid,  tiie  gas  carries  with  it  large 
amounts  of  spray  which  are  practically  im 


412 


possible  to  remove  without  slowing  up  the 
stream  of  gas  more  than  can  be  allow^ed.  .  . 
Hence  the  sulphur  may  well  have  become 
coated  with  a  film  of  moisture  which  pre- 
vented the  access  of  the  active  hydrogen." 

The  authors  have  now  repeated  the  ex- 
periments, using  a  slightly  different  experi- 
mental technique  from  that  of  the  Ameri- 
can chemists,  and  found  the  possibility  to 
demonstrate  the  presence  of  active  hydro- 
gen in  electrolysis.  Wendt  and  Landauer 
have  shown  (J.  A.  C.  S.,  Vol.  XLII.,  No. 
p.  937),  that  nitrogen  combines  directly 
with  active  hydrogen  to  form  ammonia. 
Taking  advantage  of  this  fact,  the  authors 
set  up  an  electrolytic  cell  with  platinum 
electrodes,  one  of  the  electrodes  being  a 
small  platinum  tube  .of  length  30  mm.  and 
of  internal  diameter  1.0  mm.  and  external 
diameter  1.5  mm.  It  is  perforated  with  a 
number  of  pin-holes.  A  current  of  3  to  15 
amperes  is  employed  to  electrolyse  a  dilute 
solution  of  sulphuric  acid.  During  the 
course  of  electrolysis  a  current  of  pure  ni- 
trogen is  sent  through  the  perfwated  elec- 
trode into  the  solution.  The  nitrogen'  com- 
bines with  the  active  hydrogen  liberated 
during  the  course  of  the  electrolysis  to  forin 
ammonia,  and  the  ammonia  is  fixed  as  am- 
monium sulphate.  After  a  run  of  about  12 
hours  the  electrolytic  liquid,  on  treatment 
with  alkali,  gives  unmistakable  tests  for 
the  presence  of  ammonia.  Similar  is  the 
case  with  caustic  potash  solution. 

To  confirm  the  results  obtained  above,  a 
second  series  of  experiments  is  undertaken, 
in  which  the  permeabilit  yof  iron  to  nascent 
hydrogen  at  ordinary  temperatures  is  uti- 
lised. For  this  purpose  an  fron  tube  30 
cms.  long  and  12  mm.  diameter,  closed  at 
one  end,  is  fixed  in  a  tube  provided  with  a 
nickel  electrode  and  containing  water  acidu- 
lated with  sulphuric  acid.  The  iron  tube  is 
connected  to  a  glass  bulb  containing  cold 
powdered  sulphur,  which  in  its  turn  is  con- 
nected to  a  small  glass  bulb  packed  witTi 
glasswool.  This  again  is  connected  to  a 
small  glass  bulb  containing  a  lead-acetate 
paper  kept  moist  by  dipping  in  a  solution  of 
the  acetate.  This  bulb  is  finally  connected 
to  a  rotating  exhaustion  pump.  During 
electrolysis  the  iron  tube  is  made  the  anode 
and  the  pump  is  keipt  running.  Atomic  hy- 
drogen which  diffuses  through  the  iron  tube 
yields  a  little  triatomic  hydrogen.  This 
combines  with  sulphur  to  form  hydrogen - 
sulphide  as  indicated  by  the  blackening  of 
lead  acetate  paper  in  a  few  hours. 


tflfi  CHEMICAL  NEWS. 


DECEMBEK  28,  1923 


In  this  connection  the  authors  propose 
the  following  simple  device  for  lecture  de- 
monstrations, to  show  the  production  of 
triatomic  hydroge  nduring  electrolysis.  A 
long  glass  tube,  about  150  cms.  long,  pro- 
vided with  a  small  iron  cup  at  one  of  the 
ends,  is  filled  with  mercury  and  inverted 
over  a  trough  of  mercury.  About  1  cc.  of 
pure  nitrogen  is  then  sent  into  the  Torrece- 
liau  vacuum.  Acidulated  water  is  next 
poured  into  the  cup  and  the  water  electro- 
lysed, making  the  cup  the  anode.  After  a 
time  a  few  cl's.  of  Nessler's  reagent  intro- 
duced into  the  vacuum  show  a  distinct 
brown  colouration  indicating  the  presence 
of  ammonia  in  the  tube. 

Preliminary  experiments  conducted  show 
that  the  failure  in  the  experiments  of  Wendt 
and  Landauer  is  to  be  ascribed  not  only  to 
the  protective  coating  that  the  spray  forms 
on  sulphur,  but  also  to  its  distinct  chemical 
action  on  active  hydrogen  with  the  forma- 
tion, of  hydrogen  peroxide  and  molecular 
hydr<^en.  The  reaction  may  be  repre- 
sented thus :  — 

2  H3  +  2  H^O  =  H,0,  +  4  H,. 

Research  J joh oratories, 

H.H.  ^lic  Maharajah's  College, 
Vb:mnagarar)i. 


C0HHE8P0NDENCE. 


OOSMISM. 

To  the  Editors  of  The  Chemical  News. 

Sirs, — Mathematico-physicists  as  a  body, 
rather  than  the  individual  as  thinking  unit, 
have  decided  that  the  fourth  dimension  of 
space  is  a  legitimate  conception,  and  that 
the  space-time  velocity  of  light  is  the  only 
rigid  constant.  Nevertheless,  time  is  sim- 
ply a  ratio  of  macrooosmic  and  microcosmic 
inertia;  so  that  space  is  timeless  and 
Euclidean,  and  no  ethereal  substance  exists 
other  than  the  unit  of  inertia  which  is  the 
atomic  constant  of  both  matter  and  energy. 

The  shape  of  nuclear  atoms,  having  a 
Proutian  unit  half  that  of  hydrogen,  M'as 
published  in  1897^  contemporaneously  with 
the  orthodox  electrical  theory  of  matter  and 
the  quantum  theory.  A  definite  relation- 
ship between  such  shape  and  the  combining 
capacity  of  carbon  nitrogen  and  oxygen  un- 
oxpoctedly  emerged,  and  was  published  in 
1900-  and  a^ain  in  1913''. 


DECEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


418 


Torricelli  weighed  the  atmosphere  and 
Boyle  measured  its  elasticity;  but  such 
materialistic  results  wore  rt-jected  for  forty 
years.  The  ether  likewise  can  be  weighed, 
its  elasticity  measured,  and  its  electrons 
countefl.  When  Sir  Ernest  Rutherford 
shattered  the  atomic  nucleus  of  nitrogen, 
the  real  subatomic  unit  should  have  been 
revealed.  It  had  tsj'l  times  the  velocity  *or 
hydrogen,  corresponding  to  a  mass  unit  «.  f 
one-half,  l)ut  a  cruciiil  experiment  is 
awaiV'd  to  settle  this  problem.  Likewise, 
positive  ray  parabolas  with  half  the  normal 
energy  of  hydrogen  were  obtained  in  191'.>. 
I)ut  unwarranted  assumptions  bolster  up 
the  electrical  theory  of  matter. 

The  identity  of  ordinary  mechanical 
mass  and  electrical  mass  is  responsible  for 
much  confusion  of  thought,  but  an  atomic 
ether  solves  the  problem. 

The  ether  is  a  perfect  atomic  fluid,  in 
which  the  structural  loss  of  an  atom  fcrnis 
th<'  Osborne-Reynolds  electron,  wiiich  cau 
be  intermolecular  only.  .\tomic  nundiers 
represent  potential  electrons  formed  endo- 
thermically  from  kinetic  electrons  by  sub- 
atomic aggregation  at  stellar  t<'mperature. 
Planetary  gravitational  vortices  are  immut- 
able and  indestructible  in  such  perfect  fluid. 
A  positive  ether  ipressuic  (0.5  x  10'*)  de- 
duced from  c-  =  ])  (I  and  H'  =  D/(/,  where 
c  =  3  X  10'",  while  R  =  2.46  the  refractive 
index,  and  D  =  3.5  the  density  of  diamond, 
but  such  should  be  determined  at  zero,  car- 
ries thi"  ui'gative  quanta'  dynamics  of  elec- 
tron propagation  through    the  ether    struc- 


ture by  a  virtual  l<Migitudinal  pulse,  pro- 
ducing the  concentrated  photo-electric  or 
[)hoto-chenjical  effect  as  a  molecular  pheno- 
mena. The  pressure,  p,  oiperates  the  in- 
verse Osborne-Reynolds  electron  repulsion, 
or  total  inductive  capacity,  usually  denoted 
by  K,  while  the  magnetic  permeability,  u, 
is  identical  with  the  density,  d. 

The  molecular-heat  equation  published 
in  1920''  is  unintelligible  to  a  physicist  ac- 
customed to  an  electrical  atom.  The  simple 
foi-m  of  that  equa/*^'.on  is 

fc  =  r»    log  T  (1) 

where  h  and  x  are  constants  for  any  given 
element  or  compound  at  constant  volume. 
The  single  dependent  variable,  m,  repre- 
senting the  physical  and  chemical  associa- 
tion, which  is  the  number  of  atoms  or 
radicles  per  molecule,  dissipates  all  the 
mystery  associated  with  chemical  force,  as 
an  aspect  of  entropic  force,  by  showing 
that  the  number  of  atoms  or  radicles  per 
molecule  varies  as  a  simple  inverse  func- 
tion of  the  temperature,  and  that  there  is  a 
positive  entropic  force  producing  condensa- 
tion, crystallisation,  or  solidification,  on 
the  one  hand ;  and  a  negative  entropic  force 
pnxlucing  temperature  (and  expansion)  on 
the  other. 

With  mixtures  of  chemical  elements 
whose  combining  capacity  is  a  function  of 
atomic  shape,  catastrophic  ejection  of  elec- 
trons is  liable  to  occur  con-esponding  to  the 
change  of  state  whenever  the  temperature 
appioaches  the  specific  value  relative  to  anv 


-5-95 


Vfl'S    4  t 


414 


THE  CHEMICAL  NEWS. 


DECEMBER  28,  1923. 


integral  value  of  m ;  but  the  association  m 
is  a  purely  physical  or  bulk  effect,  and  not 
a  chemical  attraction  within  the  field  of  the 
atom. 

The  agreement  of  equation  (1)  with  the 
Nernst  specific  heat  curves  (obtained  by  in- 
serting the  freedom  equation  of  711,  whose 
graiph  is  given  on  the  left  of  Fig.  1)  proves 
that  temperature  is  due  to  molecular  vibra- 
tion only,  and  that  atomic  motion  at  low 
temperature  is  not  heat.  Therefore  a 
kinetic  "Stokes"  ether  of  Proutian  sub- 
atoms,  even  with  an  intrinsic  pressure 
greater  than  that  of  solids,  to  carry  the  in- 
finitely large  negative  stresses  of  gravita- 
tion, or  the  infinitesimal  light-quanta,  is 
frictionless.  It  follows  that  stresses  in  the 
rigid  subatom  are  not  heat,  notwithstand- 
ing Lord  Kelvin's  dictum. 

One  dyne  per  square  centimetre  is  a  posi- 
tive or  negative  ethereal  pressure  of  300 
volts.  The  intrinsic  pressure  of  all  solids  at 
the  absolute  zero  is  equal  to  the  ethereal 
pressure  of  eighty-billion  tons  per  square 
inch.  ' 

Will  chemistry,  and  especially  photo- 
chemistry,^ indefinitely  accept  Bohr's  phy- 
sical interpretation  for  fact  when  chemical 
forces  with  physical  expansion  and  contrac- 
tion are  proved  by  equation  (1)  to  be  the  en- 
tropic  pressures  of  the  ether?  Van't  Hoff 
took  the  work  obtainable  in  the  evapora- 
tion of  unit  mass  as  a  measure  of  the  chemi- 
cal affinity,  which  is  thus  a  function  solely 
of  volume,  temperature,  and  atomic  mass. 

At  higher  temperatures  increasing  elec- 
trons separate  the  concomitant  molecules 
and  produce  a  negative  ethereal  pressure,  or 
voltage,  or  vapour  pressure,  w^hich  reduces 
the  intrinsic  pressure  with  its  molecular 
surface-tension  until,  at  a  specific  ternpera- 
ture,  the  intrinsic  pressure  becomes  identi- 
cal with  the  vapour  pressure,  so  that  the 
molecular  surface-tension  is  zero. 

Yours,  kc, 

Fred  G.  Edwards. 

171,  Roundivay, 

Waltheof  Gardens,  N.ll. 

November  17,  1917. 


References  to  avithor's  publications:  — 

1  S-pefn.  of  Letters  Patent  No.  1999,  a.d. 

1897. 

2  Chemistry,  J.  and  A.  Chxirchdl,  1900. 
^  Eng.  Mech.,  July  18,  1913  (iUus.). 

*  Enqinecring,  Nov.  24,  1916  (illus.). 

•'  Chem..  News,  CXX.,  277,  June  11,  1920. 

«  Chem.  Neivs,  CXX.,  292,  Ju7ic  18,  1920. 


NOTICES  OF  BOOKS. 
Tho  Principle  of  Relativity  :    A  Collec- 
tion of  Original    Memoirs  on  the    Special 
and  General  Theory  of  Kelativity,    by  H. 
A.  LoKENTZ,  A.  Einstein,  H.  Minkowski 
and  H.  Weyl,  with  a  note  by  A.  Sommer- 
feld;  being  translated  from  the  German 
by  W.  Perhett  and  G.  B.  Jeffery.     Pp. 
Vlll.  +  216.     1923.     Mes.-^rs.  Methuen  & 
Co.,     J.td.,     36,     Essex   Street,     London, 
W.C.2.     12s.  6d.  net. 
Science  advances  by  means    of  two   main 
conveyances,  viz.  :     the    pantechnicon    van 
with  a  driving  mechanism  of  a  highly  com- 
plex type,  and  the  plain  horse  and  cart  that 
requires  no  very  special  skill  to  nianiipulate. 
This  book    shows  the    development    of  the 
former  method,  and  it  is  of  necessity  highly 
mathematical.     The  pantecbnicon  affords  a 
more  elegant  means  of  transportation,  ^  l;ut 
it  d(«?s  not  necessarily  hide    worn-out  pieces 
of  furniture.    The  similes  are  poor,  but  they 
will  have  to  suffice. 

The  readers  of  these  foundation  papers, 
for  the  most  part  put  into  English  from  the 
German  by  the  labours  of  G.  B.  Jeffery  and 
W.  Perrett,  will,  of  course,  bear  in  mind  that 
some  developments  have  been  made  in  the 
science  of  relativity  since  these  papers  were 
written;  and,  as  a  result,  here  and  there  the 
views  expressed  require  readjustment. 

Notwithstanding,  all  who  are  able  to  delve 
in  this  highly  mathematical  subject  should 
possess  this  work  and  study  the  original 
methods  of  exposition. 

To  the  average  student  of  physics  niany 
statements  appear  which  will  be  appreciated 
if  he  is  seriously  interested  in  the  subject. 
Relativity  needs  no  introduction,  so  we  have 
contented  ourselves  with  a  few  selections 
from  the  text,  which  will  no  doubt  be  seized 
upon  as  gems  from  the  classics. 

LoRENTZ,  1895.— In  the  Michelson  experi- 
ment, "  a  shortening  in  the  direction  of 
motion  in  the  proportion  of  1  to  v^l — y^jc^, 
in  accordance  with  the  formulae  given  in  the 
above-mentioned  paragraph. ' ' — p. 7. 

Einstein,  1905. — "  So  we  see  that  we 
cannot  attach  any  absolute  signification  to 
the  concept  of  simultaneity,  but  that  two 
events  which,  viewed  from  a  system  of  co- 
ordinates, are  simultaneous,  can  no  longer 
be  looked  upon  as  simultaneous  events  when 
envisao^ed  from  a  system  which  is  in  motion 
relatively  to  that  system." — p.  42. 

Einstein.  1905.—"  The  laws  by  which 
the  states  of  physical  systems  alter  are  in- 
dependent of  the  alternative,  to  which  of  two 
systems  of  co-ordinates,  in  uniform  motion 


DECEMBER  28,  1923. 


THE  CHEMICAL  NEWS. 


415 


of  parallel  translation  relatively  to  each 
other,  these  alterations  of  state  are  referred 
{princiiile  of  relativity)." — p.  69.  We  tliiuk 
that  this  sentence  is  not  crystal  clear,  as  H. 
G.  Wells  would  doubtless  express  it. 

"  The  kinetic  energy  of  the  body  with 
respect  to  the  [other  bodies]  £,  »/,  ^, 
diminishes  as  a  result  of  the  emission  of 
light,  and  the  amount  of  diminution  is  in- 
dependent of  the  proiperties    of  the    body." 

1  L 
Moreover,  the  difference  K„ — K^  = v-. 

2  c' 
"From  this  equation  it  directly  follows  that : 
//  a  body  (jives  off  the  energy  L  in  the  form 
of  radiation,    its  mass  diminishes  by    L  c". 
The  fact  that    the  energy    withdrawn    from 
the  body  becomes  energy    of  radiation  evi 
dently  makes  no  differenci-,    so  that  we  an 
led  to  the  more  general  conclusion  that  th 
mass  of  a  body    is  a  measure  of  its    energ\ 
content;    if  the  energy  changes    by  L,    the 
mass    changes      in    the    same    sense     by 
L/9xl0-'',    the  energy    being   measured    in 
ergs,  and  the  mass  in  grammes. 

"It  is  not  impossible  thafc  with  bodies 
whose  energy  content  is  variable  to  a  high 
degree  (e.g.,  with  radium  salts)  the  theory- 
may  be  successfully  put  U}  the  test  [see 
Richardson's  statement  given  in  The  Che  mi 
cat  News,  lOlo,  Vol.  CXII..  page  261]  .—p. 
71. 

"  If  the  theory  corresponds  to  the  faefs, 
radiation  conveys  inertia  l)etweeil  the  eniil- 
ting  and  absorbing  bodies." 

Minkowski,  19()8. — This  paper  contains 
in  its  opening  paragrij([)h  the  famous  statt'- 
ment  about  time  and  space,  which  we  have 
italicised  :  "  The  views  of  space  and  time 
which  I  wish  to  lay  before  you  have  8i>ruiig 
from  the  soil  of  experimental  phygics,  and 
therein  lies  their  strenglli.  They  are  raili- 
cal.  Henceforth  spare  by  itself,  and  livir 
by  itself,  arc  doomed  to  fn<lr  away  \nt*>  mere 
shadows,  and  only  a  kind  of  union  of  the  two 
will  preserve  an  independent  reaUty." — ^p. 
75. 

"  I  will  state  at  once  what  is  the  value 
of  c  with  which  .we  shall  finally  be  dealiufT. 
It  is  the  velocity  of  the  ipropngation  of  li<,'ht 
in  empty  space.  To  avoid  speaking  either  of 
space  or  its  emptiness,  we  may  define  this 
magnitude  in  another  way,  as  the  ratio  (sf 
the  electromagnetic  to  the  electrostatic  unit 
of  electricity." — p.  79.  Following  Minkow- 
ski's paper  are  Notes  thereon  by  A.  Som- 
merfeld. 

Einstein,  1911. — "  One  result  yielded 
by  the  theory  of  relativity  is  that  the  inertia 


mass  of  a  body  increases  witH  the  energy  it 
contains;  if  this  increase  of  energy  amounts 
to  E,  the  increase  iu  inertia  uuiss  is  equal  to 
E/  C-,  when  c  denotes  the  velocity  of  light. 
Now,  is  there  an  increase  of  gravitating 
mass  corresponding  to  this  increase  of  in- 
ertia mass?  If  not,  then  a  body  would  iall 
iu  the  same  gravitational  field  with  varying 
acceleration  according  to  the  energy  it  con- 
tained. That  highly  satisfactory  result  of 
the  theory  of  relativity  by  which  the  law  of 
the  conservation  of  mass  is  merged  in  the 
law  of  the  conservation  of  energy  could  not 
be  maintained,  because  it  would  compel  us 
to  abandon  the  law  of  the  conservation  of 
mass  in  its  old  form  for  inertia  mass,  and 
maintain  it  for  gravitational  mass. 

But  this  must  be  regarded  as  very  im- 
probable. On  the  other  hand,  the  usual 
theory  of  relativity  does  not  provide  us  with 
any  argument  from  which  to  infer  that  the 
weight  of  a  body  depends  on  the  energy  con- 
tained in  it.  But  we  shall  show  that  our 
hviiwthesis  of  the  equivalence  of  the  sjs- 
tems  K  and  K'  gives  us  gravitation  of  energy 
as  a  necessary  consequence." — p.  101. 

Einstein,  1917. — **  The  opinion  I  enter- 
tained until  recently,  as  to  the  limiting  con- 
ditions to  be  laid  down  in  spatial  infinity, 
took  its  stand  on  the  following  considera- 
tions. In  a  consistent  theory  of  relativity 
there  can  l)e  no  inertia  relatively  to  'space,' 
but  only  inertia  of  masses  relative  to  one  an- 
other. If,  therefore,  I  have  a  mass  a  sufli- 
cient  distance  from  all  other  masses  in  the 
universe,  its  inertia  must  fall  to  zero.  W^e 
will  try  to  formulate  this  condition  mathe- 
matically."— p.  180. 

Wkvl.  1918. — "  According  to  .Einstein 
the  phenomena  of  gravitation  must  also  be 
placed  to  the  account  of  geometry,  and  the 
laws  by  which  matter  affects  measurements 
are  no  other  than  the  laws  of  gravitation." 
—p.  202. 

The  reviewer  wrote  in  1894,  as  a  note 
a<;ainst  a  paragraph  on  moCion  iu  a  book 
published  the  same  year,  the  following:  — 
"Knowledge  is  fundamentally  relative; 
even  our  knowledge  of  physical  facts  and, 
moreover,  finite  deductions  can  be  made 
when  using  infinite  postulates,  and  here 
again  we  find  the  principle  of  relativeness. 
We  cannot  get  away  from  it,  nor  should  we 
attempt  to."  It  will  be  seen  from  a  study 
of  this  book  how  vague  ideas,  such  as  this 
example  illustrates,  have  been  crystallised 
into  harmonious  form  by  a  powerful  mathe- 
matical treatment. 
In  conchision,  the  publishers    are    to    be 


416 


THE  CHEMICAL  NEWS. 


DECEMBER  28,  1923. 


oongratulated  on  the  enterprise  showTi  in 
placing  before  relativity  students  suoh  a 
monumental  work. 


Jacob  Green,  1790'1841,    Chemist,    by 

E.  F.  Smith.     Pp.  34.     1923. 

Jacob  Green  was  a  quiet,  persevering, 
and  enthusiastic  American  scientist,  whose 
retiring  nature  prevented  his  name  from 
being  as  well  known  as  his  attainments  jus- 
tified. 

Prof.  Smith,  of  the  University  of  Penn- 
eylvania,  has  now  published  a  little  bio- 
graphical sketch  of  Green,  which  should  be 
an  insipiration  to  the  young  chemists  of  to- 
day. 


The  British  Journal  Photographic  Al- 
manac, 1924,  Edited  by  George  E. 
Brown,  F.I.C.  Pp.  812.  London: 
Henrv  Greenwood  &  Co.,  Ltd.,  24,  Wel- 
lington Street,  Strand,  W.C.  Paper 
covers,  2s. ;  bound,  3s. 
The  B.J.  Almanac  for  1924  fully  main- 
tains the  high  reputation  established  by  its 
predecessors. 

In  addition  to  the  valuable  and  complete 
data  concerning  the  various  photographic 
processes  and  apparatus,  it  also  includes  a 
very  practical  article  by  the  Editor,  en- 
titled, Using  a  Hand  Camera,  and  an  epi- 
tome of  progress  in  the  subject  during  the 
year. 

This  Epitome  of  Progress  constitutes  a 
valuable  record  of  the  scientific  work  accom- 
plished by  photographers.  Whilst  no  re- 
search of  outstanding  importance  has  ap- 
peared during  the  past  year,  it  is  noteworthy 
that  steady  progress  has  been  maintained 
in  the  solution  of  the  problems  of  (photo- 
graphy, especially  in  regard  to  lenses  and  in 
colour  photography. 

As  a  reference  volume,  the  B.J.  Almanac 
is  replete  with  such  information  as  tables 
(which  have  been  revised)  of  weights  and 
measures,  chemical  and  physical  constants, 
etc.  There  is  also  a  useful  trade  directory. 
Chemists  who  are  also  photographers 
should  find  the  Almanac  indispensable. 


BOOKS  RECEIVED. 

A  Course  of  Laboratory  Experiments  on 
Physico-Chemical  Principles,  by  William 
C.  Bray  and  Wendell  M.  Latimer.  Pp. 
X.  +  120.  1928.  The  MacmiHan  Com- 
pany, New  York,  U.S.A. 

Dangerous  Goods,  by  Dr.  Jules  Aeby. 
Pp.  Xi.  +  319.  2nd  Edition.  1922.  Messrs. 
Crosby,  Lookwood  &  Son,  7,  Stationers* 
Hall  Court,  E.C.4.    30s.  net. 


This  list  is  specially  compiled  for  The  Chemical 
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Agents,  of  5,  Chancery  Lane,  London,  from  whom 
all  information  relating  to  Patents,  Trade  Marks, 
and  Designs  can  be  obtained  gratuitously. 

Latest  Patent  Api^lications. 

29S(X)  Coke,  B.'  E.— Oxidation  of  naphthalene,  etc. 
Nov.  27. 

29801 — Coke,  B.  E. — Oxidation  of  aromatic  hydro- 
carbons.   Nov.  27. 

29972 — Mathieson  Alkali  Works,  Inc.—Manufac- 
tiire  of  hypocblorites.    Nov.  28. 

29737— Stevenson,  W.  ,T. — Manufacture  of  acetyl 
cellulose.    Nov.  26. 

30438  -Atkinson,  R.  G. — Apparatus  for  chemical 
action  under  the  influence  of  light.    Dec.  4. 

3072&-  Guada^ni,  G.— Manufacture  of  acids.  Dec. 
6. 

30.535 — liiclitenthaeler,  F.  E. — Process  of  concen- 
trating aqueous  solutions  of  volatile  sub- 
stances. •  Dec.  4. 

3080.5   -Stokes,   J.  S. — Synthetic  resins.     Dec.   7. 

Specifications   Published   this    Week. 

197632^Naugatuck  Chemical  Co.  —  Processes  for 
vulcanising  rubber  with  condensation  pro- 
ducts of  ammonia  and  aldehydes  as  iic- 
celerators. 

198379— Cliemische  Pabrik  Auf  Actien  vorm.  E. 
Sche ring.— Manuf mature  of  new  barbituric 
acid  con^pounds. 

203683 — ^Soc.  d'Etudes  Chimiques  poiir  ^Industrie. 
— Process  for  the  manufacturing  from  cy- 
anamide  of  manures  containing  t-oluble  or- 
ganic nitrogen. 

207247— Gardner,  D.,  and  Taverner,  L.— Extrac- 
tion oif  iron  and  of  titanium  compoundvS 
from  titanium  ores. 

207267 — Paterson,  W.— Apparatus  for  treating 
liquidvS  with  chemical   reagents. 

199743 — Guilleminot,  P.  L. — ^Sulphonation  of  fntty 
substances  of  animal  origin. 

207476— Soc  of  Chemical  Industry  in  Basle.— 
Manufacture  of  vat  dyestuffs  derived  from 
anthraquinone. 

Abstract  Published  this   Week. 

205563— Aluminium  chloride,  alumina. — Chemische 
Fabrik  Griesheim-lOlektron,  of  51,  Gut- 
leutstrasse,  Prankfort-on-Main,  Germany. 
Aluminium  chloride;  alumina. — An  aluminium 
chloride  solution  which  may  be  obtained  by  treat- 
ing calcined  clay  with  hydrochloric  acid  (or  with 
ahiminium  chloride  solution  enriched  with  hydro- 
chloric acid)  is  evaporated  to  produce  a  crystal 
sludge  from  which  mother  liquor  is  separated. 
The  crystals  are  washed  with  h.ydrochloric  acid 
or  first  with  some  of  the  original  solution,  and 
then  with  pure  hydrochloric  acid  (for  instance  of 
20  i)er  cent,  strength),  the  mother  liquor  and 
washings  l>eing  used  to  absorb  hydrochloric  acid 
arising  from  the  calcination  of  the  crystals  to 
n])tain  alumina  (when  such  calcination  is  effected) 
or  from  other  sources,  and  used  according  to 
their  content  of  iron  either  for  washing  the  crys- 
tals or  for  treating  more  clay.  When  the  solu- 
tions accumulate  too  much  iron  they  are  evapora- 
ted and  calcined  to  produce  hydrochloric  acid. 

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FEBRUARY  1,  1924.     Index. — Supplement  to  the  Chemical  News. 


9/7 


119 


INDEX. 


ACID,     Acetic.   Consamption 
in  British   Malaya,  188. 
Chloroselenic,   and    selenium 

trioxide,   270. 
Perch romio,   81. 
Propyl-stannonio,  306. 
Acids,  Fatty,  Alteration  in  the 
heats   of    crystallisation   of 
normal,  379. 
Glutacouic,     Chemistry       of, 

270. 
Muconic  and      hydromuconic, 
302. 
AKricnItural         results,        The 

world's,    299. 
Aircraft    apprentices     for      the 

Royal   Air   I'oroe,  156. 
Algeria  mining  concessions  for 
sale,    254. 
^-Ali/.arin,  379. 
Allmand.     A.     J.,     and     A.  N. 
Campbell,      The     electrode- 
position  of  manganese,  312. 
Allmand,   A.   J.,   and  H.   J.   T. 
Ellingham.         (See     Elling- 
ham,   H.   J.   T.) 
Alloys,        Cathodic     behaviour, 

313. 
AInminium,  copper,  magne- 
sium and  magnpsium  sili- 
fide.  Constitution  and  age- 
hardening  of  the  quater- 
nary allovH  of,  189. 
crystals.    Hardness    tests   on, 

190. 
Dilatometric     study     of     the 
transformations     and   ther- 
mal treatment    of  light  al- 
loys of,  191. 
Aluminium     chloride,        Anhy- 
drous, 246. 
Alumosilicates.   186. 
American   dye   production.    169. 


4'  Amino  1  phenyl  5  methyl- 
benzothiazole  and  its  bro- 
mination  in  glacial  acetic 
acid.  385. 

Ammonia  tubes,  Metal  for  syn- 
thetic, 231. 

Analysis,  Qualitative  and 
quantitative,  X-ray  spec- 
troscopy as  a  means  of,  65. 

.\nderson,  Leonard,  Effect  of 
sucrose  on  the  rate  of  co- 
agulation of  a  colloid  by  an 
electrolyte,  328. 
InvestiKation  of  Smoluchow- 
ski's  e<iuation  as  applied  to 
the  coagulation  of  gold  hy- 
drosol,  316. 

Andrade,  E.  N.  da  C.  "The 
Structure  of  the  Atom" 
{Review),    142. 

Andrew,  R.  L.,  Colorimetrio 
estimation  of  lead  in  cream 
of  tartar,  393. 

Andrews,  E.  R.,  J.  H.  Coste 
and  W.  E.  F.  Powney.  {See 
Coste,  J.  U.) 

An^lo-8wiss  trade  in  1922,    349. 

Animals  and  plants,  Symbio- 
sis in,   197. 

Anodic  prooeeeee,  Influence  of 
obstructive  films  on.  380. 

Apparatus  for  rapid  analysis 
and  regulation  of  viscous 
substances,    228. 

Appleton.  E.  V.,  and  P.  S. 
Thompson,  Periodic  trigger 
reception,  346. 

Arenicola,  Blood  pigment  of, 
300. 

.Argentina,  Exhibition  of  edu- 
cational materials,  409. 

Arkansas,  Diamond  -  bearing 
peridotite   in    Pike   County. 


Armstrong,  £.  F.,  Enzymes, 
185. 

Arsenic,  Organic  compounds 
of,  70,  82.  113. 

Asbestos  production,  Canadian, 
235. 

Association  of  British  Chemi- 
cal Manufacturers,  Annual 
meeting,  55. 

Astbury,  Fred  W.,  Does  Can- 
ada prefer   France?  271. 

Atom,  Structure  of  the,  21. 

Atoms,  Structure  of,  and  their 
magnetic  properties,  183. 
Volumes  occupied  by  the  so- 
lute, in  certain  metallic 
solutions,  and  their  conse- 
quent hardening  effects, 
313. 

Atomic     nucleus.     Explanation 
of  the     theory  of  the  rota- 
tion of,  18,  241,  2.'>9. 
structure.     High      frequency 
spectra    and  the  tlieory  of, 

weight  of  chlorine   in    Bnrale 
apatite,     Relative    determi- 
nation,  72. 
Australia,     Foreign     trade    of, 
206. 
Oversea  trade  of.  300. 
Sodium   acetate   for,   172. 
Avogadro's    number,     Determi- 
nation from  observations  on 
bacteria,   342. 


B 


AILEY,     Cuthbert.     Smoke 
production     and   the  pot- 


420 


Index. —  Supplement  to  the  Chemical  News. 


FEBRUARY  1,  1924. 


tery  industry,  23. 
Baker,  H.  B.,  and  R.  R.  Le  G. 
Worsley.     (See  Worsley,  R. 
R.  Le  G.) 
Baker,     J.   W.,     C.     K.  Ingold 
and     J.     F.  Thorpe,     Ring- 
ohain  tautomerism,  327. 
Baly,  E.  C.  C,     A     theory     of 
chemical     reaction   and   re- 
activity,  148. 
Barcroft,  J.,   and  H.  Bareroft, 
The  iJlood  pigment  of  areni- 
eola,  300.' 
Barley,  Effect  of  a  direct  elec- 
tric    current  of   very     low 
intensity    on     the    rate    of 
growth  of  the  coleoptile  of, 
6. 
Barr,     G.,       "Recent     Develop- 
ments    in   Atomic  Theory" 
•       {Review),  351. 
Bass,     Lawrence       W.,       "The 
Chemistry  of  the  Inorganic 
Complex    Compounds"   (Be- 
view),  15. 
Bates,     L.  F.,     and    W.     Suck- 
smith.  (See  Sucksmith,  W.) 
Bauer,  Emil,     Electrode  poten- 
tials    in   non-aqueous   solu- 
tions, 3G4. 
Belaiew,  N.  T.,  Genesis  of  the 
Widmanstatten        structure 
in     meteorites     and  terres- 
trial alloys,  333. 
Benrath,     Alfred,       "Physikal- 
ische    Chemie"       {Review), 
191. 
Beraunite  in  Co.  Cork,  Ireland, 

Occurrence  of,  333. 
Beryllium  acetate  and  propion- 
ate,    Crystal  struct]jTe  and 
chemical     constitution     of, 
324. 
Bismuth,        Organo-derivativee 

of,  410. 
Bissett,  C.  C,  and  A.  H.  Mun- 
dey.     {See  Mundey,  A.  H.) 
Blackman,  V.  H.,     A.  T.  Legg 
and  F.  A.  Gregory,  Effect  of 
a  direct  electric  current  of 
very     low  intensity  on   the 
rate     of     growth       of    the 
coleoptile  of  barley,  6. 
Blacktin,  S.  C,  and  F.  G.  Try- 
horn,  (^ee  Tryhorn,  F.  G.) 
Blair,  E.  W.,  and  T.  S.  Wheel- 
er,   "The     Constitution     of 
Matter"   {Review),  46. 
Blaise.  E.  E.,  Synthesis    of  a 
diketones    by  means  of  or- 
gano-zino  derivatives,   48. 
Blood     pigment     of     arenicola, 

300. 
Bloxam,        Charles        Loudon, 
"Chemistry,  Inorganic  and  Or- 
ganic"   {Review),   230. 
Board     of       Trade     Announce- 
ments,    Dyestuffs    Advisory 
Licensing  Committee.  130. 
Dyestuffs        (Import     Regula- 
tion)    Act,     1920.     38,     188, 
253. 
Safeguarding     of     Industrie? 
Act,  133. 
Bohr,     Niels,     The   correspon- 
dence principle,  183. 
Structure  of  the  atom,  21. 
Bohr's  atom  in  relation  to  the 
problem  of  oovalenoy,  39. 


Bolton,     E.  A.,     Cause    of  red 
stains  on  sheet  braes,  173. 
Books,     Reviews,     and    Notices 
of  :— 
"Air,  Discovery  of  the  Nature 
of,  and  of  its  Changes  dur- 
ing Breathing,"  HI. 
"Alcoholic         Fermentation," 

47. 
"Alloys   Resistant     to   Corro- 
sion," 239. 
"Analysis,   Gravimetric,   Sup- 
plementary Notes  on,"  47. 
"Analysis,  Quantitative 

Chemical,      and     Inorganic 
Preparations,"  64. 
"Arsenicals,     Chemical,   Phy- 
sical and  Insecticidal     Pro- 
perties of,"  35. 
"Atom,     The     Structure     of 

the,"  142. 
"Atoms,  The  A.B.C.  of,"  351. 
"Atomic  Structure  and  Spec- 
tral Lines,"  44. 
"Atomic  Theory,     Recent  De- 
velopments  in,"  351. 
"Bacteriology,    Practical,    for 

Chemical  Students,"  128. 
"Bridge's     Modern    Millgear- 

ing,"  192. 
"British        Journal        Photo- 
graphic Almanac,"  416. 
"Canada,       Department       of 
Mines,     Report   of    Investi- 
gations made  by  the  Mines 
Branch,  1921,"  14. 
"Chemical     Industries,     Kel- 
ly's Directorv  of,"  287. 
"Chemistry,     Inorganic     and 

Organic,  '  239. 
"Chemistry,   Organic,"   79. 
"Chemistry,      Organic,     Sys- 
tematic,    366. 
"Chemistry,     Physical,   Prac- 
tical," 286. 
"Chemistry,     Practical,      for 

High  Schools,"  223. 
"The  Chemistrv     Tangle  Un- 
ravelled,"  238. 
"Clouds     and     Smokes,      the 
Properties  of  Disperse  Sys- 
tems in  Gases,"  29. 
Colloids,       "Kolloide    in     der 

Technik,"  399. 
"Corrosion,   Alloys    Resistant 

to,"  239. 
"Crops,       Field,       in     South 

Africa,"  224. 
"Electron     in        Chemistrv," 

383. 
"Electrons,     Electric     Waves 
and   Wireless     Telephonv," 
16. 
"Expert  Witness,"  834. 
"Fermentation,        Alcoholic," 

47. 

"Filtration,    Industrial,"   399. 

"Fuels,  Production  of  Liquid, 

from  Oil  Shale  and  Coal  in 

Australia,"  335. 

"Green,     Jacob,        1790—1841. 

Chemist,"  416. 
"rnorganic     Complex       Com- 
pounds, The  Chemistry  of," 
15. 
"Ivy,   Poison,     Rhus   Derma- 
titis," 207. 
"Journal  of  Scientific  Instru- 
ments," 366. 


"Kelly's  Directory  of  the 
Chemical  Industries,"  287. 
"Landolt-Borustein,  Physi- 
kalisch-Chemische  Tabel- 
^^  len,"  366. 
"Landscape     and      History," 

335. 
"Mathematical  Analysis, 

Practical,"   366. 
"Matter,     Constitution      of," 

46. 
"Matter,        Electricity       and 

Energy,"  159. 
"Millgearing,     Bridge's   Mod- 
ern,"  192. 
Morocco,  "Etude  sur  la  Tan- 
nerie  et  les  Industries  con- 
nexes  au  Maroc,"  96. 
"Uber  Naturprodukte,"  31. 
"Oil  Facts  and  Figures,"  319. 
"Oxygen     Research     Commit- 
tee, Report  of  tlie,"  287. 
"Paper-mnkers'     Directory  of 

all  Nations,"  127. 
"Peat,     Production     of     Air 

driod,"  46. 
"Petroleum         Technolo^st's 
Pocket-Book,     Redwood  and 
Eastlake'fi,"  206. 
"Phase  Rule     and  the  Study 
of     Heterogeneous      Equili- 
bria," 206. 
"Physikalische   (  liemie,"   191. 
"Radio-Activity,  "  272. 
"Redwood       and       Eastlake'= 
Petroleum        Technologist's 
Pooket-Book,"  206. 
"Relativity,      The     Principle 

of,"  414. 
"Rhus      Dermatitis      (Poison 

Ivy),"  207. 
"Thermodynamics     and      the 
Free   Energy     of   Chemical 
Substances,     15. 
"Valence  and     the  Structure 
of  Atoms     and   Molecules," 
397. 
"Ventilation  of  Public  Build- 
ings," 159. 
"Waste   Materials,   Uses  of," 
399. 
Born,   Max,   "The  Constitution 

of   Matter"    {Review^  46. 
Bosman,  G.  J.,  and  H.  D.  Lep- 
pan.      {See  Leppan,   H.   D.) 
Bossoni,  G.,  Notes  on  the  quan- 
tity and  properties  of  char- 
coal obtained  from  various 
kinds     of     Siamese     woods, 
114. 
Boyle,   Robert,   "Ventilation  of 
Public       Buildings"       {Re- 
view),   159. 
Brady,  0.  L.,  and  F.  P.  Dunn, 
Isomerism     of     the  oximes, 
379. 
Bragg,   Sir   William,     and     G. 
T.    Morgan,     Crystal   struc- 
ture  and     chemical    consti- 
tution    of     basic  beryllium 
acetate     and         propionate, 
324.  t 

Braille     and     Servers     of     the 

Blind  League,  175. 
Brass,     Sheet,     Cause     of     red 

stains   on,   173. 
Brinell  hardness  numbers,  173. 
Briquettes,  Pitch  for,  223. 
Britain  her  own  chemist,  289. 


FEBRUARY  1,  1924.         Index. — Supplement  to  the  Chemical  News. 


42i 


British  Quiana,  Eutlase  and 
platinum  from  diamond- 
washings  in,  333. 

British  Malaya,  Consumption 
of  acetio  aoid,  188. 

British  Association,  Presiden- 
tial address,  161,  177,  193. 

British  Cast  Iron  Research  As- 
sociation, 90,  132,  308. 

British  Chemical  and  Dyestu& 
Traders'    Association,   89. 

British  Empire  Exhibition, 
245,  305,  349. 

British  Flour  Millers'  Re- 
search Association,  223. 

British  Industries  Fair,  1924, 
107,  235. 

Britton,  Hubert  T.  S.,  Note  on 
the  estimation  of  chro- 
mium, 393. 

Bromides,  Crystalline,  of  lin- 
seed oil,  392. 

Brose,  Henry  L.,  "Atomic 
Structure  and  Spectral 
Lines"   (Review),  44. 

Browne,  Frank,  Flashing 
point,  221. 

Brownian  movement,  Studies 
in  the,  342. 

Brownlie,  David,  Pulveriaed 
fuel  and  efficic-iit  steam 
generation,  376. 

Brownsdon,  H.  \V..  Brinell 
hardness   numbers,   173. 

Bruce,  Sir  David,  Presentation 
of  the  All^rt  Medal  to.  78. 

Hruttini,  Arturo,  "Uses  of 
Waste  Materials"  (Re- 
view), 399. 

Bucklev.  Harold  E.,  Somo  ano- 
malous optical  pro|(ertie0 
ot  freshly-prepared  mixed 
crvstals  of  the  Seignette 
s:irt*,  3.33. 

Bulgaria,  Creosote  for,  172. 

Bulmann,  Einar.  Oxidation 
and  reduction  jKitentials 
of  organic  compounds.   368. 

Butler.   J.   A.   v..     The   signifi- 
cance of   the     electrode   po- 
tential,  326. 
Studies       in        hetorogeneoiu 
equilibria,  330,  381. 


CAMPBELL,  A.  N.,    and  A. 
J.     Allmand.       (See    All- 
inand,   A.   J.) 
Campbell,    J.     A..     Concerning 
trie     influence     of       atmos- 
pherio  conditions  upon  the 
pnlse  rate  and   oxygen-debt 
after  running,  376. 
Canada  and  France,  271. 
Britisli   catalogues   for,  172. 
Consumption      of      prepared 
non-metallic     minerals     in. 
324. 


Mineral   production     of.     111, 

230,  298. 
Non-ferrous  metals  of,  309. 
Production     of     gypsum     in, 

187. 
Production  of  platinum  group 

metals  in,   187. 
Pulp  and  paper   industry  of, 

155. 
Surgical      instruments       and 
hospital     supplies  for  Van- 
couver, 51. 
Canadian  asbestos     production, 
235. 
National  Exliibition,  62. 
Cancer  campaign,  Empire,  141, 

188.  269. 
Carbon  arc     spectrum     in     the 
extreme    ultra-violet,   341. 
compounds.  Octet  stability  in 
relation   to  orientation   and 
reactivity  in,  41. 
Cartland,     John,     and     A.     H. 
Mundey.     (See  Mundey,  A. 
H.) 
Casmey,  W.  U.,  Address  to  the 
National    Engineers'    Asso- 
ciation, 8. 
Catalytic  action,  Studies  on,  2. 
actions  in  the  system  copper, 
copper-oxide,     oxygen     and 
gaseous  reducing  agent,  185. 
Cathode,       Mercury     dropping. 

Processes  at  the,  363. 
Cathodic   behaviour     of  alloys, 

312. 
Caven,     K.    M.,     "Quantitative 
Chemical   Analysis  and   In- 
organic Preparations"   (Re- 
view), 64. 

Cell.  Peroxide  electric,  78. 

Challenger,  F.,  and  F.  Prit- 
ohard.  Action  of  inorganic 
haloids  on  organo-metallic 
compounds,  41U. 

Challenger,  F.,  and  J.  F.  Wil- 
kinson. (See  Wilkinson, 
J.  F.) 

Charcoal  density  determina- 
tion by  displacement  of 
liquids,  10. 
obtained  from  various  Siam- 
es4>  woods,  Quantity  and 
pioi>ertie8  of,   114. 

Cbatley,  Herbert,  Cohesion, 
311. 

Chatterji,  N.  Q.,  Pan  forma- 
tion in  soils  in  the  light  of 
the  Liesegang  phenomenon, 
84. 

Chemical    Industry   Club,   256. 

Chemical  Society,  125,  221,  232, 
255,  270,  301,  317,  327,  366, 
378,  409. 

Chemical  Society  of  Japan,  26. 

Chemical       industry     of     Jngo 
Slavia.   131. 
reaction   and  reactivity.  The- 
ory of.  148. 
terminologv.      Evolution      cf, 

235.   248.   263. 
What  is  a.  403. 

Chemist     in     relation     to     the 
safeguarding    of  industries, 
126. 
The  right  to  use  the  title.  108. 

Chemi«try,  Arrangements  and 
conditions  for  tlie  award  of 


National     Certificates       in, 
to  students,  116. 
at  the     British     Empire  Ex- 
hibition, 305. 
National   Certificates   in,   318. 
Organic,     Recent     researches 

in,  243,  261,  291. 
What  shall  be  taught  in  high 
schools  and  how  it  shall  be 
correlated       with        college 
chemistry,  347,  360. 

Chevenard,  Pierre,  and  Albert 
M.  Portevin.  {See  Porte- 
vin,   A.   M.) 

Chlorine  in  Bamie  apatito.  Re- 
lative determination  of  the 
atuiuic  weight  of,  72. 

Chromium  estimation,  393. 

Ciliary  movement,  376. 

Clay,  Influence  of  rapid  chill- 
ing on  the  reversible  ex- 
pansion of,  377. 

Clibbens,  D.  A.,  Absorption  of 
methylene  blue  by  cotton, 
186. 

Clinker,  R.  C,  Dynamic  model 
of  a  valve  and  oscillating 
circuit,   346. 

Coal,  Determination     of  niti-o- 
gen  in,  346. 
industry,     Situation     in   the, 

404. 
Sampling  of,  234. 

Cobalt,  111. 

Coe,  H.  I.,  Behaviour  of  metals 
under  compressive  stresses, 
191. 

Cohesion,  311. 

Collins,  Hawks  worth.  Obser- 
vations upon  and  deduc- 
tions from  the  figures  given 
in  the  international  table 
of  isotopes,  52. 

Colloid,  Eneot  of  sucrose  on 
rate  of  coagulation  of,  by 
an  electrolyte,  328. 

Colloidal  solutions.  Method  of 
measuring  the  rate  of,  over 
wide  ranges,  329. 

Colour,  Studies  of  iridescent, 
and  the  structure  produc- 
ing it.  135. 

Compounds,  Organo-metallic, 
Action  of  inorganic  haloids 
on,  410. 

Cook,  F.  C,  and  N.  E.  Molndo, 
"Chemical,  Physical  and 
Insecticidal  Properties  of 
Arsenicals"    [Review).  36. 

Copper,     aluminium,       magne- 
sium    and  magnesium  sili- 
cide,   Constitution   and   age- 
hardening  of     the     quater- 
nary alloys  of,   189. 
copppr-oxide,        oxygen     and 
gaseous        reducing     agent. 
Catalytic     actions     in     the 
system,   185. 
Eflpc'ts  of  impurities  on,   190. 
Isotopes  of,  44. 
wire,   Experiments   with,   189. 

Correspondence   principle,     183. 

Corrosion,     Atmospheric,      374, 
388. 
Atmospheric.     Report   to   the 

Research    Committee,  .'{95. 
Klectro-chemical         character 
of.    189. 

Cosmisra,   412. 


422 


Index. — Supplement  to  the  Chemical  News.      FEBRUAKY  1,  1924. 


Coste,  J.  H.,  E.  R.  Andrews 
and  W.  E.  F.  Powney,  The 
sampling  of  coal,  234. 

Coster,  D.,  High  frequency 
spectra  and  the  theory  of 
atomic  structure,  184. 
X-ray  spectroscopy  as  a 
means  of  qualitative  and 
quantitative  chemical  ana- 
lysis, 65. 

Cotton,     Absorption   of   methy- 
lene blue  by,  186. 
Empire,  and  research,  35. 
wax,   186. 

Couch,  James  F.,  The  evolu- 
tion of  chemical  termino- 
logy,  235,   248j   263. 

Cousen,  A.,  Estimation  of  se- 
lenium in  glass,  284. 

Covalenoy,  Bohr's  atom  in  re- 
lation to  the  problem  of,  39. 

Craven,  E.  C,  and  W.  R.  Or- 
mandy.     (See  Ormandy,  W. 

E.) 

Cray,  F.  M.,  and  W.  E.  Gar- 
ner, Rapid  admixture  iof 
hot  combustible  gases  with 
air,  301. 

Cream  of  tartar.  Lead  in, 
Colorimetric  estimation, 
393.  i 

Creosote  for  Bulgaria,  172. 

Crystals,  Illustration  and  de- 
tection of  inclined  anil 
horizontal  dispersion  in  bi- 
axial,  333. 

Crystallisation  efiect  on  gal- 
vanised iron  sheets,  174.  I 

Cun\ming,  William  M.,  I. 
Vance  Hopper  and  T.  Sher- 
lock Wheeler,  "Systematic 
Organic  Chemistry"  (Re- 
view), 366. 

Cunningham-Craig,  E.  H.  Re- 
cent researches  bearing  on 
the  origin  of  petroleum, 
232. 

Cyanogen  band.  Structure  of 
the  second,  126. 

Czecho  -  Slovakia's  foreign 

trade,  205. 


DAVIDSON,    F.,     Micro-tele- 
scope    and     super-micro- 
scope, 14. 
Daviee,   Edward     C,     Appoint- 
ment, 400. 
Dee,   A.  A.,     Effect,  of  quench- 
ing from  alK)Ve  the  carbide 
transition   temperature   iiji- 
-    on  the  magnetism  of  steel, 
7. 
Deighton,  T.,     The  basal  meta- 
bolism    of  a   growing     pig. 
300. 


Density  and  surface  tension. 
Relation  between,  13. 

Department  of  Overseas  Trade, 
108. 

Descloizite  from  South-West 
Africa,  100. 

Dessaeur,  Friedrich,  Studies 
on  the  physical  foundations 
of  deep  therapy  treat- 
ment, 50. 

DialDetes,   Insulin  and,   157. 

Diamond-bearing  peridotite  in 
Pike  County,  Arkansas,  22. 

Dierfeld,  Gustav  F.,  A  reliable 
apparatus  for  the  rapid 
analysis  and  regulation  of 
iiighly  viscous  substances, 
228. 

a  -Diketones,  Synthesis  by 
means  of  organo-zinc  deri- 
vatives, 48. 

Disacoharides,  Constitution, 

327. 

Disinfectant  fluid  for  South 
Africa,  269. 

Donna n,  F.  G.,     Some    aspects 

.  of  the  physical  chemistry 
of   interfaces,  209. 

Donovan,  W.,  Determination 
of  nitrogen  in  ooal,  346. 

Dorenfeldt,  Margot,  Relative 
determination  of  the  ato- 
mic weight  of  chlorine  in 
Bamle  apatite,   72. 

Downey,  W.  E.,  Relation  be- 
tween the  glow  of  phos- 
phorus and  the  formation 
of  ozone,  409. 

Drilling  system,  Modern  ro- 
tary, 397. 

Druce,  J.  G.  F.,  Propyl-stan- 
nonic  acid,  306. 

Dunn^  F.  P.,  and  O.  L.  Brady. 
{See  Brady,  O.  L.) 

Dunnicliff.  H.  B.,  "Practical 
Chemistry  for  High 

Schools"    (Review),  223. 

D.ve  industry,    Hritisli,  50. 
production,   American,   169. 

Dyes,  Red  sulphide,  350. 
Sulphur,   17. 

Dyestuffs,   British,   222. 
(Import  Regulation)  Act,  309, 

388 
Indigoid,  339,  358,   372. 
Price  of  reparation,  63 

Dynamic  model  of  a  valve  and 
oscillating  circuit,  346. 


EASTLAKE,  Arthur  W., 
"Redwood  and  Eastlakc's 
Petroleum  TechnologistV 
Pocket-Book"  (Review),  206. 
Edwardes,  F.  G.,  Cosmism,  412. 


J^gypt.  Drugs,  chemicals,  etc., 
for,  389. 

Electrical  machinery,  British 
standards  for,  62. 

Electrode,     Mechanism    of    the 
reversible,  362. 
phenomena.    Irreversible,   381. 
potential,       significance       of, 

326. 
potentials     in        non-aqueous 

solutions,  364. 
reactions  and   equilibria,  303. 

Electrodes,  Determination  of 
the  affinity  constants  of 
bases  by  the  hydrogen  and 
quinhydrone,   364. 

Electromotive  equilibrium  and 
polarisation,  382. 

Electrons,  Scattering  of  X  and 
7-rays  by  rings  of,  7. 
Valency  and,  38. 

Electroscope,   A   sensitive,   126. 

Electrovalency,  Studies  of,  270. 

Element  of  zero     atomic  num- 

•      ber.  Is  there  an,  225. 

Elements,  Are  the  natural 
groupings  of,  and  the  spec- 
tral lines  of  hydrogen  re- 
lated? 257,  273,  290,  337, 
355,  369,   386. 

EUingham,  II.  J.  T.,  and  A.  J. 
AUmand,  Irreversible  elec- 
trode phenomena,  381. 

Ellis,  David,  "Practical  Bac- 
teriology for  Chemical  Stu- 
dents" (Review),  128. 

Ellis,  E.  II.,  Dry-rot  disease  of 
timber,  402. 

Eudell,  Kurd,  Casting  process 
for  glasshouse  refractories 
in  German  glass  plants, 
378. 

Engineering,  Use  of  non-fer- 
rous metals  in,  173. 

Ennos,  F.  R.,  and  A.  F.  Halli- 
mond.  (See  Ilallimond,  A. 
F.) 

Enzyme  actions,  Relation  to 
tissue  differentiation  and 
tumour  growth,  185. 

Enzymes,  185. 

Equilibria,  Studies  in  hetero- 
geneous, 330,  381. 

Esters,  Organic,  and  other 
long  chain  <onii>ounds,  X- 
ray   investigation   of,   327. 

Etheridge,  A.  T.,  Volumetric 
estimation  of  vanadium  in 
steel,  234. 

Ethyl  cyanoacetate  and  tauto- 
meric substances  of  the 
keto-cnol  type,  Mechanism 
underlying  tlie  reaction  )ye- 
tween,  321. 

/3  -Eucaine  group.  Stereoiso- 
merism and  local  ansesthe- 
tio  action  in,  379. 

Euolase  and  platinum  from 
diamond-washings  in  Brit- 
ish Guiana,  333. 

Hvans,  G.  T.  R.,  and  H.  H. 
Paine.     (See  Paine,  H.   TI.) 

Hvans,  Ulick  R.,  Electro- 
chemical character  of  cor- 
rosion,  189. 

Influence  of  obstructive  films 
on  anodic  processes,  380, 


FEBRUARY  1,  1924.      Index. — Supplement  to  the  Chemical  News. 


423 


Law    of   definite     proportions 
in  the  light  of     modern  re- 
search,   11. 
Exhibition,     Agricultural     Ma- 
chinery, «t  Paris,  51. 

British  Empire,  245,  305. 

Canadian  National,  6.3. 

of  educational  materials,  Ar- 
gentina, 409. 


Fluids,  Motion  of  solid  bodies 
in  rotating,  324. 

Ford,  Grace  VV.,  D.  Hanson 
and  C.  B.  Marryat.  {See 
Hanson,  D.) 

Formaldehyde  solution.  Aque- 
ous, 232. 

Formosan  sugar   crop,  254. 

.Four-membered  rings.  Addi- 
tive formation  of,  378. 

Fowler,  Sir  Henry,  Use  of 
non-ferrous  metals  in  en- 
gineering, 173. 

Fowler,  R.  H.,  Bohr's  atom  in 
relation  to  the  problem  of 
covalenoy,  39. 

Frick,  Carl  E.,  Action  of  sele- 
nium oxychloride  on  pure 
rubber,  74. 

Fuel,  Pulverised,  and  efScient 
steam  generation,  376. 


FAJANS,   Kasimir,     "Radio- 
.Vctivity"  (Review),  272. 

Falk,  K.  G.,  Relation  of  cer- 
tain enzyme  actions  to  tis- 
sue differentiation  and  tu- 
mour growth,  185. 

Faraday  So<;iety,  10,  38.  312, 
328.' 
General  discussion  on  elec- 
trode ^eaction8  and  equili- 
bria, 362,  379. 
Rc'port  to  the  .\tin(isphoric 
Corrosion    Committee.    395. 

Fargher,  R.  G.,  Cotton  wax, 
186. 

Parmer.  E.  H.,  Experiments 
on  the  synthesis  of  sub- 
stances possessing  the  La- 
denburg  formula.  302. 
Muconic  and  hydromuconi© 
acids,   302. 

Farming  methods  in  Northern 
Manchuria,  86. 

Federation  of  British  Indus- 
tries,  406. 

Ferguson.  Allan,  Measurement 
of  the  surface  tension  of  a 
smalt  quantity  of  n  liquid, 
345. 
Relation  between  surface  ten- 
sion and  density,  13. 

Fertilisfers,  Questionnaire  on, 
172. 

Pierz.  H.  E.,  The  sulphonation 
and  nitration  of  naphtha^ 
lenc.  187. 

Fiudlay,  Alexander.  "Practi- 
cal Physical  Chemistry" 
(Rpvieir).  286. 

Firth.  J.  B..  Determination  of 
the  density  of  chincoal  by 
displacement  of  liquids.   10.    i 

Firth.  .T.  B.,  and  F.  S.  Watson.   ' 
Catalytic  decomposition     of 
hydrogen      peroxide        sola- 
tion  by  blood  •■hnr(r)al,  314. 

Fish  meal  and  i^uano.  98. 

Fisher.  R.  A..  Influence  of  rain- 
fall on  the  vield  of  wheat, 
309. 

Flashing  point.  221. 

Fleming.     .T.      A..     "Electrons, 
Elcftric   Waves     :ind  Wire- 
less  Telephony"      (Rrrietr), 
16. 
Thermionic  valves.  219.  228. 


C-*  ALICIAN-CANADIAN   pole 
I      tool  fishing  metliods,  3S1. 

Gardiner,     James     U.,       Glass 
making  in  England,  1. 
Sir   William     Crookes'     anti- 
glare glasses,  97. 

Gardiner,  W.  M.,  British  dye- 
stufls,  222.  ! 

Garner,  W.  E.,  and  F.  M.  CrayJ 
{See  Cray.  F.  M.) 

Garner.  W.  E..  and  F.  C.  Ran-^ 
dall.  Alteration  in  the  heats 
of  crystallisation  of  the 
normal  monobasic  fatty 
acids,  379. 

Gases  and   vapours.   Excitation 
and      ionisation     potentials 
of,  282. 
liapid  admixture  of  hot  com- 
bustible,  with   air,   301. 

Gayler,  Marie  L.  V.,  Constitu- 
tion  and  age-hardening  of 
the  quaternary  alloys  of 
aluminium,  copper,  magne- 
sium and  magnesium  sili- 
cide,    189. 

Geddes.  Sir  Erie,  Need  for  set- 
tlement of  European  situa- 
tion. 22. 

Gentiobiose,  327. 

Geological  Society.  26,  345.  377. 
394. 

Gerlacii,  Walther,  "Materic. 
Elektrizitat,  Energie"  {Re- 
view), 159. 

Germany's       iwtash     Industry. 
222. 
trade   and    industry,     37,   267, 
322    390. 

Gibbs.'    W.   E.,     "Clouds     and 


Smokes,  the  Properties  of 
Disperse  Systems  in  Gases" 
{Review),  29. 

Glass,     Effect  of  titania  on  the 
proporties  of,   283. 
Estimation     of  selenium     in, 

285. 
Lead,     Action    of     iwtassium 

carbonate   ujwn,  22. 
making  in  England,  1. 

Glasses,  Sir  William  Crookes' 
anti-glare,   97. 

Glassliouse  pots,  377. 

Glasstone,  S.,  Cathodic  1)6- 
haviour  of  alloys,  313 

Gold  hjdroeol  coagulation,  In- 
vestj^etion  of  Smoluchow- 
ski's  equation  as  applied 
to,  316. 

Goss,  F.  R.,  C.  K.  lugold  and 
J.  F.  Thorpe,  Chemistry  of 
the  glutaoonic  acids,  270. 

Gough,  H.  J.  H.,  and  D.  Han- 
sou,  Behaviour  of  metals 
subjected  to  repeated 
stresses,  341. 

Graetz,  Leo.,  "Recent  Develop- 
ments in  Atomic  Theory" 
{lleview),  351. 

Grant,  J.,  and  J.  R.  Parting- 
ton, Concentration  cells  in 
methyl  alcohol,  11. 

Gray,  Francis  W.,  "The  Chem- 
istry Tangle  Unravelled" 
(Review),  238. 

Gray,  J.,  Meclianism  of  ciliary 
movement,   376. 

Green,  Albert, /3  -Alisarin,  379. 

Gregory,  F.  A.,  V.  H.  Black- 
man  and  A.  T.  Legg.  (See 
Blackman,  V.  H.) 

Grimwood,  R.  C,  C.  K.  Ingold 
and  J.  P.  Thorpe,  The 
chemistry  of  polycyolic 
structures  in  ^relation  to 
their  homoovolic  unsatur- 
ated isomerides,  271. 

Grindley,  E.  N.,  and  S.  H. 
Piper.     {See  Piper.  S.  H.) 

Gu.tnu,  Fish  meal  and,  98. 

Gyro-magnetic  ratio.  Null 
method  of  measuring,  342. 


HAFNIUM,     Chemistry      of, 
33.   186. 
Separation     from     zirconium. 
3,W. 
Ifaldane,  J.  K.  S.,     V.  B.  Wig- 
glesworth  and  C.  E.  Wood- 
row,       Effect    of      reaction 


424 


Index. — Supplement  to  the  Chemical  News. 


FEBRUARY  1,  1924. 


changes  on  linman  carbo- 
hydrate and  organic  meta- 
bolism, 376. 
Effect  of  reaction  changes  on 
human  inorganic  metabol- 
ism, 375. 

Hallimond,  A.  F.,  and  F.  R. 
Ennos,  Stilpnomelane  from 
North  Wales,  333. 

Haloids,  Inorganic,  Action  on 
organo-metallic  compounds, 
410. 

Hanson,  D.,  and  H.  J.  Gougli. 
{See  Gough,  H.  J.) 

Hanson,  D.,  C.  JJ.  Marryat  and 
Grace  W.  Ford,  Investiga- 
tion of  the  effects  of  im- 
purities on  copper,  190. 

Harden,  Arthur,  "Alcoholic 
Fermentation"  {Review), 
47. 

Hannah,  J.  D.,  and  E.  L. 
Khead,  Crystallisation  ef- 
fect on  galvanised  iron 
sheets,  174. 

Hawkins,  E.  M.,  Streatfield 
memorial  lecture,  281. 

Hawley,  H.,  and  H.  J.  S.  Sand, 
Interaction     of      potassium 
tetroxide  with  ice,  and  with  ^ 
dilute  sulphuric  acid,  232. 

Haworth,  W.  N.,  E.  L.  Hirst 
and  D.  A.  Euell,  Constitu- 
tion of  raffinose,  328. 

Haworth,  W.  N.,  and  B.  Wy- 
1am,  Constitution  of  the 
disaccharides,  327. 

Heat  of  formation.  Propor- 
tionality and,  271. 

Helium,     Band   spectrum  asso- 
ciated  with,   127. 
spectrum.  Intensities  in,  7. 

Henetock,    Herbert,    Colouring 
of  poisons,   334. 
Explanation  of  the  theory  of 
the  rotation  of   the   atomic 
nucleus,  18,  241,  259. 

Heyrovsky,  Jaroslav,  Processes 
at  the  mercury  dropping 
cathode,  363. 

Hevesy,  G.,  Note  on  the  olieni- 
istry  of  hafnium,  33,  186. 

Hevesy,  G.,  and  V.  Thai  Jant- 
zen.  Separation  of  hafnium 
from  zirconium,  353. 

Hinton,  C.  L.,  and  T.  Macara, 
lodimetric  determination 
of  sugars,  234. 

Hirst,  E.  L.,  W.  N.  Hawortli 
and  D.  A.  Euell.  {See  Ha- 
worth, W.  N.) 

Honig,  Max,  "Uber  Naturpro- 
dukte"   {Review).  31. 

Hopper,  I.  Vance,  William  M. 
Climming  and  T.  Slierlock 
Wheeler.  {See  Cumming, 
W.    M.) 

Horder,  Sir  Thomas,  Insulin 
and  diabetes,   157. 

Horton,  F.,  Excitation  and 
ionization  iwtentials  of 
gases  and  vajjours,  282. 

Houldswortli,  H.  S.,  Notes  on 
the  influence  of  rapid  chill- 
ing on  the  reversible  ex- 
pansion of  clay,  377. 

Hughes,  A.  L.,  and  P.  Lowe, 
Intensities  in  the  helium 
spectrum,   7. 


Hunter,  R.  F.,  4'  Amino  1 
phenyl  5  methyl benzothia- 
zole  and  its  bromination  in 

*    glacial  acetic  acid,  385. 

4'  Hydroxy  1  phenyl  5  metliyl- 
benzothiazole  and  its  bro- 
mination,  4*1. 

Indigoid  dyestuffs,  339,  358, 
372. 

Mechanism  underlying  the 
reaction  between  ethyl  cy- 
anoacetate  and  tautomeric 
substances  of  the  keto-eno) 
type,  321. 

Organic  compounds  of  ar- 
senic,  70,   82,   113. 

Organic  mercury  compounds, 
202,  214,  229. 

Protein   reactions,  134. 
■    The  quantum  theory,  145,  165. 

Recent  researches  in  organic 
chemistry,  243,  261,  291. 

Red  sulphur  dyes,  350. 

Sulphur   dyes,   17. 
Hydrogen     activation       in     or- 
ganic compounds,  184. 

Are  the  natural  groupings  of 
the  elements  and  the  spec- 
tral lines  of,  related?  257, 
273,  290,  337,  355,  369,  386. 

Electrolytic  production  of 
active,  411. 

Production  of  triatomio,  182. 
Hydrogen  peroxide  solution. 
Catalytic  decomposition  by 
blood  charcoal,  314. 
4'  Hydroxy  1  phenyl  5  methyl- 
benzothiazole  and  its  bro- 
mination, 401. 


T  MPERIAL     COLLEGE       of 

•*•  Science,  ,^615,000  donation 
to,  95. 

Indigoid  dyestuffs,  339,  358,  372. 

Ingall,  Douglas  H.,  Experi- 
.  ments  with  some  copper 
wire,    189. 

Ingold,  C.  K.,  Additive  forma- 
tion of  four-membered 
rings,  378. 

Ingold,  C.  K.,  J.  W.  Baker  and 
J.  F.  Thorpe.  {See  Baker, 
J.  W.) 

Ingold,  C.  K.,  F.  R.  Goss  and 
J.  F.  Thorpe.  {See  Goss, 
F.  R.) 

Ingold,  C.  K.,  R.  C.  Grim- 
wood  and  J.  F.  Thorpe.  {See 
Grimwood,  R.  C.) 

Institute  of  Chemistry,  Pass 
list,  77. 


of  Metals,  25,  49,  88,  173,  189, 

232,  285. 
of  Physics,  285, 
Institution  of  Electrical     Engi- 
neers, 256,  282,  285,  331,  345, 
347,  365,  376,  411. 
of  Mining  Engineers,  301,  345. 
of     Petroleum    Technologists, 
232,  317,  331,  377,  397. 
Insulin  and  diabetes,  157. 
Interfaces,  Some  aspects  pi  the 

physical  chemistry  of,  209. 
Iridescent  beetles,  135. 
Iron  and  Steel  Institute,  125. 
Iron,  Cast,   research,  235. 
Galvanised,    sheets.   Crystalli- 
sation effect  on,  174. 
Isomeric  change.  Origin  of  mu- 
tarotation  and  the  mechan- 
ism of,  410. 
Isotopes,     Observations       upon 
and    deductions     from     the 
figures  given     in  the  inter- 
national table  of,  52. 
of  copper,  44. 

Origins  of  the  conception  of, 
92,   103. 
Iyer,   K.  R.   Krishna,     The  in- 
termittent  glow     of     phos- 
phorus, 321. 


JACKSON,  L.  C,  and  H 
Kamerlingli  Onues,  Mag- 
netic properties  of  some 
paramagnetic  double  sul- 
phates at  low  tempera- 
tures, 325. 

Jantzen,  V.  Thai,  and  Q. 
Hevesy.     {See  Hevesy,  G.) 

Johannesburg,  New  power 
scheme  for,  107.  . 

Jugo  Slavia,  Chemical  indus- 
try of,  131. 


K 


AYE.  G.  W.  C,  and  E.  A. 
Owen,  X-ray  protective 
materials,    122. 


FEBRUABY  1,  1924.     Index. — Supplement  to  the  Chemical  News. 


425 


King,  Harold,  Stereoisomerism 
aud  local  anaesthetic  ac- 
tion on  the  li  -eucaine 
group,  379. 

King,  W.  G.,  and  T.  Sherlock 
VVheeler.  {See  Wheeler,  T. 
S.) 

Knibbs,  N.  V.  S.,  Gas  film 
theory  of  overvoltage,  379. 

Komatsu,  Shigeru,  Hisashi 
Nakamura  and  Maeao  Ku- 
rata.  Studies  on  catalytic 
action,  2. 


LABUKATOUY      equipment, 
22. 

Ladeuburg  formula,  Experi- 
ments on  the  syntliesia  of 
substances  possessing  th«, 
a02. 

Langevin,  P.,  The  btructure  uf 
atoms  and  their  magnetic 
properties,  183. 

Lanthanum  riolet  bauds  and 
the  associated  lines,  127. 

Lavender  oultivation,  335. 

Lea,  Matthew  Carey,  chemist, 
129. 

Lead  in  cream  of  tartar,  (Jolori- 
metric  estimation,  393. 
in  potable  waters  and  urine, 
PiStimation,  S47. 

Legg,  A.  T.,  V.  U.  Blackmail 
and  F.  A.  Qregory.  (See 
Blackman,  V.  H.) 

Leppan,  11.  D.,  and  Q.  J.  Boe- 
man,  "Field  Crops  in  Sooth 
Africa"   (Review),  224. 

Levy,  H.,  "Practical  Mathe- 
matical Analysis"  (Re- 
view), 366. 

Lewis,  Gilbert  N..  Valency  aod 
electrons,  38. 
"Valence  and     the  Structure 
of  Atoms"   (Review),  3^7. 

Lewis,  G.  N.,  and  M.  liandall, 
"Thermodynamics  and  the 
Free  Energy  of  Chemical 
Substances     (Review),  15. 

Liesegang,  R.  £.,  "Kolloide  in 
der  Technik"  (Review), 
399. 

Liesegang,  R.  E.,  and  Georg  O. 
Wild.     (See  Wild.  G.  o) 

Liesegang  bands,  Formation  of 
anomalous,   12. 

Light,     Polarised,     Biochemical 
effect  of,   186. 
Scattering  by  carbon  dioxide, 
nitrous  oxide  and  some  or- 
ganic vapourp,  344. 

Lithium  and  sodium.  Separa- 
tion   and  determination  by 


precipitation  from  alco- 
holic perchlorate  solution, 
42,  57. 

Lloyd,  William  V.,  and  Ed- 
ward J.  \\  eeks.  (See 
Weeks,  E.  J.) 

Lorentz,  H.  A.,  and  Others, 
"The  Principles  of  Relativ- 
ity"  (Review),  414. 

Loriug,  i'.  H.,  Are  the  natural 
groupings  of  the  elements 
and  the  spectral  lines  of 
hydrogen  related?  257,  273, 
290,  337,  355,  369,  386. 
Is  there     an  element  of  zero 

atomic  number!'  225. 
Isotopes  of  copper,  44. 

Lowe,  P.,  and  A.  L.  Hughes. 
(See  Hughes,  A.  L.) 

Lowry,  T.  Martin,  The  eleo: 
tronio  theory    of     valency. 

Origin  of  mutarotation  and 
the  mechanism  of  isomeric 
change,  410. 
Lowson,  W.,  "Supplementary 
Notes  on  Gravimetric  Ana- 
lysis" (Review),  47. 


MACARA,    T.,    and    C.    L. 
ilinton.        (i^ee     Hinton, 
C.  L.) 

MoCoUum,  L.  R.,  Modern  ro- 
tary drilling  system,  397. 

McGillivray,  Evan  James,  The 
chemist  in  relation  to  the 
safeguarding  of  industries, 
128. 
The  right  to  use  the  title 
"Chemist,"   108. 

Mclndo,  N.  E.,  and  F.  C.  Cook. 
(See  «:ook,  F.  C.) 

McLennan,  J.  C,  Origin  of 
spe<tra,  198,  212. 

McNair.  .laiiu-sB.,  "Rhus  Der- 
matitis (Poison  Ivy)"  (Re- 
view), 207. 

Madras,  Government  of,  Re- 
I)ort  of  the  cliemical  ex- 
aminer's department,  4. 

Magnesium,  magiiesiuni  sili- 
cide,     aluminium     and  cop- 

Eer,  C'onstitution  and  age- 
ardening  of  the  quater- 
nary alloys  of,  189. 

Manchuria,  Farming  methods 
in  >iortliern,  86. 

Manganese,  Eleotrodeposition 
of,  312. 

Manures,   U»o  of  artificial,  285. 

^larrynt.  ('.  H..  I).  ILinson  and 
Grace  W.  Ford.  \S''c  Han- 
son, D.) 


Marson,  Percival,  Glasshouse 
pots,  377. 

Martin,  L.  C,  Photometric 
matching  field,  7. 

Mass  and  weight.  Experiments 
on  the  proportionality  of, 
325. 

Matter,  Electrical  structure  of, 
161,  177,  193. 

Mattern,  Louis  W.,  What 
chemistry  shall  be  taught 
in  high  schools  and  how  it 
shall  be  correlated  with 
college  chemistry,  347,  360. 

Medical  supplies  for  the  Dutch 
Government,  324. 

Membrane  potentials  considered 
as   difiusion   potentials,   184. 

Mercury  compounds.  Organic, 
202,  214,  229. 

Mesothorium,  Laboratory  ex- 
periments on  the  extraction 
of,  from  monazite  sand, 
139,   153. 

Metabolism,     Efiect  of  reaction 
changes  on     human   carbo- 
hydrate and  oxygen,  376. 
Effect  of  reaction  changes  on 
human  inorganic,  375. 

Metals,  Atmospheric  corrosion 
of.  388. 

and  alloys,  Effects  of  rate  of 
cooling  on  the  density  aud 
composition  of,  174. 

Behaviour  under  compressive 
stresses,  191. 

Non-ferrous,  Canada's,  309. 

Non-ferrous,  Use  in  engineer- 
ing, 173. 

subjected  to  repeated  stresses, 
Behayiour  of,  341. 

Meteorites,  Genesis  of  Wid- 
manstatten  structure  in, 
and  in  terrestrial  alloys, 
333. 

Methyl  alcohol.  Concentration 
cells  in,  11. 

Methylene  blue.  Absorption  by 
ootton,  186. 

Mexico,  Trade  catalogues  for, 
171. 

Mioro-telescope  and  super- 
microscope,  14. 

Milk,  Condensed,  investigation, 
62. 

Millar,  Albert,  Galioian-Cana- 
dian  pole  tool  fishing 
methods,  331. 

Mineral  production  of  Canada, 
111,  230,  298. 

Minerals,  Consumption  of  pre- 
pared non-metallic,  in  Can- 
ada, 324. 

MineralMrical  Society,  301,  332. 

Miser,  Hugh  D.,  and  Clarence 
S.  Ross,  Diamond-bearing 
peridotite  in  Pike  County, 
Arkansas,   22. 

.Missendon,   John,      Britain   her 
own  cliemist,  289. 
Odour  conditions,   217. 
Some  properties  of  the  meta- 
phosphates  of   silver,   96. 

Mitchell,  C.  A.,  "The  Expert 
Witness"   (Review);  334. 

Morjjan,  G.  T.,  and  Sir  Wil- 
liam Bragg.  (See  Bragg. 
.Sir  W.) 


426 


Indbx. — Supplement  to  the  Chemical  News.        FEBEUARY  1,  1924. 


Miiller,  Dr.,  X-ray  si)ectro- 
grapli,  297. 

Muller,  Alex.,  aud  G.  Shearer, 
Further  X-ray  measure- 
ments of  long  chain  com- 
pounds, 327. 

Mundey,  A.  H.,  and  C.  C.  Bis- 
«ett.  Effect  of  small  quanti- 
ties of  nickel  upon  high- 
grade  bearing  metal,  175. 

Mundey,  A.  H.,  and  John  Cart- 
land,  Stereotyping,   173. 

Muspratt,  Edward  Knowles, 
Obituary,  158. 

Muspratt,  Sir  Max,  Address  to 
the  Association  of  British 
Chemical  Manufacturers, 
55. 

Mutarotation,  Origin  of,  and 
the  mechanism  of  isomeric 
change,  410. 


Null  method  of  measuring  the 
gyro-magnetic  ratio,  342. 

Nuttall,  Grcorge  H.  F.,  Symbio- 
sis in  animals  and  plants, 
197. 


NADORITE     in        Cornwall, 
Occurrence  of,  333. 

Nakamura,  Hisashi,  Shigeru 
Komatsu  and  Masao  Ku- 
rata.     (See  Komatsu,  S. 

Naphthalene,  Sulphonation  and 
nitration  of.  187. 

Narayan,  A.  L.,  Scattering  of 
light  by  carbon  dioxide,  ni- 
trous oxide  and  some  or- 
ganic vapours,  344. 

National  Engineers*  Associa- 
tion, 8. 

Netherlands  Colonial  Govern- 
ment service,  Stores  re- 
quired for,  205. 

Nicaragua,  Trade  catalogues 
required  in,  37. 

Nickel,  Effect  of  small  quanti- 
ties on  high-grade  Wtaring 
metal,  175. 

Nitrogen  and  other  substances 
in  rain  and  snow,  30. 
in    coal.   Determination,   346. 

Non-polar  link.  The  nature  of, 
39. 

Norbury,  A.  L.,  Volumes  occu- 
pied by  the  solute  atoms  in 
certain  metallic  solid  solu- 
tions and  their  consequent 
hardening  effects,   313. 

Norrish,  R.  G.  W.,  Studies  of 
electrovalencv,  270. 

Norrish,  R.  G.  W.,  and  E.  K. 
Rideal.  Direct  union  of 
oxygen  and  sulphur,  232. 

Northampton  Polytechnic  In- 
stitute, 207. 

Norway,  British  r.  German 
goods  in,  24. 


OAKLEY,  H.  E.  H.,  and  T. 
S.  P.  Strangeways.       (iSee 
Strangeways,  T.  S.  P.) 

Obituary,  Muspratt,  Edward 
Knowles,   158. 

Odour  conditions,  217. 

Oil,     Castor,     Test   for    distin- 
guishing   from     other     oils 
and  determining  its  purity, 
23i. 
Linseed,  Crystalline  bromides 

of,  392. 
Linseed,     for     South    Africa, 

255. 
Machine,     for     South  Africa, 
254. 

Okubo,  Junzo,  Lanthanum  vio- 
let bands  and  the  associated 
lines,  127. 
Structure  of  the  second  cy- 
anogen band,  126. 
Xeill,  Hugh,  Hardness  tc-ts 
on  crystals  of  aluminium. 
190. 

Onnes,  H.  Kamerlingh,  Low- 
est temperature  yet  ob- 
tained,  120. 

Onnes,  H.  Kamerlingh,  and  L. 
C.  Jackson.  (See  Jackson, 
L    C  ) 

Optical  Society,  233,  346,  361, 
393. 

Organic  compounds.  Oxidation 
and  reduction  potentials  of, 
363. 

Ormandy,  W.  R.,  and  E.  C. 
Craven,  Note  on  aqueous 
formaldehyde   solution,   232. 

Orndorff,  W.  R.,  "Organic 
Chemistry"    {Review),  79. 

O'Sullivan,  J.,  Fish  meal  and 
gnano,  98. 

Overvoltage,  Gas  film  theory  of, 
379 

Owen,  E.  A.,  and  G.  W.  C. 
Kaye.   (See  Kave,  G.  W.  C.) 

Owen,  E.  A.,  and  G.  D.  Pres- 
ton, X-ray  analysis  ot' 
solid  solutions,  311.  I 

Oximes,   Isomerism  of  the,  379. 

Oxygen     and     sulphur.     Direct 
union,  232. 
Effect  on  copper,   190. 
research      committee  .  report, 
253. 

Ozone,  Relation  between  th€ 
glow  of  phosphorus  andthr 
formation  of,  409. 


PAGET,  SIR  RICHARD,  Ex- 
periments on  the  repro- 
duction of  vowel  sounds, 
343. 

Paine, 'h.  H.,  and  G.  T.  R. 
Evans,  Method  of  measur- 
ing the  rate  of  coagulation 
of  colloidal  solutions  over 
wide  ranges,  329. 

Palmer,  W.  G.,  Catalytic 
actions  in  the  system  cop- 
per, copper-oxide,  oxygen 
and  gaseous  reducing 
agent,   185. 

Para-cymene,  Preparation  aiul 
its  formation  in  sulphite 
turpentine,  2. 

Paris,  Agricultural  Machinery 
Exhibition  at,  51. 

Partington,  J.  R.,  and  J. 
Grant.     (See  Grant,  J.) 

Patents,  New,  16,  32,  48,  64,  80, 
96,  112,  128,  144,  160,  176, 
192,  208,  224,  240,  256,  272, 
288,  304,  320,  336,  352,  368, 
384,  400,  416. 

Paton,  R.  F.,  and  R.  A.  Saw- 
yer.    {See  Sawyer,  R.  A.) 

Peridotite,  Diamond-bearing, 
in  Pike  County,  Arkansas, 
22. 

Permutit,  New  rapid-generat- 
ing, 24. 

Peroxide  electric  cell,  48. 

Petroleum,  a  short  history,  26. 
origin.       Recent     researches, 
282. 

Pettet,  A.  E.  J.,  and  A.  W. 
Warrington,  A  peroxide 
electric  cell,   78. 

Phosphate  in  blooil  and  urim , 
Relation  between,  375. 

Phosphorus,  Glow  of,  and  its 
extinction  by  moist  oxygen, 
325. 
Intermittent  glow  of,  321. 
R?lation  between  the  glow  of, 
and  the  formation  of  ozone, 
409. 

Photography,  Electrically  de- 
flagrated mercury  filament 
as  a  flash  light  for  instan- 
taneous,  159. 

Photometric   matching   field,   7. 

Photomicrography,  254. 

Physical  Society,  282,  310,  343, 
393. 

Physics  in  the  textile  indus- 
tries, 271. 

Pig,  Basal  metabolism  of  a 
growing,  300. 

Piper,  S.  H.,  and  E.  N.  Grind- 
ley,  Fine  structure  of  some 
sodium  salts  of  the  fatty 
acids  in  soap  curds,  310. 

Pitch   for  briquettes,  223. 

Plants  and  animals.  Symbiosis 
in,  197. 

Platinum     and      euolase     from 
diamond-washings     in  Brit- 
ish Guiana,  333. 
crucibles.  Destruction  of,  299. 
group   metals.   Production   in 
Canada,  187. 

Poisons,   Colouring  of,   63,   334. 

Polarisation-ovcrvoltage,  De- 
pendence on  hydroxyl  and 
hydrogen  ion  concentra- 
tion, 378 


FEBRUARY  1,  1924.       Index. — Supplement  to  the  Chemical  News. 


427 


Polycyclic  structures.  Chemis- 
try of,  in  relation  to  their 
homoeyclic  un^iiturated  ieo- 
merides,  271. 

Portevin,  Albert  M.,  and  Pierre 
Che  vena  rd,  A  dilatometric 
study  of  the  transforma- 
tions and  thermal  treat- 
ment of  light  alloys  of  alu- 
minium,  191. 

Potash  industry  of  Germany, 
222. 

Pota-ssium  carlx)nate.  Action 
upon  lead  glass,  22. 

Potassium  tetroxide,  Inter- 
action with  ice,  and  with 
dilute    sulphuric   acid,   232. 

Potentials  of  gases  and  va- 
pours. Excitation  and  ioni- 
zation, 282. 

Potter,  H.  H.,  Some  experi- 
meuta  on  the  proportional- 
ity of  mass  and  weight,  325. 

Pottery  industry.  Smoke  pro- 
duction and,  23. 

-Powders,  Propertise  of,  315. 

Powney,  W.  E.  F.,  J.  H.  Coste 
and  E.  K.  Andrews.  (A'ec 
Coste,  J.   H.) 

Preston,  G.  D.,  and  E.  A. 
Owen.     (iSee  Owen,  E.  A.) 

Price.  Phyllis  U..  Gold-beaters' 
skin  test  for  tannins,  346. 

I'ridfaux,  E.  li.  K.,  Membrane 
potentials  considered  afi 
diffusion  potentials,  184. 

Pring,  J.  N.,  Determination  of 
the  affinity  constant**  cf 
bases  bv  the  hydrogen  and 
quinhydrone  electrode.  364. 

Pritchard,  F.,  and  F.  Challen- 
ger.    (See  Challenger,  F.) 

Proportionality  and  heat  cf 
formation,  271. 

Proportions,  Law  of  definite,  in 
the  light  of  modern  re- 
search, 11. 

Protein  reactions,  134. 

Pulse  rate  and  oxygen-debt 
after  running,  influence  of 
atmospheric  conditions  up* 
on,  876. 


Q 


r.VNTUM  theory.  14,5.  1R5. 


Quartz.  Colourations  of  cer- 
tain, and  their  niutal>ilitv. 
34. 


H 


ADIATION.  Test  of  a  the- 
ory of,  7. 


Raffinose  constitution,  328. 

Eain  and  snow,  Nitrogen  and 
other  substances  in,  30. 

Ralston,  Oliver  C,  Anhydrous 
aluminium  chloride,  246. 

Randall,  F.  C,  and  W.  E.  Gar- 
ner.    (See  Garner,  W.  E.) 

Randall,  M.,  and  G.  N.  Lewis. 
(See  Lewis,  G.  N.) 

Rao,  S.  V.  Raghava,  and  Y. 
Venkataramaiah,  Electroly- 
tic production  of  active 
hydrogen,  411, 

Rayleigh,  Lord,  Further 
studies  on  the  glow  of  plios- 
phorus  and  its  extinction 
by  moist  oxygen,  325. 
Studies  of  iridescent  colour 
and  the  structure  produc- 
ing it,  135. 

Rays,  Secondary  corpuscular, 
produced  by  homogeneous 
X-rays,  325. 

Reactivity,  Theory  of  chemical 
reaction  and,  148. 

Reader,  R.  C..  Effects  of  rate 
of  cooling  on  the  density 
and  composition  of  metals 
and  alloys,   174. 

Remsen,  Ira,  "Organic  Chem- 
istry"  (Review),  79. 

Besearcli,  Industrial,  with  spe- 
cial reference  to  electrical 
engineering  development, 
282. 

Resin  of  bevea  rubber,  Nature 
and  significance  of,  184. 

Rhead,  E.  L.,  and  J.  D.  Han- 
nah,    (.^ee  Ilannali,  J.  D.) 

Richmond.  U.  Droop,  Action  of 

Ktassium  carbonate     upon 
kd  ikIass,  22. 

Rideal,  Eric  H.,  Mechanism  of 
the  reversible  electrode. 
962. 

Kideal.  E.  K..  and  R.  ii.  W. 
Norrish.  (See  Norrish,  K. 
G.  W.) 

Ridley,  Geoffrey  N.,  Perchro- 
mic  acid,  81. 

Uivett,  A.  C.  D.,  "Tlie  Phase 
Rule  and  the  Studv  of 
I{eterogeneoU8  Equilibria" 
(Review).  206. 

Robinson,  11.,  Secondary  cor- 
poscalar  rays  produced  by 
homogeneous   X-rays,  325. 

Bobinaon,  Robert,  Octet  stabil- 
ity in  relation  to  orienta- 
tion and  reactivity  in  car- 
bon  compounds,   41. 

KoSH^  Clarence  S..  and  Ilugli 
D.  Miser.  (.See  Miser,  H. 
D.) 

Ross,  Sir  Ronald,  Presentation 
of  the  Albert  Medal   to,  78. 

Roth.  Walther  A..  an<l  Karl 
Scheel,  "Landold  Uorn- 
stein,  Physikalisch-Chem- 
ische  Tnbellen"  (Review), 
366. 

Riival    ./Vgricultural    Society   of 
England.  .331,   411. 
hihtitution.     2.5.   92.   Kfl,     301, 

310.  326.  378.  '.»5.  411. 
Microscupical      S<Kietv,       2.5.S. 

269,  332. 
Societv.     fi.    300.    309.    324.   311. 
.375. 


Society  of  Arts,  301,  317,  342, 

362,  392. 
Presentation     of     the    Albert 
Medal   to  Sir   David   Bruce 
and  Sir  Ronald  Ross,  78. 

Rubber,  Action  of  selenium 
oxychloride  on  pure,  74. 

Ruell,  D.  A.,  W.  N.  Haworth 
and  E.  L.  Hirst.  (See  Ha- 
worth, W.   N.) 

Russell,  Arthur,  Occurrence  of 
the  rare  mineral  nadorite 
in  Cornall,  and  of  beraun- 
ite  in  Co.  Cork,  Ireland, 
333. 

Russell,  Bert  rand,  "The  A.  B.C. 
of   Atoms"    (Review),  351. 

Russia,  Wireless  stations  in, 
253. 

Rutherford,  Sir  Ernest,  Elec- 
trical structure  of  matter, 
161,  177,  193. 


SAFEGUARDING    of  Indus- 
tries Act,  808. 

Sulamon  M.  S.,  The  plea  for 
i-tandardisation,   392. 

Sand.  IF.  J.  S..  and  H.  Hawley. 
(.See  Hawley,  H.) 

Sand.  H.  J.  S.,  and  E.  J. 
Weeks,  Dependence  of  po- 
larisation-overvoltage  on 
hydroxyl  and  hydrogen  ion 
coneontrntiou.   378. 

Sawyer,  R.  A.,  and  R.  F.  Pa- 
ton,  Vacuum-spark  spec- 
trum of  siliccm,  121. 

Scheel.  Karl,  and  Walther  A. 
Roth.     (See  Rotli.  W.  A.) 

Schlundt,  Herman,  Laboratory 
experiments  on  the  extrac- 
tion of  mesothorium  from 
monanitp  sand,  139,  153. 

Schott,  Q.  A..  Scattering  of  X 
and  y  -rays  by  rings  of 
electrons,   7. 

Schwarz,  Robert.  "The  Chem- 
istry <if  the  Inorganic  Com- 
imunds"    (Review),    15. 

Seignette  salts,  .\nomaious  op- 
tical properties  of  freshly- 
prepared  mixed  crystals  of, 
333. 

Selenium  in  frlaes,  Estimation. 
285. 

Selenium  oxychlnride.  Action 
on  pure  rubber.  74. 

Selenium  trioxide  and  chlor- 
selenic  acid,  270. 

Semmens,  F^liKulK'th  S.,  The 
biochemi<»il  effect  of  pnlar- 
ised  light,  18<;. 

Sexton,  James,  Colouring  of 
lx>isons,  63. 


4^ 


Index. —  Supplement  to  the  Chemical  News.        FEBRUAEY  1,  1924. 


6'liaxby,  J.  H.,  Studies  in  the 
Brownian  movement,  342. 

Shearer,  G.,  X-ray  investiga- 
tion of  certain  organ 'c 
esters,  and  other  long  chain 
compounds,  327. 

Shearer,  G.,  and  Alex.  Muller. 
{See  Muller,  A.) 

Sheen,  A.  R.,  and  W.  E.  S. 
Turner,  Effect  of  titania  oji 
the  properties  of  glass,  283. 

Shikita,  Masuzo,  Concentra- 
tion cells  and  electrolysis 
of  sodium  ethoxide  solu- 
tions, 365. 

Shimizu,  Takeo,  A  sensitive 
electroscope,  126. 

Sidgwick,  N.  V.,  The  nature  of 
the  non-polar  link,  39. 

Silicon,  Vacuum-spark  spec- 
trum of,  121. 

Silk,  Artificial,   79. 

Silver,  Meta-phosphates  '  of. 
Properties  of,  98. 

Silver  stibide,  Preparation  and 
properties,  319. 
Preparation  of  pure,  362. 

Simeon,  ¥.,  Carbon  arc  spec- 
trum in  the  extreme  ultra- 
violet, 341. 

Sir  John  Cass  Technical  Insti- 
tute, 172. 

Smith,  Edgar  P.,  M.  Carey  Lea. 
chemist,  129. 

Smith,  G.  Frederick,  and  H. 
H.  Willard.     (See  Willard. 

H.  n.) 

Smits,  A.,  Electromotive  equi- 
librium and  polarisation. 
382. 

Smoke  production  and  the  pot- 
tery industry,  23. 

Smoluchowski's  equation.  In- 
vestigation of,  as  applied 
to  the  coagulation  of  gold 
hydrosol,  316. 

Snow  and  rain.  Nitrogen  and 
other    substances   in,   30. 

Soap  curds.  Fine  structure  of 
some  sodiiim  salts  of  the 
fatty  acids  in,  310. 

Society     of  Glass     Technolo;-'y, 
76.  255,  28;?.  332,  377,  393. 
of  Public  Analysts,     221 
282.  343,  346,  392. 

Soddy,  Frederick,  Origins  of 
the  conception  of  iotopes. 
92,  103. 

Sodium  and  lithium.  Separa- 
tion and  determination  by 
precipitation  from  alcoho- 
lic perchlorate  solution, 
42,  57. 
salts  of  the  fatty  acids  in 
soap  curds.  Fine  structure 
of,  310. 

Sodium  acetate  for  Australia, 
172. 

Sodium  ethoxide  solutions. 
Concentration  cells  and 
electrolysis  of,  365. 

Soils,  Pan  formation  in,  in  the 
light  of  the  Liesegang 
phenomenon,   84. 

SoTiimerfeld,  Arnold,  "Atomic 
Structure  and  Spectral 
Lines"    (Beview),  44. 

South  Africa,  Chemicals  for, 
269.  ) 

Disinfectant  fluid  for,  269. 


Linseed  oil  for,  255. 
Machine  oil  for,  254. 
Report  on   the  economic  oonj 
ditions  in,  400.  ' 

Tar  or  tar  substitute,  171. 

Spectacle  trade.  Contributions 
to  the  history  of,  361. 

Spectra,   High   frequency,     and 
the  fheorv  of  atomic  struc- 
ture, 184. 
Origin  of,  198,  212. 

Spectrum,     Band,        associated 
with   helium,   127. 
Bridging  the  gap  in,  49. 
Carbon   arc,     in   the  extreme 

ultra-violet,  341. 
Vacuum-spark,        of     silicon, 
121. 

Spectrograph,   X-ray,  297. 

Spectroscopy,  X-ray,  as  ;i 
means  of  qualitative  and 
quantitative  chemical  ana- 
lysis, 65. 

topencer,  L.  J.,  Euclase  and 
platinum  from  diamond- 
washings  in  British 
Guiana,   333. 

Standardisation,  The  plea  for, 
392. 

Stead,  G.,  and  Miss  B.  Trevel- 
yan.  Production  of  tri- 
atomic  hydrogen,  182. 

Steam  generation.  Pulverised 
fuel   and  efficient,  376. 

Steel,  Effect  of  quenching  from 
above  the  carbide  transi- 
tion temperature  upon  the 
magnetism  of,  7. 
samples,  British  standard- 
ised, 127. 
Vanadium  in,  Volumetric 
estimation,   234. 

Stereotyping,    173. 

Stibine,  Preparation  from  id- 
loys,  87. 

Stilpnomelane  from  North 
Wales,  333. 

Stocks,  H.  B.,  New  test  for  dis- 
tinguisliing  castor  oil  from 
other  oils  and  determining 
its  purity,  234. 

Strangeways,  T.  S.  P.,  and  H. 
E.  H.  Oakley,  The  imme- 
diate changes  observed  in 
tissue  cells  after  exposure 
to  soft  X-rays  while  grow- 
ing in  vitro,  8. 

Streatfield  memorial  lecture, 
281. 

Sucksmith,  W.,  and  L.  F. 
Bates,  Null  method  of  mea- 
suring the  gyro-magnetic 
ratio,  342. 

Sucrose,  Effect  on  rate  of  co- 
agulation of  a  colloid  by  an 
electrolyte,   328. 

Sugar  crop,  Formosan,  254. 

Sugars,  lodimetrio  determina- 
tion of,  234. 

Sugden,  Samuel,  Determination 
of  surface  tension  from  the 
maximum  pressure  in  bub- 
bles, 302. 
Variation  of  surface  tension 
with  temperature,  and  the 
related  functions,  302. 

Sulphates,  Par<i  magnetic  douVe 
Magnetic  properties  at  low 
temperatures,   825. 


Sulphur     and     oxygen.     Direct 
union.  232. 
dyes,  17. 

Surface   tension     and     density. 
Relation   between,   13. 
tension.     Determination  from 
the  maximum     pressure  in 
bubbles,  302. 
tension  of     a   small  quantity 
of  a     liquid.     Measurement 
of,  345. 
tension.   Variation   with   tem- 
peratiire,   and   some   related 
functions,  302; 

Suyehiro.  Kyoji,  Electrically 
deflagrated  mercury  fila- 
ment as  a  flash  light  for  in- 
stantaneous photography, 
159. 

Symbiosis  in  animals  and 
plants,  197. 


TAKAHASHI,  YUTAKA. 

Band  spectrum  associated 
with  helium,  127. 

Tannins,  Gold-beaters'  test  for, 
346. 

Tautomerism,   Ring-chain,  327. 

Taylor,  Clara  M.,  "Discovery 
of  the  Nature  of  the  Air 
and  of  its  Changes  during 
Breathing"    (Reinew),  111. 

Taylor,  G.  I.,  Experiments  on 
the  motion  of  solid  bodies 
in  rotating  fluids,  324. 

Taylor,  J.  Norman,  Petroleum, 
a  short  history,  26. 
What  is  a  chemical?  403. 

Temperature,  Lowest  yet  ob- 
tained,  120. 

Terrestrial  alloys,  Genevsis  of 
Widmanstatten  structure 
in  meteorites  and  in,  333. 

Terry,  Ellen,  The  Braille  and 
Servers  of  the  Blind 
League,  175. 

Therapy  treatment,  Physical 
foundations  of  deep,  50. 

Thermionic  valves,  219,  226. 

Thomlinson,     J.     C.,      Diacetyl 
acetone  and  pseudo-cumene, 
275. 
Proportionality     and   heat  of 
formation,  271. 

Thompson,  F.  S.,  and  E.  V. 
Appleton.  (See  Appleton, 
E.  V.) 

Thomson,  G.  P.,  Test  of  a  the- 
ory of  radiation,  7. 


FEBRUARY  1,  1924. 


Index. —  Supplement  to  the  Chemical  News. 


429 


Thomson,  Sir  J.  J.,  "The  Elec- 
tron in  Chemistry"  (Re- 
view),  383. 

Thorpe,  J.  F.,  J.  W.  Baker  and 
C.  K.  Ingold.  (See  Baker, 
J.  W.) 

Thorpe,  J.  F.,  F.  R.  Gpes  and 
(f.  K.  Ingold.  (See  Goss,  F. 
R.) 

Thorpe,  J.  F.,  R.  C.  Grimwood 
and  C.  K.  Ingold.  (See 
Grimwood,  R.  C.) 

Thresh,  John  C,  Estimation  of 
lead  in  potable  waters  and 
in  urine,  347. 

Thwaites,  R.  E.,  "Production 
of  Liquid  Fuels  from  Oil 
Shale  and  Coal  in  Austra- 
lia"  (Review)    335. 

Timber,  Dry-rot  disease  of,  402. 

Tissue  cells.  Immediate  changes 
observed  in,  after  exposure 
to  soft  X-rays  while  grow- 
ing in  vitro,  8. 

Titania,  Effect  on  the  proper- 
ties of  glass,  283. 

Toms,  Harold,  Crystalline  bro- 
mides of  linseed  oiL  392. 

Tool  fishing  methods,  Galieian- 
Canadian   pole,  331. 

Trade,  Prospects  of  a  revival 
in    30. 

Trevelyan,  Miss  B.,  and  G. 
Stead.     (See  Stead,  G.) 

Trigger  reception.  Periodic. 
345. 

Tryhorn.  F.  G..  and  S.  C. 
Blacktin,  Formation  of 
anomalous  Lieeegang 

bands,  12. 

Tumour  growth.  Relation  of 
t^rtain  enzyme  actions  to 
tissue  difforentatiation  and, 
185. 

Turner,  L.  B.,  Relations  be- 
tween damping  and  speed 
in  wireless  reception,  365. 

Turner.  W.  E.  8.,  and  A.  R. 
Sheen.     (See  Sheen,  A.  R.) 


UNITED  STATES,   Chemical 
required  in,  38. 
Rai)eReed  oil   required  in,  .')1. 
Uruguay ,   Tenders  invited     for 
lubricating^  oils,  IS. 


Usherwood,  Edith  H.,  Activa- 
tion of  hydrogen  in  organic 
compounds,  184. 


V.4LENCY,      The     electronic 
theory  of,  38. 
Vanadium  in  steel,  Volumetric 

estimation,  234. 
Vapours  and  gasee.  Excitation 

and     ionisation      potentials 

of,  282. 
Venkataramaiah,  Y.,  and  S.  V. 

Raghava   Rao,     Electrolytic 

production  of  active  hydro- 
gen, 411. 
Vernadsky,       W.,       Alumosili- 

cates,  185. 
Vernon,  W.  H.  J.,  Atmospheric 

corrosion  of  metals,  %8. 
Viscous     substances,       Reliable 

apparatus  for  rapid  analy- 

su  and   regulation  of,  ^. 
Von  Rohr.  M.,  Contributions  to 

the  history  of  the  spectacle 

trade,  361. 
Von  Sanden,  Horst,  "Practical 

Mathematical  Analvsis" 

(Review),  366. 
Vowel  sounds.  Reproduction  of. 

SIS. 


WAGNER.   PERCY  A..   Dea- 
cloiisite       from       South- 
West  Africa,  100. 

Walker,  E.  E.,  Properties  ot 
powders,  315. 

Warrington,  A.  W.,  and  A.  E. 
J.  Pettet.  (See  Pettet,  A. 
E.  J.)_ 

Watson,  F.  8.,  and  J.  B,  Firth. 
(.See  Firth,  J.  B.) 

Weeks.     Edward   J..     Prepara- 
tion   and    properties   of   sil- 
ver  stihide.  319. 
Preparation  of     stibine  from 
a^oys.  87. 


Weeks,  Edward  J.,     and     Wil- 
liam F.  Lloyd,  Preparation 
of   pure  silver   stibide,  362. 
Weeks,   Edward   J.,  and  H.   J. 
S.  Sand.     (See  Sand,  H.  J. 
S.) 
Weight     and     mass.        Experi- 
ments    on  the     proportion- 
ality of,  325. 
Wheat,  iniiuonce  of  rainfall  on 
the  yield  of,  309. 
World's     supplies       and     re- 
quirements,  389. 
Wheeler,     T.   S.,     and   E.     W. 
Blair.     (See  Blair,  E.  W.) 
Wheeler,  T.  Sherlock,   WUliam 
M.   Cumming  and  I.   Vance 
Hopper.         (iSee    Cumming, 
W.  M.) 
Wheeler,  T.   Sherlock,  and   W. 
G.   King,     "Radio-Activity" 
(Review),   272. 
Whitby,     G.     S.,     Nature     and 
signiii(-ance  of  the  resin  of 
hevea   rubber,   184. 
Wiokham,    W.    G.,    "Report  on 
the      Economic     Conditions 
in  South  Africa"   (Review), 
400. 
Wiggles  worth,  V.  B.,     J.  B.  S. 
Haldane    and  C.  E.  Wood- 
row,       (^ee  Haldane,  J.  B. 
S.) 
Wigglesworth,     V.  B.,     and     C. 
E.    Woodrow,     Relation   be- 
tween    the     phosphate      in 
blood  and  urine,  375. 
WiU)erforoe,     L.     R.,     Illustra- 
tion    and   detection     of   in- 
clined   and     horizontal   dis- 
IKM  sioii  in  bi-axial  crystals, 
333 
Wild.     Georg  O.,     and     R.     E. 
Liesegang.     The  colorations 
of  otMtain  quartz  and  their 
mutability,  34. 
Wilkinson,  J.  Fk,  and  F.  Chal- 
lenger,     Organo-derivatives 
of  bismuth,  410. 
Willard,  H.  H.,  and  G.  Frede- 
rick Smith,  Ti>e  separation 
and     determination     of  so- 
dium  and  lithium     by   pre- 
cipitation     from     alcoholic 
perchlorate  solution,  42,  .57. 
Wilson,     W.,       Industrial     re- 
search,    with  special   refer- 
ence to  electrical  engineer- 
ing development,  282. 
Wireless   reception.      Relations 
between       damping         and 
speed  in,  365. 
stations  in  Russia,  253. 
Woehlk,     John     H.,     Nitrogen 
and     other     substances     in 
rain  and  snow,  30. 
Woodrow,  C.  E.,  J.  B.  S.  Hal- 
dane    and     V.   B.   Wiggles- 
worth.        (See     Haldane,  J. 
B.  S.) 
Woodrow,     C.   E.,     and     V.  B. 
Wigglesworth.        (See   Wig- 
glesworth,   V.    ^^ 
Wookock,     W.  J.    v.,     British 
Empire  Exhibition,  349. 

Worsley,  R.  R.  Le  G.,  and  H. 
B.  Baker,  Selenium  tri- 
oxide  and  ohlorselenic 
acid,  270. 


430 


Indkx. — Supplement  to  the  Chemical  News.       FEBRUARY  1.  1924. 


Wright,  Arthur,  '  "Industriai 
Filtration"   {Review),     399. 

Wylam,  B..  and  W.  N.  Ha- 
worth.  (See  Haworth,  W. 
N.) 


X-RAY  analysis  of  solid  solu- 
tions, 311. 
protective  materials,  122. 


spectroscopy  as  a  means  of 
qualitative  and  quantita- 
tive chemical  analysis,  65. 
X-Rays,  Secondary  corpuscu- 
lar rays  produce^  by  ho- 
mogeneous, 325. 


ZAGREB,  International  Sam- 
ples Fair  at,  51. 


Ziegler,  Ch.,  "Etude  sur  ie 
Tanuerie  et  les  Industries 
connexes  au  Maroc"^  {Re- 
view), 96. 

Zirconium,  Separation  of  haf 
nium  from,  353. 


[End  of  Volume  CXXVIl.j 


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