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e
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.
This list is specially compiled for the Chemical
News, by Messrs. Rayner & Co.. Rowistered Potonf
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.
This list is specially compiled for the Chemical
News, by Messrs. Rayner & Co., Registered Patent
Agents, of 5, Cliancery Lane, London, from whom
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Marks, and Designs, can be obtained gratuitously.
Latest Patent Applications.
348&1 — Etablissements Pouleno Freres. — Manufac-
ture of hydroxylated aliphatic arsenic
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
shales, coal, and other carbonaceous
materials, and apparatus thereof.
189700— Dutt, E. E.— Process for the extraction of
titanium dioxide and vanadiiim salts
from bauxite.
189701— "Willis, N. E.— Clarifying of solvents and
oils.
184153 — Chemische Fabrik Weissemstein Ges. —
Manufacture of hydrogen peroxide.
187232— Chemische Fabrik in Billwarder Vorm
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189834— Dandridge, A. G., and Thomas, J.— Manu-
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168902— Norsk Hydro-Elektrisk Kvatlstof-Aktiesl-
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18138.5 — Jacobson, B. H. — Process of making an-
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Abstract Published this Week.
Synthetic Drugs. — Patent No. 188127.— Messrs.
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Germany, have Patented in this country a pro-
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fatty acids. The product is prepared by treating
acridinium salt« of mineral acids with salts of
fatty acids of high molecular weight. Examples
are. given of the preparation of 3 :6-diamino-10-
methylacridinium stearate, 2 :7-dimethyl-3 :6-di-
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diamino-10-methylacridinium palmitate. The
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Messrs. Rayner & Co. will obtain printed copies
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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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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¶tion 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'.
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Baok to Prosperity : A New Aspect of
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268 + XI. 1923. Effingham Wilson, 16,
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The ^fathe^natical Theory of Helativitji.
by A. S. EnnixoTON. Pp. IX. + 247.
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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
all information relating to Patents, Tiada Marks,
and Designs can be obtained gratuitously.
Latest Patent Applications.
5027— Carmichiel . Co.. Ltd., J. F.— Means for
elevating and controlling supply of acids,
etc. Feb. 21.
4965 — Purand et Hnguenin Soc. Anon. — Manufac-
ture of highly chlorinated hydro-aromatic
products containing nitrogen. Feb. 20.
4873 — Lamoreaux, W. F. — Manufacture of sul-
phuric acid. Feb. 20.
r>374 — Margulies, O. — Production of organic ar-
senic compounds. Feb. 2.3.
5808 — National Benzone u^ssociation. — Process of
treating aromatic hydrocarbons. Feb. 23.
4837 — Pickett, F. N.— Method of removing chloro-
picrin from stannic chloride pentahydrate
solution. Feb. 19.
Specifications Published this Week.
170302 — Chemische Fabriken Vorm.— Process of
piirifying natural cellular structures con-
taining xanthine derivatives.
192778— Pease. E. L.— Production of material
suitable for use as a fertiliser
192842— Akt Ges fur Anilin Fabrikation.— Manu-
facture of new dvestuffs.
192941— Byrom, J. G.. and Attwater, R.— Method
of manufacturing formaldehyde conden-
sation products of phenols.
192970— Goldschmidt, H.. and Stock, A.— Process
for olectrolytically manufacturing com-
pact metallic beryllium.
191020 — Etablissements Ponlenc Freres and
Oetchslin.^ — Manufacture of aliphatic ar-
senical comiwunds.
Abstract Published this
191305— Dyes.— Soc. of Chemical
Bnsle; Basle, Switzerland.
Basle Switzerland.
Monoazo dyes, yielding fast
brown shades when chrome printed on cotton are
obtained by coupling diazotized l-amino-2-oxy-
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.
Messrr.. Rayner & Co. will obtain printed copies
of the ymblished Si')ecifications. and forward on
post free for the nrice of Is. fid. each.
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.
This 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, Trada Marks,
and Designs can be obtained gratuitously.
Latest Patent Applications.
569&-Amber Size & Chemical Co., Ltd.—Produc-
tion of aluminium hydroxide and alkali
silicates. Feb. 27.
5716— Ashcroft, E. A.— Apparatus for electrolys-
ing fused salts of metals and recovering
metals and acid radicles. Feb. 27.
5576— Boudett, A E. P.— Reduction of calcium
sulphate. Feb. 26.
5856— Coley, H. E.— Extraction of gold from ar-
senical ores. Feb. 28.
5894_Dntt, E. E.— Preparation of manganese di-
oxide. March 1.
5746— Harnist, C— Manufacture of fertilisers
from sulphur. Feb. 27.
6015 — Pinel, A.— Ripening alkali cellulose for
manufacture of cellulose xanthate. March
1.
6016 — Pomn. G. — Manufacture of p-amino-phenol.
March 1.
5877 — Royston, G. — Drying sulphate of ammonia.
March 1.
5877— Saville. W. — Drying sulphate of ammonia.
Feb. 28.
6236 — Standard Development Co. — Dehydrating
alcohol. March 3.
Specifications Published this Week.
193071— Plauson's Parent Co., Ltd. (Plauson, Dr.
H.) — Process of producing lower boiling
hydrocarbons from high-boiling hydrocar-
bons.
176779— Norsk Hydro-Elektrisk Kvaelstof-aktiesel-
skab. — Process for the manufacture of hy-
drogen, carbonic oxide or mixtures of
these gases.
193304 — Quinan, K. B.— Manufacture of super-
phosphate.
193477— O'Shaugnessy, F. R.— Method of and ap-
paratus for the de-colloiding of colloidal
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-
rous sulphate so as to obtain a blue precipitate
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.
Messrs. Rayner & Co. will obtain printed copies
of the published Specifications, and forward on
post free fo^ the price of Is. 6d. each.
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
writers o recognised authority."
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.
rms list is specially compiled for The Chemical
News, by Messrs. Rayner & Co., Registered Patent
Agents, of 5. Chance ry Lane, London, from whom
all information relating to Patents, Trade Marks,
and Designs can be obtained gratuitously.
Specifications Published this Week.
182084—800. Anon d(\s Matieres Colorantes et Pro-
duits Chimiquea de Saint-Denis, Wahl, A.
B., and Lantz ,R. — Manufacture of 2-oxy-
l-ary]-naphthylamines.
196431— Wolvekamp, M.E.— Organic mercury de-
rivatives of aurin tricarboxylic acid and
tlieir alkali salts.
Absirnct Published this Week.
194840— Dyeing cellulose acetate— R. Clavel, Aiigst,
Basle, Switzerland.
Messrs. Rayner & Co. will obtain printed copies
of the published spex'iflcations, and forward on
post free for the price of Is. 6d. each.
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.
xHis list is specially compiled for The Chemical
NeiDS, by Messrs. Rayner & Co., 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.
11900— Cassella & Co., Ges., L.— Manufacture of
alkyloxyacridines. May 2.
11971— Cassella & Co., Ges., L. — Manufaotitre of p-
dialkvlamino arylpliosphinous acids. May
3.
11849— Damard Lticquer Co., Ltd.— Phenolaldehyde
condensation products. May 2.
11616— Goldscmidt Akt. Ges., T.— Process for re-
fining tin. April 30.
12173— Harris, H.— Refining metals. May 5.
11617 — Imray, O. Y. — Maniifacture of vat dyestuffs
from anthraquinone. April 30.
12017— Johnson & Sons, Manufacturing Chemists
Ltd. — Tliermometer stand. May 4.
12502 — Gray, E. L.— Re<^'overy of caustic alkali
\ised in digesting cellulose, etc. material
and simultaneous production of oxalic acid.
May 9.
12366— New Jersey Zinc Co.— Manufacture of zinc
oxide. May 8.
12469— Soc. of Chemical Industry in Basle.— Manu-
facture of dye-stuffs of indigo tint. May 9.
Specifications Published this Week.
196658~Mehner, H.— Process and furnaces for
carrying out chemical reactions and phy-
sical processes at high temi>eratures.
196672 — King. O. — Amido-plienol compounds.
177494 — Soc. Chimique de la Grande-Paroisse.—
Synthesis of ammonia by means of hyper-
pressures.
191002— Soc. Ricard, Allenet et Cie.— Manufacture
of butyl chlorides.
Abstract Published this Week.
194840 — Dyeing cellulose acetate — R. Clavel, Augst,
Basle, Switzerland.
Aniline-black and like dyeing.— Black shades are
obtained on cellulose acetate silk, films, &c., by
imptregnating the material with diphenyl black
ase and acids, with oi' without salts or protective
colloids, and developing by oxidation. According
to examples : acetate silk' is impregnated in the
cold with a solution containing diplienyl black
base, acetic acid, lactic acid, aluminium, chro-
mium, and cupric chlorides, and sodium chlorate,
and developed in a drying room at 80° C. ; acetate
silk is treated at 50-60° C. in a bath containinsr
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,
may be added to the exhausted dyebath. Speci-
fication 182,830 is referred to.
Messrs. Rayner & Co. will obtain printed copies
of the published specifications only, and forward
on post free for the price of Is. Gd. each.
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
well-known volume on Theoretical Physi-
cal Chemistry has now reached its fifth
edition.
The important advances in physics and
chemistry made since the appearance of
the previous edition, some seven years ago,
have necessitated additions and alterations
in some chapters. That on Radioarfir'f
has been re- written, and recent work on the
Atom and in X-ray Spectroscopy has been
incorporated.
One or two minor but obvious slips have
been noted. These do not detract from the
great value of this important work.
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
work up-to-dnte and available for English
readers, has been based upon the fifth Ger-
man edition, which appeared soon after the
conclusion of the war. It therefore con-
tains much new matter. Some of this has
been commendably well condensed into
tables, where this mode of treatment was
possible.
Of thi' other new matter, English scien-
tists and chemists will be perhaps most in-
terested in the many revelations of the ex-
tremities to which German industry was
driven towards the close of the war by the
lack of fats and oils. Hydrolysis of fats for
soap production was forbidden, and oils of
any use for food oould not be used for var-
nishes, etc. Every possible source of fat,
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
mass of information upon those points for
which a bfx>k of this kind would be con-
sulted. It should prove of great value to
technical and analytical chemists.
BOOKS KECEIVED.
Experimental Researches and Reports,
by Departmknt ok Glass Teciini>logy. Pp.
ids. Vol. V. 1922. Department of Glass
Technology, The University, Sheffield.
Klinischc Kolloidchemie, by Dr. Ernst
Joel, mix einem Geleitwort von Prof. Dr.
K. Si'iRo. Pp. 124. 1923. Von Theodor
Steinkopff, Dresden und Leipzig. 2s. 2d.
PUBLICATIONS RECEIVED.
The U.S. Department of the Interior
have issued the following bulletins: —
Bulletin 686: Structure and Oil and Gas
Resources of the Osage Reservation, Okla-
homa, and Structure Maps, by David
White and others. Pp. 427.
Bulletin 730-11. : Stratigraphy of the El
Dorado Oil Field, Arkansas, as determined
by Drill Cuttings, by James Gilluly and
K. C. Heald. Pp. 8 + VI.
Bulletin 48(): Surface Water Supply of
the United States, 1918. Part X.—The
Great Basin. Pp. 271.
l^ulletin 483: Surface Water Supply of
the (nitrd States, 1018. Part XII.— North
Pacific Drainage Basins. B. Snake River
Basin. Pp. 171.
Bulletin 508 : Surface Water Supply of
the f^nited States, 1910-1020. Part VIII.
— Western Gulf of Mexico Basins, by
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Pp. 186.
Gold, Silver, Copper, Lead and Zinc in
Nevada in 1021. Mines Report, by C. C.
Heikbs.
Gold, Silver, Copper, Lead and Zinc in
Idaho and Washington in 1921. Mines Re-
port, by C. N. Gerry.
384
1
THE CHEMICAL NEWS.
JUNE 15, 1023.
Mineral Waters in 1921, by W. D. Col-
lins,
Gold, Silver, Copper, Lead, and Zinc in
New Mexico and Texas in 1921. Mines Re-
port, by Charles W. Henderson. Pp. 467-
477.
Gold, Silver, Copper, Lead and Zinc in
Colorado in 1921. Mines Report, by
Charles W. Henderson. Pp. 479-511.
Economic Geology of the Sunimerfield
and Woodsfield Quadrangles, Ohio, with de-
scriptions of Coal and other Mineral Re-
sources except Oil and Gas, by D. Dale
Condit. Pp. 156.
Manganese Deposits of East Tennessee,
by G. W. Stose and F. C. Schrader. Pp.
X., 154.
Metal-Mine Fires, by Daniel Harring-
ton, Byron 0. Pickard, and H. M. Wolf-
lin.
Quarry Accidents in the United States
during the Calendar Year 1921, by William
W. Adams.
Talc and Soapstone — Their Minitig, Mill-
ing, Products and Uses, by Raymond B.
Ladoo.
i'His 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, Trada Marks,
and Designs can be obtained gratuitously.
Latest Patent Applications.
12999 — Compagnie de Bethune. — Manufacture of
sulphovinic acid from ethylene. May 15.
13364— Goldschmidt Akt-Ges„ T.— Production of
silicon-containing aluminium alloys. May
18.
129'69— Indurit Products Co., Ltd.— Production of
articles of the phenol formaldehyde con-
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13246— Soc'. of Chemical Industry in Basle.—
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SpccificaHons Published this Week.
171684— Simonson, W. H., & Mantius, 0.— Process
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196993— Atack, F. W.— Process for sulphurising
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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-
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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-
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Messrs. Rayner & Co. will obtain printed copies
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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-
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prestige of the British dye industrj-, and at
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sive index of dyes is extremely desirable,
but up to the present the best availub1<-
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(treat Britain has the distinction of having
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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
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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
volume all the essential practical exercises
that a student should carry out. He has
not included any superfluous matter — at
least in the first part now under review.
Part I. includes a description of the pre-
paration of certain typical salts and their
gravimetric analysis, followed by exercises
in volumetric analysis. It is intended that
Part II. will contain a more extensive selec-
tion of preparations.
In general, the book follows the lines that
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-
tions, and deals with the subjects of Esters,
Oils and Fats, Sugars and other Carbohy-
drates, Cyclic Comipounds, Dyestuffs, Tex-
tile Fibres, Proteins, etc.
The publishers are Messrs. J. & A.
Churchill.
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 Maj'ks,
and Designs can be obtained gratuitously.
Latest Patent Applications.
17681 — Finch, Q. I. — Process for recovering ammo-
nia from gases or vapours. Julv ".
17130 — Lilionfeld, L. — Manufacture of cellulose
solutions. July 2.
17466— Soc. Chimique des Usines du Rhone.— Pre-
paration of diethvlchloracetamide. July 5.
17388 Soc. of Chemical Industry in Basle.—
Manufacture of alkaline-earth metal com-
pounds of the organic phosphorus com-
pound in milk casin. July 4.
Specifications Published this Week.
17375(V-Brynes, C. P.— Partial combustion
methods for treating aliphatic hydrocar-
bons.
19947.5 — Ix^ssing, Dr. R. — Manufacture of neutral
sulphate of ammonia.
199607 — Westermann, J. T. — Process for manufac-
turing pure sodium chloride.
181388— Chemische Fabrik Griesheim Elektron.—
Process of the production of ba«ic magne-
sium oarbtonate.
Abstract Published this Week.
197863— Phosphorus pentoxide.— Threlfall, Sir B.,
of Oakhurst, Church Road. Edgbaston,
Birmingham.
Phosphorus i)entoxide made by burning phos-
phorus in a stream of dry air is condensed at a
temperature of 125 to 200° C. in a compact, crys-
talline form. To avoid the presence of a small
amount of the amorphous, bulky variety a portion
of the vapour at about 160° C. is led through a
filter containing glass wool to a second condensing
chaml)er.
Messrs. Rayner & Co. will obtain printed copies
of the published specifications and abstract only,
and forward <Mi post free for the price of 1«. 6d,
each.
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.)
£15,000 DONATION TO IMPERIAL
COLLEGE OF SCIENCE.
It is with pleasure that we are able to
record an offer by the Clothworkcrs Com-
pany of the City of London of an annual
contribution of £'3,000 for the period of five
years, 1923-1927, to the Governing Body of
the Imperial College of Science and Techno-
logy, South Kensington, to be applied to-
wards the maintenance and development of
the City and Guilds (Engineering) College,
one of the three constituents of the Imperial
College of Science. This donation is sup-
plemental to the sum voted some years ago
by the Goldsmiths' Company, a gift
amounting to £85,000, which enabled the
Engineering College to extend its premises,
and is quite distinct from the annual vote
of £5,000 from the City and Guilds of Lon-
don Institute, which has been paid to the
Imperial College since the Charter was
granted some fifteen years ago and applied
to the City and Guilds (Engineering) Col-
lege. It is another indication of the value
whicB practical men in. the City of London
attach to the research and general teaching
in science, specially in relation to industry.
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
of scientific method edited by E. R. Th<Mnns,
M.A., M.Sc, Headmaster of the Royal
(rrammnr School, Newcastle-on-Tyne, and
tho object of the series is to iprf>vide repro-
ductions of the great masterpieces of
science in convenient form, together with an
account of the action and reaction of ideaii
which, through the pnxjess of time, led up
to the crucial experiments carried out and
described by some great master, and the
hope is expressed that a reader taking up a
volume of the series dealing with a branch
of science of which he is ignorant will be
able, without further help, to trace the
steps by which the human mind has passed
from chaotic ignorance to ordered know-
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.
A great many of the memoirs referred to
are quoted in full, particularly that of
Lavoisier on the respiration of animals and
the changes which occur in air as it passes
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
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Edition, 1923. Messrs. Dean & Son, Ltd.,
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i'His list is specially compiled for The Chemical
Newt, by Messrs. Rayner « Co., Registered Patent
Agents, of 5. Chancery Lane, London, from whom
all information relating to Patents, Tradft Marks,
and Designs can be obtained gratuitously.
Latest Patent Applications.
19218 — Kenkel et Cie.— Treatment of ammonium
chloride lyes in iron vessels. July 26.
19299 — Michael & Co., J.— Manufacture of nitrate
of potassium. July 27.
18944 — Pratt, J. T. — Desulphurising iron, steel,
and ferro-alloys. July 24.
Specifications Published this Week.
17528 — Posseyer Abwaseer-und-Wasserreini-Gungs
Ges. E. — Removal of phenol and its homo-
logues from waste waters.
178824 — Metz, H. A. — Complex arseno-stibino com-
pounds and process of making the same.
200760 — Koppers Co. — Recovery of alkali thiosul-
phates from solutions.
200151— Howards & Sons, Ltd., and Blagden, J. W.
—Manufacture of thymol.
200160— riauson's (Parent Co.), Ltd.— Manufacture
of cellulose derivatives and fibrous pro-
ducts.
200167— Adam, W. G., Siderfin, N. E., Murdoch,
D. G., and Galbraith, W. L.— Chemical
reduction of organic compounds.
200176— Spensley, J. W., and Chemical Engineer-
ing Co. (Manchester), Ltd. — Production,
mixing, blending, or refining of food pro-
ducts containing fats,
200186— Zdanowich, J. O.— Manufacture of cellu-
lose acetates.
Abstract Published this Week.
^
198829— Pyrazolone derivative; dyes. — Soc. of
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.
Monoazodyes which dye wool in yellow shades
similar to those of tartrazine but faster to light
are obtained by coupling the above described pyra-
zolone derivative with diazo compounds of the
benzene or naphthalene series; in an example
diazo-benzene is used.
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.
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the Director of the Chemical Laboratories.
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AUGUST 24, 1923.
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
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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
a classified index to commercial prospec-
tuses.
The work has been produced with the
usual thoiroughnes& and care, and cannot
fail to be of interest and value in the paper
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
News, by Messrs. Rayner & Co., Registered Patent
Agents, of 5. Chancery Lane, London, from whom
all information relating to Patents, Trada Meurks,
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
of the published specifications and abstract only,
find forward on post free for the price of Is. 6d.
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.
'I'^is list is specially compiled for The Chemical
News, by Messrs. Rayner « Co., Registered Patent
Agents, of 5. C'lianoery Lane, London, from whom
all information relating to Patents, Trade Marks,
and Designs can be obtained gratuitously.
Latest Patent Applications.
20385— Gaillard, E. A.— Manufacture of sulphuric
acid. Aug. 10.
20132— Juoker & Co., Chemische Fabrik.— Recover-
ing chromic salts from residues. Aug. 7.
Specifications Published this Week.
201231— Merrill Co.— Process of precipitating
metals from solutions.
201302— Farbwerke vorm. Meister, Lucius & Brun-
ing. — Manufacture of a complex amino-
argentomercaptobenzene-carboxylic acid.
185728 — Etablissements Poulene Freres.— Process
for the commercial preparation of amino-
nhenyl-arsenic acids and of their deriva-
tives.
201488— Vains, A. R. D. — Continuous chlorination
of ligno and pectro-cellulose by nascent
chlorine for the purpose of obtaining
pure cellulose.
197932— Pereira, H.— Process for manufacturing a
dye from dioxyperylene.
Abstract Published this Week.
199154 — Tsatine arylides, Stephan C, of Altona,
Germany.
I satine-... -arylides are isolated from their solu-
tions in sulphuric acid as sulphurous acid com-
pounds by treatment with ammonium sulphite or
bisulphite in quantity corresponding with the
whole sulphuric acid content; preferably the
sulphiiric acid solution is introduced into the
sulphite solution in the form of a spray. Ammo-
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.
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.
CITY OF CAEDIFF EDUCATION
COMMITTEE.
THE TECHNICAL COLLEGE.
Principal — Chaules 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
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tical training in a branch of industrial
chemistry chosen from the following: —
(1) Fuel.
(2^ General Iron and Steel Manufacture.
(3) Gas Manufacture.
(4) Foundry- work.
(5) Tin-plate manufacture.
(6) Refractories and Cement.
(7) Electro Chemistry.
(8) Brewing.
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Examinations which are also catered for
by the Course include : —
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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
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examinations.
OPEN SCHOLARSHIPS, covering
tuition fees and maintenance grants of £40
per annum for three years, are offered for
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entry to the above Department are eligible
to compete.
For further particulars of Full-time and
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Scholarships, Fees, etc., apply to the
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ceived by the 17th September.
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Director of Education,
City Hall, Cardiff.
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.
1HI8 list is specially compiled for The Chemical
News, by Messrs. Rayner & Co., Registered Patent
Agents, of 5. Chanoery Lane, London, from whom
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Latest Patent Applications.
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ture of formic acid. Aug. 20.
Specifications Published this Week.
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and Carmichael & Co., Ltd., J. P.— Fur-
naces producing sulphurous gases.
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•ach.
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: —
(1) Fuel.
(2) General Iron and Steel Manufacture.
(3) Gas Manufacture.
(4) Foundry- work.
(5) Tin-plate manufacture.
(6) 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, 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-
mission to the Entrance Scholarship Ex-
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,"
Vol. III. (1851).
^ 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,"
1821.
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.,
1823.
^' Kels, H. W. : "Onomatologia Chymfca
Practica." Vim, 1791.
OCTOBER 19, 1923.
THE CHEMICAL NEWS.
253
=*" Klaproth, M. H., and Wolff, F. : "Dic~
tionaire de Chemie." Trans, by BeuUlon-
Layrange, E. J. B. Paris, 1810.
^* de Morveau, Lavoisier, Bertholet, et
de Fourcroy: "Methode de Nomenelature
Ghimique." Paris, 1787.
" Proust, J. : J. Phys. Chim. et d'His-
toire Naturelle, 59, 321-349 (1804).
*^ Proust, J. : J. Phys. Chim. et d'His-
toire Naturelle, 59, 383 (1804).
" Roscoe and Schorlemmer : "A Treatise
on Chemistry," Ed. 4, Vol. 1 (1911).
" Silliman, B.: Am. Min. J., 1, 88-93
(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,
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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
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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\
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It is very apparent that many alterations
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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
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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. +
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1923. Messrs, Hell, York House P-rtn^'al
Street, W,C.2, 18s. 6d. net.
Recent Developments in Atomic Theory,
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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
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The Electrothermic Metallurgy of Zinc,
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BROOK, Richard V. AcxEton, and Harry E.
TUFFT. Pp. VII. + 72.
Water-Gas Tar Emulsions, by W. W.
Odell. Pp. IV. + 51.
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NEVELD and Edmund S. Leaver. Pp. V. +
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Agents, of 5. Chanoe-y Lane, London, from whom
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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.
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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
News by Messrs. Kayner & Co., Registered Patent
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
of the published specifications and abstract only,
and forward on post free for the price of Is, fid.
each.
NOTICES.
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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,
NOTICES OF BOOKS.
Oil Facta and Fiyurea, October, 1923.
Pp. 62. London : F. C. Mathieson i^
Sons, 16. Copthall Avenue, E.C.2. Is. ('4.
This b(X)k contains a list of the producing
oil companies, with the area and situation
of the oil fields and the number of wells.
Besides the v ual financial details, it
gives the end of viie financial year and the
highest and lowest prices of shares for the
years 1920 to (mid-October) 1923. The
monthly output of a number of comipanies
is contained in a separate table.
The large amount of information in a
small volume makes it a valuable pocket
reference book. Future editions might also
indicate to which combine any particular
company belongs. G.H.M.
BOOKS RECEIVED.
Practical Mathematical Analysis, by H.
VON Sanden, with examples by the trans-
320
THE CHEMICAL NEWS.
NOVEMBER 16. 1923.
lator, H.Levy, M.A., D.Sc, F.R.S E
Pp. XL + 195. 1923. Mesi^rs. Methuen &
Co., Ltd., 36, Essex Street, W.C. lOs. 6d.
net.
Die Atomic, von Jean Perrin, mit auto-
risation des Verfassers deutsch herausgege-
ben von Dr. A. Lottermoser. Pp. XX. +
213. 1923. Verlag von Theodor Steinkopff,
Eesidenzstrasse, 12b, Dresden, Blasewitz.
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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.
26736~Bliopal Produce Trust, Ltd. — Recovery of
oxolates, etc. Oct. 25.
26.572 -British Cellulose & Chemical Manufactur-
ing Co., Ltd. — Treatment of cellulose oce-
tate, etc. Oct. 24.
26526 — Henshaw, S. — Production of neutral
phate of ammonia. Oct. 24.
26680 — Leigh, R.— Hampers for acid carlx)ys,
Oct. 25.
Specifications Published this Week.
20.5224— Houseman, C. R., and British Oxygen Co.,
Ltd. — Manufacture of siilphur dioxide and
apparatus for iisc therein.
Abstract Published this Week.
2033.52 — Titanium oxide and sulphate. — Weizniann.
C, and Blumenfeld, J., of 16, Addison
Crescent, London.
Titanium sulphate and oxide; ferrous sulphate.
— To obtain titanium compounds free from iron,
an ore such as ilmenite is heated to 1.50-180° C.
with sulphuric acid of 70-90 per cent, strength.
The solid product is leached with a limited quan-
tity of water in presence of a reducing agent, pre-
ferably spongy iron, most of the iron sulphate
being left in the solid form. The water is added
little by little at a temperature not above 50° C.
The reduction is completed when a brown-violet
coloration sliows the presence of titanous salts.
The solution is then treated to hydrolyze the ti-
tanium sulpliate in any known way, and the first
washings of the i)recipitated hydroxide are
effected with water acidulated with sulphuric
acid and containing a titanous salt so as to avoid
any oxidation of ferrous salts which would injure
the colour of the product. The precipitate is cal-
cined under oxidizing conditions, for instance by
blowing air through the container or through the
material during calcination, or, according to the
Provisional Specification, by calcining in the pre-
sence of sulphuric acid, the object being to pre-
vent any reduction owing to organic matter that
might be present. The ferrous sulphate left with
the undissolved residue of the ore is recovered by
solution and crystallization, and may be treated
to recover the sulphuric acid. According to the
Provisional Specification, the solution of titanium
sulphate is protected from oxidation during hy-
drolysis by means of a film of oil, vaseline or the
like."
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.
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NOVEMBER 23, 1923.
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
PuMMERER. Pp. XL + 209. 1923. Verlag
von Theodor Steinkoipff, Residenzstr., 12b,
Dresden und Leipzig. 4s.
I
This list is specially compiled for The Chemtcal
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.
27376— Albert, A.— Process for producing organic
comi>ounds of mercury. Oct. 31.
27233— Cassella & Co., Ges. L.— Production of acri-
dinium compounds. Oct. 30. , • ,
27048— Chance & Hunt, Ltd.— Treating crude oxide
and carbonate of zinc. Oct. 29.
27219— Farbwerke vorm. Meister, Lucius & Brun-
ing.— Manufacture of acid azo-dyestutfs.
Oct. 30. . rrr ,
Specifications Published this Week.
205141— Robinson, C. S.— Recovery and refining ot
sulphur. . „
205288— Goodwin, C. J.— Manufacture of oxides ot
nitrogen and nitric acid.
205301— Weymann, G.— Drying of ammonium sul-
phate. „ . ,,
197315— Compagnie de Bethune Soc. Anon.— Manu-
facture of ethyl alcohol from sulphovinic
acid. - „
205528— Mach ay, H. S.— Methoil of and means tor
roasting metallic ores. ^, , .
205563— Chemische Fabrik Greishcim Elektron.-
Process for the production of alumininm
chloride and alumina.
191363— Pereira, H.— Process for manufactunnp;
dioxyperylene.
194719-Consortium fur Elektrochemisohe .Iiulus-
trie Ges.— Manufacture of anhydrides of
fatty acids of low molecular weight.
Abstract Published this Week.
203749-Sodium silicate .-Clayton, W of Arderry.
Allerton Drive, Mossley RiH, Liverpool,
and Richards, H. W., of 9, Hawarden Ave-
nue, Wallasey, Cheshire.
Sodium silicate solution is evaporated by spra^-
iny into heated air. The solution may be ot 1(H)
Tw and may contain 2.1 parts by weight of silica
to 1 part by weight of Na^O. The spraying may
b? effected with the liquid at 45° C. by means of an
air pressure of 65 lb. per sq. in. Beneath the let
of liquid is a high velocity air jet at right angles
to the liquid jet as in milk spraying, a pressure
of 150 lb per sq. in. being suitable. instead ot
an air jet superheated steam or flue gases may be
^ Messnt-B. Rayner Co. will obtain printed copies
of the published specifications and abstract only,
and forward on post free for the price of Is. bcl.
each.
NOTICES.
EDITORIAL. — All Literary communica-
tions and Books, Chemical Apparatus,
&c., for review or notice to be addressed
to the Editors.
SUBSCRIPTIONS £1 12s. per aanum,
payable in advance, should be addressed
to the Manager.
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purchased on application to the
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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
Messrs. Rayner & Co. will obtain printed copies
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and forward on post free for the price of Is. 6d,
eaoh.
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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.
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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.
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.
206229-Chance & Hunt, Ltd., Calder, W. A. S., and
and Palmer, W. H. — Process for condens-
ing the acid fumes evolved during the con-
centration of sulphuric acid.
186589 — Hansgirg, Dr. F. — Process and apparatus
for the extraction of zinc from zinkiferous
materials.
29313— Chemische Fabrik in Billwarder vorm..
Hell & Sthamer Akt-Ges. — Manufacture of
pure anthracene and oarbazol. Nov. 20.
Specifications Published this Week.
206671— Stacey, F.— Electric apparatus for the
production of peroxides of nitrogen.
206711— Lacy, iS. A. De.— Frame to make possible,
in the same apparatus, solvent recovery by
distillation after extraction of a sub-
stance has been made by that solvent.
201914 — Krupp Akt-Ges., F. — Articles requiring a
high resistibilitv against corrosion by am-
monium chloride solutions.
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.
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.
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
\eifs 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 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.
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.
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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