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HARVARD UNIVERSITY
LIBRARY OF THE
BIOLOGICAL LABORATORIES
HARVARD COLLEO!! I.'P'^' 5''
WAY 4 194S
THE JOURNAL
—OP THK—
AMERICAN CHEMICAL SOCIETY.
VOLUME XVIII.
1896.
COMMITTEE ON PAPERS AND PUBLICATIONS:
Edward Hart, Editor,
J. H. Long,
Thomas B. Osborns.
Photolithograph Reproduction
By Permission of The American Chemical Society
JOHNSON REPRINT CORPORATION
New York, N. Y., U. S. A.
kcff /•-■/
• ^^
HARVARD
UNIVERSITY
LIBRARY
copyright, 1896,
By Edward Hart, John H. Long,
AND Thomas B. Osborne.
Committee on Papers and Publications of thcT
American Chemical Society.
PHCrrOLITHOGRAPHED BY
THE MURRAY PRINTING COMPANY
WAKEFIELD, MASSACHUSETTS
Vol. XVIII. [August, 1896.] No. 8.
THE JOURNAL
OF THE
AMERICAN CHEMICAL SOCIETY.
PHOTOMETRIC METHOD FOR THE QUANTITATIVE DETER-
niNATION OF LIHE AND SULPHURIC ACID.'
By J. I. D. Hinds.
Received May 14, itgd.
THE want of a rapid method of determining with a close
approximation the amount of lime and sulphuric acid in
drinking water led me to the study of the opacity of fine white
precipitates suspended in water. I precipitated in weak solu-
tions lime with ammonium oxalate, and sulphuric acid with
barium chloride, then measured the height of a column of the
liquid containing the precipitate through which the flame of a
common candle was just invisible. I expected only a rude
approximation, but to my surprise, I found that between cer-
tain limits, an accuracy is attainable equal to that of the ordi-
nary volumetric methods.
APPARATUS.
The only apparatus needed is a cylinder graduated from the
bottom in centimeters and tenths. The cylinder should have a
plain polished bottom, like Nessl'er cylinders, and should have a
lip at the top. The one I use was made for me by Eimer and
Amend. It is four cm. wide and twenty cm. high. The gradu-
ations runs to eighteen cm. This cylinder, however, is not
absolutely necessary. A common beaker may be used and the
depth of the liquid measured with a small ruler.
1 The manuscript of this srticle was sent similtaneously to the Chemical News and
to this Jonmal. Owing to the absence from home of Professor Hinds, his proof was de-
layed too long to allow of publication of the article in the July issue.
/.■- i
B'*
Com*
^ /^
O.OS73
0.0570
o.05«
0.0570
Itlution of the
very slightly.
)re dilute with
0.0595
0.0589
0.0597
0.0591
0.0591
0.0S91
0.0594
.... O.OS93
.... 0.0587
.... 0.0590
imber obtained
the solution by
: is just invisi-
by taking the
is an hyperbola
is
liagram. The
oi per cent, to
lution, observe
/ \ 'J- '
f /
/
HARVARD UNIVERSITY
LIBRARY OF THE
BIOLOGICAL LABORATORIES
HARVARD COLLEC!^ I'P^' ^'v
MAY 4 1949
666 J. I. D. HINDS.
cipitate the whole of the calcium. The solution was then poured
into the photometric cylinder and the depth measured as in the
case of sulphuric acid. Portions of ten or twenty cc. of water
were successively added and the depth observed after each addi-
tion. The results are given in the following table. In column
I is the number of the solutioti ; column 2 shows the per cent,
of calcium carbonate ; columns 3, 4, 5, 6, and 7 contain the
measured depths of the liquid at which the flame became invisi-
ble ; column 8 contains the means of these depths, and column
9 the product of these means by the per cents, in column 2, rep-
resented as before by xy. The three determinations in the
fifth series were made simply as a check. Many other indepen-
dent determinations were made in order to ascertain whether
there was a change of opacity, and whether the precipitation
would be different in the weaker solutions. No material differ-
ence was found.
Per cent,
calcium
No. carbonate. cm. cm. cm. cm. cm. x. xy.
1 0.0333 2.1 2.3 2.3 ' 2.4 2.250 0.0750
2 0.0250 2.8 2.9 2.9 2.9 2.875 0.0718
3 o.oioo 3.5 3.6 3.5 3.5 3.525 0.0705
4 0.0167 4.1 4.2 4.1 4.1 4.2 4.14 0.0691
5 0.0143 4-7 4-8 4.7 4.7 4.725 0.0676
6 0.0125 5.3 5.5 5-3 5.3 5-35 0.0669
7 o.oiii 6.0 6.1 5.9 6.0 6.0 0.0666
8 0.0100 6.6 6.8 6.6 6.7 6.675 0.0668
9 0.0091 7.3 7.4 7.3 7.4 7-4 7-36 0.0670
10 0.0083 8.0 8.0 8.0 8.1 8.03 0.0666
II 0.0077 ^-8 8.6 8.6 8.8 8.7 0.0670
12 0.0071 9.5 9.3 9.3 9.5 9.4 0.0667
13 0.0067 10.2 0.9 9.9 10. 1 9.9 lo.o 0.0670
Examining the values of xy, we find that they are not con-
stant. They diminish rapidly at first, then more slowly. The
equation is, therefore, not so simple as in the case of sulphuric
acid. It appears, however, to be an hyperbola, and we may
assume that its equation has the form
xy-^by^a,
in which b and a are constants whose values are to be deter-
mined. Substituting the values of x and^ from the above table,
UMB AND SUIrPHURIC ACID. 667
we obtain thirteen observation equations. The values of a and
6 are then found according to the method of least squares by
forming and solving the two sets of normal equations. The first
set will be the same as the observation equations ; the second
set is obtained by multiplying each equation by its cofficient of
d. These equations are as follows :
0.0750 + O.Q333 d == a 0.002500 + o.ooiiii d =s 0.0333 a
Q.0718 + 0.0250 b =s a 0.001795 4- 0.000625 d = 0.0250 a
0.0705 + o.oaoo b =^a 0.001410 4 0.000400 d = 0.0200 a
0.0691 + 0.0167 6 ss a 0.001151 -h 0.000271 b = 0.0167 a
0.0676 + 0.0143 b =s a 0.000967 + 0.000204 b = 0.0143 a
0.0669 + 0.0125 b ssa 0.000836 4- 0.000156 b ^ 0.0125 a
0.0666 + o.olii b ^a 0.000740 + 0.000124 b 3B o.oiii a
0.0668 + o.oioo b =s a 0.000668 4* o.oooioo b ss o.oioo a
0.0670 + 0.0091 b^a 0.000610 + 0.000083 b = 0.0091 a
0.0666 -f- 0.0083 b^sza 0.000553 + 0.000069 b ^ 0.0083 «
0.0670 + 0.0077 b-^a 0.000516 -+- 0.000059 b = 0.0077 a
0.0667 + 0.0071 b == a 0.000474 -f- 0.000050. b = 0.0071 a
0.0670 + 0.0067 ^ = a 0.000449 + 0.000045 b ^ 0.0067 ^
Adding the equations together, we have
0.8886 + 0.1818*= 13a. 0.012668-1-0.003304* = 0.18 i8a.
Dividing by the coefBicient of a and eliminating, we have
a = 0.0642 * = — 0.3
The required equation is therefore
xy — 0.3 * = 0.0642,
or, solving for^
0.0642
X —o,^
For the per cent of CaO the equation is
0.0360
^= — .
^ — 0.3
This is the equation of an hyperbola referred to one of its
asymptotes as the axis of x and to an axis of y three-tenths cm.
to the left of the other asymptote. The abscissas are centime-
ters and the ordinates are o.oi per cent, to the cm. The curves
are shown in the accompanying diagram.
As an example, let us suppose that the observed depth is four
and seven-tenths cm. Subtract 0.3 and divide 0.0642 by the
;. I. D. HINDS.
DUcram i.
remainder. The quotient 0.0146 is the per cent, of calcium car-
bonate. Dividing this by 1000 we have 14.6 parts to the 100,000.
PROBABLE ERROR.
To determine the probable error of an observation we may
compare as before the numbers fdund by observation with those '
computed from the equation, as follows :
StrcDKth Slrencih
X. us«d. computed. v, i^.
3.9 0.0350 O.oa47 0.0003 0.00000009
3.5 0.0100 o.oaor o.oooi o.oooooooi
4.1 0.0167 0.0170 0.0003
UMK AND SULPHURIC ACID.
669
Strength,
used.
strength.
jr.
computed.
V.
t4.
4.7
0.0143
0.0146
0.0003
0.00000009
5-35
0.0125
0.0127
0.0002
0.00000004
6.0
O.OI 1 1
O.OI 12
O.OOOI
O.OOOOOOOI
6.7
O.OIOO
O.OIOO
0.0000
0.00000000
7-4
0.0091
0.0091
0.0000
0.00000000
8.0
G.0083
o.oo8>;
0.0002
O.OOOOOOQ4
8.7
0.0077
0.0077
o.oono
0.00000000
9-4
0.0071
0.0071
0.0000
0.0000000(>
lO.O
0.0067
0.0066
O.OOOI
Sum 2t^
0.00000901
0.00000038
Using the
same value for error as
before, in which in this case
n, the number of observations, is 12
, and ^» the number of con-
stants in
the equation is
r= 0.6745^.
2, we have
= 0.00013 per cent.
0.000P0038
12 — 2
That is, the probable difference between an observed and com-
puted strength of a solution is 0.00013 percent., or thirteen parts
in ten million.
SOURCES OF ERROR.
The principal sources of error in this method are two. In the
first place a light of constant intensity should be used. It makes
but little difference what the light is, so it is the same as that
with which the constant in the equation is determined. I
employed the flame of an ordinary candle as the most con-
venient. A brighter and steadier light would give better results.
Any change of light will of course change the constants.
The second source of error is the personal equation. Each
individual can determine this for himself. The error dependent
upon the eye can be almost eliminated by using it in the usual
way, that is with or without glasses.
A9y one can obtain the constants for himself by making a
few determination with solutions of known strength. The best
strength to use is that between o.oi and 0.03 per cent. Great
care must be used in measuring. If ten cc. of a decinormal
solution are taken, a difference of one drop in the measurement
may make an error ten times as gpreat as that involved in the
method.
670 HERMANN FI^ECK. SEPARATION OF
PRACTICAL APPLICATION.
I have so far used the method and tested it only in sanitary
water analysis and in the analysis of urine. To the water analyst
it will be of great value. It gives the lime and sulphuric acid
with almost the accuracy of the gravimetric method. It is more
accurate than the soap test and is but slightly affected by the
presence of magnesium salts.
For determining the sulphuric acid in urine I have found it
quite satisfactory. The urine has to be diluted with nine vol-
umes of water and then the color does not sensibly affect the
determination.
I see no reason why this method may not be successfully used
with all fine white precipitates. It is not suitable for precipi-
tates that settle rapidly or gather quickly into flakes. Whether
colored precipitates may be determined in this way is still to be
investigated.
I desire to acknowledge obligation to Professor A. H. Buchanan
for assistance in determining the equations and probable errors.
Chemical Laboratory, Cumberland University,
Lebanon, Tbnn.
[Contributions from John Harrison Laboratory op Chemistry.
No. 12.]
THE SEPARATION OF TRIHETHYLAMINE FROil
AnMONIA.
By Hermann Fleck.
Received May 8. XB96.
THE quantitative estimation of trimethylamine in presence of
ammonia is, I believe not mentioned in the literature,
although a number of publications have appeared in which the
detection of trimethylamine, in presence of ammonia, by means
of the different solubilities of their hydrochlorides in absolute
alcohol, has been successfully carried out.
Dessaignes* prepared and analyzed with good results the plati-
num double salt of trimethylamine, by conducting the mixture
of ammonia and trimethylamine vapors into hydrochloric acid,
evaporating to drynesst extracting with absolute alcohol, pre-
cipitating with platinic chloride and recrystallizing the precipi-
tate formed several times from hot water.
I Ann. Ckem. (Uebig).8i, 106.
TRIMBTHYI«AMINB PROM AMMONIA.
671
Wicke' adopts the same method, using, however, alcohol-
ether extract.
Winkeles,' in using this method, further states that while
ammonium chloride is soluble to some extent in absolute alco-
hol, it is rendered totally insoluble by the presence of salts of
such bases as trimethylamine.
Eisenberg,' by a similar procedure, obtained the platinum
double salt in crystals of great purity and perfection.
The success in each case is undoubtedly due to the fact that
large quantities of hydrochlorides were used. Winkeles,^ for
example, employed the hydrochlorides obtained from twenty-six
gallons of herring brine. Further the mixtures were very rich
in trimethylamine.
This method applied to a substance containing a low percent-
age of the latter yielded results, which clearly show that tri-
methylamine hydrochloride does not render ammonium chloride
insoluble in absolute alcohol, and further does not serve as a
good means of qualitative, much less of quantitative, separation.
A portion of the mixture containing trimethylamine and ammo-
nia was saturated with hydrochloric acid, evaporated to dryness
and extracted several times with portions of several times the
volume of boiling absolute alcohol. The alcoholic extract
evaporated to dryness gave eighteen per cent, of supposed tri-
methylamine hydrochloride. To identify the latter, the residue
was taken up with alcohol and platinic chloride added. The
precipitate formed was redissolved in boiling water and the dif-
ferent fractional crystallizations, consisting of octahedra, anal-
yzed.
Pt fontid.
First crystallization 43.6
Last '* 39.5
Required for
(NH^ClXPtCl^. 43.84
Corresponding to a
mixture of
1 Ann. Ckem. (Liebig), gx, lai.
*Ann. Chem. (Uebig), 93, 331.
*Ber. d. ehem, Ges., 1880, 1669.
4 Loc. cit.
2ANH,Cl),PtCl4W
3(N(CH,),.HClVptCl„
which require 39.4 per cent. Pt.
672 SEPARATION OP TRIMBTHYLAMINB PROM AMMONIA.
Intermediate crystallizations gave intermediate, gradually
decreasing results, showing that the isomorphous forms of the two
salts crystallized together.
Duvillier, Buisine' extract the mixed sulphates to prepare pure
trimethylamine from the technical product. The suggestion led
to the use of the following method which yielded satisfactory
results.
The mixed hydrochlorides are repeatedly extracted with por-
tions of a total of five or six times the volume of boiling absolute
alcohol and the solvent distilled off in a three-quarter liter dis-
tilling bulb. An excess of caustic soda is added to the residue
and the gases formed on boiling driven over into a large quan-
tity of water. Litmus is added, followed by the exact quantity
of dilute sulphuric acid required to neutralize. The liquid is
evaporated to dryness and extracted with one liter cold absolute
alcohol, in which trimethylamine sulphate dissolves, leav-
ing ammonium sulphate undissolved. The alcohol is dis-
tilled off, the residue transferred to a weighed dish, dried and
weighed. In this manner 32,910 grams of the carefully dried
mixed chlorides gave two and five-tenths grams trimethylamine
sulphate, corresponding to 2.21 grams hydrochloride, or 6.71
per cent.
That the extraction was complete is evident from the total
absence of the fishy odor when the extracted residues are treated
with alkali. That the extracted material is pure is shown by
the following analyses of the octahedral crystals of the platinum
double salt prepared from the trimethylamine sulphate :
Required for
[N(CH,),.HCl]tPtCl4.
Per cent Pt. Per cent. Pt.
I. 0.0985 gram gave 36.92 ....
II. 0.3017 *• ** 37.12 36.93
1 Ar.n. Oum,^ (Liebig) (s) S3, 399.
ZIRCONIUM TETRAiODIDE.
By h. M. Dennis and a. B. Spbncbr.
Received June 9, i8p6.
WITH the exception of the tetraiodide all of the normal
halides of zirconium have been prepared and described,
the fluoride, chloride, and bromide being white, crystalline, sub-
limable solids.
A few attempts to make the iodide are recorded in the jour-
nals, but in no case was the normal compound, zirconium tetra-
iodide, Zrl^* obtained. Melliss' passed the vapor of iodine over
a glowing mixture of zirconia and carbon ; he also treated zir-
conium tetrabromide with potassium iodide, but in neither case
did zirconium tetrachloride result. Hinsberg' added an aqueous
solution of barium iodide to a solution of zirconium sulphate,
filtered off the barium sulphate, and evaporated the filtrate over
concentrated sulphiuic acid. He obtained a compound of the
formula Zr,I,0„ or Zrl (OH),. He also passed the vapor of
iodine over a heated mixture of zirconium dioxide and carbon
and states that no reaction whatever took place. Bailey' states
that '* zirconium* is acted upon by chlorine and bromine,
in which, on gentle heating, it undergoes vivid combustion,
forming the tetrahaloid derivatives, and this is, indeed, a con-
venient method for obtaining these bodies. The iodide could
not be obtained."
In the work here to be described, the authors first attempted
to prepare zirconium tetraiodide by passing the vapor of iodine
over heated zirconium. The zirconium first used was made by
reducing zirconium dioxide with magnesium powder, the two
substances being mixed in the proportion employed by Winkler^
and demanded by the equation
ZrO, + 2Mg = Zr + 2MgO.
This mixture was heated in hydrogen in the usual manner
and the resulting black powder was removed from the boat,
thoroughly ground, and again heated in hydrogen to insure
1 Ztsehr. Chem., 1870, 296 : Jsb., /870, 328.
^Ann. Chtm. (Uebig), 939, 253.
s Chtm News.y 60, 8.
* Prepared by the reduction of zirconia with maflrnesium powder.
S Ber. d. ckem. Ges., 33, 2664 ; 94, 888.
674 I'- M. DENNIS AND A. B. SPENCBR.
conplete redaction. To free it from magnesia, the product was
treated with a saturated solution of ammonium chloride. Dur-
ing this treatment a gas of very disagreeable odor was evolved.
It is doubtless similar to that observed by Winkler at this point.
The powder was then warmed with dilute twelve per cent, hydro-
chloric acid and, after collecting it on a filter, it was washed
with water containing hydrochloric acid, then with alcohol and
ether, and finally was dried in a current of hydrogen. The
analysis gave
Per cent
Zirconium 80.670
Silicon 0.807
Magnesium 0.117
Hydrogen 0.362
Oxygen (diff.) 18.044
100.000
These results agree quite closely with those obtained by
Winkle^,' and indicate that the product of the reduction is chiefly
zirconium monoxide rather than zirconium.
Although the powder probably contained but very little free
zirconium, it was nevertheless heated in hydrogen and vapor of
iodine was passed over it. An examination of the product gave
no satisfactory indications, however, that an iodide of zirconium,
had been formed.
Inasmuch as the failure to obtain union between the zirconium
and iodine might reasonably be ascribed to absence of free zir-
conium in the above product, it seemed advisable, before
attempting any modification of the iodine treatment, to prepare
zirconium by some other method and especially by some pro-
cedure in which the presence of any appreciable amount of oxy-
gen is avoided. Under the circumstances the method of Berze^
lius,* the reduction of potassium fluozirconate with metallic
potassium, seemed the most promising and was therefore em-
ployed.
The potassium fluozirconate was prepared from zircon. The
zircon was finely ground, sifted through bolting cloth, and
digested with concentrated hydrochloric acid until the acid gave
1 Ber. d. chem. Ges., as» 2667.
^Ann. derPkys, (Pogg), 4. "7
ZIRCONIUM TETRAIODIDE. 675
no reaction for iron. The powdered zircon, which was now
almost perfectly white, was dried and mixed with four times its
weight of sodium carbonate. The mixture was fused in an
assay crucible furnace, allowed to cool, pulverized, and repeat-
edly extracted with water. The residue, consisting of zirconia
and unattacked zircon together with some silica and ferric oxide,
-was heated with concentrated hydrochloric acid, evaporated to
dryness, and heated in an air-bath to 120° to render the silica
insoluble. The dried mass was treated with a little hydrochloric
acid, water was added, and the silica and other insoluble matter
was filtered off. The filtrate, now containing zirconium chloride
and some ferric chloride, was largely diluted with water, and
ammonium hydroxide was added until there was formed a slight
but permanent precipitate which was then dissolved by adding
as little hydrochloric acid as possible. Sulphur dioxide was
then passed into the solution until the liquid smelled strongly of
the gas. In many cases a precipitate of basic zirconium sul-
phite formed at once, but, as the compound seemed to be some-
what soluble in an excess of sulphurous acid, the solution was
always boiled for from ten to fifteen minutes to insure complete
precipitation. In the reaction free hydrochloric acid is formed
both by the conversion of the zirconium chloride into the basic
sulphite and by the reductfon of the ferric chloride to the ferrous
salt. As this acid would dissolve the zirconium sulphite, it was
partially neutralized by the addition, from time to time, of a few
drops of dilute ammonium hydroxide. The zirconium precipi-
tate not being wholly free from iron, it was dissolved in hydro-
chloric acid and again precipitated with sulphur dioxide. The
pure zirconium basic sulphite thus pbtained was dissolved in
hydrochloric acid and zirconium hydroxide was precipitated by
adding ammonium hydroxide. The well-washed hydroxide was
dissolved in hydrofluoric acid, potassium fluoride was added,
and the resulting potassium fluozirconate was dissolved in hot
water and recrystallized.
The potassium fluozirconate thus prepared was reduced with
metallic sodium, the operation being carried out in a cast-iron
crucible. The crucible is cylindrical in form with an internal
diameter of two inches and depth of five inches. The wall and
676 I,. M. DENNIS AND A. E. SPENCER. '
bottom are over one inch in thicknebs. At the top it has a
flange seven inches in diameter and is provided with a cast-iron
cover one inch in thickness, which can be firmly fastened to the
flange by means of six one-half inch bolts.
In charging the crucible, sodium chloride, finely ground and
thoroughly dried, was first put in to the depth of about an inch
and a half, and this was then well pounded down with a wooden
plunger to compact the salt and expel the enclosed air. On top
of the salt were placed alternate layers of potassium fluozircon-
ate, also thoroughly dried, and metallic sodium, these being
pounded down as before. The remaining space in the crucible
was then filled with sodium chloride and, after pounding this
down, the top was bolted on and the crucible was heated for
about three hours with three triple burners. This heat, how-
ever, was not suflScient to raise the crucible to redness.
The crucible was then allowed to cool and, upon opening it,
the charge was found to be so compact that it had to be loosened
with a chisel. On treating the mass with water the metallic
zirconium, together with a small amount of the oxide which had
formed, settled to the bottom while the sodium chloride and
potassium and sodium fluorides dissolved.
The zirconium and zirconium oxide were separated by first
floating off the lighter zirconium with water and then digesting
it with dilute hydrochloric acid at 40^ until all of the oxide had
been dissolved. The resulting product was a black, amorphous
powder which, after washing with water, alcohol, and then with
ether, showed no trace of impurity before the spectroscope
except a slight amount of sodium.
Vapor of iodine was pass^ over some of this zirconium heated
to dull redness in a current of hydrogen, but with no better suc-
cess than with the other sample. We then concluded to substi-
tute hydriodic acid gas for the iodine. Considerable difficulty
was encountered in finding a suitable method of preparing the
gaseous hydriodic acid. That described by*Merz and Holzmann'
was finally found to answer admirably. It consists in passing
dry hydrogen and vapor of iodine through a red hot tube filled
I Ber. d. chem. Ges., aa, 867.
ZIRCONIUM TETRAIODIDE. 677
with pumice stone and freeing the hydriodic acid gas from
iodine by passing the gases through cotton.
In treating the zirconium wiih hydriodic acid gas the follow-
ing apparatus was used.
Iodine was placed in a small tubulated flask connected on one
side with an apparatus furnishing pure, dry hydrogen and on
the other side with a long piece of combustion tubing. The
half of this tube nearest the iodine flask was filled with pieces of
pumice stone and rested in a combustion furnace. The other
half, extending beyond the combustion furnace, w^as filled with
cotton. The end of this tube was connected with another com-
bustion tube resting in a second combustion furnace. The por-
celain boat containing the zirconium was placed in this second
tube.
The hydrogen was first passed through the whole apparatus
for several hours and then the first furnace was lighted. When
the pumice had become red hot the flask containing the iodine
was gently heated. The tube containing the zirconium soon
became filled w^ith the hydriodic acid gas, whereupon the second
furnace was lighted. As the temperature rose, a brownish-yel-
low substance collected in the cold end of the combustion tube,
but as the heat became greater the color entirely disappeared
and there remained an amorphous white sublimate. No further
sublimate was formed until the tube had almost reached a bright
red heat when there appeared just beyond the point where the
tube was red hot a white crystalline sublimate, different in ap-
pearance from that which first formed. The gas escaping from
the end of the tube contained hydriodic acid, hydrogen, some
iodine, and a trace of iron, the last probably being present in
traces in the zircotlium and volatilizing as ferrous iodide. The
tube was kept at a bright red heat for from three to four hours.
The gas was then turned off and when the boat had cooled con-
siderably the heating of the iodine fla.sk was discontinued. The
first furnace was then shut off and the whole apparatus was
allowed to cool in the current of hydrogen.
The material in the boat had changed from a black to a gray-
ish-white color, but a chemical examination showed that it con-
tained ver>' little iodine. The amorphous sublimate which first
678 ZIRCONIUM TETRAIODIDE.
formed was found not to be zirconium iodide but to contain
chiefly iron and iodine.
The crystalline sublimate which w^as formed only at a red heat
was next analyzed. These crystals were found to be insoluble
in water, nitric acid, hydrochloric acid, aqua regia, and carbon
disulphide. They were decomposed and dissolved by concen-
trated sulphuric acid ; they were also decomposed, but not com-
pletely, by concentrated nitric acid, iodine being liberated and a
white powder, insoluble in the nitric acid, remaining. This
residue was soluble in concentrated sulphuric acid and from this
solution ammonium hydroxide threw down a white gelatinous
precipitate. Upon dissolving this precipitate in hydrochloric
acid and dipping turmeric paper into the solution, the orange
color characteristic of zirconium was obtained . The solution
gave no reaction for iron.
The zirconium in the compound was quantitatively deter-
mined by expelling the iodine by heating a portion of the salt
with a mixture of sulphuric, nitric, and nitrous acids, dissolving
the residue in concentrated sulphuric acid, diluting with water,
and precipitating the zirconium with ammonium hydroxide.
The precipitate was washed, dried, and ignited, and the zirco-
nium weighed as the dioxide.
The iodine was determined by fusing some of the compound
with about five times its weight of a mixture of potassium and
sodium carbonate. The mass was then treated with water, fil-
tered, and after acidifying the filtrate with nitric acid the
hydriodic acid was precipitated with silver nitrate and weighed
as silver iodide.
The results were
Calculated (or Zrl4. Pound.
Per cent. Per cent. Per cent. Per ceut.
Zirconium 15.15 15.17 15.00 15.37
Iodine 84-85 85.34 85.27
The crystals when examined under the microscope proved to
be clear, colorless cubes which showed no double refraction.
When heatedjor some hours in hydrogen the zirconium tetra-
iodide becomes black and iodine and hydriodic acid are formed.
Heated in the air the iodide melts and sublimes. A weighed
amount was placed in a porcelain crucible, covered with water,
PHTHAUMID. 679
and evaporated to dryness. No change in weight and scarcely
any in color resulted after two such treatments. This behavior
toward water is surprising, for from the published descriptions
of zirconium tetrachloride and tetrabromide, it was to be
expected that the iodide would prove to be a hygroscopic com-
pound easily decomposed by water. It seems, however, to
more nearly resemble the fluoride which Deville states to be a
colorless crystalline substance volatile at a white heat and iti-
soluble in water or acids.
Cornell Ukivbrsity, Ithaca. N. Y.
PHTHALiniD,*
Br J. A. Matrbws.
Receired June 9, tMg6.
A NUMBER of years ago Prof. C. E. Colby and Mr. Dodge,
of Columbia University were led to try the effect produced
by heating together, under pressure, mixtures of (i) fatty acids
and fatty nitrils; (2) fatty acids and aromatic nitrils ; (3) fatty
nitrils and aromatic acids ; and (4) aromatic acids and aromatic
nitrils. The reactions were carried on in sealed tubes. The
score or more reactions that they tried were done at tempera-
tures ranging from 235** to 280° C. As the result of their work
they reached these conclusions regarding what is likely to take
place, at least when monobasic acids and mononitrils are em-
ployed.'
1. Fatty nitrils and fatty acids give secondary amids.
2. Fatty nitrils and aromatic acids give fatty acids and aro-
matic nitrils.
3. Aromatic nitrils and fatty acids give mixed secondary
amids.
4. Aromatic nitrils and aroniatic acids gave secondary amids,
except in one case when exceptionally high heat was used (280'')
in which case the cyanide of the higher radicle was formed.
In regard to dibasic acids and dicyanides not so much has
been done. Miller first tried reactions with succinic acid and
ethylene cyanide.' He found that succinimid resulted from
each of the following experiments :
1 Re«d before the American Chemical Society. New York Section, June, 1896.
* Am. Chem.J.^ 13. i8^t.
t This Journal, 16, 443, 1B94.
68o J. A. MATHEWS.
1. Ethylene cyanide and acetic acid heated in a sealed tube.
2. Acetonitril and succinic acid, and
3. Ethylene cyanide and succinic acid.
Some other acids in this series have been tried. Malonic acid
was rather imperfectly tested. In every case the tubes ex-
ploded and malonimide was not obtained at all.
Seldner' reports parallel results to those obtained by Miller
when he used glutaric acid and trimethylene cyanide. In the
following trials which he made glutarimid resulted every
time:
1. Glutaric acid (i mol.) and acetonitril (2 mols.).
2. Glutaric nitril (i mol.) and acetic acid (2 mols.).
3. Glutaric acid and glutaric nitril, equal molecules.
Until the writer, at Prof. Colby's suggestion, made the experi-
ments hereinafter recorded no one, to my knowledge, had applied
these methods to aromatic, dibasic acids. The results of the
first experiments are very gratifying and I hope in the near
future to try the reaction with other dibasic, aromatic acids.
Since no information regarding phthalic nitril could be
obtained I was obliged to do without it. The experiments
were therefore made with phthalic acid and propionitril.
Four sealed glass tubes each containing phthalic acid ( i mol.)
and propionitril (2 mols.), plus about three drops of acetic
anhydride were heated in an oven for varipus lengths of time
and at different temperatures.
Tube I. The first tube was opened after ten hours heating at
180° C. The contents of the tube had a pungent acid odor and
were treated with cold dilute potassium carbonate solution. A
residue consisting of needle-like crystals remained. These
were filtered off, washed with water, and dried. The crystals
then had a melting point of 228° C. I immediately suspected
from this melting point that phthalimid had been formed by the
reaction
C.H,(COOH). + C,H,CN = C.H,(CO).NH + C.H.COOH.
The yield of phthalimid in this experiment was about sixty
per cent, of the theoretical.
^ Am. Chem.J.^ 17, /^.
PHTHALIMID. 68 1
Tube II. On heating the remaining three tubes higher No.
2 broke at about 215^.
Tube III. After further heating of eight hours at 200** to 215**
C the third tube was opened and the contents treated with
potassium carbonate solution. The crystals remaining were not
so light colored as those from Tube I, and were so different in
appearance that it was thought some other reaction had taken
place. The melting-point, however, was about the same as in
the first case, viz,, 227'', Yield eighty-four per cent.
Tube IV. Exploded at 258* C.
Since the theoretical equation requires only one molecule of
nitril to one of phthalic acid two more tubes were prepared, each
containing equal molecules of phthalic acid and propionitril.
Tube V. After three and a half hours at i8o*-2oo** C. the fifth
tube was opened and treated with potassium carbonate solution
as before. Residue crystalline; melting-point 228.5®, yield
eighty-eight per cent.
Tube VI. Heated five and a half hours at i8o*'-200*', melting
point of residue, insoluble in cold, dilute potassium carbonate
solution, 228.3" C., yield 92.5 per cent.
The crystals of phthalimid were all more or less colored, the
color being darkest in the case of the third tube which had been
subjected to long, high heat. In no instance was any outward
pressure noticed on opening the tubes.
Portions of the products were recrystallized from acetic acid,
from alcohol, and from alcohol with the addition of ani-
mal charcoal to decolorize. The melting points of the recr>'s-
tallized products were a little higher than before purification,
viz., 230**, 229.5** and 229.5'*, respectively. These agree very
closely with the point given in Beilstein.
Biedermann* gives the melting-point as 228° or 229** C.
Michael* gives the corrected melting-point as 233.5'* C. The
decolorized crystals from alcohol form beautiful long needles.
Notwithstanding the close agreement of the melting-points
obtained with those given by the authorities, some other tests
were made to show that the product was nothing else than
1 Ber. d. ckem, Ges.^ lo, 1166.
« Ber. d. ckem. Ces.. 10, 579.
682 N. J- LANE. DETERMINATION OF SULPHURIC ACID.
phthalimid. A portion of the crystals heated with potassitiin
hydroxide went into solution with evolution of ammonia . Another
portion of the cr3'stals were covered with concentrated ammo-
nia and allowed to stand for some time. They were soon con-
verted into microscopic crystals of phthalamid
(=C.H,(CONH,),).
These crystals were filtered oflF, washed, and dried. They
melted at 217.5^ (uncorrected) with an evolution of ammonia,
which began at about 200^. The phthalamid was further
proved by its insolubility in cold water, alcohol, and ether, and
by boiling it with water it was decomposed, giving off ammonia
and on cooling phthalimid, melting at 230** C, crystallized out.
The results of these tests show conclusively that the product
is phthalimid and that when it is made by the action of equal
molecules of acid and nitril the yield is large. The reaction
works comparatively readily, and at a much lower temperature
than was needed to affect the reactions recorded by Colby and
Dodge. It is highly probable that with slight changes of con-
ditions any one of a variety of nitrils would give the same
result. I hope to report further experiments with phthalic acid
and other dibasic aromatic acids at a later day.
Orgaivic Labokatort, Columbia
University, New York.
DETERMINATION OF SULPHURIC ACID.
By N. J. Lane.
Rereivcd May 19, itp6.
SOME months ago, before hearing of the controversy between
Dr. Lunge and Mr. Gladding, some experiments were
made on this subject, the results of which sustain Mr. Gladding's
case. The determinations were made on nearly normal sul-
phuric acid to establish its strength with the following results :
Barium chloride Barium chloride
added suddenly. added by drops.
1. Sulphuric acid 5o-03 49-23
2. " *' 4990 4932
3. " " 50.14
And the average of several practically identical titrations on
C. P. sodium carbonate gave sulphuric acid 49.33.
The above results were obtained with the greatest care, and
every precaution used to insure accuracy. This, in my opinion,
conclusively proves the accuracy of Mr. Gladding's statements.
NOTE ON THE SOLUBILITY OF BISMUTH SULPHIDE IN
SODIUM SULPHIDE, WITH SPECIAL REFERENCE TO
THE ESTiriATION OF SMALL AflOUNTS OF
BISnUTH IN ANTI-FRICTION ALLOYS.
By Thomas B. Stxllman.
Received June i6, 1896.
THE method of separation of lead, copper and bismuth from
antimony, arsenic and tin by the use of sodium sulphide
is quite general. This is dependent upon the usually accepted
statement that the sulphides of bismuth, lead and copper are
insoluble, and the sulphides of arsenic, antimony and tin are
soluble in sodium sulphide. This process of separation is
employed in the analysis of various alloys, especially of anti-
friction alloys, containing lead, tin, antimony, etc.
An alloy, used for similar purposes, but containing, in addi-
tion to lead, copper, antimony and tin, a very small amount of
bismuth, was recently submitted to me for analysis.
After complete solution of the alloy in hydrochloric acid with
a few drops of nitric acid, the acid was neutralized with sodium
hydroxide, sodium sulphide solution (1.06 sp. gr.) added and
the heat applied for twenty minutes. The solution was filtered
and the filtrate examined for the antimony and tin with satisfac-
tory results.
The precipitate of insoluble sulphides remaining upon the
filter was found to contain lead and copper, but no bismuth.
This indicated that the small amount of bismuth which was
present in the alloy had gone into solution in the sodium sul-
phide.
To prove this theory, I weighed 0.128 gram of pure bismuth
nitrate, dissolved it in twenty-five cc. of water with a few drops of
nitric acid, the clear solution neutralized with sodium hydroxide,
seventy-five cc. solution of sodium sulphide added, and warmed
to a temperature near boiling for twenty minutes. The solution
was filtered from the bismuth sulphide, remaining insoluble in
the sodium sulphide. The clear filtrate was rendered faintly
acid with hydrochloric acid, when a brownish-black precipitate
immediately formed. This precipitate was filtered, dissolved in
684 SOLUBILITY OF BISMUTH SULPHIDE.
hot nitric acid and evaporated to dryness and ignited in a
weighed porcelain crucible. The residue obtained was 0.031
gram of bismuth trioxide, and strongly yellow in color. It was
dissolved in a few drops of hydrochloric acid, and the three fol-
lowing confirmatory tests for bismuth were made :
1 . A portion of the solution was poured into a large amount of
water, forming immediately a white precipitate of bismuth oxy-
chloride.
2. A portion was tested by Schneider's test, the most delicate
test for bismuth, the reaction obtained being strong and charac-
teristic.
3. A portion was diluted with water, not enough to cause pre-
oipitation, and the solution saturated with hydrogen sulphide.
The precipitate formed was brownish-black in color.
These three tests are absolutely confirmative of the presence
of bismuth, and also show the absence of the other metals. By
thus using pure bismuth nitrate for this test, lead, copper, anti-
mony and tin are not present.
If now an analyst should weigh twelve grams of an alloy,
composed approximately of lead eighty per cent., antimony fif-
teen per cent. , tin 4.75 per cent., and bismuth 0.25 per cent.
('* magnolia metal,)'' and sodium sulphide solution be used for
the separation of the tin and antimony from the lead and bismuth,
ali of the bismuth present would pass into solution and escape
determination by the analyst.
No analyst, however, would use as much as twelve grams of
such an alloy for analysis, but rather one or two grams.
If one gram be taken and sodium sulphide used as above
indicated, three per cent, of bismuth might be present and a// of
it pass into solution in the sodium sulphide instead of remain-
ing as an insoluble sulphide with the lead sulphide.
Dbpartmekt op analytical Chemistry,
Stevens Institute op Technology.
ON THE ESTIMATION OF SULPHUR IN PYRITES.
By G. Lunob.
Received June 19. s8g6.
IT has taken Mr. T. S. Gladding six months to reply to my
last paper on the above subject. I will not take much more
than six days from the date of receiving the May number of the
Journal of before dispatching my final reply to that gentleman.
Mr. Gladding avoids any mention, and of course offers no
refutation, of the charges I had brought against him, but he
again puts me into a totally false light, by saying that I
** attempt no further support of my position by chemical experi-
ment." This suppresses the fact that I had referred to my more
than sufficient experimental proof for Mr. Gladding's and his
assistants' inability to handle my process, i^hich has been in
daily successful use by scores, if not hundreds, of chegiists for a
number of years past, and is that employed in Presenius' own
laboratory, as I hear from his son-in-law and laboratory chief.
Dr. Hintz. Mr. Gladding now exacts a further reply from me,
more especially on the strength of some new comparative tests
of what he states to be the main point at issue, namely the
necessity of a very slow addition of the barium chloride.
I am convinced that our readers are as tired of this dispute as
I am, but as some of them might construe my silence into the
admission that Mr. Gladding is right on this point, and might
saddle themselves with a total unnecessary complication in their
daily work, I will not shirk a further reply, although I think it
unnecessary after having quoted already in March, 1895, eleven
experiments by entirely independent chemists, refuting all Mr.
Gladding's assertions.
In his former paper Mr. Gladding states that the error caused
by the rapid addition of the barium chloride solution is from
two-tenths to three-tenths per cent, of sulphur, and according to
his last paper it is even one-half per cent. He appeals to inde-
pendent chemists to settle this discrepancy between his state-
ments and my own. I have taken this up in the following man-
ner : I instructed one of my assistants, Mr. U. Wegeli, a skilled
686 G. LUNGE. SULPHUR IN PYRITES.
worker, but entirely ignorant of the above dispute, to make a
series of very careful tests of a sample of pyrites, just arrived for
analysis and belonging to an important commercial case. I
enjoined him to give me absolutely unvarnished results (which
in our laboratory it would not have been at all necessary to say),
and I told him, as we must be quite sure of the matter, he must
not merely employ all the ordinary precautions, but also try both
the usual quick addition of the barium chloride and a process
recently very much recommended, namely, the very slow addi-
tion of the precipitant ; I did not express any opinion of my own
upon that point, and left it entirely for him to find out what
there was in the matter. I had just then to undertake a short
journey, and on my return he handed to me the following
results.
A. Quick addition \^i, <?., pouring in the hot barium chloride
solution in about ten portions, occupying about half a minute
in all, and stirring the mixture all the time, as every chemist
would do).
I. 39.83 2. 39.65 3. 39.65 per cent, sulphur.
B. Slow addition from a burette, one drop per second (exactly
as described by Mr. Gladding).
4- 3963 5- 39.69 6. 39.44 per cent.
This means : In No. 2 and 3 the quick addition has given
idejitical results with the slow addition in No. 4 and 5. No. i
shows a little more. No. 6 a little less. I have suppressed noth-
ing, and I give these results as well, although they are evi-
dently not as reliable as the other four, entirely concordant,
results ; but even if we admit the less reliable results in striking
an average, we find a difference of only one-tenth per cent,
between the quick (39.71) and the slow (39.59) process. Such
a difference is evidently within the limits of ordinary experi-
mental error.
Zurich.
[This discussion closes with the present .paper. — Ed.]
BACTERIA IN HILK SUGAR.
Bt Albert R. Lbbds.
Receircd June 6. 1896.
CERTAIN phases of bacteriological investigations command
universal and profound popular interest, and any publica-
tion relating to the connection of a specific organism with a
zymotic disease, elicits general attention and discussion. This
intimate connection of bacteriology with questions of life and
death, has led many to regard the study as the proper province
of medical specialists, despite the first uses made of bacteriologi-
cal methods by Pasteur and his followers and to neglect them as
instruments of chemical research. But the morphology, the
classification, the physiology, and the botany of the bacteria are
in such a rudimentary and unsatisfactory condition that the
most valuable methods of bacteriological investigation are still
of a chemical nature. The preparation of the culture fluids, the
application of the tests, and the isolation of the products are
chemical operations, and the advances to be made in the near
future are to be looked for mainly on the chemical side of the
subject. For this reason the absence from the columns of this
Journal of papers resting upon the bacteriological questions, has
been a matter of surprise to the writer, and the important con-
tributions which have been herein recently made by Dr. Schwei-
nitz, Dorsett, Bennett, Pammel, and Mason, a source of con-
gratulation. Their results foretell the rich harvest of the future
when the complete quantitative value of the chemical actions
involved are known, and the different views which they may be
expected to inaugurate as to the nature of many bodies now
grouped closely together, but which deport themselves very dif-
ferently when bacteria are. the reagents made use of.
It is for these reasons that the writer desires to put on record
the slight observations which he has made during the course of
ordinary chemical work. They spring out of some anomalous
behavior of specimens of milk sugar, which were being examined
for purity. All the samples of pulverized milk sugar coming
from the drug stores, which he examined, proved to contain a
ferment when their solutions were kept at the optimum tempera-
688 A. A. BENNETT AND L. A. PLACEWAY.
ture for a sufficient length of time. The lactic acid produced
was isolated in the form of calcium lactate. This was not the
case with some lactose crystallized in nodular masses of pris-
matic crystals which had been obtained originally from Kahl-
baum, and had been standing for twenty-five years in a stoppered
jar. It was sterile. With the exception of this specimen, all the
others gave an abundant crop of bacteria when definite weights
dissolved in sterilized water were submitted to ordinary gelatin-
peptone culture. The maximum number obtained in this
medium was 1400 colonies per gram of milk sugar. In studying
these colonies I looked more particularly for the bacillus acidi
lactici and the other ten or twelve species, which are at the pres-
ent time classified as the specific milk bacteria, but without suc-
cess. With a lactose-litmus gelatin solution a still larger num-
ber of colonies was obtained and possibly larger search in this
medium, might have revealed the specific milk bacteria of lactic
acid fermentation. But my immediate object had been attained,
and the presence of bacteria as a common impurity in lactose,
to be looked for and avoided by the chemist and the druggist,
sufficiently demonstrated.
THE QUANTITATIVE DETERMINATION OF THE THREE
HALOGENS, CHLORINE, BROMINE AND IODINE,
IN niXTURES OF THEIR BINARY COH-
POUNDS.
By a. a. Bbnnbtt ahd L. A. Placbwily.
Received June t. i996.
CHEMICAL literature contains many records of methods for
the quantitative estimation of the halogen elements, and
for any one of these elements in the absence of the others they
are as satisfactory as may be required. There are also, it is
true, many suggestions and several proposed methods for the
separation and estimation of these elements when present together
or when some two are found in the same mixture, although they
are generally unsatisfactory for one reason or another. The
methods for qualitative determinations as s:iven by Hart and
by Kebler^ inthe /(mrnai o/AnafyHcai CA^mistfy.sxe thorovLghly
satisfactory. A very convenient qualitative method that is in use
CHI<ORINK, BROMINB, AND lODINB. 689
in this laboratory consists in first using chlorine water, or
enchlor, (made from potassium chlorate and hydrochloric acid),
which immediately determines the presence or absence of iodine
and in its absence that of bromine. Carbon bisulphide is used
as the final indicator. If iodine is present more chlorine water
is added and the whole is heated until the iodine color is re-
placed by the light yellow color due to bromine. This point is
easily discerned. If now one or more of these halogens are
present a portion of the original solution is treated with concen-
trated nitric acid and boiled until both of these elements are
removed. This solution is now tested for chlorine by the usual
methods.
There are several methods for the quantitative estimation of the
halogens by the formation of their silver salts, the further treat-
ment depending on whether two or three of these elements are
present. In all cases, however, much time is required for the
analysis and great care in the manipulation of the precipitates.
Sexton says, in his work on Quantitative Analysis, Third^ Edi-
tion, that there is no known method by which the two acids,
hydrogen bromide and ^hydrogen chlorine can be coi^pletely
separated. He recommends their precipitation as silver salts,
the weighing of this product and the conversion of the bromide
present into the chloride by passing chlorine gas over the fused
mixtures. Frpm the results the amount of each halogen is
determined. Of course the general procedure could be used if
an iodide were associated with the chloride but would not be
applicable in case all three halogens were present.
Dr. Prescott, in the Journal of Analytical Chemistry^ 8,
gives an acceptable method for the estimation of bromine in the
presence of chlorine and calls attention to several others that
have been employed. Fresenius gives, on pages 592 to 600 in
the Second American edition of his work on Qualitative Analysis,
elaborate methods for determining these elements in all possible
mixtures of the binary compounds of these elements. They are
generally difficult of application and employ rare reagents. It
may be said, in general, that all methods of indirect estimation
of the halogens in mixtures of their binary compounds are troub-
lesome, although some of the recent modifications of these
692 CHIX>RINS, BROMINE, AND lODINB.
utes time was used for each distillation, but less time was usually
sufficient. In fact most of the halogens were driven over during
the first few minutes of heating after boiling temperature was
reached. In case very great accuracy is not required an esti-
mation can be completed in a few minutes.
It is evident that in all cases there must be relatively large
excess of reagents. When the distillations were complete the
iodine set free in the receiver was titrated against decinormal
sodium thiosulphate. The titration can be made in the receiver
but it was found most convenient to pour the liquid into a six-
inch evaporating dish before estimation. •
The contents of the flask are now removed to a beaker and
the excess of the permanganate reduced by ferrous sulphate,
adding sulphuric acid enough to render the solution clear. The
solution was slightly warmed to hasten the action. It was then
cooled and made .up to a definite volume and an aliquot part
estimated by precipitation with silver nitrate. There was noth-
ing to prevent the estimation of the chlorine by titration, but no
determinations were made by that method.
The following tables give the results of the work :
Potas- Iodine Potas- Bromine Potas- Chlorine
sium in potas- sium in potaa- sium in potas-
iodide ainm Iodine bromide sium Bromine chloride slum Chlorine
taken, iodide, found, taken, bromide, found, taken, chloride, foand.
1 0.986 0.0754 0.0745 0.198 O.T330 0.1329 0.994 0.4869 0.4829
2 0.493 0-0377 0-0374 0.198 0.1330 0.1299 0.994 0.4869 0.4859
3 0.493 0.0377 0.0377 0.099 0.0665 0.0658 1.988 0.9738 0.9699
4 0.493 0.0377 0.0376 0.099 0.0665 0.0662 0.994 0.4869 0.4870
5 0.493 0.0377 0.0378 0.099 0.0665 0.0659 0.994 0.4869 0.4858
6 0.493 0.0377 0.0375 0.0495 0.0332 0.0328 0.994 0.4869 0.4867
7 0.493 0.0377 0.0375 0.0495 0.0332 0.0331 0.994 0.4869 0.4857
8 1.972 0.1508 0.1499 0.099 0.0665 0.0664 1.988 0.9738 0.9679
9* 1.972 0.1508 0.1484 0.099 0.0665 0.0659 0.497 0.243 0.241
10 0.493 0.0377 0.0375 0.0495 0.0332 0.0329 0.497 0.243 0.242
The tabular statement needs no particular explanation. The
quantities represented are the amounts in grams in each case.
It may be well to note that this general method is applicable
for rapid technical estimations of bromine or of iodine either by
themselves or in case of mixtures of the same. Single analyses
can be readily made in ten to fifteen minutes.
Iowa Agricultural Colleob, amb8, Iowa.
ON THE INVERSION OF SUGAR BY SALTS. NO. a.
By J. H. Long.
Reed red June a^, 1896.
IN a recent paper* I have shown that in their behavior with
cane sugar solutions many so-called neutral salts closely
resemble weak mineral acids. Salts of the heavy metals in
general have the power of inverting sugar solutions, and in some
cases very rapidly, especially at an elevated temperature. The
same fact has been pointed out for certain salts by others, nota-
bly by Walker and Aston,* who determined the speed of inver-
sion of four nitrates, comparing them with dilute nitric acid.
This inversion is due to the hydrolysis of the salts in question,
the hydrogen of the acids formed being in all cases, probably,
the active catalytic agent.
In my former paper I gave some results obtained in a prelimi-
nary investigation on ferrous iodide with very strong sugar solu-
tions, and in the present paper I shall give the results obtained
with other salts, as well as more extended tests with the iodide.
METHOD.
In the experiments before reported I made very strong syrups
containing usually fifty grams of sugar in loo cc, and to these
syrups before final dilution weighed amounts of the salts were
added, the volume being brought up to loo cc. with distilled
water. In the following series of tests the amount of sugar
present is much smaller, being in all cases fifty grams in 250 cc.
of the finished solution. This solution is much stronger than is
usually employed in inversion experiments, but with many of
the salts dissolved weaker sugar solutions could not be well
used. The ferrous salts, especially, require relatively large
amounts of sugar to hold them in clear solution, and as many of
the experiments given below were made on such salts, it was
decided to employ the same weight of sugar in all cases. For
each experiment, therefore, fifty grams of pure sugar was dis-
solved in water in a 250 cc. flask by aid of heat. The strong
syrup was cooled and to it was added the salt in the powdered
form or dissolved in a little water. After securing a complete
i This Journal, i8, lao.
«/. Chem. Soc., July, 1S95.
694 J- H. IX>NG.
solution in either way, it was diluted to the mark and shaken to
mix thoroughly.
The syrup so made was poured into small tubes of thin glass
for inversion. These tubes held about twenty cc. and were
three-fourths filled. They were cleaned for use by boiling in
hydrochloric acid and then in distilled water repeatedly. After
having been employed for several series of tests it was found
sufficient to soak them twenty-four hours in weak acid, and
then in distilled water, rinsing thoroughly finally. After receiv-
ing the sugar solutions they were closed with perforated rubber
stoppers holding each a short glass tube with capillary opening.
The tubes were placed in a receptacle, which was finally
immersed in the water of a thermostat holding over twent>'
liters. The receptacle for the tubes consists essentially of two
copper disks, twenty-five cm. in diameter, soldered six cm. apart
on a copper rod as an axis. The lower disk is furnished with
fine perforations, and the upper one with larger openings to
receive the tubes. The copper axis below the lower disk ends
in a hardened point, resting in a socket, and is extended above
to a length of fifteen cm., ending in a grooved pulley around
which a belt passes. Power applied to this belt rotates the tube
receptacle, which at the same time keeps the water of the ther-
mostat in motion. The thermostat itself consists of a large
copper oven covered with asbestos boards on five sides. The
top has perforations for the temperature regulator, thermometer
and rotating axis of the tube receptacle. A section of the top
can be quickly removed to take out tubes, but at other times
should be left closed to exclude light. The capillary tubes in
the stoppers closing the inversion tubes project about two cm.
above the water.
With the apparatus employed it was possible to maintain a
constant high temperature with a little watching through ten
hours. A temperature of 85° was held with variation of less
than o. I** in either direction. With many salts the rate of inver-
sion is exceedingly slow at ordinary temperatures, in fact almost
imperceptible. For convenience in working, therefore, it was
found necessary to invert at a high temperature, and 85° was
INVBRSIOK OP SUGAR BY SAINTS. 695
chosen. In a few instances a slightly higher temperature was
employed, but the results obtained are not included below.
The reaction between the sugar and salt is probably in most
instances analogous to that between sugar and weak acids, and
the rate of inversion may therefore be expressed by the same
differential equation :
The integration of this for / and x = o, together, leads to the
well known formula :
K '=^—r nat. log. —1 ,
where A represents the amount of sugar present at the beginning
of the inversion, x that inverted at any time, /, of an observation,
and ^the ** constant** or ** coefficient'* of inversion.
As the reaction is most easily followed by means of the polar-
istrobometer, A is conveniently measured by the total change in
rotation which is observed between the beginning of the reac-
tion and after complete inversion, x is measured by the change
of rotation from the beginning up to the time, /, of any observa-
tion. For convenience common logarithms are employed in all
the calculations below. As the sugar solutions were mixed with
the inverting substances at a low temperature, the intervals, /,
could be reckoned only from the time when the mixtures in the
tubes had reached the constant temperature of the experiment.
Preliminary tests were therefore made to determine several
points of practical manipulation. The thermostat was first
brought to a temperature of about 87**-88**, and the filled experi-
mental tubes and their receptacle immersed in it. From this a
fall of temperature resulted, because of the low temperature of
the solution. In five or six minutes the constant temperature of
Z^ was reached, and by regulation of the gas flame this was
maintained. In another set of expervpients it was found that
the solutions in the experimental tubes could be brought to a
temperature of 85** from the room temperature in four to six
minutes. It appeared, therefore, that ten minutes was amply
sufficient time to allow, after introducing the tubes into the
696 J. H. LONG.
thermostat, before beginning the actual observations, and this
was done in all cases in the experiments given below. In the
case of. bodies which invert but slowly there is little objection to
the loss of this first ten minutes of the reaction, but in a few
instances it was found to be a decided drawback, as will be seen
below.
Usually 250 cc. of the solution was prepared for experiment,
and this was filled into fifteen or sixteen tubes, and put into the
thermostat. At the end of ten minutes a tube was withdrawn
and cool6d very quickly by immersion in cold water, or by hold-
ing it under a flowing hydrant. The contents were then poured
into a polarization tube and polarized at the constant tempera-
ture of 20"* in most cases. In a few tests made in warm weather a
temperature of 25^ was maintained in the dark room and in the
water flowing around the observation tube. This first observa-
tion gives the initial rotation, and the time of removing the tube
may be put as /= o. Tubes were removed at different inter-
vals following and treated in the same manner. The results of
the polarizations were always very constant during the first few
hours heating in the thermostat, as was found by removing and
polarizing the contents of three tubes, but after five or six hours
less regular results were found, and I adopted the plan of taking
the mean result obtained by examining two or three tubes.
With fifteen or sixteen tubes I made observations at eight or
nine intervals.
After polarizing the liquids in the last tubes removed, the
contents were mixed, returned to a tube and heated longer to
obtain the end point of the reaction, that is, the point of com-
plete inversion. The point found in this manner does not
always agree with that calculated from the known weight of
pure cane sugar in the original solution. Even with dilute
acids the phenomenon of inversion is not as simple a thing as
usually represented. As shown by Gubbe* and others, the
specific rotation of invert sugar depends not only on the concen-
tration, but on the time, temperature and acid used. Prolonged
heating with salts produces in many cases, apparently, a slight
1 Bn-. d. chem. Ges., i8, 2207.
INVERSION OP SUGAR BY SAI.TS. 697
decomposition of the levulose, from which the negative rotation
of the invert sugar is found smaller than it should be theoretic-
ally. In a few instances, however, the negative rotation of the
invert sugar was increased. From the experiments of Gubbe it
may be calculated that fifty grams of cane sugar in 250 cc.
would yield a solution after inversion, which in a 200 mm. tube
should show a negative rotation of -—8.6°. The rotation observed
in my experiments was usually about — 8.3^, but an accurate
determination was not always possible, as some of the solutions
became slightly colored before inversion was quite complete, and
in other cases a negative rotation once observed seemed to grow
slightly less on longer heating, making the exact end point
somewhat uncertain. The discrepancies were not large in any
case, however, and I decided to take — 8. 3'' as the true end point
for the 200 mm. tube, and — ^4.15* for the 100 mm. tube.
With some of the salts examined the velocity coeflBcient, A', is
practically constant, with others it increases with the time,
while in still other cases it decreases.
The sugar used in all the experiments was crystallized cut
loaf of high degree of purity, and selected for the purpose.
With fifty grams in 100 cc. it yields a solution of almost perfect
clearness, which can be easily polarized in a 400 mm. tube.
Weaker solutions yield, on inversion, results which agree per-
fectly with the theoretical requirement.
POTASSIUM ALUM.
Solutions of this salt invert very rapidly. A sample of pure
alum was crystallized several times from distilled water to secure
a product free from traces of uncombined sulphuric acid, some-
times present in the commercial article. This carefully purified
salt was used in all the inversion tests. In the tables below, t
refers to the time in minutes, and under a is given the observed
angle of rotation in degrees and hundredths.
69S
J. H. lOHG.
\l,(SO.),.24H.O.
250 cc., fifty grams
of sugar
+ 0.617 S™n of alum.
^ = 33.03*
•
/. a.
^» •
t "^ A^
0 24.7s*'
« • • •
• * • *
• V • s
15 ao.15
4.58^
0.06483
0.00432
50 16.16
8.57
0.13045
0-00434
60 9-75
14.98
OLJ6243
0.00437
90 4*
19.88
0-39998
O.OCH44
lao 1.25
23.48
0.53891
0.00449
I5D —1. 3D
26.^5
0.67581
0.00449
210 —4-88
29.61
0.98488
0.00468
270 -6.40
51.13
I.240I6
OJOKHS9
K,Al,(SO.),.24H.O.
In 250 cc., fifty grains
/.
2.
N
of sagar-|- 1.234 gnuns of alum.
^ = 32.37-
X.
0
24.or
■ * • •
IS
J 7.83
6. 24'
30
12.92
11.15
60
550
18.57
90
0-75
23-32
120
-2.48
26,55
150
-4.76
28.83
210
—7.00
31.07
270
-7.80
31.87
ill* ^
^' A^x
' lor ^
0.09300
0.00620
0.18339
0.0061 «
0.37026
0.00612
0.55349
0.00615
0.74522
0.00621
0.961 14
0.00641
1.39620
0.00661
I.81II7
0.00670
inversion op sugar by salts. 699
Experiment 3.
K,Al,(SOj,.24H.O. -^
In 250 cc., fifty grams of sugar + 2.468 grams of alum.
A = 31.25.
/.
a.
X.
] log. /
t A-^x
0
22.95^
. • . •
. • . •
....
15
T4.80
8.15°
0.13124
0.00875
30
8.79
14.16
0.262 I I
0.00873
60
1.07
21.88
0.5231 I
0.00872
90
—3.03
25.9«
0.77304
aoo859
120
-5.64
28.59
1.06997
0.00891
180
—7.53
3048
1.55533
0.00864
340
—8.15
31.10
2.31866
0.00966
0.00886
Experiment 4.
K,Al.(SO,),.24H.O. ^.
In 250 cc., fifty grams of sugar + 4.936 grams of alum.
A = 30.03.
/.
a.
X,
A—x
» log ^
t * A^x
0
21.73''
a . • •
....
• ■ • •
15
11.23
10.50°
0.18686
0.01245
30
4.45
17.28
0.37205
0.01240
60
-2.87
24.60
0.74276
0.01238
90
—5.95
27.68
1. 10649
0.01230
120
—7-34
29.07
1.49529
0.01244
180
-8.18
29.91
2.39838
0.01332
0.01255
Experiment 5.
K.Al,(SO,),.24H,0. ^.
In 250 cc, fifty grams of sugar + 9.872 grams of alum.
A = 29.19.
/.
a.
X.
log.-l_.
A-^x
; log. ^-^
/ A-^x
0
20.89<5
. . . •
« • • •
•
• • • •
10
10.89
10.00°
O.18216
0.01822
25
2.10
18.79
0.44820
0.01793
50
—4.70
25.59
0.90893
O.OI818
9U
*— 7.73
28.62
1.70936
0.01899
150
—8.25
29.14
2.76626
0.01844
0.01835
TOO J. e. LONG.
An attempt was made to invert with a half normal solution
but at the temperature employed the rate was found to be too
rapid for accurate obsen-ation.
With the first four solutions no difficult}* was found in mak-
ing accurate polarimetric obsen'attons in the 200 mm. tube.
The last solution, however, became final!)' somewhat colored,
and slightly turbid from precipitation of what appeared to be
aluminum hydroxide. A portion, heated 180 minutes, became
too turbid for direct reading and had to be examined in the 100
mm. tube after filtration. The rotation was found now to be
— S-to", corresponding to — 7.20° for the 200 mm, tube, instead
of — 8,25° or — 8.30°. From the slight concentration due to the
filtration a still greater negative value instead of a lower one
should be expected. We have here an illustration of the fact
referred to abo^-e, ru., that prolonged heating makes the end
point determination somewhat uncertain at times.
It is interesting to note the relation existing between the con-
centrations of the solutions and their rates of inversion in the
above examples. For comparison we can call the lowest con-
centration unity and arrange them as follows :
Cone A"
-- I 0.00446
■'' 1 0.0063?
^^ S O.OIJ55
Inspection ot the table shows that the coefficient. A", increases
rapidly with the concentration, but is not directly proportional
to it. It is apparent that the numbers in the third colnmn i-ary
approximately as the square nx>is ot tho^ in the second, which
is cleariy s^hown in the next table.
I coo44^ 0.00116
»t4l
INVERSION OF SUGAR BY SAI.TS. 7OI
The regular results obtained from the aluminum salt are
probably due in a measure to the inertness of the hydroxide
toward sugar, as well as to the behavior of sulphuric acid in
inversion. The bases of the other salts examined below form
combinations with sugar more or less readily, not only with sac-
charose, but also with the products of inversion, so that the nor-
mal results of the reaction may be modified in a manner difficult
to compute. The rather rapid rate of inversion in the above
points to a relatively great degree of hydrolysis in the alum.
Walker and Aston* found something similar in a half normal
solution of the nitrate, studiedat a temperature of 80". From their
polarizations a value of 0.0077 ^^^ ^ was found, and this was
much in excess of the values found for other salts at the same
time.
FERROUS SULPHATE.
A sample of the purest obtainable sulphate was reccystallized
from water containing a trace of sulphuric acid, then dissolved
in distilled water and precipitated by alcohol. The crystal
meal secured was washed several times with alcohol and dried
by fanning. The finished product was bright green and gave a
nearly clear solution with pure water. It still held a trace of
alcohol as disclosed by the odor. The experimental solutions
were made by dissolving the sugar first and adding to this s^Tup
the weighed sulphate meal. The mixtures were shaken to com-
plete solution without application of heat, and then poured into
the tubes for inversion. The solutions soon became turbid on
warming and a minute amount of flocculent precipitate sepa-
rated, making direct polarization impossible. The readings
could be made therefore only after filtration, which was not
without slight effect on the result. The total amount of sepa-
rated hydroxide or basic salt was and remained through the
test, minute.
1 Loc. eiL
702
J. H. LONG.
EXPBRIMBNT 6.
FeSO,.7H,0. ^.
In 250 cc, fifty grams of sugar + 17.38 grams of sulphate.
A==i 17.12.
/.
o
15
45
75
135
195
255
375
495
a.
12.97
12.48
11.50
10.40
8.43
6.72
5"
2.87
1.03
X.
. . . •
0.49
1-47
2-57
4.54
6.25
7.76
10.10
11.94
log.
A^x
I
log.
A^x
O.OI261
0-03899
0.07064
0.13382
0.19727
0.26222
0.38716
O.51917
0.00084
0.00086
0.00094
0.00099
O.OOIOI
0.00102
0.00103
0.00105
0.00099
Experiment 7.
FeS0,.7H,0. N,
In 250 cc, fifty grams of sugar + 34.75 grams of sulphate.
/!= 17.10.
/.
a.
X.
'^' A-x
X , A
i '"^A^x
0
12.95
....
15
12.45
0.50
0.01289
0.00086
45
11.26
1.69
0.04520
O.OOIOO
75
10.08
2.87
0.07980
0.00106
135
8.07
4.88
0.14593
0.00108
195
6.30
6.65
0.21388
O.OOIIO
255
4.70
8.25
0.28606
O.OOII2
375
2:25
10.70
0.42682
0.00II4
495
0.15
12.80
0.59953
O.OOI2I
0.00107
Other tests were made with a second preparation of ferrous
sulphate from which the alcohol had not been as completely
removed. For a half normal solution the coefficient, 0.00094^
was found, and for a normal solution the value, o.ooioo, both
results being but a trifle lower than those obtained from the
pure products. It is possible that the differences may be due
to the presence of the trace of alcohol. In any case it is evi-
INVERSION OF SUGAR BY SALTS. 703
dent that with solutions as strong as those used the larger
amount of sulphate inverts but little more rapidly than the
smaller.
AMMONIUM FERROUS SUPHATE.
But one experiment was made with this salt, a very nice crys-
tallized preparation being used.
Experiment 8.
(NHj,Pe(SO.),.6H.O. 4'
In 500 cc.y 100 grams of sugar + 49 grams of sulphate.
A = 17.08.
• • . •
0.44
0.01 134
. 0.00066
1.19
0.03137
0.00069
2.00
0.05409
0.00072
2.80
0.07776
0.00074
4.33
0.I269S
0.00077
563
0.17368
0.00077
8.33
0.29048
0.00084
10.08
0.38739
0.00083
10.73
0.42972
0.00082
o 12.93
17 12.49
45 "-74
75 10.93
105 io.13
165 8.60
225 7.30
345 4.60
465 2.85
525 2.20
0.00076
The coefficient is seen to be low, but nearly a constant. In
this case, as in that of the ferrous sulphate, the mixture became
slightly turbid on heating.
ZINC SULPHATE.
It is practically difficult to secure a good preparation of zinc
sulphate crystallized without the addition of a trace of sulphuric
acid. In absence of the acid crystallization is very slow. The
preparation used below was made from a chemically pure com-
mercial sample, by crystallizing with a trace of acid first and
then from pure water, after heating the solution with pure zinc.
The final crystallization to secure fifty grams required weeks for
its completion. In my former paper attention was called to the
fact that Inversion with zinc sulphate is very slow, which is well
shown below. The experiment was closed when the sugar was
704 J. H. LONG.
about half inverted, and as the coefficient is not regular, it is
not possible to estimate accurately the mean rate for the whole
period.
Experiment 9.
ZnSO,.7H.O. 7'
In 250 cc, fifty grams of sugar -f- 17.94 grams of the sulphate.
A = 17.25.
/.
a.
X.
A
^ A—x'
' lair '*
/ ^^" A^x
0
13.10
• • • •
15
12.88
0.22-
o.oossS
0.00037
45
".35
0.75
0.01935
0.00043
105
11.34
1.76
0.04674
O.O0Q44
165
10.40
2.70
0-07393
O.OOQ45
^5
8.48
4.62
013539
0.00048
405
6-51
6.59
0.20933
0.00052
525
4.68
8.42
0.29083
o.ou.>S5
M.\NG.\XOUS SULPHATE.
After several attempts a salt was obtained crystallized from
perfectly neutral solution. Some of the cr>-stals were so irregu-
lar in outline that it was not possible to determine from inspec-
tion whether they contained four or five molecules of water.
Determination of SO^ in the product showed, however, that a
very small amount only of the latter salt was present. In mak-
ing the solutions I assumed for conx-enience that the compound
had the formula MnS0«.4H,0, and weighed out accordingly.
As I pointed out in my former paper, a solution of manganous
sulphate and sugar undergoes a peculiar decomposition when
heated, in which a ver>' fine dark substance is thrown out from
solution. The amount of this is so small that I could not collect
enough for tests, in the work done, but it is still sufficient to
make the polarimeter readings ver>' difficult. All solutions had
to be filtered before examination, but even with this precaution
the readings were often obscure.
INVERSION OP SUGAR BY SALTS. 705
EXPERIMENT 10.
MoSO,.4H.O, ^•
In 250 cc, fifty grams of sugar +13.94 g^ams of sulphate.
A = 34.80.
o 26.50° ....
45 26.33 0.17° 0.00213 0.000047
75 26.15 0.35 0.00439 0.000058
135 25.76 0.74 0.00934 0.000069
195 25.05 1.45 0.01848 0.000095
315 22.33 417 0.05543 0.000176
435 19.84 6.66 0.09226 0.000212
535 16.75 9.75 0.14277 0.000257
Experiment ii.
MnS0..4H,0. N,
In 250 cc, fifty grams of sugar + 27.88 grams of sulphate.
^ = 34.75.
/. or. X, 10^.;^. -^^o^i^-
o 26.45^ . • . .
15 26.25 0.20^' 0.00250 0.00017
45 26.00 0.45 0.00566 0.00013
75 25.75 0,70 0.00883 0.00012
135 24.90 1.55 0.01981 o.ooois
195 23.00 3.45 0.04541 0.00023
315 18.20 8.25 0.1 1 770 0.00037
435 14-45 '2.00 0.18397 0.00042
555 9-50 16.95 0.29053 0.00052
Experiment 1.2.
MnS0,.4H,0. 2N,
In 250 cc, fifty grams of sugar + 55.76 grams of sulphate.
A = 34.42.
/. a. X, 'o^'iih' -r" ^°»- T^lr'
o 26.12^ —
30 2^.12 1. 00 0.01280 0.00043
90 22.80 3.32 0.04405 0.00049
150 17.82 8.30 O.I 1984 0.00080
220 12.33 13.79 0.22231 O.OOIOI
338 4.60 21.52 0.42622 0.00126
450 0.27 25.85 0.60383 0.00134
570 —3-80 29.92 0.88360 0.00155
706 J. H. LONG.
EXPERIMBNT 13.
MnS0,.4H,0. 3N.
In 250 cc., fifty grams of sugar -|- 83.64 grams of sulphate.
A = 34.00.
t a cT. log— d — _!_ log. -A—^
O 25 • 7^ •*.. •*•• *...
30 24.22 1.48° 0.01933 0.00064
90 T8.76 6.94 o.%99i5 o.ooiio
150 11.50 14.20 0.23481 0.00156
220 4.75 20.95 0.41587 0.00189
338 —2.69 28.39 0.78252 0.00232
450 — 6.25 31-96 1. 22185 0.00272
570 —8.05 33.75 2.13354 0.00363
The rates of inversion cannot be directly compared in the
above experiments because the latter were not carried to com-
pletion. In the first case over one-third of the sugar originally
present was inverted, in the second case almost exactly one-half,
in the third case about six-sevenths, while in the last case the
inversion was very nearly complete. By plotting the results it is
possible to determine approximately the rate of inversion when
just one-half of the sugar has been inverted and this I have
done. The results are given below, and show that the coeffi-
cients, K^ are nearly proportional to the concentrations, these
being referred to that of the half-normal solution as unity.
Cone. K.
1 (0.00032)
2 0.00054
4 0.00109
6 0.00172
The first coefficient, 0.00032, is uncertain because it was
found by a rather wide extrapolation, but between the others
there is fair agreement.
MANGANOUS CHLORIDE.
The salt used was purified by several crystallizations from the
best obtainable Schuchardt product.
invbrsion op sugar by sai«ts. 707
Experiment 14.
MnCl,.4H,0. ^•
In 250 cc., fifty grams of sugar +6-18 grams of chloride.
A = 35.00.
/.
a.
X,
log./*
0
26.70°
• • • •
• . ■ .
... a
15
26.60
0.10°
0.00124
0.00009
45
26.30
0.40
0.00499
O.OOOII
75
26.00
0.70
0.00878
O.OOCI2
135
2525
1.45
0.01838
0.00014
255
22.66
4.04
0.05327
0.00021
375
18.75
7.95
O.I I 190
0.00030
The high
initial rotation here is '
very extraordinary, corres-
ponding to a specific
rotation of 66.75'.
«
Experiment
15.
MnCl,.4H,0. -^•
In 250 cc.
, fifty grams of sugar +
12.35 grams
of chloride.
A = 34.84
•
0
a.
•26.54^
X,
....
log.-!-.
A^x
• • • •
t A^x
....
15
26.45
0.09°
0.001 13
0.00008
45
26.16
0.38
0.00476
O.OOOII
75
25.85
0.69
0.00869
0.00012
135
24.52
2.02
0.02594
0.00019 '
255
22.26
4.28
0.05693
0.00022
375
17.15
9-39
0.13639
0.00036
495
13.00
13.54
0.21370
0.00043
555
11.52
15.02
0.24498
0.00044
Experiment 16.
MnCl,.4H,0. N.
In 250 cc, fifty grams of sugar -|- 24.70 grams of chloride.
A = 34.63.
L
a.
X.
log. "
A^x
■T-'^iaF
0
26.33°
• • • •
• • . .
• • • •
15
2)S.I2
0.21°
0.00264
0.00018
30
25.86
0.47
0.00593
0.00020
60
25.15
1. 18
0.01505
0.00025
120
23.05
3.28
0.04321
0.00036
180
20.07
6.26
0.08659
9.00048
300
15.60
10.73
O.16105
0.00054
708 J. H. LONG.
Experiment 17.
MnCl,.4H,0. 2iV.
In 250 cc, fifty grams of sugar + 49.40 grams of chloride.
A = 34.18.
/.
a.
X,
'o«^- At.-
I , A
0
25.88^
• • • ■
• • • ■
• • • •
15
25.38
0.50^
0.00640
o.cx)Q43
45
23.91
1.97
0.02578
0.00057
75
22.21
3.67
0.04933
0.00065
135
18.25
763
O.IO97I
0.00081
195
14.80
11.08
O.I 7016
0.00087
345
5.25
20.63
o.<doi83
0.00116
No very plain relation can be found connecting these rates of
inversion. The coeflScients corresponding to the time of com-
pletion of one-third of the inversion are here given.
COQC. IC.
I (0.00038)
2 0.00041
4 0.00055
8 0.00088
The first coefficient had to be estimated and is uncertain.
FERROUS CHLORIDE.
Considerable difficulty was experienced fn preparing a solu-
tion of ferrous chloride devoid of traces of free acid. A weighed
excess of pure iron wire was covered with water in a small flask
and then the calculated volume of titrated hydrochloric acid was
added in amount just sufficient to produce the solution of
required strength. The mixture was gently warmed and allowed
to stand a short time. Wanning was repeated at intervals
through several hours, until the liberation of hydrogen became
very feeble. The solution so obtained stood five days in the
presence of the excess of iron, being boiled twice in the interval,
and was then filtered cold into the sugar solution, which was
made up to the proper volume with fresh distilled water.
The actual strength of solutions made in this manner was
determined by titration later. The two following were almost
exactl}' normal and half-normal.
Both solutions became turbid on heating and had to be fil-
INVERSION OP SUGAR BY SALTS. 709
tered before polarization for the first tests. After the lapse of
about two hours the cloudiness disappeared and the solutions
then taken from the thermostat were clear enough for direct
polarization.
KXPBRIMBNT 18.
Feci, ^.
In 250 cc, fifty grams of sugar + 7.925 grams of chloride.
A = 16.18.
/.
a.
X.
log. '^ .
A'^x
; log.-/
/ A'-x
0
12.03°
....
....
....
15
9-47
2.56°
0.07507
0.00500
45
7.44
4.59
0.145 1 7
0.00322
105
5.00
703
0.24783
0.00236
165
3.83
8.20
0-30725
0.00186
285
1.90
10.13
0.42749
0.00150
405
—0.50
12.53
0.64696
0.00160
525
— 2.01
14.04
0.87884
0.00167
KXPBRIMBNT 19.
FeCl,. iV.
In 250 cc, fifty grams of sugar + 15.85 g^ams of chloride.
A = 15.71.
/.
a.
X.
log. '^ .
A'-x
__ log. —
/ A^x
0
11.56'^
....
• • • •
• • • •
15
9.40
2.16°
0.06424
0.00428
45
6.88
4.68
0:15360
0.00341
105
4.75
6.81
0.24679
0.00235
165
3.56
8.Q0
0.30913
0.00188
285
1. 15
10.41
0.47190
0.00165
405
—1.42
12.98
0.76002
0.00187
525
—3.25
14.81
I.24194
0.00236
These results are very surprising, inasmuch as they show but
little difference between the rates for the two concentrations. In
both instances the rates rapidly decrease from the beginning
and after the sugar has been about half inverted they increase a
little. I give next some results from solutions which had not
been boiled so thoroughly, and which may have held a little
free acid.
yio
J. H. LONG.
Experiment 20.
FeCl,. o.52A^.
In 250 cc, fifty grams of sugar H* 8.242 grams of chloride
A = 34.00.
A I ,__ ^
/.
a.
X.
0
25.70°
• • • •
15
20.00
5.70'
45
12.80
12.90
75
9.00
16.70
105
6.19
19.51
165
2.42
23.28
285
—1.95
27.65
345
-3.96
29.66
405
—5.30
31.00
lOf.
A^x
0.07969
0.20720
0.29343
0.37041
0.50129
0.72771
0.89399
1.05436
i A — X
0.00531
0.00460
0.00391
0.00353
0.00304
0.00256
6.00258
0.00260
Experiment 2 1 .
FeCl,. 0.98^.
In 250 cc, fifty grams of sugar -|- 15.53 grams of chloride.
A = 33.60.
A
t,
O
15
45
75
105
165
285
345
a.
25.30^
19.84
14.20
11.80
9.88
7.65
1.45
—1.50
X.
....
5.46°
II. 10
1350
15.42
17.65
23.85
26.80
ioi:.
A—x
_i_
log.
A^x
0.07702
O.I 74 16
0.22314
0.26675
0.32358
OS53734
0.69383
0.00513
0.00387
0.00297
0.00254
0.00196
0.00x88
0.00201
T^he effect of free acid is not apparent. Six other experiments
ere macie with normal and half-normal ferrous chloride solu-
^2j ^' ^^^ results of which were very similar to those above. In
tjozj ^^^ ^^e constant was found to increase before the comple-
Th^ ^ invei^sion.
^^^*aa ^^^stant for 0.00 1 A^ hydrochloric acid was determined
^^e ^ ^J^^iison at the same temperature, /= 85**, and with the
^^'^nt of sugar. It was found
A^= 0.0051,
'^Ai ^^ ^ FBRROUS BROMIDE.
^s of this salt ipvere made by adding the proper amouflt
INVERSION OF SUGAR BY SALTS.
711
of bromine to an excess of iron and water. A reaction soon
begins which is hastened by heat. Finally the solution is thor-
oughly boiled, which eliminates all free bromine and leaves the
iron in the ferrous condition. It is then filtered into the cold
sugar solution and is ready for use. A solution so made is prac-
tically neutral.
Experiment 22.
FeBr,. 0.54 N.
In 250 cc, fifty grams of sugar -|- 14.58 grams of bromide.
A
t.
O
»5
45
75
105
165
285
345
a.
23.13*
16.76
9.76
6.07
4.00
0.68
•-4.03
— 5-6o
X,
...
6.3/-
13-37
17.06
19-13
22.45
27.16
28.73
log.
A-'X
-7-lOff-
A—x
0.09836
0.24062
0.33988
0.40743
0.54406
0.86691
1.06598
0.00655
0.00534
0.00453
0.00388
0.00329
0.00304
0.00309
Experiment 23.
FeBr,. 1.04 N.
In 250 cc., fifty grams of sugar + 28.08 grams of bromide.
A = 29.50.
/.
a.
X.
^^«^- A^x
1 , A
i '^'A^x'
0
21.20°
• • • »
....
....
15
13.60
7.60°
0.12938
0.00862
45
6.22
14.98
0.30785
0.00684
75
2.90
18.30
0.42060
0.00561
105
0.75
20.45
O.513I7
0.00489
165
— 2 70
23.90
0.72163
0.00437
285
—6.35
27.55
I. 17979
0.00414
345
—7.50
28.70
1.56673
0.00454
The normal solutions here invert but little faster than the
half«normal. The rates in both cases diminish rapidly from the
start, but after the middle of the inversion become nearly con-
stant, as was observed with the ferrous chloride. The first three
of the solutions taken from the thermostat had to be filtered
before polarizing.
712 J. H. LONG.
FERROUS IODIDE.
A half-normal solution was made by mixing 15.87 grams of
iodine with an excess of iron and water, in the usual manner.
On complete disappearance of the iodine the solution was boiled
and filtered into a cold sugar solution. Water was finally added
to make the volume up to 250 cc. The amount of sugar present
is not sufficient to prevent some decomposition on heating, but,
as in the other cases referred to, the turbidity at first noticed
disappeared after longer warming in the thermostat. The first
polarizations were made after filtering, and those later were
made directly.
Experiment 24.
Pel, 4.
In 250 cc, fifty grams of sugar + 19.37 grams of iodide.
A = 32.03.
f\ 2^7 "s .... .... ...•
15 17.45 6.28'^ 0.09478 0.00632
30 13.57 10.16 O.I657I 0.00552
45 11.62 1 2. 1 1 0.20627 0.00458
60 9.73 14.00 0.24956 0.00416
90 7.50 16.23 0.30690 0.00341
150 4.40 19.33 0.40176 0.00268
270 0.90 22.83 0.54177 * 0.00200
390 —2.80 26.53 0.7^520 0.00196
In my former paper a preliminary" experiment with ferrous
iodide was described in which the coefficient appeared to be
nearly constant and much smaller than here. The experiments
are, however, not comparable, as in the former case the sugar
solution was very strong, containing, in 250 cc, 125 grams of
sugar. In such a solution the degree of dissociation of the
iodide would be necessarily very different from that in a weaker
solution. In the strong solution no separation of ferrous hydrox-
ide or other compound appears, even on warming. A strong syrup
is much more stable than a weak one, and the lower rate of
inversion may be thus easily accounted for.
INVERSION OF SUGAR BY SAWS. 713
CADMIUM CHtORIDB.
One solution of cadmium chloride was tested as to its invert-
ing power. It was made with a salt purified by several crj's-
tallizations at a low temperature, free from uncombined acid.
KxPBRiMBNT 25.
CdCl,. o.94iV.
In 250 cc, fifty grams of sugar -j- 42.958 grams of chloride.
^ = 29.71.
/.
a.
X.
_-«. log.
0
21.41°
• • • •
•
15
12.80
8.61°
0.14862
0.00990
30
6.59
14.82
0.30001
O.OIOOi)
60
—1.33
22.74
0.62967
0.01049
90
-4.89
26.30
0.94015
0.01044
150
—7.70
29.11
1.69475
O.OII29
The rate of inversion is about as rapid as with 0.Q02N hydro-
chloric acid at the same temperature and same sugar concentra-
tion.
LEAD NITRATE. .
A single test was made with a solution containing lead
nitrate. The salt was recrystallized from a pure Schuchardt
specimen and was weighed in proper amount directly.
Experiment 26.
Pb(NO.).. ^-
In 250 cc, fifty grams of sugar + 20.65 grams of nitrate.
A = 33.70-
o 25.40° ....
15 22.86 2.54^ 0.03403 0.00227
45 17*38 8.02 0.1 1803 0.00262
75 12.10 i3'3o 0.21800 0.00284
135 2.28 23.12 0.50314 0.00372
195 —3.63 29.03 0,85831 0.00440
345 —7-70 33-IO 1.74948 0.00507
The coefficient here is found to increase very rapidly, as was
noticed by Walker and Aston in their experiments/ which were
^Loc. cil.
714 J- H. LONG.
carried out with a half normal nitrate solution at So^, but with a
weaker sugar solution. The mean value they give from the
results of polarization at three intervals is 0.00159, but the inver-
sion was not carried nearly to completeness, as in the above
case.
The experiments given show in a marked manner the extreme
variations in the value and constancy of the inversion coefficient
and the data obtained may be roughly tabulated as follows :
Potassium alum K constant.
Ferrous sulphate '* increases slowly.
Ammonium ferrous sulphate *'
Zinc sulphate
Cadmium chloride
Manganous sulphate '* *' rapidly.
Manganous chloride **' *' • "
Lead nitrate " *'
Ferrous chloride " decreases rapidly.
Ferrous bromide " ** **
Ferrous iodide " " **
In the cases of the last three salts the values of K decrease
very rapidly at the beginning of the heating, but become nearly
constant later, finally, in fact, appearing to increase a little.
This behavior seems to bear some relation to the stability of the
salts in aqueous or weak saccharine solution. As was mentioned
these ferrous halogen solutions became turbid in the thermostat,
and the first three or four portions withdrawn in each case for
polarization had to be filtered. Later, the liquids became per-
fectly clear under the influence of longer heating.
During the turbid stage of the reaction, owing to the tempo-
rary separation of a trace of base in insoluble form, the amount
of free acid present would be relatively increased, and would
therefore greatly accelerate the speed erf inversion. With the
clearing of the solutions on longer heating the normal hydroly-
sis only would obtain and then the reaction should approach in
•regularity that due to the presence of a small constant amount of
mineral acid.
It was mentioned that the solutions with ferrous sulphate and
ferrous ammonium sulphate became likewise turbid on heating.
But here the very slight opalescence persisted through the
INVERSION OF SUGAR BY SALTS. 715
whole time of heating, and was perhaps greater at the end of
the reaction than at the beginning. Other experiments also
show in this respect a marked difference between ferrous sul-
phate and chloride. In my former paper I referred to solutions
of these salts which had been used qualitatively. Portions of
these solutions that had not been heated are still in existence.
After standing eight months in the light I find that the chloiide
is practically clear, while the sulphate has become much changed.
The bottle contains a decided flocculent precipitate. My former
experiments with a strong solution seemed to indicate that at a
temperature of loo"* the first slight precipitate which forms dis-
appears, but this is not true of the weaker solutions at 85^.
The slight precipitate of ferrous chloride and other halogen
compounds being temporary, while that of, ferrous sulphate is
apparently permanent, we should expect just such irregularities
in the speed of inversion, as the experiments actually show. A
solution of manganous sulphate with sugar becomes also slightly
decomposed on heating, and the decomposition increases with
the time and temperature. At a temperature of 100° a solution
of fifty grams of sugar and ten grams of the sulphate in 100 cc.
becomes so dark that an exact polarization is not possible, even
after filtering. The solution in the present case is much less
concentrated, but the precipitate is still marked and its forma-
tion is undoubtedly attended by the separation of a little free
acid. We should therefore expect an acceleration in the rate of
inversion as before.
These considerations do not aid us in explaining, however,
the increase in K for manganous chloride, cadmium chloride or
lead nitrate. The solutions with these salts are clear and remain
so throughout the reaction. In the case of manganous chloride
it must be remembered that an almost complete loss of color fol-
lows after heating. The pink fades, and in a few hours at the
temperature of the thermostat becomes imperceptible in a small
volume of the liquid. The color is not restored by cooling. We
have here evidently a reaction in which a change takes place in
the form of combination of the manganese, with a necessary
alteration in the degree of dissociation of the salt.
7l6 INVERSION OF SUGAR BY SALTS.
It is true, as already said, that most of the bases under con-
sideration form compounds with the sugars, so that we should
expect from this cause a slight disturbance at least in the appar-
ent rate of inversion. Too little is known of the optical proper-
ties of these saccharose, dextrose and levulose metallic compounds
to say just what effect they would have on the rotation, but that
they have some action is suggested by the results of some of the
polarizations to determine the end point in the inversion. This
was usually found a little below the theoretical, — 8.6° for a 200
mm. tube, but in several cases it was found above after pro-
longed heating. This was also true of a solution of sugar with
manganous chloride, which stood exposed to the light several
months.
It must be remembered also that solutions of dextrose are
easily oxidized, and those of levulose much more so. The dark
color often seen near the end of the reaction, points to such a
decomposition.
It will be recognized that a determination of the hydrol3'sis of
many of the heav}*^ metallic salts cannot be measured with great
accuracy, because of these several disturbing influences, but a
comparison of some little value in the above cases may be made
by considering the results obtained at the beginning of the reac-
tions in which the coefficient is an increasing one, and near the
end of the reaction in cases where it decreased and then became
nearly constant. By taking the mean of the first two values in
the one case, and of the last two in the other, we obtain the
second column of the table below as the most probable values of
the coefficient for half- normal solutions.
In the third column is given a calculation of the extent of
hydrolysis of the salts, expressed in per cents, of total salt pres-
ent, and based on a comparison with hydrochloric acid acting in
o.ooi normal solution at the same temperature on same amount
of sugar. This comparison is at best a rough one, assuming as
it does complete hydrolysis of the acid, and weglecting the effect
of the excess of undecomposed salts on the rate of inversion.
DBTERMINATION OF IRON AND ALUMINA. 717
Salt bydrolyzed in
K. p«r cent.
Lead nitrate 0.00244 0.096
Manganous chloride •. 0.00095 0.035
Manganous sulphate 0.00052 0.020
Ferrous sulphate 0.00085 0.033
Ferrous ammonium sulphate 0.00068 0.026
Zinc sulphate 0.00040 0.016
Ferrous chloride 0.00164 0.063
Ferrous bromide (0.54^) 0.00300 o. 109
Ferrous iodide •0.00198 0.078
Potassium aluminum sulphate, — 0.01835 i<440
Cadmium chloride 0.94 A^ o.oiooo 2.080
The amount of hydrolysis is small in all cases except those of
the alum and cadmium chloride.
My thanks are due to Mr. S. R. Macy for much assistance in
the experimental work of the above.
K0RTHWB8TRRX University,
Chicago.
DBTERMINATION OF IRON OXIDE AND ALUHINA IN
PHOSPHATE ROCK BY THE AMMONIUM ACETATE
METHOD.
By Thomas S. Gladding.
Received Jua» 30, 1896.
THE oldest method of separating alumina and iron phos-
phates from lime phosphate is, probably, the ammonium
acetate method. This has been severely criticised, and just at
present seems to be under condemnation. The following inves-
tigation has convinced the writer that, when properly carried
out, not only does the method give an accurate separation of
iron and alumina from lime phosphate, but also gives a neu-
tral phosphate of uniform composition from which the iron oxide
and alumina present may be accurately estimated.
' In brief, the method used is this. If a weakly acid solution
of phosphates of iron and alumina together with a large amount
of calcium phosphate be slowly poured into a strong solution of
ammonium acetate made acid with acetic acid, the iron and
alumina are precipitated as phosphates, upon digestion for a
short time at a gentle heat. This precipitate, however, con-
7X8 THOMAS S. GLADDING. IRON AND ALUMINA
tains more or less calcium phosphate, which is removed by sev-
eral reprecipitations. I shall demonstrate by experiment :
First, That upon continued reprecipitations of iron and
alumina as phosphates in this manner, there is no appreciable
diminution of the quantity of either finally obtained, provided
there always be a large excess of phosphoric acid present.
A standard solution was made by dissolving twenty grams of
ammonia alum (C. P.) in distilled water. This was slightly
acidified with hydrochloric acid, in order to prevent the alumina
from separating on standing, and diluted to one liter. This
solution, upon being standardized, was found to contain the
theoretical amount of alumina, that is,
Ten cc. r= 0.0225 grams A1,0,.
One precipitation, in the manner described above, of the
alumina in ten cc. gave
AlsOs.PaOft, found. Al,Ot.
1 0.0545 0.0298
2 0.0549 0.0229
3 0.0546 0.0228
4 0.0540 0.0226
5 0.0545 0.0228
Three successive precipitations, in which one gram of ammo-
nium phosphate was added before each precipitation, gave
AlaOs.P,0». Al,Os.
1 0.0550 0.0230
2 0.0547 0.0229
3 0.0544 0.0227
Five successive precipitations were also tried under the same
conditions, with the following results :
AlfOi-P^Oft. Al,Oa.
1 0.0536 0.0224
2 0.0530 0.0222
When, however, the excess of phosphoric acid was omitted
before the reprecipitations, there was a loss of alumina.
An iron solution was made by dissolving C. P. iron wire in
hydrochloric acid and oxidizing it with nitric acid. When care-
fully standardized it was found that
Ten cc. = 0.0296 Fe,0,.
BY THE AMMONIUM ACETATE METHOD. 719
Three successive precipitations, adding one gram ammonium
phosphate before each, gave
Pe,0a.Pi05.
Fc.Oj.
I
0.0545
0.0289
2
0,0550
0.0291
3
0.0548
0.0290
Five successive precipitations, in the same way, gave
PesOs.PtO». PetOg.
1 0.0550 0.0291
2 0.0560 0.0297
Second, That upon three successive precipitations in the pres-
ence of a large amount of calcium phosphate, as is the case in
the analysis of rock phosphate, the precipitate of the phos-
phates of iron and alumina is sufficiently pure to be taken as
such. Of the standard solutions, five cc. of each would together
give a precipitate of combined phosphates about equal to that
usually found in one gram of phosphate rock. The mixture so
analyzed was made up as follows :
Five cc. alumina solution = 0.01125 A1,0,.
Five cc. iron solution = 0.01480 Fe^O,.
0.7000 grams calcium phosphate.
This was given three precipitations, the excess of phosphoric
acid being supplied before the second and third precipitations.
Phosphates obtained. Al^Oi obtained. P^sOa obtained.
1 0.0552 0.OII5 0.0146
2 0.0540 O.OIIO 0.0146
3 0.0537 0.0109 0.0146
4 0.0536 0.0109 0.0146
The iron oxide was determined by volumetric method in the
ignited precipitate and the alumina by subsequent calculation.
In addition twenty cc. alumina solution containing 0.0450
grams A1,0„ together with 0.700 grams calcium phosphate, were
given three successive precipitations in the same way with the
following results :
AlsOs.Pips obtained. AlaO. obtained.
Grams. Grams.
1 0.1092 0.0456
2 0.1074 0.0449
In order to prove that the aluminum phosphate precipitated
was the normal phosphate, the ignited precipitates were fused,
and the phosphoric acid in them estimated.
720 THOMAS S. GI.ADDING.
A.I,Oa.PtO». P,0»obUined. AlfOs by diff. Al,Oa by calc.
1 0,0538 0.0313 0.022$ 0.0225
2 0.0533 0.0312 0.0221 0.0223
The phosphate of alumina is multiplied by the factor 0.418 to
obtain the alumina.
Therefore, in determining iron oxide and alumina in phos-
phate rocks proceed as follows :
Pour grams of the finely ground sample, previously freed
by a magnet from any metallic iron derived from the iron mortar
used in grinding the sample, are digested for half an hour, at a
temperature just below the boiling-point, with about thirty cc.
dilute hydrochloric acid (i-i). This will prevent the solution
of any pyrites if present. Filter and wash thoroughly into a 200
cc. flask, add a little nitric acid, and boil to oxidize the iron,
cool, and fill to mark with water. Take two portions, fifty cc.
= one gram, twenty-five cc. = one-half gram, and proceed with
each as follows :
Almost neutralize the solutions with strong ammonium
hydroxide until the precipitate formed dissolves with difficulty,
and thoroughly cool by placing the beaker in a dish of cold
water. The neutralization is then completed by carefully adding
dilute ammonium hydroxide until the precipitate remains per-
manent, then just dissolve by adding dilute hydrochloric acid,
drop by drop, stirring well. Have ready in another beaker a
mixture of fifteen' cc. of a strong solution of ammonium acetate
(made by neutralizing thirty per cent, acetic acid with strong
ammonium hydroxide) and five cc. of acetic acid. Carefully
pour the cold faintly acid solution of phosphates in a fine stream
into this mixture, stirring all the while. Digest at 60"* C. from
one-half hour to one hour, until the supernatant liquid is clear
and the flocculent precipitate is well settled to the bottom.
Filter and wash the precipitate once with a ten per cent,
ammonium acetate solution, merely rinsing out the beaker in
which the precipitation was made. Dissolve the precipitate
from the paper into the same beaker with a few cubic centime-
ters of hot dilute hydrochloric acid (1-4). Use as little acid as
possible in order to keep the bulk of the solution small. Add
one gram of ammonium phosphate, neutralize with ammonium
IRON AND ALUMINA. 72 1
hydroxide and add hydrochloric acid until the precipitate just
dissolves as before and pour into a mixture of fifteen cc. ammo-
nium acetate solution and five cc. acetic acid. Digest at do"* C.
for one-half to one hour and filter, and wash once with the ten
per cenf . ammonium acetate solution. Redissolve and repeat the
precipitation, being careful to again add one gram of ammonium
phosphate to the solution, in order that there be a sufficient
excess of phosphorus pentoxide to precipitate all the alumina as
a neutral phosphate. Wash the precipitate three times with
dilute ammonium acetate solution.
Take the filter, while wet, from the funnel and ignite in a
tared platinum capsule, using a very low flame until the filter
paper is thoroughly charred. The heat is increased gradually
until the paper is completely consumed , and finally the blast lamp is
used for a minute. Weigh as combined phosphates of iron and
alumina. The iron is determined volumetrically in the solution
of the weighed precipitates. The iron oxide present in the rock
is also determined separately by volumetric process, preferably
the bichromate method, in a solution of five grams of the rock in
dilute hydrochloric acid (i-i), reducing all iron to protoxide
and titrating with bichromate.
The ignited precipitate from one of the duplicate precipitations
may, if desired, be dissolved and subjected to a fourth precipita-
tion and the filtrate tested for lime by adding ammonium oxalate
and heating. My thanks are due to our assistant, Thomas Brown,
Jr., for valuable aid in the above analytical determinations.
I^BORATORY OF STILLWBLL <^ GLADDING,
New York City.
A NEW METHOD FOR THE ESTIHATION OF IRON OXIDE
AND ALUMINA IN PHOSPHATE ROCK.
By Thomas S. Gx^dding.
Received June 90. 1896.
THE method for the separation of alumina from phosphate
of lime by three successive precipitations with ammonium
acetate is tedious, though accurate if proper precautions be taken,
as shown in the preceding paper on this subject.
The following modification suggested itself as saving both
722 THOMAS S. GLADDING. A NEW MBTHOD
time and labor. This modification consists of the separation of
alumina from calcium phosphate and iron by means of its solu-
bility in an excess of caustic potash. To demonstrate the accu-
racy of this method, a solution of ammonia alum, twenty grams
in a liter, was used as in the previous experiments, ten cc. con-
taining 0.0225 grams A1,0,. The caustic potash solution was
made by dissolving 500 grams of caustic potash in distilled water
and diluting to one liter. Chemically pure caustic potash, puri-
fied by barium, was used and was carefully tested for alumina,
as much so-called chemically pure potash contains an apprecia-
ble amount of alumina.
To a solution of mixed phosphates of alumina, iron, and lime
were added fifteen cc. of the C. P. potash solution. The mixture
was digested for an hour at a temperature of 70^ C, with occa-
sional stirring. It was then filtered, the filtrate neutralized
with hydrochloric acid, and the alumina was precipitated as
a phosphate with ammonium acetate as described in my ammo-
nium acetate method.
Ten cc. standard alumina solution -|- 0.030 gram iron oxide +
0.500 gram calcium phosphate gave
AltOa.PfOg found.
AltO,.
Grams.
Grams.
I
0.0538
0.0225
2
0.0542
0.0227
3
0.0543
0.0227
4
0.0543
0.0227
Comparative tests were made on phosphate rocks between this
method by solution in C. P. potash and by three successive pre-
cipitations with ammonium acetate.
By new potash method. By acetate method.
AlfOi found. A1«0| found.
Per cent. Per cent.
1 1.05 1.03
2 1. 19 Z.16
3 1.86 I.61
4 1.07 0.99
5 1.88 1.98
These results show the accuracy of this method, both in
obtaining a known amount of alumina and in showing close
agreement with results by the acetate method.
FOR IRON AND ALUMINA. 723
This method has been in use in our laboratory for over a year.
A reprint of an article by M. Henri Lasne' has just been
received, giving a method for the separation of alumina from
phosphates of iron and lime very similar to this. M. Lasne uses
caustic soda instead of potash and precipitates his aluminum
phosphate with ammonium hyposulphite instead of ammonium
acetate. I have made a few comparative tests by my method
and that of M. Lasne and find closely agreeing results.
Using ten cc. standard alumina solution ^- 0.500 grams cal-
cium phosphate I found
By my method. By Lasne's method.
Al«0|.PtO(. AlfOg. Al,Oa.PtO«. Al«Oa.
Grams. Grams. Grams. Grams.
I 0.0542 o.o2ao 0.0540 0.0226
2 0.0538 0.0225 0.0533 0.0223
In the analysis of a phosphate rock I found
By mr method. By Lasne's method.
Al«Ot found. Al|Ot found.
Per cent. Per cent.
1-75 1-73
1.80
The detailed method used in my work is as follows : Treat
the finely ground rock phosphate with a magnet to remove any
metallic iron derived from the iron mortar used in the prepara-
tion of the sample. Dissolve four grams of the rock in thirty cc.
dilate hydrochloric acid (i-i), heating just below the boiling-
point for half an hour. This prevents the solution of pyrites.
Filter into a 200 cc. flask, add a few drops of nitric acid, and
boil to oxidize the iron, cool and dilute to mark. Take fifty cc.
containing one gram of rock and run into twenty cc. of the solu-
tion of C. P. caustic potash. Digest for an hour at 70° C, stir-
ring occasionally. Let the precipitate settle and filter on a large
paper, first decanting the supernatant liquid on the paper and
finally washing on the precipitate. Wash two or three times
with hot water.
To the filtrate add one gram of ammonium phosphate, acidify
with hydrochloric acid, add ammonia until a permanent precipi-
tate is formed and dilute hydrochloric acid, drop by drop, until
it is just dissolved. Add a mixture of fifteen cc. neutral ammo-
1 Prom the BuUeHn de la SocUU ckimique de Paris, [3] 15, xi8. 1896.
724 CLARENCE L. SPBYERS.
nium acetate solution and five cc. acetic acid (thirty per cent.)
and digest for half an hour at 70** C, by which time the precipi-
tation is complete.
Filter, washing five or six times with hot ammonium acetate
solution (ten per cent.)i stirring up the precipitate with the jet
each time. Ignite with a low flame until the paper is charred,
increase the heat, and, when the paper is completely consumed,
blast for a minute. The precipitate is the normal aluminum
phosphate and its weight multiplied by the factor 0.418 gives
the A1,0,.
The iron oxide is determined volumetrically, preferably by
the bichromate method, in a solution of the precipitate of iron
oxide and calcium phosphate thrown down by the caustic potash.
It is also determined separately, by the same method, in a solu-
tion of five grams of the rock in dilute hydrochloric acid ( i-i ) .
My thanks are due to Mr. H. E. Cutts, A.M., for valuable
assistance in the above investigation.
Laboratory of Stillwell & Gladding.
New York City.
SOME THOUGHTS ABOUT LIQUIDS.
fiY Clarence L. Speyerb.
Received Tune 3. 1896.
CONSIDER an empty closed space. Imagine a quantity of
liquid put into it, enough to fill the space with vapor and
leave some liquid over. A portion of the liquid changes into
vapor and passes into the previously empty space above the
liquid and continues doin'g so until the pressure of the vapor
reaches a certain value, when the vaporization ceases.
The usual way of explaining this vaporization starts out by
assuming that, with the exception of the surface, the liquid is
perfectly homogeneous in a physical sense. That is, there is not
a single particle of the liquid which for any appreciable length
of time is different from any other particle, but of course,
spaces between the particles of liquid are recognized. At the
surface of the liquid, however, a distinction is to be made. For
outside the surface, the activities are different from those within
the surface, otherwise there would be no boundary. So that the
SOMB THOUGHTS ABOUT UQUIDS. 725
particles at the surface are subjected to activities that are differ-
ent in different directions, and consequently the particles ft
situated will behave differently from those particles entirely
within the liquid.
In van der WaaPs theory the mutual attractions of the parti-
cles of the liquid are considered as the restraining force to keep
the particles more or less together. This assumed force must be
very great — a good many hundred atmospheres. Inside the
liquid, below the surface, the attraction is equal in all direc-
tions, but at the surface it acts only in one direction, inwards,
normal to the surface. Now, although the force restraining the
particles of liquid from separating is so great, yet the theory of
common acceptance assumes that some particles do break away
from the mass of the liquid and form vapor. The liquid is said
to evaporate. It is hard to accept this view of the case, particu-
larly as electrical results point towards an exceedingly quiet
condition of affairs within the body of liquids.
Still admitting that the particle does break away from this
attraction, it cannot do so without an abundant supply of energy,
which must be accounted for. It does not seem right to find
this energy in the heat of vaporization, for a particle of liquid
will voluntarily take heat energy from the liquid to do this work,
and so go off as a particle of vapor at the sacrifice of the energy
of the liquid.
It is not possible to prevent a liquid from vaporizing by refus-
ing to give it heat ; it will take the required heat from the rest
of the liquid. In other words, the condition of the liquid state
strongly favors vaporization.
The common theory tries to get over this difl&culty by claim-
ing that the particle which gets away, gets away by virtue of an
inherent kinetic energy greater than the attractic energy of the
particies of liquid, that is, greater than the force denoted by van
n "^
der Waal by A'= ~y, and that it possesses this excess of kinetic
energy in the body of the liquid, before it got away, and that it
got away only by virtue of this excess of kinetic energy. Simi-
larly with all particles in the liquid having a kinetic energy
should exl>«<:' , ^„. Uq»* ■ \^iat««" \«it. "" „e«>i °
^y and so '«
SOME THOUGHTS ABOUT LIQUIDS. 727
due to the escape of the particles with great kinetic energy jrom
the liquid. But all of the lost kinetic energy cannot be absorbed
here in the liquid, some must also go into the vapor particles.
It may take the form of heat, as we have suggested in the case
of the liquid, but then we have to assume that the kinetic energy,
while within the liquid, of the particles that escape is of just
such a value that, after they have all got out of the liquid, the
diminution in their mean kinetic energy, due to the attraction of
the liquid plus this correction, brings the kinetic energy left to
them to the mean kinetic energy of the liquid, which is absurd.
Nor does the attractive energy seem to be stored up as poten-
tial energy, as in the case of a stone raised above the surface of
the earth, for there is no evidence at all that a vapor particle
tends toward the liquid as the stone does toward the earth.
When the partkle gets out of the liquid it seems to be utterly
indifferent to the liquid.
Of course the mutual attraction that all bodies have for each
other is left out of account.
Nor is there any sign of electrical action, at least if the ex-
periments made up to the present time are conclusive.
There are then a good many very serious objections to the
present theory of vaporization.
First, in accounting for the escape of the vapor.
Second, in accounting for the temperature of the vapor.
Third, in accounting for the kinetic energy lost by the particle
in getting through the surface of the liquid and beyond the
sphere of action of the liquid particles.
Let us now turn our attention to another view of the case.
Consider a liquid which has no vapor-tension of its own, a non-
volatile liquid, but which can dissolve gases. The liquid and
gas are supposed to act according to Henry's law,' that is, the
ratio of concentration of the gas in the liquid part and in the
gaseous part is to be constant, or in other words, the quantity
of gas dissolved by the liquid is to be proportional to the pres-
sure on the gas.
In such a system there are three constituents to be considered.
The gas in the gaseous state, the gas in solution, and the sol-
vent.
72S CLARENCE L. SPEYEES.
The state of the dissolved gas is not positively known, but in
all probability it is in a state corresponding to a gas under high
pressure for these reasons. In the first place, it is hard to see
how a substance like nitrogen, for example, could be in the
liquid state in a solution of moderate concentration. Great
pressure is required to liquefy it even when the temperature is
far below the ordinary temperature, and at the ordinary tem-
perature it has hitherto been found impossible to liquefy nitro-
gen, no matter how great the pressure. Still it would be con-
sistent with the ordinarily accepted theory to claim that the
attraction of the particles of solvent could overcome the great
internal energy of the gas particles and bind them down to a
lesser activity and produce the liquid state. But on the other
hand, modern investigation has very plainly shown that dis-
solved substances have a gaseous nature ; the particles of the
dissolved body are free to assert their physical individuality.
That is to say, the solvent is to be considered rather as a medium
through which the dissolved body can be put under certain con-
ditions, the conditions varying to some extentwith each solvent,
but all solvents having the common action of aUowing a sort of
gasification of the substance dissolved, In general the solvent
is not to be considered as a substance which unites with the dis-
solved body, forming a new compound. For example, consider
anhydrous calcium chloride. When this is treated with water
there is strong evidence of combination of the two to form cal-
cium chloride hydrate. If the quantity of water is properly
adjusted the whole of it combines with the calcium chloride,
forming a crystallized hydrate. If this crystalline substance is
treated with more water, solution begins and during this process,
which is the real solution, there is no sign of chemical action.
It is true, some scientists, particularly those of the English
school, have denied this and have claimed to find strong evi-
dence of a chemical action during the process of solution, but so
far all such claims have turned out to be mere opinions based
upon very doubtful measurements.
So we are to look upon solution as being a change in which
the dissolved body is gasified. Sometimes a further change,
electrolytic dissociation, takes place, but that is outside the
SOMB THOUGHTS ABOUT LIQUIDS. 729
scope of this article. It is in best accordance with what we know
about other bodies to assume that the dissolved nitrogen is in the
form of a gas, and to recognize two states in the solution, the
gaseous state of the substance in solution and the liquid stat^ of
the solvent.
Let us now pass on to a liquid which gives off vapor. The
purpose of this article is to justify the view that this vapor
behaves toward the liquid just as the nitrogen did toward its
solvent in the previous case, of course, with the obvious limita-
tions due to identity in the composition of vapor and liquid.
The boundary dividing vapor from liquid is commonly sup-
posed to be at the surface of the liquid, although the possibility
of a differentiation occurring inside the liquid does not seem to
be denied, for so far as could be found out by the writer, the
question of such a possibility has never been raised.
The tendency for a liquid to vaporize and the pressure of its
saturated vapor is evidently a function of temperature only.
There seems to be no reason, therefore, why the fluid should
not separate into vapor and liquid within the surface of the
liquid. That it is possible for vapor to be there follows from
what we know about the gaseous nature of the substances in
solution. It is rather odd that this view of the case was not
adopted at the outset by chemists.
According to this view, when we heat a liquid we increase the
energy of translatory motion, we increase its temperature. But
besides this we cause a separation of some of the liquid particles
from the body of the liquid, bringing them into a state of free-
dom, such that they can behave just as the particles of any
other substance would do in the same solvent. This of course
will consume considerable energy. These free particles of vapor
in the liqiiid we shall call dissolved vapor particles. So that on
heating in liquid we produce dissolved vapor and raise the tem-
perature of the whole fluid ; possibly we do more, but at any
rate we do these two things. Now by Clausius' theory of the
true specific heat, the heat required to raise only the tempera-
ture of a unit mass of substance one degree, should be the same
whatever the state of the substance may be, and the value of the
true specific heat should be the value of the specific heat when
730 CLARENCE L. SPEYERS.
the substance is in such a state that the heat added can only-
change its temperature and not do any other internal work,
namely when the substance is in a state of gas. So if we sub-
tract from the specific heat of the liquid the specific heat of the
gas, the remainder should be the heat consumed in other inter-
nal work, and if no other internal work is done than the rise
in temperature and production of dissolved vapor, we should get
the heat required to change some of the liquid into dissolved
vapor. The quantity changed into vapor however is so far
unknown.
The dissolved vapor is supposed to be produced until its
energy balances the energy of the liquid part.
Suppose, for example, we heat one gram of water one degree
in a closed vessel which does not allow it to give off gaseous
vapor. The heat required will be about one calorie, depending
upon the initial temperature; one calorie is near enough for our
purpose. A part of the heat goes to increase the translatory
motion and is the true specific heat ; but another part, perhaps
the whole of the remainder, we claim goes to produce dissolved
vapor. Subtracting the true specific heat of water, namely the
specific heat of water vapor at a high temperature = 0.4776, we
have left 0.5224 as the heat required to change a certain un-
known quantity of water into dissolved water vapor, provided
that no internal work is done but the two kinds we have con-
sidered. We shall assume this to be true until there is evi-
dence of a more complex change.
Now suppose a space be made over the liquid, to let a certain
quantity, say one per cent., be changed into gaseous vapor. It
is of course evident, if the theory be at all tenable, that the vapor
arising from the liquid comes from the dissolved vapor and bears
to the dissolved vapor the same relation that the nitrogen did to
the dissolved nitrogen. Comparatively little heat should be
required in this process, for most of the change has been effected
in the body of the liquid. Whatever is required here should be
looked upon as the true heat of vaporization ; that which is
usually so called we are to consider as including the beat
required to change a unit mass of liquid into dissolved vapor as
well as the heat required to vaporize the unit mass of dissolved
SOME THOUGHTS ABOUT LIQUIDS. 73 1
vapor. The two quantities should evidently be kept carefully
separated.
Let us now proceed to determine the concentration of the dis-
solved water vapor. As the dissolved water vapor is supposed
to be like a dissolved gas, Henry's law should give us some aid
in finding the quantity. We might assume, in the first place,
that the relative vapor density of a liquid at two different tem-
peratures gives the relative osmotic pressures of the dissolved
vapor at those temperatures, were it not for the uncertainty as
to tow the temperature affects the pressure of the vapor and the
osmotic pressure of the dissolved vapor. It would not do to
assume that each was affected in the same degree by a change
in temperature. But our theory does allow us to claim in
the c£se of a given liquid at a constant temperature that two dif-
ferent vapor-tensions will correspond to two different concentra-
tions of the dissolved vapor by Henr>''s law, and that the rela-
tive vtpor-tensions are as the relative concentrations of the dis-
solved vapor. Now we can change at will, within quite a wide
range, the vapor tension of a liquid without changing its tem-
perature and without introducing any complications.
To understand this let us refer back to the original conception
of the dissolved vapor. If we have liquid water in a vessel with
any number of gases under moderate pressure, the partial pres-
sure of the saturated water vapor will be ver}' nearly the same
as if it alone were present in the space containing the gases.
So when we dissolve a substance in water it would seem as if
we might argue that the osmotic pressure of the dissolved sub-
stance should not affect the pressure of the dissolved water vapor.
However the conditions in the two cases are very different. In
the first case there is abundant space for the water vapor so
that all that is necessary is time for the concentration of the
water vapor to reach the same value no matter how many gases
may be present, provided of course that the total pressure be
not very great. When however the total pressure is great, the
vapor-tension of the liquid diminishes very much. This is just
the condition^that holds in a liquid. The volume available for
a dissolved substance is very small, and so anything put into this
space will very materially lessen the space available for the dis-
732 CLARENCE L. SPEYERS.
solved vapor, particularly as the quantities used in solutions are
generally very much greater than those used in the gaseous state.
Suppose we have n gram-molecules of a substance whose
molecules do not dissociate on dissolving, say sugar, and dissolve
it in water. Let y be the number of gram-molecules of dissolved
vapor after the n gram-molecules of substance have been dis-
solved, then the total number of gram-molecules present in solution
will be y-i-n, and the relative number of gram-molecules of sub-
stance dissolved to total number of gram-molecules in solution is
v-|- n '
Now Jet J be the concentration of the dissolved vapor when
alone in the liquid, and f its concentration after the new sub-
stance has been added, in this case the sugar, j — / will be the
decrease in the concentration of the dissolved water vapor due
the addition of the n gram-molecules of sugar, and since a gram-
molecule of all substances occupies the same volume, the
decrease in concentration/ — / will be the same whate\er the
substance dissolved may be, provided the same number of gram-
molecules be taken in each case, or the decrease in concentration
of the dissolved vapor is proportional to the number of gram-
molecules dissolved in a certain fixed volume of solution. If the
temperature is constant the concentration of the dissolved water
vapor cannot rise above the value y, which it has when only dis-
solved vapor is present ; when we trj*^ to get above this value the
dissolved vapor turns to liquid water. Hence the number of
gram-molecules in a unit volume must be fixed, if the tempera-
ture is constant, that is
y-^-n = constant.
We have, therefore,
J y + n
where a is a constant.
J — f can be calculated by van't Hoff's law, and n is known,
but the other quantities are not, so neither / or y can be calcula
ted from this equation.
SOMB THOUGHTS ABOUT LIQUIDS. 733
There is however another relation that can be deduced.
The concentration of the dissolved vapor is measured b}- its
osmotic pressure.
Let n^ ^, be respectively osmotic pressure and osmotic volume
of the dissolved vapor, when it alone is present ; n\ ^\ the cor-
responding quantities when a substance is in solution \ p,v, the
pressure and volume of the vapor in contact with the pure sol-
vent ; p\ v\ the corresponding quantities when a substance is
in solution.
Consider an isothermal reversible cycle composed of the fol-
lowing parts.
* By means of a semipermeable diaphragm let a gram^molecule
of dissolved vapor pass from the pure solvent, the work will be
— n^ = —RT,
Let the g^am-molecule of vapor expand until it has a pres-
sure of n the work will be
— I ^n = —R Tl —,.
Let it then pass into the solution ; the work will be
-f.;r'^'=: + /?7'.
Let X gram-molecules pass out of the solution in the form of
vapor ; the work will be
— xp'v'=.—xRT,
w^here x denotes the number of gram- molecules of gaseous vapor
necessary to make one gram-molecule of dissolved vapor.
Let the x gram-molecules of vapor be compressed until the
pressure equals p ; the work will be
J^x^ vdp=^'xRTl{,,
Let the x gram-molecules be driven into the pure solvent ;
the work will be
'\'Xpv=^xRT.
734 CLARENCE L. SPEYERS.
Thus the cycle .is completed. The quantity of solution is
supposed to be so large that the addition and removal of the
quantity of the solvent used in the cycle will have no appreciable
effect upon the concentration of the solution.
The sum of the changes of energy must be zero, so
--RT — RTl^ + RT— xRT-h xRTl-^ + xRT = o;
n P
We shall assume that x equals i ; there is no good reason for
thinking otherwise, and the simplicity in the structure of dis-
solved bodies favors this assumption.
From the theory we have
J ^
We have therefore from i through 3 and 2,
(3>
/' p—p' n , .
but from experiment,
p-p'_ n
(5)
p N+ n
where A^ is the number of gram-molecules of liquid in which n
gram- molecules of substance have been dissolved.
Hence,
n n
^—T = Art (6)
Now as equation (6) is true for any small value of n it will
be true for a value so small in comparison with v and N, that it
may be neglected, and so
an _ n
or,
« = ^ (7>
SOME THOUGHTS ABOUT LIQUIDS. 735
Substituting in (6) we have
y n n
N y+n N+n*
or,
y=iJV (8)
That is, the concentration of the dissolved vapor is the same
as the concentration of the liquid, or in other words, all the sol-
vent is to be considered as dissolved vapor.
This is very interesting, for it is in effect the same conclusion
that van der Waals reached in his celebrated treatise, though
he pursued a very different method.
It would seem from this result that matters were left in about
the same state that they were in at the outset; that the view of
dissolved vapor was no better than the old view, which claimed
that the change into vapor took place only on the surface of the
liquid. But we have really gained several things.
In the first place we have found that reasoning from the
analogy that a dissolved gas and the same gas in contact with
the solvent bears to the liquid and its vapor we got to the idea
of dissolved vapor and from that to a result in agreement with
a much older theory.
Secondly, we have found that a liquid is to be looked upon as a
condensed gas, not simply condensed in the sense that it is a mat-
ter compressed into smaller space, but condensed in the sense
that the gaseous activity, pressure, is carried into the liquid con-
dition, and we are to treat a liquid as we would a gas.
Thirdly, it follows from this view that a substance dissolved
is simply brought into the same condition that the liquid is in,
and consequently should have the same property of exerting an
osmotic pi'essure that the liquid has.
Finally, what causes the condensed gaseous state ? Until this
is answered the problem of liquid and gas is essentially unsolved.
That it is due to an attraction between the molecules, is hardly
possible, as we have seen at the beginning of this paper. Indeed
so soon as we begin to reflect upon the complications that are
introduced the moment the ideas of molecule and attraction are
brought into an investigation, and these complications are all
736 SOME THOUGHTS ABOUT LIQUIDS.
the time increasing instead of diminishing, the more natural
and simple appears the view of Ostwald that we shall find a
better solution of such problems in energy alone, matter being
only a collection of energies in space.
Now as to the value of the osmotic pressure in some liquids.
In looo cc. of water there are
looo , .
= 55-55 gram-molecules.
i8
Every gram-molecule at 25** C. (=298® absolute temperature)
in 1000 cc. has a pressure of
22222 298 ,
. . 0.70 m.
1000 273 '
Hence for the 55.55 gram- molecules of water we have
22222 298 ^ 1000 ^ ,
n = . — ^. 0.76 — r— = 1024 meters of mercury.
1000 273 '18
In 1000 cc. methyl alcohol there are
i^. 0.79 gram-molecules.
and hence for methyl alcohol we have
22222 298 , 1000
n = .-^--. 0.76 . 0.79 = 455 m.
1000 273 * 32 '^ ^^"^
In 1000 cc. ethyl alcohol there are
1000 , -
— 2~' 0.79 gram- molecules,
46
and hence for ethyl alcohol we have
22222 298 , 1000
«' = . — ^-. 0.76 — 7—. 0.79 = 316 m.
1000 273 46
In 1000 cc. propyl alcohol there are
i^. o,,o,„„.^,.u.«,
and hence for propyl alcohol we have
22222 298 , 1000 o
n ■=: .-^-. 0.76 — r-. 0.80 = 249 m.
1000 273 46
VOLUMETRIC ESTIMATION OP LEAD. 737
In looo cc. chloroform there are
lOOO - ,
. 1.52 gram-molecules,
and hence for chloroform we have
22222 298 ^ 1000
n = .— ^-. 0.76 . 1.52 = 235 m.
xooo 273 119
In 1000 cc. toluene there are
'"^ . 0.88 gram-molecules,
92
and hence for toluene we have
22222 298 - 1000 „„ ^
n ■=. . — ^^. 0.76 . 0.88 = 176 m.
1000 273 92
RUTGRRS COLX.BGB,
[Contributions from the Laboratories of the School of Mining,
Kingston, Ontario.]
VOLUriETRIC ESTiriATION OF LEAD.
By Fred. J. Pope.
Received May at, 1896. «
aUITE frequently of late, the attention of readers of chemi-
cal journals has been directed to various methods' for
estimaFing lead volumetrically . But, while some of these methods
are superior to any previously made public, yet, for none of
them is that degree of accuracy claimed which is so essential in
a reliable quantitative operation. The chief objection to all of
these methods is the use of an outside indicator. However, by
using an inside indicator and modifying slightly the usual
preliminary steps (necessary for the conversion of the ore into
the sulphate) results have been obtained by the writer which
are quite satisfactory.
The operation may be briefly outlined as follows : The lead is
first converted into lead sulphate, then into lead acetate. Excess
of standard potassium bichromate is added, which precipitates
the lead as lead chromate. The unused potassium bichromate
is reduced by excess of standard arsenious acid, and this latter
IThis Journal, 17, 90Z ; Engineering and Mining Journal^ July 7, 1894.
73^ FRED. J. FOPB.
titrated with iodine solution, using starch paste as an indicator.
PREPARATION AND STANDARDIZING OP SOLUTIONS.
Taking tenth normal solution of iodine as the standard, 4.995
grams of arsenious add per liter and 4.763 grams of potassium
bichromate per liter give standard solutions of equivalent value
per equal volumes.
Iodine. — 12.7 g^ms are dissolved in concentrated potassium
iodide solution and made up to one liter.
Arsenious Acid. — Dissolve 4.95 grams in twenty or thirty cc.
of saturated, filtered solution of sodium carbonate, gently warm-
ing. If too strong heat is applied the arsenious acid cakes and
dissolves with difficulty.
By means of a burette accurately measure ten to fifteen cc. of
arsenious acid solution, running it into a large porcelain dish.
Acidify faintly with sulphuric acid, add fifty cc. saturated solu-
tion of pure sodium bicarbonate, add starch paste and titrate
with the iodine.
Potassium Bichromate. — Weigh out approximately five grams,
dissolve and make up to one liter. Remove twenty-five cc. to a
porcelain dish, add fifty cc. of the standard arsenious acid and
proceed with titration as already indicated.
Note. — Since all commercial sodium bicarbonate will decolor-
ize more or less iodine, it is well in neutralizing to get the neu-
tral point exactly. When this is attained, add fifty cc. sodium
bicarbonate and deduct its iodine value from the quantity con-
sumed.
The Operation in Detail. — Take from three to seven grams of
ore, according to its richness in lead. Place this in a deep
three-inch porcelain dish, thoroughly moisten it with water,
cover the dish with a watch-glass and for each g^am of ore used
add four to five cc. of a previously prepared mixture of two parts
by volume of sulphuric acid, three parts by volume of nitric
acid and one part by volume of water. When the reaction,
which first results, diminishes, evaporate as nearly to dryness as
is possible without spurting. Cool, fill the dish with cold water,
stir well and allow to settle for two or three minutes. Filter and
wash with cold water until most of the acid is removed. Convey the
VOLUMETRIC ESTIMATION OF LEAD. 739
filter paper with the precipitate to a 300 to 400 cc. beaker or
Erlenmeyer flask and neutralize any remaining acid with dilute
ammonia. To the porcelain dish add ten to fifteen cc. strong
ammonium acetate, made decidedly acid with acetic acid. Add
an equal volume of water and boil for two or three minutes,
washing the sides of dish so as to remove any remaining lead sul-
phate. This solution is then added to the flask containing the
precipitate and the whole boiled from seven to ten minutes with
frequent stirring. Cool, neutralize with ammonia, add 100 cc.
of standard potassium bichromate, stirring well. Filter into a
half liter measuring flask, moistening the filter paper with
dilute ammonia or ammonium acetate. Wash precipitate as
much as is possible in the flask, using hot water. The filtrate
make up to the mark, and for titrating remove 100 cc. to a large
one and one-half liter porcelain basin. Add ten to twenty cc.
(or less if ore is rich in lead) of standard arsenious acid. Make
decidedly acid with forty per cent, sulphuric acid and stir until
the yellow color disappears or the liquid has a greenish tinge. A
large excess of sulphuric acid is to be avoided. Neutralize with
saturated solution of sodium bicarbonate and then add an excess
of fifty cc. If the solution has a deep greenish tinge dilute it with
distilled water. Finally add starch paste and titrate with stand-
ard iodine solution.
As a test of the accuracy of method, five portions of pure lead
sulphate were acted upon and the following results obtained :
Grams taken. Grams found.
1.0 1.000568
1.1 1.099375
1.2 1.200467
1.3 1.300673
1.4 I.39957I
With a specimen of galena containing quartz and calcium car-
bonate, the writer obtained the following percentages :
Grams taken. Per cent, lead found.
0.7 ' 81.89
0.7 81.96
0.71 S1.94
0.68 81.90
740 SULPHIDES IN CALCIUM CARBIDE.
As a test of the method in the hands of inexperienced opera-
tors, it was outlined and explained to four junior students, who
with the galena ore already mentioned, obtained the following
results :
Grams taken. Per cent, lead found.
R. H = 0.7 81.86
G. E. R. = 0.7 81.78
S. D. I ' = °-7 82.00
12 = 0.85 81.89
G. E. S = 0.7 81.95
With another ore containing five per cent, of copper, twenty-
six per cent, of iron, quartz and gypsum, one of the students
obtained the following results :
Grams taken. Per cent, lead found.
3.0 15.89
3.5 16.01
4.0 15.97
ESTIMATION OF SULPHIDES IN CALCIUil CARBIDE.
Bt Prbd. J. Pope.
Received May 31, 1896.
A WEIGHED quantity of calcium carbide was conveyed to
a dry Erlenmeyer flask provided with a stop-cock funnel
and a delivery tube, which latter led to a ten ounce wash bottle,
this in turn being connected with a smaller one. The wash bot-
tles contained 150 cc. lead acetate of known strength (about
tenth normal) . By means of a stop-cock water was carefully added
until there was no further evolution of acetylene. On the reac-
tion ceasing, twenty-five to forty cc. sulphuric acid (1:3) was
run into the flask and the whole gently boiled, the liberated
hydrogen sulphide passing into the wash bottles and precip-
itating the lead as lead sulphide. When the reaction had
ceased the flask and liquid was washed free of hydrogen
sulphide by a current of air and the contents of wash
bottles filtered. The filtrate containing unconsumed lead ace-
tate was made up to a half liter. To 100 cc. of this solution
were added standard potassium bichromate, arsenious acid, etc.,
(as indicated in preceding article) and total amount of uncon-
sumed lead acetate estimated. The difference between this
OIL IN BOILBR SCALB. 741
amount and the quantity of lead acetate started with gave
amount precipitated by the hydrogen sulphide from which the
sulphur existing as sulphide was calculated.
Grams calcium carbide taken. Per cent, sulphur found.
2.4492 3-37
3- "34 3-57
No attempt was made to check the application fi the method.
It is obvious that the impure calcium carbide may have
evolved other products capable of removing lead from the solu-
tion. It is the writer's intention to investigate this and other
points connected with this method.
NOTE ON THE PRESENCE OP OIL IN BOILER 5CALE.>
By CRAaLBS A. DoaBMUft.
Received June 9. iBg6.
IT is difficult to remove cylinder oils, whether pure mineral or
mixtures of mineral and animal from condensed exhaust
steam. The practice of recovering steam either for the prepara-
tion of distilled water or for boiler feed water is now so general
that opportunities for observing the troubles attending the pro-
cedure are not wanting.
This sample of water was obtained by melting the **core " of
cakes of artificial ice. The sediment is fine» flocculent and of
red color. When removed from the water and dried it is pul-
verulent. There is very slight evidence of oil in the dry mass,
the moist sediment does not appear oily. The large proportion
of oil extracted by ether shows how inefficient the filters were in
purifying the condensed steam. Yet ver>' great pains were taken
at the ice plant to secure pure distilled water, and there was no
visible oiliness in the water as it flowed to the freezing cans.
Here however the corrosive action of the distilled water on the
galvanized iron produced a mass of iron and zinc hydrates which
in being pushed to the centre by the gradual formation of ice
gathered the oil and carried it to the core.
Another specimen is one obtained from a steamboat trafficing
on the Hudson river and using salt or brackish water in the
surface condensers. The boilers were said to be foul with masses
1 Read before the New York Section. June 5th. 1886.
742 OIL IN BOILBR SCALE.
of oil coating the sides and tubes. Having determined the
presence of the salts of sea water in the boiler, due to leaky
condensers, a treatment was suggested which caused a fine pre-
cipitate. This precipitate gathered the oil in masses easily
brushed from the crown sheets. When this mass is treated with
ether a dry powder remains and oil dissolves.
A third specimen sent for examination from a large plant in
Chicago, evaporating 2500 gallons of filtered river water and
25,000 condenser water every twenty-four hours. Lubricating
oil, mineral with ten per cent, animal, is freely used, and the
fine clay in the water has together with some incrusting in-
gredients, caused the oil to form into balls.
The next two specimens are in striking contrast to the fore-
going. This is light colored, one-quarter inch thick, has a layer
of dense nature near what must have been the heated surface on
which the scale formed while the bulk of the incrustation is
fibrous. The incrustation consists of calcium carbonate and
sulphate, with which is intermingled clay and organic matter,
the latter partly oil.
The general appearance of the next sample is quite different.
The incrustation is in thin sheets about three-sixteenths inch
thick, of light slate color, and made up of alternating la^'ers of
deposit of varying hardness. The ingredients are again calcium
carbonate and sulphate and clay, while there is much organic
matter. This can be separated from the mineral in great part
by a little acid. The presence of oil is then noticeable. The
boiler of this plant is fed wnth Lake Michigan water and con-
denser water. The latter goes directly to the hot well of twenty
barrels capacity. While there are no oil filters the boiler is
provided with a skimmer, which draws off floating materials
from just below the water line. The lubricating oil used is
mineral with fifty per cent, animal.
Notwithstanding the skimmer, the scale has formed and baked
into a hard mass. It is highly non-conducting. It can beheld
by the fingers quite near to where a portion is heated in a Bun-
sen flame, the heat of which distils out and ignites the oil. A
few pieces of this scale heated in an improvised retort made
from a test tube yield quite a gas flame. The presence of oil
AMINES IN THE JUICE OP SUGAR CANE. 743
to the extent of from twenty to fifty per cent, in the deposits
and scale of marine boilers filled with fresh water, any loss
being made up from the exhaust or from sea water has been
fully set forth by I<ewes/ who also gives the causes thereof and
remedies therefor. He also alludes to the possibilities of this
type of scale forming in stationary boilers.
The specimens presented serve to illustrate the importance of
critically examining the nature of the ''organic matter'^ of
incrustations, the statement '*loss of ignition" being far too
general.
[COMTRIBUTBD FROM THE LA-BORATORY OP THE LOUISIANA EXPERIMENT
Station and Sugar Schooi,.]
OCCURRENCE OP THE AfllNES IN THE JUICE OP SUGAR
CANE.
By J. L. Bebson.
Received June 15, X896.
THE presence of amines in the products of the sugar beet
has long been known, but until this sugar season they
have not been known to exist in the juices of sugar cane. Last
December, while working with the precipitate formed by the addi-
tion of lime water to cane juice, it was noticed that the product
dried at about no'' C. had a fishy odor. Upon heating some of
this in a test tube over a burner, an alkaline vapor was given
off which had a fishy ammoniacal odor. So about 300 grams of
the dried substance was gradually heated in a hard glass retort
upon a sand bath until an almost complete destructive distilla-
tion was effected. The products evolved were passed through a
condenser and then through a series of [) tubes, each of which
was kept at a temperature a little below the boiling-points of
each of the principal amines. A solid collected in the condenser
tube, and an illuminating gas escaped from the last (j tube, which
was kept at — 10** C. These products were not examined. There
collected in the first receptacle about twenty cc. of an acid
liquid. This was made alkaline with caustic soda and dis-
tilled. The products as before were passed through the series
of tubes maintained at the different temperatures, when there
1 Chew, News^ 63, 181.
744 EXTRACTION APPARATUS FOR FOOD-STUPP ANALYSIS-
collected in the first, along with some water, about five cc. of
clear liquid, which was strongly alkaline, had a pungent fishy
odor, combined with hydrochloric acid, and otherwise manifested
the general properties of the amines. An attempt was made to
further purify it by freeing it from the water, but the amount
was too small to bring to a definite boiling-point. The remain-
ing liquid was neutralized with hydrochloric acid, and slowly
evaporated down, whereupon a few crystals, slightly colored and
deliquescent, were obtained. The quantity was too small to
admit of an elementary analysis, so it was not possible to say
whether the product was a single amine or a mixture of amines.
The filter cake, the refuse from the clarification of cane juice,
gave the same odor and alkaline vapor upon heating. It was
my aim to subject several pounds of the filter cake to the same
treatment in order to fully clear up the question, if possible, but
the amount of other work required of me prevented. The clear-
ing up of the matter is of the greatest scientific and practical inter-
est to the sugar industry, as it will doubtless throw light upon
the nature both of the amido and albuminous bodies of the cane
juice. I write the account of the work with the hope that some
chemist may be induced to continue the work, as the writer will
discontinue sugar work.
[Contributed from the Laboratory op the Louisiana Ezpbrxmbnt
Station and Sugar School.]
A SIMPLE AND CONVENIENT EXTRACTION APPARATUS
FOR FOOD-STUFF ANALYSIS.
Bt J. L. Bkbson.
Received Tans 15, 1896.
THE apparatus shown in the accompanying illustration I
have adapted from the Johnston extractor, for the general
use of the average student in the laboratory aiming at simplicity,
greater compactness, convenience, rapidity of operation, and accu-
racy. The extraction tube -£", which is rather short, is provided
as usual with a perforated platinum disk fused into the bottom,
and in addition with a specially devised funnel stopper of ground
glass, by means of which the weighed sample can be rapidly
NBW BOOKS.
745
and effectively dried to constant weight in a current of dry
hydrogen or other inactive gas for the es-
timation of the moisture, and at the same
time preparing the sample for extraction.
Rubber caps are placed over the two
ends of the tube during the cooling and
weighing. For the extraction of the
sample, the tube displaced in a Stutzer
tube S as shown in the figure, which id
connected as usual with an ether flask
below, and by means of either a cork or
mercury joint with a short bulb conden-
ser above. The funnel stopper, placed
as shown, directs the returning drops of
the liquid upon the center of the sam-
ple, and especially it prevents the loss of
the sample by spattering. This is a
source of objection to all forms of open
extractors. Owing to the very small
percentage of fats or ether extracts in
most food stuffs a small loss of the sam-
ple from this cause makes a very large
analytical error in the work, whether es-
timated from loss of the sample orgain in weightoftheetherflask.
During two years use in this laboratory we have obtained with
the apparatus very concordant results between duplicate analyses,
and would commend it for the use of students especially. By
means of a seven mm. glass tube, six tubes and samples are dried in
a current of hydrogen at a time in a water-oven. The whole
apparatus may be had of Max Kaehler and Martini, Berlin.
NEW BOOKS.
Chbicistry por Enginbbrs and Manttfacturbrs. By Bbrtram Bi^oukt
AND A. G. Bu)XAM. In two Yolumes. VoIvUMB I, Chbmistry op Bn-
GiNBBRiNG, Buii«DiNG AND Mbtali^urgy. 8vo. 244 pp. London :
Charles Griffin & Co., Ltd. Philadelphia : J. B. Lippincott Co.
This work is a compilation of material intended to cover the
chief branches of chemical industry. The first volume deals in
74^ NEW BOOKS.
the first part with the chemistry of building materials, fuel,
steam making and lubrication. The second part is entirely de-
voted to metallurgy.
The scope of the work necessitates condensation, yet tbe
reader will be impressed at times with the meagemess of descrip-
tion , especially as the treatment of other subjects seems dispropor-
tionately extended. An appearance of unevenness in treatment
is thus given, which might have been avoided.
Books of this class are more difficult to write as the limits of
technical Science are widened and there is room for much judg-
ment in holding a proper balance between the necessities of the
reader and the restricted space of a hand book or text book . While
this book will be very serviceable to the large class of engineers
and manufacturers for whom it is especially written, and even
to the student of industrial chemistry, it can hardly be of much
interest to ** the expert in any one of the branches touched
upon" {vide preface). The touch is entirely too light as a rule
for those who seek extended information. The entire absence
of references, also, deprives the work of much of the usefulness
it might have had for professional readers in subjects not strictly
their own.
The illustrations are good as far as they go, but are much less
freely supplied than the nature of the book requires.
The subjects of gaseous fuel and water for steam making
are well and clearly treated. Of boiler cpmpositions the authors
justly say that '* none should be used without a knowledge both
of its composition and of that of the water to be treated, ' * and that,
* ' all are sold at prices bearing but a remote relation to their
intrinsic values.'* As to the preservation of iron by paint, the
statement that red lead paint is the best will hardly meet un-
qualified assent.
The treatment of the metallurgy of iron is very full, and
contains a good though brief discussion of the influence of
foreign elements on the quality of iron. The statement that **the
chief gold-producing countries are Australia, America (Cal-
ifornia), and Russia'* is more compact than edifying. Electro-
metallurgical processes are given in treating of many of the
metals. The commercial production of aluminum is described
BOOKS RECEIVED. 747
briefly but no allusion is made to the part which the United
States liave played in the development of this industry, nor do the
names of Cowles or Hall appear in the text.
The second volume will treat of the chief chemical industries
other than those referred to.
A. A. Breneman.
Laboratory Experiments in General Chemistry. By Charles R.
Sanger, A.M., Ph.D. Paper. St. Louis. Published bv the Author.
1896.
Experiments in General Chemistry and Qualitative Analysis. By
Charles R. Sanger, A.M., Ph.D. Paper. St. Louis. Published by
the Author. 1896.
These two little books by Professor Sanger contain well se-
lected collections of experiments for beginners in chemistry. The
first collection was prepared for students in a general college
course, while the second collection appears to have been arranged
for students beginning a medical course. In the first collection
for college students there is evidence that the author had in mind
the needs of those who spend but part of a year in the labora-
tory. What the student is told to do is clearly indicated and his
attention is directed at every step to the important points in the
reactions considered. The experimental course offered to med-
ical students is not as extended as the present writer would like
to see, but is as full as this class of students is supposed to need,
and has, besides, the advantage of systematic arrangement.
' J. H. Long.
BOOKS RECEIVED.
Eighth Annual Report of the Kentucky Agricultural Experiment Sta-
tion of the State College of Kentucky, for the year 1895. Lexington, Ky.
Ixvi, 150 pp.
North Carolina Weather during the Year 1895. North Carolina Agri-
cultural Experiment Station, Raleigh, N. C. lii, 264 pp.
Bulletin No. 122. Cost of Nitrogen, Phosphoric Acid and Potash.
Proper Use of Tables of Analysis of Fertilizers. Connecticut Agricultu-
ral Experiment Station, New Haven, Conn. 16 pp.
Reduction of Nitrates by Bacteria and Consequent Loss of Nitrogen.
By Ellen H. Richards and George William Rolfe. 20 pp. Reprinted
from the Technology Quarterly, Vol. IX, No. i, March, i89i5.
Nitro-Explosives. A Practical Treatise. By P. Gerald Sanford, F. I. C,
74^ OBTITART NOTE.
F. C S. LondoD : Croabj, Lockvwid & Sod. 1896L zii, 270 pp. Price,
EmbAlmiag mod Embalming Fluids, with the BibliogiaphT of Em-
balming. Thesis hj Charles W. McCnrdj. Sc.D., Ph.D. Wooster. Ohio :
The Herald Pnblishiiig Co. April. 1896L 84 pp.
Bnlletio No. 64. Analysis of Commercial Fertilizers. Keotnckj Ag-
ricnltnral EiEperiment Station of the State of Kectockj. Lexington, K j.
JBI7, 1896. 16 pp.
OBITUARY NOTE.
Peter Coluer, Ph.D., was bom in Chittenango, New York,
August 17, 1835. He graduated A.B. at Yale College in iS6i
and later Ph.D. He also graduated at the Sheffield Scientific
School, and was for some time an assistant and instructor in that
School. From 1S67 to 1S77, he was Professor of Ph\-sics and
Chemistry in the University of Vermont, and also Professor of
Chemistry in the Medical Department of that University, and
for some time Dean of the Medical Faculty. In 1S73 he was ap*
pointed one of seven scientific commissioners to the Vienna
Exposition, by President Grant. From 1S77 to 1S82 he was
Chief Chemist to the Department of .Agriculture of the United
States, at Washington. During his omcial term, he gave very
great attention to the problems of cultivating sorghum and
manufacturing sugar from it. From 1SS2 to 1S35 he still re-
mained in Washington, engaged in chemical pursuits and writ-
ing for scientific and agricultural publications. From 1S87 to
I S95 he was Director of the New York State Experiment Station
at Geneva, New York, where he instituted much experimental
work especially upon fertilLzers and dairy problems. He had a
wide acquaintance with scientific men, and himself possessed
great energy and force. Illness obliged him to resign his posi-
tion last year and he came to Ann Arbor last December. He
died on June 29.
A. B. Prescott-
ERRATA.
Oa pazc 651. Ja!y aamber, 15th lice frcrm top, for 159.000 rtraJ 166,000.
On pa.^e 653, 7th line frozn bcttozn. for 159 000 riraJ 166.000.
On page 654. 4th line from top, for 156. 5 19.5 r^J 116,519.5.
Vol. XVIII. [September, 1896.3 No. 9.
THE JOURNAX
OF THE
AMERICAN CHEMICAL SOCIETY.
THE DETERMINATION OF REDUCING 5UQARS IN TERHS
OF CUPRIC OXIDE.
By George Depren.
Received July 9. 1896.
IT is now approximately fifty years since alkaline metallic
solutions were first used in determining quantitatively the
various reducing sugars. During this period of time many
investigators have worked on the subject, and much has been
done towards perfecting the method of analysis, so that to-day
there are several admirable processes in use for the exact esti-
mation of these carbohydrates.
The quantitative methods of determining reducing sugars
may be divided into two main classes : those based upon the
volumetric plan, and those which depend on a gra\nmetric esti-
mation of the precipitated cuprous oxide.
Of the first class many processes have been suggested which
have met with more or less success. The volumetric methods
are mainly used for factory control work , where the progress of
some processes require a rapid and fairly accurate idea of the stage
of manufacture. In expert hands the volumetric methods are
capable of giving excellent and concordant results, and are,
therefore, used in the laboratories of many consulting chemists,
and even in scientific institutions.
The main objections to the use of the volumetric methods are
that each freshly prepared quantity of Fehling solution requires
accurate standardization against the same kind of pure sugar as
that which is undergoing analysis. Different dilutions and the
75^ GBORGB DBPRBK.
*
time of boiling affect the results materially. The exact deter-
mination of the "end point" also requires considerable practice
and skill.
On the other hand, the Fehling liquor used in the gravimetric
processes need not be made up as accurately as is required for
volumetric work. The gravimetric methods, however, ordi-
narily require more time. A possible loss of cuprous oxide by
filtration, and an incomplete oxidation to the higher oxide are
also potent factors, though where the requisite degree of care is
exercised these need not cause anxiety. The same statement
regarding dilution and time of boiling holds true with as much
force in gravimetric as in volumetric work.
The gravimetric methods are generally employed for scientific
and accurate analytical work. Here the processes are compara-
tively few, all depending upon the oxidation of the total
sugar present in an excess of the alkaline copper solution.
The tables in use for the determination of reducing sugars are
mainly constructed in terms of metallic copper. As the
amount of metal precipitated per gram of carbohydrate is not a
constant for all dilutions of any sugar, specially constructed
tables are generally employed. Several such tables have been
prepared, as for instance Allihn's table of reduced copper for
dextrose, Wein's table for maltose, and Soxhlet's table for lac-
tose, etc.
Various modifications of the alkaline copper solutions are used
for the determination of the different sugars, each requiring
special treatment. Therefore a chemist in determining the
amount of malt sugar in, say beer, must, if he uses Wein's table
for maltose, follow exactly Wein's method for the estimation of
that sugar.
Where a varietj- of work is carried on in a laboratory, it is
therefore necessary to have several different Fehling solutions on
hand for each special kind of determination. If all the tables
for the estimation of the different carbohydrates could have been
prepared for use under uniform conditions, the existing state of
affairs would be much simplified.
In order to supply this need. I have constructed such tables,
using a method which I have employed for some time, in deter-
DBTBRMINATION OP RBDUCING SUGARS. 75 1
mining reducing sugars. This method, proposed by O' Sullivan'
in 1876, is used to some extent in England, but as it seems to be
not generally known, I here give the procedure in detail :
To fifteen cc. of the copper sulphate solution, prepared as given
below, are added fifteen cc. of the alkaline tartrate solution, in an
Brienmeyer flask having a capacity of from 250-300 cc. The
mixture is diluted with fifty cc. of freshly boiled distilled water
and placed in a boiling water bath for five minutes. Twenty to
twenty-five cc. accurately measured from a calibrated burette of
an approximately one-half per cent, solution of the sugar to be
analyzed, are then run into the hot Fehling liquor and the
whole kept in the boiling water bath for from twelve to fifteen
minutes. The flask is then removed from the bath and the pre-
cipitated cuprous oxide is filtered as rapidly as possible, either
through filter paper or asbestos in a Soxhlet's tube or porcelain
Gooch crucible, and washed with boiling distilled water until the
wash water no longer reacts alkaline. It is ignited and weighed
as cupric oxide as described below. The corresponding amounts
of dextrose, maltose or lactose are ascertained by reference to
the tables at the end of this article. It should be noted that the
above directions must be closely followed. The volume of the
Fehling liquor and the added sugar solution should be from
ioa-105 cc.
The Fehling solution used is made up according to Soxhlet's
formula, with a very slight modification. 69.278 grams of pure
crystallized copper sulphate, pulverized and dried between filter
paper, are dissolved in distilled water. It is advantageous to
add one cc. of strong sulphuric acid to this, as recommended by
Sutton.' The whole is then made up to one liter with distilled
water and kept in a separate bottle. The alkaline tartrate solu-
tion is made by dissolving 356 grams of crystalline Rochelle salt
and 100 grams of sodium hydroxide in distilled water and mak-
ing up to one liter. This is also kept in a separate bottle.
Two methods of filtration of the precipitated cuprous oxide
and further treatment are generally adopted. In the first double
" washed " filter paper is used ; in the other the precipitate is
ly. CAem. Soc.. a, ijo, /Sjd,
s Sutton : Fourth edition, (1883), 256.
752 GEORGE DEFREX.
retained by a layer of asbestos. After washing the precipitate
on the filter paper as above described, it is dried in the usual
manner and ignited in a previously weighed porcelain crucible »
taking care to bum the filter paper cautiously, heating for fif-
teen minutes to a red heat, cooling the crucible over sulphuric
acid in a desiccator and weighing as cupric oxide. Additional
treatment with nitric acid has been found of no practical advan-
tage, the results by direct ignition being very exact, providing
the filter paper is slowly burned. The chief objection to the
employment of filter paper to retain the precipitated cuprous
«
oxide, is that some of the finely divided particles are liable to
go through, thus causing low results.
As a substitute for paper carefully selected asbestos is often
used for filtering purposes. To insure a layer of asbestos which
shall be kept at constant weight under the action of hot Fehling
liquor, it is advantageous to boll the mineral with nitric acid
(1.05-i.iosp. gr. > for a short time, washing the acid out with
hot water, and then boiling with a twenty-five per cent, solution
of sodium hydroxide. This is also washed out with hot water.
Reboiling with the above reagents as before diminishes the
liability of leaving any soluble portions. As thus prepared the
filtering material may be kept indefinitely under water in a wide-
mouthed bottle ready lor use.
The objections of some chemists' to the employment of asbes-
tos on the ground that it loses weight on using, does not seem
to hold, when it is prepared as above. A sample boiled as stated
with acid and alkali three times, lost only two-tenths milligram
when two "blanks " of hot dilute Fehling solution, as used in
the process above described, were passed through the mineral in
a t>orceIain Gooch crucible.
For use, a layer of asbestos, about one centimeter in thick-
ness, is placed in a porcelain Cooch crucible, to retain the finely
tiivuied precipitate, which is filtered by means of suction, in the
u^l2al manner. The crucible containing the cuprous oxide is
the.i dropped into a triangular frame, made ot platinum wire,
sa>penced within an iron radiator, or shell, heated to redness.
Th:** quietly ai^vi thoroughly drio the asbestos without cracking
DBTBRMINATION OF REDUCING SUGARS. 753
I
the crucible. After about five minutes the crucible is trans-
ferred by means of a pair of nippers to a red hot platinum cruci-
ble and heated for about fifteen minutes. It is then quickly
transferred to a desiccator near at hand to prevent cracking,
allowed to cool and weighed. As cupric oxide is somewhat
hygroscopic, it is advantageous to weigh quickly and to keep
the balance case as dry as possible. Prolonged heating in the
iron radiator would have changed the cuprous oxide to the
cupric state. The advantage of transferring the porcelain cru-
cible to a red-hot platinum crucible, is that the oxidation is
quickly completed, as a much higher temperature is available.
If pressed for time, another determination can be made in the
same crucible without cleaning it. As a rule, it is, however,
advisable to wash out the cupric oxide by means of hot nitric
acid ( 1. 05-1. 10 sp. gr.) and then with hot water. The crucible
is then heated, cooled and weighed as before. It must necessarily
be weighed, because this treatment with hot nitric acid dissolves
some of the asbestos.
If preferred, a Soxhlet's tube may be used to retain the pre-
cipitated cuprous oxide. As a porcelain Gooch crucible possessed
obvious advantages over this apparatus, I have used it in all my
determinations with success.
The cupric reducing powers of dextrose, maltose aud lactose
were determined by the method given above. A table for invert
sugar was not constructed because most invert sugar determina-
tions are made by double polarization in a saccharimeter.
DEXTROSE.
The * 'cupric reducing power'* of dextrose was first determined.
This is defined as **the amount of cupric oxide which 100 parts
100 IV
reduce." * This may be represented by jz — , in which W^is
the weight of cupric oxide obtained by the given weight of any
sugar, and D the weight of cupric oxide formed by an equal
weight of dextrose.* Hence, if the amount of cupric oxide
formed by one gram of dextrose be known, the amount of cupric
oxide reduced by one gram of any other substance, calculated
I/. Chem. Soc., 2, 130. 1876.
ay. CA€m. Soc., Trans., 606, 1879.
754 GEORGE DEPREN.
upon this number as a percentage, will represent the cupric oxide
reducing power of the substance, which we denote by the sym-
bol A".
The amount of cupric oxide has been determined by O' Sulli-
van* to be 2.205 grams per gram dextrose. The factor for dex-
trose in terms of cupric oxide is, therefore, the reciprocal of
2.205 or 0.4535. This value, 0.4535, ^as assumed to be a con-
stant for all amounts of dextrose when used with Fehling's solu-
tion in the manner indicated. As such it was a very convenient
quantity, it being only necessary to obtain the weight of cupric
oxide formed by the action of a dextrose solution, multiply this
by 0.4535, and the amount of dextrose corresponding was
obtained. No tables are needed if this assumption be true.
Consequently the determination of dextrose was indeed a very
simple one.
On an extended investigation of this subject, using various
amounts of dextrose on the same volume of Fehling liquor in
each determination, I find that the value 2.205, above given as
representing the quantity of cupric oxide obtained by the action
of one gram of dextrose, is not as was heretofore assumed, a
constant for all weights of dextrose taken, the amount varying
from 2.27 grams cupric oxide per gram dextrose for small quan-
tities of sugar, to 2.22 grams cupric oxide for the largest amount
of dextrose permissible. AUihn,' boiling his sugar solutions with
the Fehling liquor and reducing the cuprous oxide to copper,
obtained analogous varying results.
The purity of the dextrose used was first determined, dextrose
anhydride being employed. 10.008 grams of anhydrous dextrose
were disssolved in distilled water and the solution boiled to pre-
vent birotation. It was then transferred to a flask, the capacity
of which at 15.5** C. was 100.08 cc, thus giving a solution which
contained o.ioo gram dextrose anhydride per cc.
The specific gravity of the above solution at 15.5* was deter-
mined in the usual manner by means of a picnometer with ther-
mometer attached.
Capacity picnometer (at 15.5^) = 55-ao55 cc.
Dextrose solution (at 15.5^) = 57*5083 grams.
I Loc. cit.
ij.praki, OUm., (a). M.63.
DETBRMINAl'ION OF REDUCING SUGARS. 755
On calculating from these values we find the specific gravity
of a dextrose solution containing ten grams dextrose in lOO cc.
to be 1.03809 at 15.5**.
The specific rotatory power was determined by the usual
method, a Schmidt and Haensch saccharimeter being used in
polarizing the dextrose solution. The polarizations were carried
out in a 200 millimeter tube at 20**. To change from the read-
ings of a saccharimeter to the rotary degrees, it is necessary to
multiply the reading observ^ed by 0.344, as shown by Reinbach.*
I have verified this value with concordant results, a Laurent
polariscope being used for comparison. The rotation of the above
solution was 30.7 divisions. This gives by means of the usual
av
formula — [a]5 = -^ —a specific rotatory power of 52.8 , which
is in accordance with that obtained by other observers.' The
dextrose used was consequently pure.
For the determination with Fehling liquor, twenty-five cc. of
the dextrose solution at 15.5° were accurately measured from a
calibrated burette and made up to 500 cc. with distilled water at
the same temperature. This consequently gave a solution, each
cubic centimeter of which contained five milligrams dextrose.
Various quantities of this were then taken to ascertain the cupric
reducing power of dextrose. The results in detail are given
below. In each case the combined volumes of the Fehling
liquor and the sugar solution were made up to 105 cc. as
described above.
Milligrrams
Cupric oxide
obtained.
Cupric oxide
Dextrose
Mean dextrose
dextrose.
per grram dextrose.
equivalent.
equivalent.
I2i
I2i
0.0283
0.0285
2.264
2.280
0.4416)
0.4386 y
0.4401
25
25
0.0569
0.0565
2.276
2.260
0.4393 \
0.4425 i
0.4419
50
O.I 129
2.258
0.4429 \
0.4452 i
0.4440
50
O.II23
2.246
62i
0.1407
2.251
0.4443 \
0.4454 ^
0.4449
62i
0.1403
2.245
75
0.1683
2.244
0.4457 I
0.4467 f
0.4462
75
0.1679
2.239
^T^¥
1 Ber. d. chem. Ges.^ 87, 2282.
< Pribram : Monat.f, Chem., 9, 399; Landolt : Ber. d. chem. Ges., si, 191.
MilUfframs
dextrose.
Cupric oxi
obtained
lOO
0.2233
■
lOO
0.2227
"5
0.2776
"5
0.2782
"5
0.2770
"5
0.2774
125
0.2777
140
0.3105
140
0.3100
756 GEORGE DEPREN.
Cupric oxide Dextrose Mean dextrose
per gram dextrose, equivalent. equivalent.
2.233 0.4478 1 „.^3
2.227 0.4489 »
2.221 0.4503
2.225 0.4493
2.216 0.4512 |- 0.4503
2.219 0.4506
2.222 0.4500 J
2.218 0.4508) ^^5„
2.215 0.4515 J
The foregoing values of the amounts of cupric oxide per gram
dextrose are given graphically in cur\'e A, Plot I, and the dex-
trose equivalents of this in A, Plot II.
From this we get the amount of dextrose corresponding to a
given weight of copper oxide by means of the formula :
D = (0.4400 -f- 0.000037 ^) ^»
in which D is the amount of dextrose, and W the weight of
cupric oxide.
The dextrose table given in this article is based on this for-
mula, the values of W^ varying from 30 to 320.
MALTOSE.
The cupric reducing power of dextrose is given as 100.
Using this as a basis, the reducing force of maltose, as given by
O'Sullivan,* is 65. Brown and Heron* place the value some-
what lower, claiming that 61 is more exact. The results which
I have obtained agree very well with this latter number.
In the case of maltose, as with dextrose, it was found that the
amount of cupric oxide obtained per gram of sugar was not a
constant. The cupric reducing power of various amounts of
maltose was, however, found to be almost exactly a constant
when referred to the cupric oxide from equal weights of dex-
trose. That is, calling the reducing power of dextrose 100 for
different aliquot parts of that sugar, the cupric reducing power
of maltose referred to this standard was always 61.
The specific gravity of maltose was determined in the usual
manner. 9.7558 grams maltose anhydride were dissolved in dis-
tilled water to 100.08 cc. at i5-5°-
1 Loc. a'l.
«y. CAem. Soc., 1879, Trans., 619.
DETBBHINATION OP REDUCING SUGARS.
GEORGE DBPRBI4.
DBTERMINATION OP RBDUCING SUGARS.
759
Maltose solution at 15.5*^ = 57*3049 grams.
On calculating this we find the specific gravity of the above
solution to be 1.03803. For a solution containing ten grams
maltose anhydride in 100 cc. it would consequently be 1.03900
at 15.5**.
The specific rotatory power was determined as usual. The rota-
tion of the above solution at 20*^, in a 200 millimeter tube, was
74.4 divisions on the saccharimeter scale. This gives [flf]? =
I36.6'.
As maltose anhydride is somewhat difficult to prepare, the
solutions used to determine the cupric reducing powers were
made up to approximately ten per cent, from the maltose
hydrate. The specific gravity of the solutions was then deter-
mined. Subtracting from this value i .00000— the specific gravity
of water — and dividing the remainder by 0.00390, we get the
amount of maltose anhydride in 100 cc. of solution.
Maltose solution at 15.5** = 57.2511 grams,
which gives a specific gravity of 1.03754, or 9.501 grams mal-
tose anhydride in 100 cc.
The solution for Pehling determinations was made in the
same manner as the dextrose solutions above. Each cubic cen-
timeter of the diluted maltose solution therefore contained 4.75
milligrams maltose anhydride.
Milllfirnims
maltiMe.
23-75
2375
47-5
cupric oxide Cupric oxide per
obtained.
47.5
71.25
7125
95.0
950
118.75
118.75
142.5.
142.5
190.0
190.0
237.5
237.5
0.0329
0.0327
0.0656
0.0654
0.0983
0.0979
0.1304
0.1300
0.1623
O.1619
0.1940
0.1934
0.2572
0.2566
0.3198
0.3193
Strain maltose.
.386
377
381
377
380
374
373
369
370
367
361
357
353
350
347
345
Maltose
equivalent.
0.7218 )
0.7263 i
0.7243 1
0.7263 /
O.72A7 >
0.7278 )
0.7286 1
0.7308 i
0.7302 1
0.7336 J
0.7345 \
0.7369 r
0.7284)
0.7406 J
0.7429 \
0.7437 '
Mean maltose
equivalent
0.7240
0.7253
0.7263
0.7297
0.7319
0.7354
0.7395
0.7433
760 GEORGE DEFREN.
The maltose equivalent in terms of copper oxide is shown in
B, Plot II. From this we get the amount of maltose corres-
ponding to a given weight of cupric oxide by the formula :
J/= (0.7215 +0.000061 W) W,
in which Af is the weight of maltose, and IV the amount of
cupric oxide obtained. It will be seen that these values make
the cupric reducing power of maltose 0.61 that of dextrose.
LACTOSE.
Lactose was investigated in the same manner as the preced-
ing. 10.008 grams lactose anhydride were dissolved in distilled
water, boiled, and made up to 100.08 cc. at 15.5^.
The above solution, polarized in a 200 millimeter tube at 20",
gave a rotation of 30.7 divisions. This gives the specific
rotary power of lactose of 52.8".
The amounts of cupric oxide found by the reduction of known
weights of lactose were determined as in the previous cases with
the following results :
Milligrams
Cupric oxide
obtained.
Cupric oxide per
Lactose
Mean lactose
lactose.
gram lactose.
equivalents.
equivalents.
20
0.0319
1-595
0.6269 )
0.6289
20
0.0317
1.585
0.6308 i
^
50
0.0798
1.596
0.6266 \
0.6274
50
0.0796
1.592
0.6282 i
/ ~
75
O.I 188
1.584
0.6313 \
.0.6334 *
0.6323
75
O.I 184
1-579
100
0.1577
1.577
0.6340 1
0.6369 i
0.6355
100
0.1570
1.570
125
0.1955
1.564
0.6395 \
0.6^79
125
0.1964
1. 561
0.6363 i
%j § f
150
0.2345
1-563
0.6397 I
0.6410 >
0.6404
150
0.2340
1.560
175
175
0.2729
0.2724
1.56c
1-557
0.6412)
0.6424 /
0.6418
200
O.3II2
1-556
0.6425 \
0.6430
200
0.3107
1.553
0.6436 i
^^
The cupric oxide values per gram lactose are presented graph-
ically in curve C, Plot I, while the reciprocals of these quanti-
ties are shown in C, Plot II. For this latter the amount of
lactose corresponding to the weight of cupric oxide obtained is
determined by the following :
DETERMINATION OF REDUCING SUGARS.
761
L = (0.6270+ 0.000053 W) W,
in which L is the lactose, and W the amount of copper oxide.
The acompanying table for lactose is constructed on this basis.
It will be seen from the above results that the amount of
cupric oxide produced by the action of one gram of reducing
carbohydrate on Fehling liquor, in the manner described, is not
a constant for all dilutions.
The cupric reducing power of maltose is 0.61 that of dextrose.
The following tables for the determination of the reducing
sugars in terms of cupric oxide are based on the analytical results
presented above, and can be used in the process outlined in the
same manner as any other table for the same purpose :
P«rts
Parts
dextrose.
Parts
maltose.
Parts
lactose.
Parts
copper
oxide.
Parts
dextrose.
Parts
maltose.
Parts
lactose.
30
13.2
21.7
18.8
57
25.1
41.3
35.9
31
13-7
22.4
19.5
58
25.5
42.1
36.5
32
14. 1
231
20.1
59
26.0
42.8
37.1
33
14.6
23.9
20.7
60
26.4
43.5
37.8
34
15.0
24.6
21.4
61
26.9
44.3
38.4
35
15.4
253
22.0
62
27.3
45.0
39.0
36
159
26.1
22.6
63
27.8
45.7
39.7
37
16.3
26.8
23-3
64
28.2
46.5
40.3
38
16.8
27.5
23.9
65
28.7
47-2
40.9
39
17.2
28.3
24.5
66
29.1
47-9
41.6
40
17.6
29.0
25.2
67
29.5
48.6
42.2
41
18. 1
29.7
25.8
68
30.0
49.4
42.8
42
18.5
30.5
26.4
69
30.4
50.1
43-5
43
19.0
31.2
27.1
70
30.9
50.8
44.1
44
19.4
31.9
27.7
71
31.3
51.6
44.7
45
19.9
32.7
28.3
72
31.8
52.3
45.4
46
20.3
33.4
29.0
73
32.2
53.0
46.0
47
20.7
34.1
29.6
74
32.6
53.8
46.6
48
21.2
34.8
30.2
75
331
54.5
47.3
49
21.6
35.5
30.8
76
33.5
55.2
47.9
50
22.1
36.2
31.5
77
34-0
56.0
48.5
51
22.5
37.0
32.1
78
34.4
56.7
49.2
52
23.0
37-7
32.7
79
34.9
57-4
49.8
53
23.4
38.4
33.3
80
35.4
58.1
50.5
54
238
39-2
34.0
81
35.9
58.9
51. 1
55
24.2
39.9
34-6
82
36.3
59-6
51.7
56
24.7
40.5
35-2
83
36.8
60..^
52.4
762
OBORGB DBPRBN.
Parts
Parts
S2fl?.'
Parts
Parts
Parts
SSC:^
Parts
Parts
Parts
dextrose.
maltose.
lactose.
dextxx»e.
maltose.
lactose.
84
37-2
61.1
53.0
127
56.5
92.5
80.4
85
37.7
61.8
53.6
128
569
93-3
8x.i
86
38.1
62.5
54.3
129
57.3
94.0
81.7
87
38.5
63.3
54.9
130
57.8
94.8
82.4
88
39.0
64.0
55-5
131
58.2
95.5
83.0
89
39.4
64-7
56.2
132
58.7
96.2
83.6
90
399
65.5
56.8
133
59.1
97.0
84.2
91
40.3
66.2
57.4
134
59-6
97-7
84.9
92
40.8
66.9
58.1
135
60.0
98.4
85.5
93
41.2
677
58.7
136
«o.5
99.2
86.1
94
41.7
68.4
59-3
137
60.9
99.9
86.8
95
42.1
69.1
60.0
138
61.3
100.7
87.4
96
42.5
69.9
606
139
61.8
101.4
88.1
97
430
70.6
61.2
140
62.2
102. 1
88.7
98
43.4
71.3
61.9
141
62.7
102.8
89.3
99
43.9
72.1
62.5
142
63.1
103.5
90.0
100
44.4
72.8
63.2
143
63.6
104.3
90.6
lOI
44.8
73.5
63.8
144
64.0
105.0
91-3
102
45-3
74.3
64.4
145 .
64.5
105.8
91.9
103
45-7
75.0
65.1
146
64.9
106.5
92.6
104
46.2
75-7
65.7
147
65.4
107.2
93.^
105
46.6
76.5
66.3
148
65.8
108.0
93.9
106
47.0
77-2
67.0
149
66.3
108.7
945
107
47.5
77.9
67.6
150
66.8
109.5
95-2
108
48.0
78.7
68.2
I5»
67.3
1 10.2
95.8
109
48.4
79-4
68.9
15^
67.7
III.O
96.5
no
48.9
80.1
69.5
153
68.3
111.7
97.1
III
49.3
80.9
70.1
154
68.7
112^
97.8
112
49.8
81.6
70.8
155
69.2
1 13.2
98.4
"3
50.2
82.3
71.4
156
69.6
113.9
99.1
114
50-7
83.1
72.0
157
70.0
1 14. 7
99-7
"5
5« I
83.8
72.7
158
70.5
115-4
100.4
116
51.6
84.5
73-3
159
70.9
1 16. 1
10 1. 0
"7
52.0
85.2
74.0
160
7'.3
1 16.9
101.7
118
52.4
85.9
74.6
161
71.8
1 17.6
102.3
119
52.9
86.6
752
162
72.3
1 18.4
103.0
I20
53.3
87.4
75.9
163
72.7
119.1
103.6
121
53.8
88.1
76.6
164
73.2
1 19.9
104.3
122
54-2
88.9
77-2
165
73.6
120.6
104.9
123
54.7
89.6
77.9
166
74.1
121.4
105.6
124
551
90.3
78.5
167
74.5
122. 1
106.2
"5
556
91. 1
79.1
168
74-9
122.9
106.9
126
56.0
91.8
798
169
75-4
123.6
"*7-5
DBTBRHINATION OP KBDUCING SUGARS.
763
Parts
Parts Parts
dextrose, maltose.
Parts
lactose.
Parte
Parte ]
dextrose, mt
'arte
tltose.
Parts
lactose.
170
75.8 ]
[24.4
108.2
213
95.3 3
156.3
136.0
171
76.3 ]
[25.1
108.8
214
95.8 ]
157. 1
136.7
172
76.8 ]
[25.8
109.5
215
96.3 3
157.8
137.3
173
77.3 3
[26.6
1 10. 1
2X6
96.7 1
[58.6
138.0
174
77.7 '
127.3
1 10.8
217
97.2 3
1593
138.6
175
78.2 ]
[28.1
III.4
218
97.6 :
[60.0
139.3
176
78.6 :
[28.8
1 12.0
219
98.1 :
[60.8
139.9
177
79.1 ]
129.5
II2.6
220
98.6 ]
161.5
140.6
178
79.5
^30-3
"3.3
221
99.0 :
162.3
I41.2
179
80.0 ]
131-0
113.9
222
99.5 :
[63.0
141 .9
180
80.4 ]
t3i.8
114.6
223
99.9
163.7
142.5
181
80.8 ]
132.5
115. 2
224
100.4 ^
164.5
143.2
182
81.3 ]
t33.2
I15.8
225
100.9 ^
165.3
143.8
183
81.8 ]
134.0
1x6.5
226
101.3 :
[66.0
144.5
184
82.2 ]
134.7
117.1
227
101.8 :
[66.8
145. 1
185
82.7 ]
^35.5
1 1 7.8
228
102.2 ]
167.5
145.8
]86
83.1 ]
136.2
1 18.4
229
102.7 ^
[68.3
146.4
187
83.5 3
136.9
1 19. 1
230
103. 1
169. 1
147.0
188
84.0 ]
137.7
1 19.7
231
103.6 ]
[69.8
147.7
189
84.4 ^
138.4
120.4
232
104.0 ]
[70.6
148.3
190
84.9 J
f39.i
I2X.O
233
104.5 ^
I7«.3
149.0
191
85.4 3
^399
121. 7
234
105.0 ]
[72.1
149.6
192
85.9 3
[40.6
122.3
235
105.4 ]
[72.8
150.3
193
86.3 1
[41.4
123.0
236
105.9
'73.6
150.9
194
86.8 ]
[42.1
123.6
237
106.3 ]
174.3
151. 6
195
87.2 1
[42.8
124.3
238
106.8 :
175-1
152.2
196
87.7 J
143.6
124.9
239
107.2 :
175.8
152.9
197
88.1 1
144.3
X25.6
240
107.7 ]
[76.6
153.5
198
88.6 ]
[45.1
126.2
241
108. 1 ]
177.3
154.2
199
89.0 ]
145.8
126.9
242
108.6 ]
[78.1
154.8
200
89.5 3
[46.6
127.5
243
109.0 ]
[78.8
155.5
201
89.9 ^
147-3
128.2
244
109.5 ^
179.6
156.1
202
90.4 ]
[48.1
128.8
245
109.9 1
180.3
156.8
203
90.8 ]
[48.8
129.5
246
110.4 ]
[81. 1
157.4
204
91-3 J
[49.6
130. 1
247
I X0.9 ]
[81.8
158.1
205
91.7 3
150.3
130.8
248
111.3 J
[82.6
158.7
206
92.2 ]
[51. 1
UI.5
249 •
111.8 ]
183.3
159.4
207
92.6 1
[51.8
I32.I
250
112.3 1
184.1
160.0
208
93.1 3
:52.5
132.8
251
112.7 ]
[84.8
160.7
209
93-5 J
153.3
133.4
252
113.2 :
185.5
161 .3
210
94.0 ]
1 54.1
134.1
253
"3.7 3
186.3
162.0
211
94.4 i
t54.8
134.7
254
114.1 ]
[87.1
162.6
^12
94.9 3
155.6
135.4
255
1 14.6
[87.8
163.3
764
GEORGE DEFREN.
Parts.
copper
oxide.
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
Parts
dextrose.
II50
"5-5
1 16.0
1 16.4
116.9
II7-3
117.8
118.3
118.7
1 19. 2
119.6
1 20. 1
120.6
121. 0
121.4
121. 9
122.4
122.8
123.3
123.7
124.2 ,
124.6
125. 1
125.6
1 26. 1
126.5
127.0
127.4
127.9
12S.3
128.8
129-3
129.7
Parts
lualtose.
188.6
189.3
190. 1
190.8
191.6
192.4
193- 1
193.9
194.6
1954
196. 1
196.9
^1977
198.4
199.2
199.9
200.7
201.5
202.2
203.0
203.7
204.5
205.2
206.0
206.8
207.5
208.3
209.0
209.8
210.5
211.3
212. 1
212.8
Parts
lactose.
163.9
164.6
165.2
165.9
166.5
.167.2
167.8
168.5
169. 1
169.8
170.4
171. 1
171. 7
172.4
173.0
173.7
174.4
175.0
175.7
176.3
177.0
177.6
178.3
178.9
179.6
180.2
180.9
181.5
182.2
182.9
183.6
184.2
184.9
Parts.
copper
oxide.
289
290
291
292
293
294
295
296
297
298
299
300
.301
302
303
304
305
306
307
308
309
310
311
312
313
3M
315
316
317
318
319
320
Parts
dextrose.
30.2
30.6
31. 1
31.5
32.0
32.5
33-0
33.4
33-9
34.3
34.8
35-3
35.7
36.2
36.6
37.1
37.6
38.0
38.5
38.9
39.4
39-9
40.3
40.8
41.2
41.7
42.2
42.6
431
43-6
44.0
44.5
Parts
maltose.
213.6
214.3
215.I
215.9
216.6
217.4
218.2
218.9
219.7
220.4
221.2
221.9
222.7
223.5
224.2
225.0
225.8
226.5
227.3
228.1
228.8
229.6
230.4
231. 1
231-9
232.7
2334
234.2
234.9
235.7
236.5
237- 2
Parts
lactose
185.6
186.2
186.9
187.6
188.2
188.9
189.5
190.2
190.8
191.5
192. 1
192.8
193.4
194. 1
X94.7
195.3
196.0
196.6
197.3
197.9
198.6
199.3
199.9
200.6
201.3
202.0
202.6
203.3
203.9
204.6
2053
205.9
SUPPLEMENTARY T.ABLE FOR GLUCOSE ANALYSIS.
The amounts of cupric oxide given above are those obtained
by the use of absolute weights of sugar. The tables are con-
structed on this basis. In the case of a^iixed product, like com-
mercial glucose, which may be considered made up of the sim-
ple bodies, dextrin, maltose, and dextrose, it is far more- con-
venient to determine the total carbohydrates present in solution
by means of the specific gravity than by drying the glucose and
DETERMINATION OF REDUCING SUGARS. 765
obtaining in this way the total solids. For this purpose an
arbitrary value is taken which shall represent the influence of
one gram of a mixture of the three substances above mentioned
on the specific gravity if dissolved to 100 cc. in distilled water.
Brown and Heron' claim that this influence on the specific
gravity of one gram starch conversion product in 100 cc. is
0.00386. This value has been determined to be correct for
solutions of cane sugar » and is much used for glucose work.
As above mentioned the specific gravity of a dextrose solution
containing ten grams dextrose anhydride in 100 cc. is 1.03809 at
15.5*. To determine the cupric reducing power of a substance
using the value 3.86 as a divisor, it therefore becomes necessary
to change the figures given in the tables to conform to this new
factor, that is, the dextrose equivalents must be multiplied by
.AA Aiaa l;\;^ij
1 vi\/u^ ivri
\.vfuv^uiv:ii
N.^ \Jl. l.Si\\
.A^U^^ 111
following
table :
obtained.
Dextrose
equivalent.
obtained.
Dextrose
equivalent.
Copper
oxide
obtained.
Dextrose
equivalent.
5
0.4461
no
0.4500
215
0.4540
10
0.4463
"5
0.4502
220
0.4542
15
0.4465
120
0.4504
225
0.4543
20
0.4467
125
0.4506
230
0.4545
25
0.4468
130
0-4508
235
0.4547
30
0.4470
135
0.4510
240
0.4549
35
0.4472
140
0.4512
245
0.4551
•40
0.4474
145
0.4513
250
0.4553
45
0.4476
150
0.4515
255
0.4555
50
O.447S
155
0.4517
260
0.4557
55
0.4480
160
0.4519
265
0.4558
60
0.4482
165
0.4521
270
0.4560
65
0.4484
170
0.4523
275
0.4562
70
0.4485
17s
0.4525
280
0.4564
75
0.4487
180
0.4527
285
0.4566
80
0.4489
185
0.4528
290
0.4568
85
0.4491
190
0 4530
29s
0.4570
90
0.4493
195
0.4532
300
04572
9S
0.4495
200
0.4534
305
0-4574
100
0.4497
205
0.4536
310
0.4576
105
0.4498
210
0.4538
315
0.4578
I Loc. cit.
320
0.4580
766 JAMBS OTIS HANDY.
Thus a solution containing loo milligrams of mixed carbo-
hydrates, using the factor 0.00386, if it formed 20d milligrams
cupric oxide by reduction of the Fehling solution in the manner
above described, would have a cupric reducing power, or K^^k
of 90.68.
MASSACMUSSTTS IltaTITUTB OP Tbchnologt,
Boston. M Asa.
ALUMINUn ANALYSIS.
B^* Jambs Otis Hakot.
ALTHOUGH the aluminum industry is not a large one
in the sense that the iron industry is, it is growing
ver>* rapidly* The output of the United States in 1894 was
550^000 pounds, and in 1895 it was about 850,000 pounds. The
Pittsburg Reduction Company, with works at New Kensington,
near Pittsburg, Pa., and at Niagara Falls, N. Y., is the only
American producer of aluminum. The material is made by the
electroh^sis, in carbon-lined pots, of alumina dissolved in a fused
bath of fluorides^ The product of each pot is ladled out at inter-
vals and is graded according to the analyses of the Pittsburgh
T^s^ing Laboratory. Limited. Some of the aluminum is sold as
it i$ made and some is alIo3red to modify its physical properties.
Allv^ys of aluminum with three per cent, nickel, or with three to
seven per cent, copper, or similar amounts of xinc are very ose-
tul on account of increased strength with only slightly incseased
spec^Sc gravity. The aluminum at present produced with the
5st vves av^ilabue contains troa
«» to cv; g rer cent, o: jLl:im:aurs,
o. t to 0.0^ per cent, o: silkoa corsbined aad crarbitic^.
o. ^o to o o rer cent- o: cocrer,
o >? to 0.0 per cent oc iron.
O— * iT"i.ie ■^*'*;^'****7^ CO— tlilSS ^'i -^^A~~.<r ^r ^r*
. •. * »
« .^^.. —.»««.. >>...-vV <^ Jl^K.^ .rv-.^ ■ .fcfc>^i
AI^UMINUM ANAI<YSIS. 767
nium, with aluminum ; alumimim solders, containing tin, zinc,
and phosphorus ; aluminum hydrate, bauxite, and electrode
carbons ; hydrofluoric acid and fluorides.
akai^ysis op commercial aluminum. (95 to 99.9 pbr cent.
pure).
In the analysis of aluminum we are offered a choice of sol-
vents.
Solubility of Aluminum : Hydrochloric acid of thirty-three
per cent., (/. ^., one part of hydrochloric acid of 1.2 sp. gr. to
two parts water) is a rapid solvent.
Sulphuric acid of twenty-five per cent, dissolves aluminum
completely on long boiling.
Nitric acid of one and two-tenths specific gravity dissolves
aluminum on prolonged boiling.
Acid mixture : A qiixture of the three acids which we term
' • Acid Mixture* ' is made of
100 cc. nitric acid of 1.42 sp. gr.
300 cc. hydrochloric acid of 1.20 sp. gr.
600 cc. sulphuric acid of twenty-five per cent.
It is a very useful solvent for aluminum because it supplies
oxidizing conditions during solution and so prevents loss of
combined silicon as hydride. The sulphuric acid content of the
acid mixture furnishes a means of rapidly dehydrating the silica.
Sodium hydroxide solution of thirty-three per cent, is a useful
solvent when it is desired to separate the metallic impurities
from the bulk of the aluminum at once. Weaker solutions do
not work as quickly or completely. Solution succeeds best in
an Erlenmeyer flask.
Fifteen cc. of the sodium hydroxide solution suffice for one
g^am of aluminum.
Commercial soda lye may be used if dissolved and filtered
through asbestos.
OTHER REAGENTS AND STANDARD SOLUTIONS USED IN AI,UMI-
NUM ANALYSIS.
Sodium carbonate, chemically pure.
Soda ash : *' Solvay" soda ash, a saturated solution in water,
filtered.
768 JAMES OTIS HANDT.
Powdered zinc : Practically free from iron and copper.
Fifteen per cent, nitric wash : (Fifteen parts 1.42 nitric acid
to eighty*fi\-e parts water).
Standard potassium permanganate : 5.76 grams in two liters.
One cc. equals 0.005 grams iron.
Standard potassium cyanide: Forty-five grams in two liters.
One cc. is made to equal 0.005 gram coppper.
SPBCIAL APPARATUS.
Two narrow glass tubes, graduated roughly, one to hold one
gram of powdered zinc and the other one gram of chemically
pure sodium carbonate.
The evaporating dishes which are used are, preferably, about
four and a half inches in diameter, and are covered with five-
inch glasses.
The Erlenmeyer flasks are of about twelve ounce capacity and
furnished with porcelain crucible covers.
THH METHOD.
Determination, of Silicon^ Iron^ and Copper in Comwumai
Aluminunt. — One gram of aluminum drillings is dissolved in a
four and a half inch evaporating dish in thirty cc. of *'acid
mixture." If the drillings are thin it is best to add only fifteen
cc. at first. Placing cold water on the cover glass sometimes
prevents loss from too energetic foaming*. Solution having^
been completed by warming slightly, evaporate quickly to strong^
fumes of sulphuric acid and continue heating lor five minutes.
Experience will show on what parts of the hot plate these solu-
tions can be evaporated without spattering at the time when
aluminum sulphate begins to cr>*stallize out. Remove the
dishes from the plate by means of an iron fork, and in a fe^v
moments add to the contents of each seventy-five to 100 cc. of
water and ten cc. of twenty-five per cent, sulphuric acid, break
up the residue in each dish with a short, heavy glass rod, and
place the dishes back on the hot plate. Boil until all aluminum
sulphate dissolves. Add to each dish one gram of metallic zinc
powder, measured. Be careful to pour the zinc into the middle
of the liquid. If it touches the sides of the dish it sometimes
AtUMlKUM ANAI^YSIS. 769
becomes firmly fixed there. Keep the dish contents at6o®*to 70®
C. until the zinc has dissolved, leaving the iron reduced and
the copper precipitated. Filter and wash well with hot water.
Cool, titrate the filtrates with standard potassium permanganate.
One cc. equals 0.50 per cent, iron when one gram of aluminum
has been used. Placing new receivers under the funnels, treat
each residue twice with hot fifteen per cent, nitric acid wash.
Wash out with water, and in the solutions thus obtained, titrate
the copper with standard potassium cyanide, after adding satu-
rated soda ash solution until the precipitated copper carbonate
redissolves. The end point of the titration is very satisfactory.
Th^ cyanide solution should be standardized with copper of
known purity in about the amount usually found, z^>., 0.005 to
o.oio gram. The residue of silicon and silica are burned off
in numbered crucibles and each fused with one gram of chemic-
ally pure sodium carbonate (measured). The crucible con-
taining the fused mass is placed in fifteen cc. of water in the por-
celain dish originally used, and twenty-five cc. of twenty-five
per cent, sulphuric acid are added. Solution takes place quickly
without separation of silica, and after rinsing out and removing
the crucible, the solution is evaporated to five minutes fuming
on the hot plate. After cooling add seventy-five to 100 cc. of
water and boil to disintegrate the silica. Filter and wash well
with water. Bum off and weigh silica and crucible, treat with
hydrofluoric acid and a drop of sulphuric acid if impurity is sus-
pected. Evaporate, ignite, and weigh again. Loss equals
silica ; calculate to silicon.
DeUrminaHan of Crystalline {Graphitic) Silicon in Aluminum.
— ^Dissolve one gram of aluminum in thirty cc. of thirty-three
per cent, hydrochloric acid (two parts of water to one of hydro-
chloric acid) in a platinum dish ; add about two cc. of hydro-
fluoric acid, stir, and filter at once through a No. o nine cm.
filter, contained in a funnel which has been thinly coated with
paraffin. Wash with water and burn off in a platinum crucible.
Fuse with one gram of sodium carbonate, cool in fifteen cc. of
water in a four and a half inch evaporating dish. Add twenty
cc. of twenty-five per cent, sulphuric acid. Rinse out the cru-
cible. Evaporate to fumes, cool, add seventy-five cc. of water.
770 JAMES OTIS HANDY.
boil up and filter o£F the silica. Wash, ignite, and weigh.
Calculate to silicon.
The determinations of silicon, copper, and iron are the every
day methods of grading- aluminum. It is recog^zed that
sodium and carbon occasionally exist in aluminum, and they are
determined by methods described. In certain samples it is
desirable to know the approximate percentage of graphitic and
combined silicon. These determinations are also described.
We determine nitrogen, if present, by a special method.
DETERMINATION OF SODIUM IN ALUMINUM.
One gram of drillings is dissolved in a porcelain evaporating
dish in fifty cc. of 1.3 sp. gr. nitric acid and sufficient hydro-
chloric acid to effect solution. Boil down until all hydrochloric
acid has been removed. Rinse the solution into a large plati-
num dish and evaporate to dryness. Heat over a good Bunsen
burner until nitric oxide fumes cease to be evolved. Grind the
residue finely. Mix it by grinding with one gram of chemically
pure ammonium chloride and eight g^msof chemically pure cal-
cium carbonate. Heat the mixture in a large covered platinum
crucible. For the first fifteen minutes have a Bunsen burner
flame just touching the bottom of the crucible, and for the next
forty-five minutes, have the whole crucible heated bright red by
a full Bunsen burner fiame. Cool, and treat the residue with
hot, distilled water until it becomes just friable under pressure.
Avoid adding an excess of water beyond that necessary to make
the sintered mass just friable. Grind it in a wedgewood mor-
tar and rinse out with hot distilled water. Filter, rejecting the
well washed residue, and treat the filtrate at the room tempera-
ture with saturated ammonium carbonate solution in slight
excess. Stir very thoroughly. The precipitated calcfum carbon-
ate is at first fiocculent, but on standing for about ten minutes,
it becomes crystalline. Filter into a platinum dish ; reject the
residue and evaporate the solution on the water-bath to dryness.
Heat carefully to dull redness to expel ammonium salts. Dis-
solve the residue in a little water and add a few drops of ammo-
nium carbonate solution. If this produces a precipitate, add
sufficient ammonium carbonate solution to precipitate all of the
ALUMINUM ANALYSIS. 77 1
remaining lime. Stir well, wait ten minutes, filter, evaporate to
dryness, heat to dull redness, and weigh sodium chloride.
Deduct any sodium chloride found in a blank determination,
using acids, etc., as above, and finally eight grams of calcium
carbonate and one gram of ammonium chloride.
NaCl X 0.39316 = Na.
Care should be taken when heating up the residue of sodium
chloride, etc., after evaporating on the water-bath. If the plati-
num dish an4 contents are heated for a few minutes on sheet
asbestos on the hot plate before placing over the lamp, spatter-
ing may be avoided. Sodium is generally absent from alumi-
num, but it has been found in amounts as high as 0.20 per cent.
and is considered a cause of the occasional deterioration of the
metal in water.
DETERMINATION OF CARBON IN ALUMINUM. ( MOI^SAN'S METHOD
MODIFIED.)
Triturate two grams of drillings in a Wedgewood mortar with
ten to fifteen grams of mercuric chloride, powdered and dissolved,
or partly dissolved, in about fifteen cc. of water. Reaction takes
place rapidly and a heavy gray residue is left. Persistent tritu-
ration removes the last particles of metallic aluminum. Evapo-
rate on the water-bath to dryness. The dry residue is heated in
a current of pure hydrogen to expel mercuric compounds. The
remaining material is then placed in a boat in a combustion tube
and burned off as in carbon determination in steel. The carbon
dioxide is caught ^s barium carbonate, and the excess of barium
hydroxide determined by means of standard acid. We are work-
ing on a more generally applicable method for carbon in alumi-
num.
DETERMINATION OF NITROGEN IN ALUMINUM.
Aluminum, when overheated in re- melting, is believed to have
the property of combining with nitrogen. The metal becomes
weaker. Moissan's method for determining nitrogen in alumi-
num may be found in Compt. Rend,, 119, 12. Nitrogen thus
absorbed would undoubtedly exist as nitride of aluminum and
solution of sodium hydroxide with subsequent distillation
772 JAMES OTIS HANDY.
would seem to be the best method of procedure. We are work-
ing up this method.
DETERMINATION OF ALUMINUM IN METALLIC ALUMINUM.
Dissolve one gram of metal in thirty cc. of thirty-three per
cent, hydrochloric acid in a porcelain dish and evaporated cau-
tiously to complete dr>'ness. Redissolve, by boiling, with ten
cc. of concentrated hydrochloric acid and seventv-five cc. of
water. Wash into a twelve ounce beaker; dilute to 250 cc.
and pass hydrogen sulphide until saturated. Filter into a beaker
and boil off hydrogen sulphide. Oxidize by adding one cc. of
concentrated nitric acid and continuing to boil for ten minutes.
Cool and make the solution up to 500 cc. ' Remove fifty cc. of
the solution, and having diluted to 250 cc. and heated to boil-
ing, add ammonium hydroxide in slight excess and boil well for
twenty minutes. Let settle ; filter, and wash thoroughly with
hot water. It is necessary to wash the precipitate off from the
filter, break it up, and wash it back again. Finally bum off in
a thin-walled platinum crucible, igniting most- intensely, and
weighing the instant the crucible and content are cool. We
have found that alumina is one of the most difficult oxides to
dehydrate completely, and when dehydrated it absorbs atmos-
pheric moisture even more rapidly than calcium oxide does.
Moissan prefers to precipitate aluminum by ammonium sul-
phide. Having prepared a solution in hydrochloric acid, he
takes an amount equal to 0.15 gram of aluminum, neutralizes it
in the cold with ammonia, and precipitates it by ammonium sul-
phide, which has been recently prepared. He then digests for
one hour, filters, washes with hot water, ignites and weighs.
ANALYSIS OF ALLOYS OF ALUMINUM WITH SMALLER AMOUNTS
OF OTHER METALS.
Copper Alloys. — Three to thirty per cent, copper, and no zinc
or nickel.
Dissolve one-half gram or one gram in fifteen cc, of thirty-
three per cent, sodium hydroxide solution in an Erlenmeyer
flask of twelve ounce capacity. If the flask is covered and set
in a warm place, solution is complete in a few minutes, even if
ALUMINUM ANALYSIS. 773
the drillings are quite coarse. Dilute to thirty cc. with hot
water and filter through a coarse, lintless filter paper (Whitall,
Tatum & Co.'s five inch). Wash well with hot water. Dis-
solve residue, atter washing it off the filter paper into a twelve
ounce beaker, by warming with five cc. of concentrated nitric acid.
Cool, add saturated commercial sodium carbonate solution until
re-solution occurs. Titrate with standard potassium cyanide
solution to the disappearance of the b\ue color. Standardize the
cyanide for about the same amount of copper.
For commercial reasons, twenty per cent, alloys are made in
the reduction pots, and these alloys are subsequently used for
making copper allo3's of low percentage.
DETEKMINATION OF NICKEL IN ALUMINUM ALLOYS.
The three per cent, nickel alloy is now used. The addition of
three per cent, of nickel increases the tensile strength of alumi-
num by several thousand pounds per square inch.
One gram of drillings is dissolved in fifteen cc. of thirty-three
per cent, sodium hydroxide solution in a twelve ounce Erlen-
meyer flask. Dilute to fifty cc. and filter through a five-inch
lintless paper, washing the residue thoroughly with hot water.
Rinse the residue back into the flask and add three to five cc. of
concentrated nitric acid, and a drop of concentrated hydrochloric
acid. Boil, and when dissolved, cool, and make up to 250 cc.
In 100 cc. determine the copper by neutralizing with ammonia,
adding two cc. of cot^centrated hydrochloric acid, warming and
passing hydrogen sulphide. Filter and wash with ammonium sul-
phide. Bum it off carefully in a porcelain crucible, and having
weighed, dissolve in five cc. of concentrated nitric acid. Then
dilute to twenty cc, add excess of sodium carbonate solution
and titrate with standard potassium cyanide. Boil the filtrate
from the cupric sulphide, oxidize with one cc. of nitric acid, and
precipitate with ammonium hydroxide. Do not boil, but digest
for a few minutes just below the boiling point. Filter, wash, re-
dissolve in hot fifteen per cent, nitric acid wash. Dilute to 150
cc. and again precipitate with excess of ammonium hydroxide,
being careful to avoid boiling or prolonged digestion. Filter
and wash. Bum off and weigh ferric oxide, etc. In a second
774 JAMES OTIS HANDY.
loo cc. of the main solution, precipitate nickel hydroxide, cnpric
oxide, ferric hydroxide, etc., by thirty-three per cent, chemically
pure sodium hydroxide solution, added in slight excess to the
boiling solution. Boil for fifteen minutes, filter, and wash most
thoroughly with hot water. Bum off and weigh nickel oxide,
cnpric oxide and ferric oxide. Deduct cupric oxide and ferric
oxide already found. Calculate nickel oxide to metallic nickeL
ANALYSIS OP ALUMINT7M-MANGANESB ALLOYS.
DeierminaHon of Manganese. — Place one gram of drillings in.
a twelve ounce beaker. Add thirty cc. of thirty-three per cent,
hydrochloric acid (one part of concentrated hydrochloric acid to
two of water). When dissolved, add twenty-five cc. of nitric acid
( 1 .42 ) , and boil down to ten cc. Add fifty cc. of colorless nitric
acid (1.42) and boil. Precipitate the manganese with pow-
dered potassium chlorate, added cautiously, and proceed as
described under manganese in steel by Williams' method.*
ANALYSIS OF CHROMIUM-ALUMINUM ALLOY.
Determination 0/ Chromium, — Dissolve one gram in a twelve
ounce beaker in thirty cc. of thirty-three per cent, hydrochloric
acid, and when dissolved add fifty cc. of sulphuric acid (1.84),
and evaporate carefully until fumes of sulphur trioxide escape*
Cool, add sixty cc. of water and boil. After five minutes, if all
aluminum sulphate has been dissolved, add powdered potassium
permanganate until the solution has a distinct pink color. Boil
until the excess of potassium permanganate is decomposed. Filter
through washed asbestos and determine the chromium in the
filtrate as in chrome steel.'
ANALYSIS OF TUNGSTEN- ALUMINUM ALLOY.
Determination of Tungsten, — Dissolve one gram in thirty-
three per cent, hydrochloric acid in a four and a half inch evap-
orating dish. Add thirty cc. of nitric acid (1 .42) and evaporate to-
dryness. Redissolve in thirty cc. of hydrochloric acid (1.20),
dilute to about ninety cc., and boil for two hoars. Filter and
wash thoroughly. Bum off and weigh Si + SiO, + WO, +
crucible. Treat with three drops of twenty-five per cent, sul-
1 BUir's ''Chemical Analysis of I
s Galbraith's MeUiod. See BUir's '* Chemical Aaal3rsis of I
AI^UMINUM ANAI^YSIS. 775
phuric acid and about two cc. of hydrochloric acid. Evaporate
carefully over an Argand burner, re-ignite, and weigh crucible
and silicon and tungstic oxide. Fuse with one gram of sodium
carbonate, cool, place in dish, and add fifteen cc. of water and
twenty cc. of twenty-five per cent, sulphuric acid, remove cruci-
ble and evaporate until white fumes escape. Cool, redissolve
in about fifty cc. of water. Filter, wash, ignite, and weigh
silica (from silicon), tungstic oxide, and crucible. Treat with
sulphuric acid and hydrofluoric acid, evaporate, ignite, and
reweigh. Loss equals silica. Calculate to silicon and add to
the weight of silica lost by treatment of first insoluble residue.
Deduct this sum from the weight of silicon, silica, and tungstic
oxide first found and the remainder equals tungstic oxide.
Calculate to tungsten.
ANALYSIS OF AI^UMINUM-TITANIUM ALLOY.
Determination of Titanium, — Two grams of the alloy in a
twelve ounce Erlenmeyer flask are dissolved by addition of fifty
cc. of ten per cent, potash solution. Dilute with distilled water
to about 125 cc, boil up, and filter as quickly as possible.
Wash ten times with boiling water. Bum off the residue in a
porcelain crucible, crush it in a Wedgwood mortar, fuse in a
large platinum crucible with ten grams of potassium bisulphate.
Conduct the fusion exactly as follows : Choose a good Bunsen
burner, and protect it from draught by a sheet-iron chimney ;
make the flame one and a half inches long, and place the
triangle carrying the upright crucible just at the point of the
flame. Increase the heat gradually until in ten minutes the
lower fourth of the crucible is red hot. Allow it to remain at
this temperature ten minutes, moving the lid slightly to one side
every two minutes, and giving the crucible (held firmly in the
tongs) a gentle rotating movement, then turn up the light until
the flame reaches the top of the crucible and envelopes it. Five
minutes of this treatment melts down any potassium bisulphate,
etc., which have risen on the sides. The flame is lowered and the
lower fourth heated for ten minutes longer. Cool, dissolve in
about 200 cc. of water ; filter, rejecting the residue, if ignition
and treatment with hydrofluoric acid show it to be only silica.
^^6 JAMBS OTIS HANDY.
If it contains anything more, fuse with four grams of potassium
bisulphate again. The filtrate contains all the titanic oxide
and the ferric oxide. Add ammonia until a slight perma-
nent precipitate is formed, then add dilute sulphuric acid from a
pipette or burette until this precipitate just redissolves. Finally
add one cc. more of twenty-five per cent, sulphuric acid and
dilute to 300 cc. If the solution is high in iron (which will be
indicated by its distinct yellow color) sulphur dioxide gas
must be run into it until it is decolorized and smells strongly
of sulphur dioxide, but if the solution is nearly colorless, indi-
cating a low percentage of iron, only sulphur dioxide water
need be added for the reduction. Boil well for one hour, adding
water saturated with sulphur dioxide occasionally. Filter o£F
the titanic oxide through double filters and wash well with hot
water. Bum off and weigh as titanic oxide. If the precipitate
is yellow, indicating the presence of iron, it may be fused with
one gram of potassium bisulphate, the fusion dissolved in ten cc.
of dilute sulphuric acid, and the iron determined in this solu-
tion by reducing with one gram of zinc, and titrating with per-
manganate. This is not often necessary. Calculate titanic
oxide to titanium. TiO, X 0.6 = Ti.
DETERMIN.\TION OP ZINC IN ZINC- ALUMINUM AI.LOT. FIRST
METHOD.
Dissolve one gram in thirt>' cc. of thirty-three per cent, hydro-
chloric acid in a twelve ounce beaker. Dilute to 200 cc. and
heat nearly to boiling. Pass hydrogen sulphide till all copper
is precipitated. Filter and boil off hydrogen sulphide, oxidize
with one cc. nitric acid by boiling ten minutes. Add sodium
hydroxide solution until neutral, then make barely acid with
hydrochloric acid, and stir until the aluminum hydroxide all
dissolves. Add ten grams of sodium acetate and 500 cc. of
water, boil up, and filter at once. Dissolve the washed precipi-
tate in hydrochloric acid and repeat the acetate separation.
Heat the united filtrates to boiling and pass hydrogen sulphide.
Filter off the zinc sulphide on double filters, wash thoroaghly
with hot water. Bum off in a porcelain crucible, and weigh zinc
oxide. Calculate to zinc. This method may be used when
ALUMINUM ANALYSIS. 777
only a small quantity of the sample is available, but when this
is not the case, it is better to use the method given below.
DETERMINATION OF ZINC IN ZINC-ALUMINUM ALLOYS.
SECOND METHOD.
Dissolve one gram of drillings in thirty-three per cent, sodium
hydroxide solution in a twelve ounce Erlenmeyer flask. Filter
as soon as dissolved through a four inch lintless filter paper.
Wash thoroughly with 'hot water. Rinse the residue of zinc,
iron, copper, silicon, etc. , back into the flask. This may require
25 cc. of water. Add .five cc. of hydrochloric acid and boil.
Dilute to 150 cc. with hot water and pass hydrogen sulphide.
Filter and boil off hydrogen sulphide, reoxidize by adding one
cc. nitric acid and boiling ten minutes. Add sodium hydroxide
till neutral, then add dilute hydrochloric acid till just acid, and
then ten grams of sodium acetate, and 300 cc. of boiling water,
and boil for five minutes. Wash well. If the precipitate is small,
resolution and re precipitation are not necessary. Pass hydro-
gen sulphide through the filtrate. Filter off zinc sulphide
through double filters. Wash well. Ignite in a porcelain cru-
cible, heating finally over the blast, to zinc oxide. ZnO X
0.8032 = Zn.
ANALYSIS OF ALUMINUM SOLDERS.
Determination of Tin, Phosphorus^ and Zinc, — Aluminum sold-
ers generally contain phosphor-tin, and zinc. As presented for
analysis, they usually consist of a soldered joint, from which
the solder must be scraped and analyzed. The analysis, there-
fore, involves a separation of the elements aluminum, zinc, tin,
and phosphorus. It is a difficult matter to determine whether
aluminum was a constituent of the solder when only a soldered
joint is available for examination. It is best to dissolve all
adhering aluminum from the pieces chosen for analysis by
treatment with thirty-three per cent, sodium hydroxide solution
after which the residue is filtered off, dried, and weighed out
for analysis. Dissolve or decompose three-tenths to five-tenths
gram in a twelve-ounce beaker by means of twenty cc. of nitric
acid (1.42). If necessary, five cc. of hydrochloric acid (1.2)
may be used to effect complete decomposition. Evaporate to
778 JAMBS OTIS HANDY.
complete dryness on a hot plate. Cool, add twenty-five cc. of
nitric acid (1.13), and boil thoroughly. Filter. The residue
contains all of the tin, most of the phosphdrus, and possibly
some zinc. Bum it off in a porcelain crucible and, after pul-
verizing the residue in an agate mortar, mix it with two grams
of sodium carbonate and two grams of sulphur, fuse it in a cov-
ered porcelain crucible over a Bunsen burner for about half
an hour. Give it three minutes of gentle blast flame at the last.
Cool, boil .out with 150 cc. of water in a twelve-ounce covered
beaker. Filter and wash. Extract any possible zinc sulphide,
etc., from the residue, by dissolving in nitric acid, boiling off
hydrogen sulphide, and adding this to the first filtrate
obtained after evaporating to dryness with nitric acid. The
sodium sulphide solution contains the tin and phosphorus. Add
to it hydrochloric acid until just acid. Warm slightly and pass
hydrogen sulphide. Filter off stannous sulphide and wash
thoroughly with hot water. Bum off in a porcelain crucible
and weigh stannic oxide. Calculate to metallic tin. The
filtrate from the stannous sulphide is boiled to expel hydrogen
sulphide and then oxidized by adding two cc. of nitric acid and
boiling for fifteen minutes more. Filter off any sulphur which
separates, and in this filtrate, which should amount to only
about 100 cc, precipitate the phosphorus by adding pure
sodium hydroxide solution till alkaline, then nitric acid till dis-
tinctly acid, heating to 85® C, and adding fifty cc. of filtered
molybdate solution. Stir or shake well for five minutes, filter
on a weighed filter paper, and after washing with one per cent,
nitric acid wash, dry at 100* C. and weigh. Yellow precipitate
multiplied by 0.0163 equals phosphorus. The nitric acid solu-
tion obtained after evaporating the first solution to dryness, etc.^
is now neutralized with sodium hydroxide solution, and then
made just acid with hydrochloric acid. Ten grams of sodium
acetate are now added, and 300 cc. of water (hot) . Boil up for five
minutes, then filter and wash. If the precipitate is of consider-
able size, it is probable that aluminum was a constituent of the
solder. Redissolve it in a little hydrochloric acid, neutralize,
acidify, and make a basic acetate separation as before. Precipi-
tate the zinc in the acetate solutions by hydrogen sulphide.
ALUMINUM ANALYSIS. 779
Filter, wash, ignite in a porcelain crucible, and weigh as zinc
oxide. Calculate to metallic zinc. Dissolve the precipitate of
aluminum acetate in hydrochloric acid, dilute to 250 cc, and
precipitate with ammonia. After filtering, washing, igniting,
and weighing as alumina, calculate to metallic aluminum.
Solders containing lead are sometimes met with. In such cases,
evaporate the nitric acid filtrate from the metastannic acid to
small bulk, add twenty-five cc. of twenty-five per cent, sul-
phuric acid, and evaporate until white fumes escape. Cool, add
100 cc. of water, stir, and let stand for an hour in a warm place.
Filter and wash with water containing five per cent, of sulphuric
acid . Bum off in a porcelain crucible at a low temperature. Reoxi-
dize any reduced lead oxide and restore its sulphur trioxide by
adding a few drops of nitric acid and sulphuric acid and evapo-
rating. Finally weigh lead sulphate. Calculate to metallic lead.
Zinc is determined in the lead sulphate filtrate.
«
ANALYSIS OF ALUMINA.
Alumina is made from bauxite or cryolite. It is usually pur-
chased in the hydrated form.
HYDRATED ALUMINA.
Hydrated alumina is analyzed for water, silica and sodium
carbonate.
Water, — Ignite one gram in a closely covered crucible, at first
gently and then intensely for fifteen minutes over the strongest
blast. The loss on ignition includes water and the carbon
dioxide of the sodium carbonate. Calculate the carbon dioxide
from the sodium oxide found and deduct it from the loss on
ignition.
Silica. — Hydrated alumina is soluble in sulphuric acid of 42^
B. The silica, however, is left undissolved. 42** B. sul-
phuric acid is made by mixing 900 cc. of concentrated sul-
phuric acid with 1290 cc. of water. Five grams of hydrated
alumina are treated with twenty-five cc, of 42® B. sul-
phuric acid and heated until the alumina appears to be all dis-
solved. Dilute to 100 cc. and boil. Filter, wash, ignite and
fuse the residue with one gram of potassium bisulphate and
cool. Dissolve in water, filter, wash, ignite, and weigh in cru-
7^0 JAMES OTIS HANDY.
cible, treat with sulphuric acid and hydrofluoric acid, evaporate,
ignite and weigh again. Loss equals silica.
Soda. — The method for the determination of soda is the same
in calcined and hydrated alumina. The method is that of J. L-
Smith, and is described under ** Sodium in Aluminum." Cal-
culate sodium chloride to sodium carbonate, if the sample is
hydrated, and to sodium oxide if the sample is calcined alumina.
CALCINED ALUMINA.
Water and soda are determined as in hydrated alumina.
Silica, — Fuse one gram of the finely ground alumina with ten
grams of potassium bisulphate. If this does not make a clear
fusion add two g^ams of bisulphate and heat up again. Dissolve
the fusion when cool in water and filter. Bum off the insoluble
residue. Fuse it with one gram of sodium carbonate and cool
in fifteen cc. of water in a four and a half inch evaporating dish.
Add twenty-five cc. of twenty-five per cent, sulphuric acid.
When all soluble matter has dissolved, remove the crucible and
evaporate down until sulphuric acid kimes escape. Cool, dilute
with water, boil, filter, ignite, and weigh silica plus crucible,
treat with sulphuric and hydrofluoric acids, and weigh again.
Loss equals silica.
ANALYSIS OF BAUXITE.
Method adopted, May, 1895.
No unusual apparatus or reagents are required.
One and five- tenths grams of very finely ground bauxite (pre-
viously dried at loo** C. and bottled), is taken for analysis.
Weigh into a five inch porcelain evaporating dish and dissolve
in fifty cc. of acid mixture. This mixture is the same as that
used for aluminum analysis. Boil the solution down until fumes
escape and keep the residue fuming strongly for about fifteen min-
utes. Cool, add 100 cc. of water, stir and then boil for ten minutes.
Filter, wash well with water, receiving the filtrate in a beaker
of about 300 cc. capacity. The filtrate and washings should
amount to about 175 cc. Bum off the insoluble residue (which
consists chiefly of silica, with a little titanic acid, oxide of iron,
and alumina) and weigh it in the crucible, add three drops of
twenty-five per cent, sulphuric acid and about five cc. of hydro-
ALUMINUM ANALYSIS. 781
fluoric acid and evaporate slowly to dryness. Ignite very
strongly and weigh. The loss in weight equals silica. Add to
the residue in the crucible one gram of potassium bisulphate and
fuse quickly and thoroughly over a Bunsen burner, cool and place
the crucible in the beaker containing the main sulphuric acid
solution. The small residue from this fusion will be silica, and
is to be added to the silica already found. Having obtained the
sulphate solution containing all the alumina, ferric oxide and
titanic oxide, make it up to 550 cc. and mix. Then fifty cc.
will equal three-tenths gram bauxite. Take fifty cc. and dilute
to 300 cc. Add two cc. of concentrated hydrochloric acid and
ammonia in slight excess, boil for five minutes, let the precipi-
tate settle, filter and wash very thoroughly with hot water. Test
the filtrate for further alumina by boiling. Bum off the filter
paper and ignite the precipitate very strongly after crushing all
the lumps of alumina. Weigh alumina, ferric oxide and titanic
oxide.
Titanic Acid, — Take 100 cc. of the original sulphate solution
(six-tenths gram), add ammonia until a slight permanent pre-
cipitate is formed, then add sulphuric acid from a pipette or
burette until this precipitate just redissolves. Finally add one
cc. more of twenty-five per cent, sulphuric acid and dilute to
400 cc. If the bauxite is high in iron (which will be indicated
by the distinct yellow color of this solution) sulphur dioxide gas
must be run into it until it is decolorized and smells strongly of
sulphur dioxide, but if the solution is nearly colorless, indicat-
ing a low percentage of iron, only sulphur dioxide water need
be used for the reduction. Boil well for one hour, adding water
saturated with sulphur dioxide occasionally. Filter off the
titanic oxide through double filters and wash well with hot water.
If the precipitate is yellow, indicating the presence of iron, it
can be fused with one gram of potassium bisulphate, the fusion
dissolved in water, and the iron determined in this solution by
reducing with zinc and titrating with permanganate. This is
not often necessary.
Oxide of Iran, — Take fifty cc. of the sulphate solution, add ten
cc. of dilute sulphuric acid and one gram of granulated zinc,
782 CHARLBS GI«ASBR.
and set the beaker in a warm place. When reduced, filter and
titrate the iron with standard potassium permanganate. More
zinc is used for bauxites high in iron.
METHOD FOR IRON DBTBRMINATION, USING A LARGBR QUAN-
TITY OP BAUXITB. (APPI,ICABI,B TO PURBST ORBS).
Place a half gram of the finely powdered ore in a large plati-
num crucible and add three cc. of twenty-five per cent, sulphuric
acid and five cc. of hydrochloric acid, and evaporate very slowly
to fumes ; drive oS the excess of sulphuric acid by heat, boil out
the residue with water and add ten cc. of dilute sulphuric acid.
Remove the crucible and reduce with zinc, as above, and titrate.
WdUr and Organic Matter. — Ignite three-tenths gram, cau-
tiously at first and finally very strongly in a covered crucible.
The loss of. weight equals water and organic matter.
ESTIHATION OF THORIA. CHEMICAL ANALYSIS OF
nONAZITE SAND.
By Charles Glaser.
Received July 9, 1896.
SINCE the introduction of the Auer-Welsbach light, the com-
mercial importance of monazite sand has grown greatly,
and chemists are now asked to determine the percentage of true
monazite, and especially that of thoria, in samples of the sand.
This has heretofore been accomplished indirectly ; the quantities
of iron, titanium and silica were determined and the remainder of
the material calculated as monazite. A sample treated in this
manner gave the following results :
Per cent
Iron oxide 3.50
Titanic acid 4.67
Silica 6.40
Monazite, by difference 85*43
100.00
The sample contained 18.38 per cent, phosphoric acid, which
calculated as cerium phosphate (factor 3.32) equals 61.10 per
cent.
From analyses printed in Dana's Mineralogy, it was inferred
ESTIMATION OF THORIA. 783
that after elimination of nitile and silica, the remainder would
be found to consist chiefly of phosphates of the cerium gropp, but
this is not true.
For the determination of the actual composition of the mona-
zite sand in question, it was decided to attempt an estimation of
each of its components, by means of methods to be found in the
available literature. As chief sources of information, Graham-
Otto's Chemistry and Crookes' Select Methods in Chemical
Analysis were used ; due regard was also given to the work
which has appeared in the chemical journals of recent years. I
was not able, however, to make an exhaustive examination of
the literature.
It became evident that no reliable method could be worked
out until examination had been made of all the work which had
been done in the field, and it seemed necessary to investigate
the whole question. In the following statements of preliminary
experiments a large portion of analytical data has been omitted,
because otherwise this paper would have been bulky. Only the
outlines of a general plan of procedure will therefore be given.
So far as possible, it was my intention to examine all the
methods proposed for estimation of thoria, but in one notable
instance this could not be done. In Volume XVI of the Ameri-
can Chemical Journal, L. M. Dennis and F. L. Kortright
describe a method for estimation of thoria by means of potassium
hydronitride, KN,. An attempt to work by the method proved
a failure in my hands, partly because of a mishap while prepar-
ing the reagent, only enough of which was saved for a single
qualitative reaction ; but chiefly because Mr. Dennis declined,
when requested, to give me further information. He replied
that he was not then at liberty to detail his experience, *' as the
potassium hydronitride process is more than an analytical one.
It is a commercial process for the preparation of pure thoria,
which is, I think, unequalled by any of the methods employed
by the Welsbach chemists, Shapleigh included. Some of them
have tried to use the method and have failed. I think I know
why they failed. But I do not think it quite fair for them to
ask me to help them out of their difficulties."
Although the publication was made in a scientific journal, it
784 CHARLBS GLASBR.
seems to have been but a partial statement. For which reason
criticism is invited and the value of the work is thrown some-
what in doubt. No further attempt was made to follow it out.
By means of fusion with alkali carbonates, an attempt was
made to separate monazite sand into two parts. According to
Wohler all titanic acid ought to become soluble provided the
fusion is made at a su£Bciently high temperature. Therefore a
blowpipe was used. In later work I employed the highest tem-
peratures afforded by a muffle, and for as many as two hours.
But at no time was more than a fraction of the titanic acid ren-
dered soluble in water. Moreover, Wohler's directions to pour
the fusion upon an iron plate, and afterwards to powder it, are
not practicable because of loss likely to ensue. It was found
best to let the fusion soak in water over night, sometimes even
for several days, or until perfect disintegration resulted. But
such a procedure may have decreased the solubility of titanic
acid in water. Phosphoric acid and alumina (and also silica to
a large extent) were completely dissolved out of the fused mass.
The portion insoluble in water was rendered soluble by the well
known treatment with strong sulphuric acid, and also by fusion
with acid potassium sulphate. The solution thus obtained,
after being freed from silica, was boiled to separate titanic acid»
from four to seven hours during the first experiment. Later,
after addition of sodium sulphite, this was accompanied by satu-
rating with hydrogen sulphide, first in the hot and then in the
cooled solution. This method is preferable to the first.
After separation of titanic acid and the metals of the fifth
group, various methods were tried for separation of thoria from
the other earths. It was found that the solution must not be
strongly acid when treated with ammonium oxalate for precipi-
tation of thoria and the metals of the cerium group, or traces of
thoria will remain in solution. It is best to nearly neutralize
with ammonia, and to precipitate in boiling solution.
During the earlier experiments some difficulty was found in
keeping in solution all of the zirconia, which is. accomplished
only by a large excess of the reagent, while yttria and glucina
readily form soluble double salts. Under these conditions oxa-
lates of the cerium metals precipitate immediately, while thorium
ESTIMATION OF THORIA. 785
oxalate separates upon cooling. Attempts to separate thorium
oxalate from oxalates of the metals of the cerium group by fil-
tration of the hot solution, gave unsatisfactory results. The
oxalates will pass through the filter for a long time. Bumping
of the liquid made it impracticable to keep it boiling until the
entire precipitate became crystalline. But if large quantities of
thoria are to be separated from small ones of the other oxalates
the method works wdl.
After the insoluble oxalates were separated by filtration and
were washed with water, they were converted into oxides by
heating and were redissolved as sulphates. In this strongly con-
centrated solution, made nearly neutral by ammonia, an attempt
was made to separate thoria from the other metals by boiling
with sodium hyposulphite. In no instance was a complete sep-
aration effected, but such portions as were obtained proved to
be quite pure. The single exception was that in which the
whole of the cerium was precipitated, for reasons not ascer-
tained. Attempts were made to free thoria from most of the
cerium by fractional precipitation with weak ammonia, but no
considerable advantage was gained thereby, since tepeatedly the
second fraction showed traces of thorium.
To determine the solubility or insolubility of the different sub-
stances left in the insoluble residue from fusions, such residue
was treated with dilute hydrochloric acid both cold and hot.
The solution was found to contain all the iron and titanium, the
larger part of the silica, and about one-half of the earths present ;
these consisted of relatively large portions of zirconia and glu-
cina. Thoria seems not to enter into solution, but is left with
the remainder of the earths.
An attempt was made to separate thorium oxalate from the
mixed precipitated oxalates, by boiling with ammonium oxalate.
Such boiling, filtering and crystallizing yielded oxalates, which
after ignition, corresponded to 2.29 per cent, of oxides. The
earths were, however, of a deep orange color, and contained
both cerium and zirconia. The latter was present because an
insufficient quantity of ammonium oxalate had been used in the
first precipitation. In the oxalates of the cerium metals found
insoluble in the above treatment, the presence of thoria could be
786 CHARI^BS GI^ASBR.
distinctly proven by means of sodium hyposulphite, for which
reason the work proved unsatisfactory.
To facilitate a comparison of the more important reactions of
the elements herein studied, the table on the next page has been
prepared partly from their known behavior, and partly from the
results obtained during this investigation.
With the view of obtaining further knowledge of the behavior
of thoria, fragments of Welsbach mantles were subjected to
analysis. They weighed 0.6591 gram, which, after ignition,
fell to 0.6552 gram. Prolonged treatment with boiling sul-
phuric acid left a residue of 0.0883 gram, which became solu-
ble in water after fusion with acid potassium sulphate. The solu-
tions thus obtained were examined by the same method, but
separately, as follows : After neutralizing with ammonia the
greater part of the free acid, the solutions were heated to boiling
and hot solution of ammonium oxalate was added.
In solution I a precipitate appeared, but dissolved rapidly
upon addition of more of the reagent.
In solution II a slight turbidity appeared, there was no pre-
cipitate, and it soon became perfectly clear.
Upon cooling, solution I yielded a moderate quantity of a
crystalline deposit, while solution II gave a copious one. Both
precipitates were collected on one filter, washed, ignited, and
weighed. They yielded o. 1 124 grams of thoria.
The filtrate from I gave a copious precipitate with ammonia,
while that from II gave only a slight one : both of these were
washed on one filter, redissolved in dilute hydrochloric acid, and
again precipitated by ammonia. An excess of ammonium car-
bonate entirely dissolved the precipitate. Potassium hydroxide
gave a precipitate not soluble in excess of the precipitant, indi-
cating zirconia, the weight of which was 0.5580 gram. An
attempt to purify it from occluded alkali, by again precipitating
with ammonia, failed through an accident, in which part of the
material was lost. Calculating by difference, the weight of zir-
conia ought to have been 0.5428 gram. Both precipitates were
pure white.
Therefore, this analysis afforded the following composition of
the mantles : thoria 17.15 per cent., zirconia 82.85 per cent.
I
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788 CHARLES GLASBK.
The separation of the two earths was effected without diffi-
culty and the thoria was used in the following experiments :
0.0487 gram was weighed, dissolved, and mixed with the
solution of cerium metals from a previous experiment. The
solution was nearly neutralized with ammonia, heated to boil-
ing, a hot solution of ammoni'am oxalate added, and the mix-
ture allowed to cool. The precipitate was caught on a filter and
washed with cold water, extracted in boiling ammonium oxalate
solution, caught on a filter, and washed hot : the filtrate was
allowed to cool (precipitate i). The residue was macerated in
a hot solution of ammonium acetate, filtered (residue A), and
filtrate examined for thoria, as follows : hydrochloric acid was
added to separate thoria as oxalate, which fell in part only
and the remainder was obtained by sodium hydroxide (precipi-
tate 2). Both these precipitates afforded batapart of the thoria
originally weighed, the greater part being held yet with the
cerium metals. The method had failed.
The residue (A) upon the filter was reduced to oxide and dis-
solved as sulphate. After neutralizing with ammonia, the
liquid was heated to boiling, and there was added an excess of
ammonium oxalate with some ammonium acetate : after filter-
ing, the filtrate was treated with sodium hydroxide (precipi-
tate 3).
The precipitates, thus obtained in three fractions, were ignited
and found to weigh 0.0774 gram, showing that the thoria was
very impure. The grayish mass was fused with acid potassium
sulphate, and unfortunately, a small fraction of the fused
mass was lost. However, from the saved portion a pure thona,
weighing 0.0402 gram, was obtained.
In the next experiment, 0.0343 gram of thoria and 0.1004
gram of impure cerium oxide were dissolved as sulphates, and
aium oxalate and acetate, as for precipitate
precipitating the filtrate with ammonia there
o of impure thoria, which, after purification,
im. Cerium oxide reco\-ered weighed 0.0935
Mention to what has been observed frequently
iments. If thorium oxalate, held in solution
ESTIMATION OF THORIA. 789
by ammonium acetate, be precipitated by ammonia, the earth so
obtained, when washed with the greatest care and redissolved
in a mineral acid, cannot from an almost neutral solution be
again completely precipitated by ammonium oxalate ; even if
the earth had been ignited after re-solution. It will also be found
that a considerable increase has occurred in its solubility in
liquids containing much potassium or ammonium sulphate.
When enough thoria has been collected, it is my intention to
iurther examine this peculiar behavior.
SYSTEMATIC METHOD OP ANALYSIS.
From the analytical data given, the following method has
been deduced :
It is essential that the mineral be divided to the greatest pos-
sible degree. Prolonged powdering in an agate mortar is indis-
pensable. Solution is effected either by prolonged heating with
strong sulphuric acid, or by fusion with acid potassium sul-
phate. In the latter case, the cooled mass is warmed with so
much sulphuric acid that the product, after cooling, may be
poured from the crucible. The first method takes more time
than the second, but it introduces less of the objectionable
potassium salts. It is advisable to fuse only those portions
which are insoluble in sulphuric acid.
For estimation of silica the sulphuric acid treatment is pref-
erable, in which case it is best to evaporate once on a sand-
bath to dryness to render silica insoluble, and then to add fresh
sulphuric acid. The resulting mixture should be added slowly
to ice cold water, which dissolves the mass excepting silica and
tantalic acid, with possibly traces of titanic acid, thoria, and
zirconia. After filtering, the residue should be ignited and
weighed. Silica is eliminated by repeated treatment with
hydrofluoric acid. Any residue remaining should be moistened
with sulphuric acid, to convert the fluorides of the earths into
sulphates, which, after ignition at a high temperature, are
weighed as oxides, and silica determined by the loss in weight.
The residue of tantalic acid, with possibly traces of the bodies
mentioned above, is treated with sulphuric acid and hydrofluoric
acid. Tantalic acid remains insoluble, and may be filtered off
79^ CBARLBS GIASBR.
and weighed. The matter soluble may be added to tbe main
solution.
The original solution is saturated with hydrogen stilpbtde,
first at boiling and then at the ordinaiy temperature. Titanic
acid is precipitated, together with metals of the fifth group.
That sodium sulphite assists in the precipitation of titanic acid
has not been verified in my work.
When completely settled, the liquid is filtered and the filtrate
boiled to expel hydrogen sulphide. Any free acid may be
nearly neutralized with ammonia ; to the boiling liquid is added
an excess of a boiling solution of ammonium oxalate, as much
as loo cc. of the cold saturated solution for two grams of mona-
zite sand. The excess necessarily must be large. The mixture
is then permitted to cool, best for an entire night. The solu-
tion will contain phosphoric acid, the oxides of iron, manganese,
aluminum, glucinum, yttrium, zirconium, and calcium. In the
precipitate will be found thoria and the oxides of the cerium
group.
If the bodies in solution are to be estimated, add ammonia to
precipitate the metals as phosphates. Filter and wash thor-
oughly, preserve the filtrate for estimation of phosphoric add
and alumina. Ignite the precipitate and fuse it with mixed car-
bonates of potassium and sodium. The fused mass is exhausted
with hot water, filtered, and the residue well washed with hot
water. The filtrate is added to that containing phosphoric acid
and alumina.
The remaining oxides and carbonates are dissolved in sulphuric
acid and precipitated with ammonia. Lime is estimated in the
filtrate therefrom.
When an attempt is now made to dissolve the precipitated hy-
droxides on the filter by dilute hydrochloric acid, it sometimes
occurs that zirconia in part remains. Therefore it is best, after
this operation, to incinerate the filter. Then neutralize the so-
' ■■ '* aia as far as practicable. Pour this slowly,
ing, into a mixture of ammonium carbonate
Iphide, prepared as follows : To a solutiofi of
late more than enough to neutralize the free
above indicated, and to hold in solution the
ESTIMATION OF THORIA. 79 1
earths to be dealt with, add enough of ammonium sulphide (usually
a few cc.) to precipitate the metals of the fourth group. The
latter will be precipitated, while zirconia, yttria, and glucinum
remain in solution. Iron and manganese may be determined by
the usual methods.
If the carbonate solution be boiled for one hour the earths are
completely precipitated. They may be caught on a filter and
dissolved in hydrochloric acid ; or the carbonate solution may
be treated directly with that acid, carbon dioxide expelled by
boiling, the solution cooled and treated with an excess of sodium
hydroxide. Zirconium and yttria are completely precipitated
while glucina remains dissolved : to precipitate this, boil the
solution one hour.
To separate zirconia from yttria, dissolve the hydroxides in
hydrochloric acid, warm, then saturate the solution with sodium
sulphate. When cold, zirconia separates in the well-known
manner. From the filtrate ammonia separates yttria.
As the earths are apt to occlude alkali salts, it is best to dis-
solve and again precipitate them (with ammonia) before they
are ignited and weighed.
Separation of the precipitated oxalates of thoria and of the
cerium group is accomplished as follows : The oxalates are
reduced to oxides by ignition, then converted into sulphates,
the greater part of the free acid neutralized with ammonia, the
solution boiled, and boiling ammonium oxalate added in excess.
After a short time (as soon as oxalates of the cerium metals
have formed but before the liquid has cooled) , a few cc. of solu-
tion of ammonium acetate are added. When cold, the entire
cerium group is precipitated as oxalates, while thoria remains
in solution. After prolonged standing, best over night, the
insoluble oxalates are removed by filtration ; in the filtrate, pre-
cipitate thoria with ammonia in excess, filter, ignite, and
weigh.
Separation of cerium from lanthanum and didymium is easily
accomplished by the well known method. Pass a current of
chlorine through the liquid containing the hydroxides. Which
have been freshly precipitated by a fixed alkali.
Separation of lanthanum from didymium was not attempted.
792 ESTIMATION OP THORIA.
An analysis of the monazite sand used in my work, made as
indicated in the foregoing notes, gave results as follows :
Titanic acid 4.67
Silica 6.40
Phosphorns pentoxide ^ 18.38
Lead trace
Alumina 1.62
Lime 1.20
Cerium oxide (CeO) 32.93
Lanthanum and didymium oxides 7.93
Thoria 1.43
Ferric.oxide 7.81
Zirconia and yttria i3-9o
Glucina 1.25
Tantalic acid 0.66
Not determined 1.72
100.00
Titanic acid and silica was determined in a separate portion.
The determination of tantalic acid was only approximate,
since a part of it is dissolved by fusion with acid potassium sul-
phate, and thus escapes weighing. As several such fusions were
made, it is probable that the greater part of the matter ' 'not deter-
mined" ought to be reckoned as tantalic acid. The quantity
stated was an average of three determinations (minus or plus
0.05) from the residue of repeated fusions.
Through the courtesy of Mr. H. B. C. Nitze, of the Geologi-
cal Survey of North Carolina, I have received a number of sam-
ples of monazite sand mined at various localities in that state.
Two of these had been prepared by a new process and were
found to be practically free from rutile and garnets. They were
excellent material for my methods of analysis, and they gave
results as follows :
Anai«vsis of a Coarse Monazite Sand prom Shelby, NoRTrf Caro-
lina.
Silica 3.20
Titanic acid 0.61
Cerium metals as CeO ^3*^
Phosphorus pentoxide 28. 16
Thona 2.32
Zirconia, glucina, yttria 1.52
Manganese trace
No iron, alumina, or lime 0.00
99.61
The color of this sand was honey-yellow.
PRECIPITATION OP BARIUM SUI.PHATE. 793
Analysis op k Pinb Monazitb Sand prom Bbllbwood, North Caro-
lina.
Silica 1.45
Titanic acid 1.40
Cerium metals as CeO < . . . 59.09
Phosphorus pentozide 26.05
Tbona 1. 10
Zirconia» glucina, yttria 2.68
Tantalic acid 6.39
Iron and manganese oxides 0.65
Alumina 0.15
9905
The color of this sand was honey-yellow.
Laboratory op Lbhkann Sl Gx^abbr,
Saltimorr.
[Contributions prom Metallurgical ItAboratory op thb Ohio
Statk University, Columbus, Ohio.]
THE EFFECT OF AN EXCESS OF REAGENT IN THE PRE-
CIPITATION OF BARIUM SULPHATE.
' By C. W. F0UI.X.
Received July 6, tBfb.
* <T7XCESS of reagent*' is a term often used by writers in
L/ quantitative chemistry, and the necessity in any given
case for adding more of a precipitating reagent than is just suffici-
ent for complete reaction is well known to analysts ; but what con-
stitutes such excess, whether it differs for different salts, whether
its effect is counteracted by the presence in the solution of other
bodies not taking part in the reaction, or whether the effect of
such bodies may be counteracted by the addition of a greater
amount of precipitant, etc., etc., are questions, the answers to
which are difficult to find in chemical literature.
With a view to answer, in part at least, these questions, the
following work on the precipitation of barium sulphate was
undertaken.
A preliminary experiment, which perhaps is worth noting,
was first tried :
A solution of 140 cc. water and five cc. concentrated hydro-
chloric acid was heated nearly to boiling and 0.1984 gram pure
recently ignited barium sulphate was added. This was then
stirred up and set aside for one hour, when it was filtered and
794 C. W. FOULK.
the barium sulphate washed well with hot water. The filter
and the contents were then ignited and weighed, when it was
found that ten milligrams of the sulphate had been dissolved.
The filtrate was now divided, and to one-half some sulphuric
acid was added, and to the other some barium chloride solution.
A precipitate of barium sulphate was produced in both cases.
Standard solutions of sulphuric acid and barium chloride were
now prepared. These were standardized by precipitation from
pure water solutions.
The sulphuric acid used in this work was the chemically pure
acid of the laboratory, tested for the ordinary impurities.
The barium chloride was recrystallized from the chemically
pure salt.
The hydrochloric acid was the chemically pure acid of the
laboratory tested for sulphuric acid.
The graduated ware was calibrated and found to be good.
All the precipitates of barium sulphate were ignited by fold-
ing up the moist filter, putting into a platinum crucible, '* pre-
cipitate end" up and so adjusting the flame that the paper
would be charred away "without letting the crucible become red
hot. Finally the heat was raised and the ignition finished. No
lid was used on the crucible. By following this plan no reduc-
tion to sulphide need be feared.
A number of the precipitates were moistened with sulphuric
acid and ignited. No change was noticed.
In the course of the work the following solutions were made :
Sui^PHURic Acid Solution.
Solution A.
cc. Barium sulphate.
1. 20 0.1978
2. 20 0.1975
3. 20 0.1970
4. 20 0.1978
Average o. 1970
Solution B,
cc. Barium sulphate.
1. 50 0-3277
2. 50 0.3271
3- 50 0.3279
Average 0.3275
PRECIPITATION OP BARIUM SULPHATE. 795
Solution C.
cc. Barium sulphate.
I- 5 0.1944
2. 5 o. 1940
Average*. 0.1942
Solution D.
cc. Barium sulphate.
1. 25 0.1544
2. 25 0.1534
3- 25 0.1543
4. 25 0.1538
5. 25 0.1535
6. 25 0.1546
7- 25 0.1539
Average 0.1542
Rejecting Nos. 2 and 5.
Barium Chu»ridb Solutions.
Solution A,
cc. Barium sulphate.
1. 20 O.I181
2. 20 O.1812
3. 20 o. 181 1
4. 20 0.1792
5. 20 0.1802
Average o. 1805
Rejecting No. 4.
Solution B.
cc. Barium sulphate.
1. 50 0.1985
2. 50 0.1980
3. 50 0.1086
4. 50 01985
Average # 0.1984
Solution C,
cc. Barium sulphate.
1. 10 0.4004
2. 10 0.4002
3. 10 0.4006
Average 0.4004
Solution D,
cc. Barium sulphate.
1. 10 0.3998
2. 10 0.3994
3. 10 0.3996
Average 0.3996
79^ C. W. FOULK.
Note. — The apparent discrepancies in some of the above aver-
ages are to be explained by the fact that before beginning the
work the burette used had been very carefully calibrated, and
the averages were calculated to correct number of cubic centi-
meters from the readings as given on the burette. In the course
of the work this refinement was found to be wholly unnecessary
and was therefore disregarded.
The equation of solutions of sulphuric acid and of barium
chloride is: Twenty cc. barium chloride solution = 21.8 cc.
sulphuric acid. That is, when mixed in these proportions
they will, theoretically, mutually precipitate each other and
give 0.1970 gram barium sulphate.
The effect of bringing these two solutions together in this pro-
portion was first tried. The barium chloride solution plus water
to make the whole volume up to 140 cc. was heated to boiling
and the sulphuric acid run in from the burette.
Barium snlphate. Error.
1. 20CC. BaCl,yH-2i.8cc. HjSOi^ 0.1966 —0.0004
2. 20 ** *• •* ** " 0.1973 40.0003
3. 20 •* '• " '* •• 0.1979 +0.0009
Solutions of BaCl,^ and H,SO«, when brought together in
their molecular proportions, weighed as follows :
Barium salptaate. Error.
1. 50 CC. BaCl^-h 30.2 cc. HjSO^^ 0.1979 —0.0005
2. 50 •• *• " •* " 0.1976 — OlOOOS
These had stood twenty-two hours before filtration, and the
results, while not very close, show at least that in water solu-
tions precipitation is practically complete without the presence
of an excess of reagent.
A series of precipitations was now made in order to determine
the ettect of \-ar>'ing quantities of hydrochloric acid upon the
precipitation when the two reagents were brought together in
their molecular proportions.
The barium chloride solution, water to mabe the volume np
to 14c* cc., and the hydrochloric acid were heated to boiling and
the sulphuric acid run in cold from the burette.
The same quantities of barium chloride and sulphuric acid
were usevi as aV\-e. The time of standing before filtration is
PRECIPITATION OP BARIUM SULPHATE. 797
marked over each set. Three precipitations were made with
each portion of the hydrochloric acid.
Sbribs I.
1. a. 3* 4-
Five cc. Ten cc. Fifteen cc. Twenty cc.
hydrochloric hydrochloric hydrochloric hydrochloric
acid. acid. acid. . acid.
Twenty-five Twenty-nine Thirty-three Forty-four
hours. hours. hours. hours.
Barium sulphate. Barium sulphate. Barium sulphate. Barium sulphate.
I P-I90^ 0.1879 0.1837 0.1875
2 0.1902 0.1870 0.1844 0.1863
3 0.1904 O.1881 0.1838 0.1873
It was thought that after standing twenty-four hours precipita-
tion would be complete and a longer time would have no effect.
The results of series No. 4 seem to show differently, however.
Accordingly another series was run in which the time of stand-
ing was regulated. Otherwise the precipitations were made as
above.
These stood twenty- three hours before filtration.
Shribs II.
I. 2. 3.
Five cc. Ten cc. Fifteen cc.
hydrochloric hydrochloric hydrochloric
acid. acid. acid.
Barium sulphate. Barium sulphate. Barium sulphate.
I 0.1902 0.1870 0.1852
2 0.1884 6.1854 0.1849
3 0.1904 0.1846 0.1827
4. 5- 6.
Twenty cc. Twenty-five cc. Thirty cc.
hydrochloric hydrochloric hydrochloric
acid. acid. acid.
Barium sulphate. Barium sulphate. Barium sulphate.
I 0.1832 0.1822* 0.1766
2 0.1885 0.1793 0.1833
3 0.1850 0.1789 0.1733
The above results show three things : (i) That less barium
sulphate is precipitated in the presence of larger amounts of
hydrochloric acid, but this solubility is not proportional to the
amount of hydrochloric acid. (2) That the greatest variation
of results takes place in the presence of the larger amounts of
acid. In other words parallel precipitations don't '* check.*'
(3) A much longer time is required to reach the maximum of
precipitation in the presence of the larger amounts of hydro-
chloric acid. See No. 4, Series I.
798 c. w. FOULE.
The efiect of a small excess of sulphuric acid was dqw tried.
Three solutions each containing fifty cc. barium chloride B,
sixty cc. water and twenty cc. hydrochloric add were heated to
boiling and the amounts of sulphuric acid B, indicated below,
were run in from a burette.
These stood twenty-four hours and weighed as follows :
Series III.
Barium lulpfaatf. Smr.
1. 50 CC. BaCl, B + 31.3 cc. H,SO, f « t cc. exceu = 0.1839 — «-oi45
a. 50 " " +33.3 " " —a " " — 0.1881 —0.0103
3. 50 " . " + 33a " " =3 " " — o-'97i —0.0013
The filtrates from the above gave no further precipitate on
standing several days.
Another series was run, using five cc. hydrochloric acid in-
stead of twenty cc, but conducted otherwise in the same man-
ner except that they stood from Friday to the following Monday
and undoubtedly the maximum of precipitation was reached.
Sbriks IV.
Barinm ■nlpbatt Bnvr.
I. 50 CC BaCl) B -H 31.3 cc. H,SOt B = \tx. excess = 0.1951 0.0033
a. 50 " " '• +33.3 " " " =3 " " =0.1963 0.003I
3. 50 •' " " 4-33-3 " " " =3 " " =0.1964 0.0030
It was now decided to use lai^er amounts of sulphuric acid
in excess, but in order to hurry matters along, cut down the
time of standing before filtration.
In the following series, accordingly, the barium sulphate was
filtered off after standing three hours. The whole volume of
solution in each case was 150 cc.
Series V.
.^^B
f^
ih
u
"g^'p"
t Barium
Srrar.
50
SO
'5
15
35'
40.3
45-3
SO. a
S
30
o.i«8
0.1590
0.1688
0..7fa
0.05«
0.0394
0.0^
lowing the larger amounts of sulphuric
■ be noted that 30.2 cc. sulphuric acid in
PRECIPITATION OF BARIUM SULPHATE. 799
three hours did not bring down so large a precipitation as 31.2
cc. sulphuric acid did in twenty-four hours though in the pres-
ence of a larger portion of hydrochloric acid. See Series III.
In order to get comparative results the various conditions of
the precipitation had to be more carefully regulated. The
above results show this very plainly.
Accordingly, the following problem was set : How great an
excess of sulphuric acid is required to precipitate completely as
sulphate, the barium from fifty cc. of barium chloride B, in the
presence of five cc. hydrochloric acid in one hour, the whole
volume of solution, after adding the sulphuric acid, to be 150CC. ?
Instead of adding a certain number of cc. in excess the sul-
phuric acid was now measured in equivalents, 30.2 cc. the exact
amount to precipitate fifty cc. barium chloride was called one
equivalent and different multiples of it were taken.
The barium chloride, water, and hydrochloric acid were
heated on the water-bath and the sulphuric acid run in cold
from the burette.
Series VI.
Hydro.
Barium chloric
chloride^, acid.
Sul-
phuric
acid B.
Eqivalents
sul-
phuric
acid.
Barium
sulphate.
Error.
cc. cc.
I
50 5
37.8
1.25
0.1564
0.0420
2
50 5
45-3
1.50
0.1624
0.0360
3
50 5
52.8
1.75
O.I7S4
0.0200
4
50 5
60.4
2.00
O.1S57
0.0127
5
50 5
68.9
2.25
0.1842
0.0142
The fact that No. 5 was lower than No. 4 was referred to the
lowering of temperature produced by the addition of the sixty-
eight cc. cold sulphuric acid.
The following plan was now adopted :
The sulphuric acid was measured out into beakers and also
heated on the water-bath. It was then added to the barium
chloride solution, the beakers being washed out three times with
hot water, using about four or five cc. each time and the wash-
ings also added.
8oo
C. W,
FOULK.
Sbribs vn
. (Continued from above. )
Hydro-
Barium chloric
chloride J?, acid.
Sul.
phuric
acid B.
BquivalenU
sulphuric
acid.
Barium
sulphate.
Srror.
cc.
cc.
6
50
5
67.9
2.25
0.193 1
--O.OQ53
7
50
5
75.5
2.50
0.1935
—0.0049
8
50
5
83.0
2.7s
0.1956
—0.0028
9
50
5
90.5
3.00
0.1963
— 0.0021
lO
50
5
39-4
4.00
0.196 I
—0.0023
II
50
5
49.2
5.00
0.1962
—0.0022
Note. — The last two results were obtained with a stronger
sulphuric acid solution, which was run in cold.
A rapid increase is seen with the first additions of sulphuric
acid, the difference becoming less as the sulphuric acid increases.
Another peculiarity was also seen in each one of these series.
Although the solutions had been well stirred on bringing the
reagents together, had settled clear in a few minutes, and the
supernatant liquid had remained clear, yet in running through,
the filter the filtrates soon became cloudy and a copious pre-
cipitate of barium sulphate settled out.
This could be due only to the agitation produced by running
through the filter. Later an experiment was tried on this point.
Fifty cc. of barium chloride solution, 0.0992 barium sul-
phate -f- five cc. hydrochloric acid and water to make the total
volume up to 150 cc, was heated in a flask and two equivalents
of sulphuric acid added. This was then shaken for ten minutes,
allowed to settle for fifty minutes, and then the precipitate was
filtered off and weighed.
It gave barium sulphate 0.1979, a minus error of 0.0013 as
against an error of — 0.0127 in Series VI, with two equivalents.
It seems that in the presence of hydrochloric acid unless there
is a sufficient amount of sulphuric acid present to effect com-
plete precipitation, a delicate balance is formed which is affected
by a difference in time of standing, in temperature, and amount
of agitation on stirring. To avoid adding so large a volume of
sulphuric acid solution ** C" was prepared.
Series VIII was now run. Both solutions wer^ heated on the
water-bath and brought together as described above. Solution
PRBCIPITATION OP BARIUM SUI^PHATB. 8oi
in each case was stirred one and one-half minutes and allowed
to settle one hour.
Series VIII.
Hydro-
Barium chloric
chloride^, acid.
Snl- Equivalents
phuric sulphuric
acid C. acid.
Barium
sulphate.
Error.
cc. cc.
cc.
I
50 5
20.4 4
O.I971
—0.0013
2
50 5
255 5
0.1978
—0.0006
3
50 5
30.6 6
O.I981
—0.0003
4 •
50 5
35-7 7
0.1980
—0.0004
5
50 5
40.8 8
0.1984
0.0000
6
50 5
45-9 9
0.1985
+0.0001
7
50' 5
51.0 10
0.1984
0.0000
8
50 5
56.1 II
0.1985
+O.OOOI
At last the proper excess to effect complete precipitation un-
der the conditions described above had been found. Seven or
eight times the theoretical amount seems necessary. It is to be
noted that the change is extremely slow when near the critical
point.
A short series was precipitated and weighed, using other
solutions, the equation of which was as follows :
Fifty cc. BaCl,, ;r = i cc ±: H,SO, D = 0.1992 BaSO,.
Series IX.
Barium
chloride x.
Hydro,
chloric
. acid.
Sul.
phuric
acid D.
Equiva-
lents sul-
phuric acid.
Barium
sulphate.
Error.
cc.
cc.
cc.
I
50
5
3
3
0.1957
--O.OO35
2
50
5
4
4
0.1992
0.0000
3
50
5
5
5
0.1983
—0.0009
3
50
5
5
5
0.1992
0.0000
In this series the sulphuric acid was run in cold.
The maximum amount of precipitate seems to be reached here
with less sulphuric acid than when a more dilute solution was
used. The same is true of the precipitations made in the pres-
ence of ten cc. hydrochloric acid.
Series X was now run, the precipitations being made in ex-
actly the same manner as those of Series VIII, except that ten
cc. of hydrochloric acid was put into the solutions instead of
five cc.
8o2
C. W.
FOUI.K.
Series X.
Bariam
chloride B.
Hydro-
chloric
acid.
Sol-
phuric
acidC
Bqaiva-
lenU lal-
pharic
acid.
Bariam
sulphate.
BiTor.
cc.
cc.
I
SO
10
30.6
6
0.1964
^-0.0020
2
50
10
35-7
7
0.1974
— O.OOIO
3
50
10
40.8
8
O.1981
—0.0003
4
50
10
45.9
9
0.1982
^-0.0002
3
50
10
40.8
8
O.X970
— O-OOI4
4
50
10
45-9
9
0.1982
^-0.0002
In the presence of ten cc. hydrochloric acid then, a somewhat
greater excess of sulphuric acid is required than with five cc.
hydrochloric acid.
A short series with the stronger solution gave
Barium
chloride J?.
cc.
1 50
2 50
3 50
3 50
Series XI.
Eqniva>
Hydro> Sul- lenta snl-
chloric phuric phuric Barium
acid. acidZ). acid. sulphate.
cc.
10 5 5 0.1975
10 6 6 0*1982
10 7 7 0.1992
10 7 7 0.1991
Srror.
0017
0010
O'OOOO
0001
Series XII. was conducted exactly as Nos. VIII. and X., ex-
cepting that fifteen cc. hydrochloric acid was used.
Hydro-
Barium cnloric
chloride B. acid.
Series XII.
Eqniva-
Sul- lents sul-
phuric phuric
acid C. acid.
I
2
■
3
4
5
6
7
cc.
50
50
50
50
50
50
50
cc.
15
15
15
15
15
15
15
30.6
35-7
40.8
45-9
510
56.1
61.2
6
7
8
9
10
II
12
Barium
sulphate.
0.1957
0.1955
0.1965
0.1973
0.1972
0.1984
0.1983
Error.
0027
0029
0019
.0011
.0012
0.0000
.0001
The point to be noted in this series is that more sulphuric
acid is required in the presence of the larger amount of hydro-
chloric acid.
The other side of the question was now taken up, namely, the
precipitation of sulphuric acid with an excess of barium chlo-
ride in the presence of hydrochloric acid.
PRECIPITATION OF BARIUM SULPHATE. 803
A new difficulty at once presented itself. The old trouble in
filtering barium sulphate was experienced. When a small
amount of hydrochloric acid was present it was found utterly
impossible to do it under the conditions which had previously
been followed.
Various experiments were made to avoid this trouble and at
last the following scheme was adopted :
The volume was kept at 150 cc. as in the other work. The
sulphuric acid, water, and hydrochloric acid were heated on the
water-bath and the barium chloride solution, also hot, was added
drop by drop with constant stirring. The beakers were then set
back on the battf and the solutions stirred at intervals for thirty
minutes. They were then set off and stirred at intervals again
until cold.
Just before pouring upon the filter the precipitate* was stirred
up and the filter filled several times. At first a small portion
ran through, but this was poured back, and, generally, the rest
could be filtered without trouble.
A series was run according to this description, except that the
volume was 250 cc.
The exact time of standing before filtering was not noted in
this case. It was probably about four or five hours.
Sbribs XIII.
Sul-
phuric
acid^.
Hydro-
chloric
acid.
Eqivalents
Barium barium
chloride C. chloride.
Barium
sulphate.
Error.
cc.
cc.
cc.
I
30.2
10
14.9
3
0.1967
—0.0017
2
30.2
10
19.8
4
0-1959
—0.0025
3
30.2
xo
14.9
5
0.1965
^.0019
There was nothing satisfactory to be derived from this series,
so Series XIV was run. The volume here was kept down to
150 cc.
Series XIV.
Sul-
phuric
acid^.
Hydro-
chloric
acid.
Houivalents
Barium barium
chloride C. chloride.
Barium
sulphate.
Error.
cc.
cc.
cc.
I
30.2
10
14.9
3
0.1975
—0.0009
2
30.2
10
19.8
4
0.1994
-f O.OOIO
3
30.2
10
24.9
5
0.1983
— O.OOOI
4
30.2
10
29.8
6
0.2005
-H>.002I
804 C. W. FOULK.
Two of these precipitates weigh heavier than theory demands.
This could come only from contamination with barium chloride.
To test this No's 3 and 4 were transferred to beakers, boiled up
with about seventy-five cc. of water and again filtered, ignited,
and weighed.
They then gave
3. 0.1980 barium sulphate = — o.cxx34 error.
4. 0.1987 ** ** as +0.0003 "
Another series was run in exactly the same manner, except
that more care was taken in washing. Each precipitate was
washed with boiling water until the filtrate no^ longer reacted
with silver nitrate.
Sbriks XV.
Sul-
ptauric
acid^.
Hsrdro-
chloric
acid.
Barium
chlofide
Bquivalents
Darium
C chloride.
Barium
sulphate.
Brror.
cc.
cc.
I
30.2
10
9-9
2
0.1965
—0.0019
2
30.2
10
14.9
3
0.1982
— O.OOOI
3
30.2
10
19.8
4
0.1975
—0.0008
4
30.2
10
24.9
5
0.1988
+0.0004
5
30.2
10
29.8
6
0.1994
+0.0010
No*s 4 and 5, on being boiled up with water and reweighed,
gave
3. o. 198 1 = —0.0003 error.
4. 0-1975 = —0.0009 '*
At its best, however, this method of working was unsatisfac-
tory. The precipitate seemed always on the point of running
through the filter and indeed traces generally did go through.
The following scheme was accordingly tried in Series XVI.
The volume was kept as before at 150 cc, but thirty cc. of
hydrochloric acid instead of ten was put into each solution.
The precipitates were not stirred up after being thrown down.
In presence of this large excess of acid the precipitates soon
became coarse and crystalline and settled rapidly. No troubU
whatever was experienced in filtering them.
PRBCIPITATION OP BARIUM SULPHATE. 805
Sbriss XVI. (These had stood about four hours. )
Sul-
phuric
acid^.
Hydro-
chloric
acid.
BquiTalents
Barium Darium
chloride C. chloride.
Barium
sulphate.
Brror.
cc.
cc.
I
20
30
4.6
1.5
0.0947-
—0.0289
2
20
30
6.2
2.0
0.0997
—0.0239
3
20
30
9.3
3.0
0.III4
—0.0122
4
ao
30
12.4
4.0
O.I 169
—0.0067
5
20
30
15.5
5.0
0.1207
—0.0029
6
20
30
18.6
6.0
O.I 192
—0.0044
These filtrates, on standing over night, all showed further
precipitates of barium sulphate. The series was .accordingly
continued, this time the solutions standing about seven hours
before being filtered.
The precipitates were crystalline and filtered easily and
rapidly and the filtrates, on further standing, showed no traces of
barium sulphate.
In spite, however, of the greatest care in washing, it was im-
possible to get rid of the occluded barium chloride before igni-
tion.
Sbribs VII.
Sul-
phuric
acid£.
Hydro-
chloric
acid.
Barium
chloride
C.
BquivVs
Barium
chloride.
Barium
sulphate.
Error.
I
20
30
18.6
6
0.1258
-I-0.0022
2
20
30
21.7
7
0.1252
4-0.0016
3
20
30
24.8
8
0.1268
+0.0032
4
20
30
27.9
9
0.1260
-f"O.0O24
Nos. 2, 3 and 4 were boiled up with water, re washed, ignited
and weighed.
Barium sulphate. Error.
2 0.1236 0.0000 Filtrate reacted strongly with silver nitrate.
3 0.1238 +0.0002
4 0.1253 +O.OOI7 *' *• slightly "
No. 4 boiled up the second time 0.1237 BaSO^ = + 0.0001
error. The filtrate in this case reacted strongly with silver
nitrate.
To test this boiling up process No. 4 was treated the third
time. This time the precipitate weighed 0.1235 and the filtrate
did not react with silver nitrate.
A last experiment was made to determine the effect of barium
8o6 C. W. POULK.
chloride upon the direct solubility of barium sulphate in hydro-
chloric acid.
0.1248 {^am barium sulphate was put in 120 cc. water and
thirty cc. hydrochloric acid and beaker marked **^."
o. 1228 gram barium sulphate was weighed into another beaker
with 105 cc. water, thirty cc. hydrochloric acid and fifteen cc.
barium chloride C. This beaker was marked ''^.'*
Both were heated on the water- bath with frequent stirring and
then stood over night.
On being filtered and weighed,
** w4 " gave —0.1 106 bftrium snlphate = 0.0142 loss.
•«^»» •« —0.1228 " *• s 0.000 ••
To further test precipitate '*^ " it was boiled up with water
as those of Series XVII, and re-weighed. It lost by this oper-
ation 0.0002, which is practically nothing.
Prom the results obtained in this investigation the following
conclusions seem justified :
(i) In the precipitation of a barium salt with sulphuric acid
in the presence of hydrochloric acid, a ^ery large excess of sul-
phuric acid is required.
(2) This excess should be greater the greater the amount of
hydrochloric acid present in the solution.
(3) It should be greater the shorter the time of standing
before filtration. In fact a very great excess seems to effect
immediate precipitation.'
(4) The greater the excess of sulphuric acid the less stirring
seems necessary to bring down the precipitate in a given time.
( 5 ) While barium sulphate obtained by precipitating a barium
salt with sulphuric acid in the presence of hydrochloric acid is
coarse, crystalline and easily filtered/ that obtained by precipi-
tating sulphuric acid with a barium salt in the presence of
hydrochloric acid is fine and much disposed to run through the
filter unless special precautions are taken.
(6) In general a large excess of barium chloride is required
to completely precipitate the sulphuric acid in the presence of
hydrochloric acid.
PRECIPITATION OF BARIUM SULPHATE. 807
(7) As the hydrochloric acid increases the amount of barium
chloride should also be increased.
(8) The greater the amount of hydrochloric acid present the
coarser and more crystalline in character is the precipitated
barium sulphate. In precipitating in the presence of large
amounts of hydrochloric acid the solution should be quite con-
centrated.
(9) The barium sulphate so obtained, will, however, be con-
taminated with adhering barium chloride, and no amount of
washing before ignition can entirely free it from this occluded
chloride. If, after ignition, the precipitate be boiled up with
water, again washed, ignited and weighed, and this process be
continued until a constant weight is obtained, the sulphate may
be entirely freed from the barium salt.
Some subsequent work in this line has shown that heavy pre-
cipitates sometimes require three or four treatments before a con-
stant weight is obtained.
(10) Both in the precipitation of barium with sulphuric acid
and of sulphuric acid with barium, very concordant results may
.be obtained if the conditions under which the precipitations are
made are similar, but these results may be quite far from cor-
rect. A note of this commonplace occurrence in analytical
work is made here, because by following the usual method of
testing the filtrate for an excess of the precipitating reagent, a
strong reaction might be obtained and yet not more than ninety
per cent, of the original precipitate be down.
In conclusion I wish to express my thanks to Professor N. W.
Lord for helpful suggestions during the course of this work.
Discussion.' — ^T. S. Gladding: I have already shown (see
this Journal, 16, 398; 17* 181, 397, 772; 18, 446) that correct
results may be obtained if the barium chloride solution be added
drop by drop instead of all at once. This is confirmed by I^ane
(18, 682) and is now virtually admitted, by Lunge, who precipi-
tates (18,686) by *' quick additions (1. r, pouring in the hot
barium chloride solution in about ten portions, occupying about
half a minute in all, and stirring the mixture all the time, as
every chemist would do.)**
1 Bttfialo McctiniTi Aug., 1896.
THE ACTUAL ACCURACY OF CHEHICAL ANALYSIS.*
BV PRBOSftIC P. DSWBV.
Received July 14. it96.
THE subject of this paper does not embrace the consideration
of ways and means for the increase of analytical accu-
racy» or the question, what can be or should be attained in that
direction. I desire simply to call attention to the degree of
accuracy exhibited in actual ever>' day practice. In estimating
this, little weight will be given to the evidence afforded by the
agreement of duplicate or multiple determinations by the same
chemist ; for I am convinced that such agreement is a delusion
and a snare. Nor will special importance be attached to the
agreement of two or even three analysts in special cases, or to
the agreement between two methods practiced by the same
analyst. I propose to compare the results obtained by several
chemists, working upon the same sample and by various
methods, in order to exhibit, as I have said, the actual condi-
tion of practice.
The available material for illustrating this phase of the ques-
tion is unfortunately scanty ; but something has been done ;
and I hope, by calling attention to some of the work in this line,
to stimulate further work in the same direction by inducing
others to prepare suitable samples and submit them to various
chemists who are competent and willing to make the necessary
determinations and fully describe the methods they employ.
I draw most of my illustrations from the * ' Transactions of the
American Institute of Mining Engineers,'' the ** Proceedings of
the Association of Official Agricultural Chemists," and from
personal experience.
MANGANESE IN STEEL.
In May, 1881, Mr. William Kent presented a paper to the
American Institute of Mining Engineers entitled *' Manganese
Determinations in Steel," * in which he gave twenty-four deter-
minations of manganese, made by ten different chemists,
employing two main methods, on samples from a plate of steel.
1 Read before the Washingtoa Section of the American Chemical Society. May X4tli,
1896. and published jointly with the American Institute of Mining Engineers.
3 Trans. A. I. M. E-. xo. loi.
ACCURACY OP CHEMICAL ANALYSIS. 809
These results presented the remarkable range of from 1.14 to
^•3<^3 percent., and one chemist reported results ranging from
1. 14 to 0.434 per cent.
A portion of this variation was undoubtedly due to variations
in the sample, since the same sample was not used throughout
by the different chemists.
Throwing out the anomalous result of 1.14 per cent, we have
twenty-three determinations running from 0.619 P^r cent, to
0.303 per cent., with an average of 0.415 per cent. Thus show-
ing that at that time the determination of manganese in steel,
when only about four- tenths per cent, was probably present,
might exhibit an extreme variation between the highest and the
lowest results of about three-tenths per cent., or seventy-five per
cent, of the amount of manganese present.
These results were certainly very discouraging ; but if they
did nothing else they served to call attention to the very unsat-
isfactory character of the determination of manganese in steel at
that time.
I do not recall any recent symposium on the determination of
manganese in this class of material, but in 1886 Capt. A. £.
Hunt,* in giving a measure of the accuracy of the colorimetric
method, speaks of a variation of 0.02 per cent, in steels contain-
ing 0.15 to one and five-tenth's per cent, of manganese
as •' sufficiently accurate for all practical w^ork,*' thus clearly
intimating that the current results of analj'sis by other methods
were at least as good. This degree of accuracy, if attained by
different chemists upon the same sample, must be considered a
satisfactory advance over the results reported by Mr. Kent.
Early in 1883 Mr. G. C. Stone began a series of contributions
on the ** Determination of Manganese in Spiegel.'** In his first
paper he reported thirteen determinations by five chemists, all
working upon the same ** works'* sample, showing from 15.49
to 13.83 per cent., and also twenty-six determinations by ten
chemists, all working upon a sample of the same spiegel, pre-
pared with especial care jointly by Mr. Stone and one of the
other chemists, showing from 14.56 to 10.36 percent. But some
of the low results were obtained by experimental methods.
1 Trans. A. I. M. E., I5t 104.
STrans. A. I. M . K.. 11, 323 : 12, 295 and 514.
8lO PRBDERICK P. DEWEY.
In the fall of 1883 Mr. Stone reported twenty additional
determinations by five other chemists, ranging from 14.20 to
10.76 per cent. ; the extremes being reported by the same chemist
when working by different methods, his favorite method giving
from 13.84 to 13.65 per cent., and three low results, less than
eleven per cent., being obtained by the Williams' method. In
this connection Mr. Stone presented an interesting table, divid-
ing the methods used into four classes and the results into three
classes, giving respectively, below thirteen per cent., between
thirteen and fourteen per cent., and above fourteen per cent.
In the spring of 1884 Mr. Stone reported twenty -seven new
results, nineteen by four new chemists, and eight by one pre-
viously reported, whose new results were obtained by several
methods.
We have thus seventy-three determinations by nineteen differ-
ent chemists. Of these two are thrown out on account of the
method used, and eleven ** because the chemists were not
entirely satisfied with them," leaving sixty determinations by
eighteen chemists, using twelve methods.
These sixty results range from 14.47 to 12.60 per cent., and
average 13.39 per cent . Leaving out eight determinations by one
method which is considered to give low results, the lowest
determination becomes 12.92 per cent, and the average 13.48
percent., showing an extreme variation of 1.45 per cent, of
manganese between the highest and lowest results, and showing
only forty-four per cent, of the results within two-tenths per cent,
of the average.
In the discussion of Mr. Stone's second paper, Mr. J. B.
Mackintosh' presented an analysis of Mr. Stone's first forty-six
results, retaining the results by the Williams' method, from
which he argued that the evidence pointed to 12.956 per cent, as
the true content of manganese in this Spiegel. If this is the
case, then there is a very decided tendency to get too high
resultb in this class of work.
Taken as a whole, this investigation would seem to show that
variations of five-tenths per cent, in the determination of man-
ganese in this grade (ten to fifteen per cent, manganese) of
I Trans. A. I. M. B.. ta, 300.
ACCURACY OP CHEMICAI, ANALYSIS. 8ll
Spiegel are to be expected, and much wider variations may be
found.
PHOSPHORUS IN PIG IRON.
Early in the 8o*s, Messrs. Potter and Riggs, of St. Louis,
Mo., sent out a sample of pig-iron for the determination of
phosphorus.
This examination yielded twenty-six results, by eleven chem-
ists, using five methods, ranging from 0.181 to 0.141 per cent.,
and averaging 0.160 per cent, and showing an extreme varia-
tion of 0.040 per cent. The maximum variation reported by
any one chemist was 0.017 P^r cent., while three reported dupli-
cated agreeing with o.ooi per cent. These results have never
been published. One of the chemists discovered arsenic in the
sample, which would account for some of the variation in the
series. His determinations in duplicate were 0.151 and 0.152
per cent.
In February, 1882, Mr. F. E. Bachman presented a paper to
the American Institute of Mining Engineers,* in which he
reported forty-four results by eighteen chemists, using four
methods, ranging from 0.165 to 0.096 per cent, and averaging
0.143 per cent. The extreme variation was 0.069 P^r cent.
The maximum variation reported by any one chemist on straight
duplicates was o.oi per cent., and the minimum 0.0004 P^r cent.
Experimental determinations by Mr. Bachman, using different
processes, yielded variations amounting to 0.043 per cent.
At the Atlanta meeting in October, 1895, Mr. Geo. Thackray
presented a paper, entitled ' ' A Comparison of Recent Phos-
phorus Determinations in Steel.*" He first gives a table of
determinations of phosphorus by two chemists on eight samples
ranging from 0.033 to 0.012 per cent., one chemist uniformly
getting high results. One chemist found from 0.080 to 0.074
per cent., and the other 0.1 16 to 0.088 per cent in these steels.
These results were manifestly unsatisfactory.
A second table shows results by three chemists, the buyer's,
the seller's and an arbitrator. By the arbitrator's determinations
these steels carried from 0.080 to 0.063 P^>^ cent, of phosphorus.
1 Trans. A. I. M. £., xo, 33a.
f Trans. A. I. M. B., as, 370.
8l2 FREDERICK P. DEWEY.
The maximum difference in any set of three results "was
0.017 percent., and the minimum 0.005 per cent.
These results were obtained in the settlement of sales. As a
result of the discussion which accompanied the matter, two sam-
ples of steel were prepared and sent to various chemists. A
fourth table gives thirty-six results obtained from twenty-three
chemists, using twenty-nine methods on one steel, showing re*
suits averaging 0.0496 per cent., and ranging from 0.055 too.045
percent., an extreme variation of only o.oio per cent. Any-
individual result was practically within 0.005 per cent, of the
average.
On the second sample thirty-eight results were reported avtrag^-
ing 0.0835 per cent., and ranging from 0.091 to 0.076 per cent.,
an extreme variation of 0.015 per cent.
My own results on these steels are not given, as they were not
reported in time ; but they add two more results by one more
chemist in each case, and the results fall within the limits.
These results must be regarded as highly satis&u:tory, and
show that here, at least, is one determination that can be made
by many chemists, working in different ways, and yet with
results agreeing ver>- closely together. While it may not be
necessary* to determine many things as closely as phosphorus in
steel, yet it would be highly satisfactory if we could do so ; and
this is a good standard of excellence for us to aim at.
PHOSPHORIC ACID.
As compared with the accuracy secured in the determination
of phosphorus in steel, the 1S94 report of the Association of
Official Agricultural Chemists,* shows that on one sample thirty-
nine determinations of insoluble phosphoric acid by eighteen
chemists, working by the oflBcial method, showed results rang-
ing from 0.45 to 0.03 per cent., with an average of 0.27 per
cent., the extreme variation being 0.42 per cent., or over one
and one-half times the average determination.
By another method, on the same sample, thirty-six determina-
tions by nineteen chemists showed results varying from 0.34 to
1 PToce«^.ai;s of :hc HTevrnth Annua! Cocveotion of the Associatioa of HIKi ial Acii-
cii!tQraI Chrcu<:5. Ancust 73. 24. ^ *'>S4 Bu;:mn 4k.v f. S^ Dgprinif ■? of A^rtcwltBrT.
Division of Chemistry, p. "^
ACCURACY OF CHEMICAL ANAI^YSIS. 813
0.04 per cent., with an average of 0.19 per cent., the extreme
variation being 0.30 per cent., or over one and one-half times
the average.
We have thus seventy-five determinations by nineteen chem-
ists working by two methods, showing results ranging from 0.45
to 0.03 per cent., with an average of 0.233 P^r cent., the
extreme variation being 0.42 per cent., or nearly twice the
average determination.
On another sample thirty-three determinations by seventeen
chemists working by the official method, showed results rang-
ing from 3.85 to 2.24 per cent., with an average of 2.82 per
cent., the extreme variation being 1.61 percent., or considerably
more than one-half of the average.
By another method, on the same sample, tliirty-five determi-
nations by seventeen chemists showed results ranging from
3.49 to 2.18 per cent., with an average of 2.83 per cent., the
extreme variation being 1.31 per cent., or nearly one-half the
average.
Summing up again, we have sixty-eight determinations by
eighteen chemists working by two methods, showing results
ranging from 3.85 to 2.18 percent., with an average of 2.82 per
cent., the extreme variation being 1.67 per cent.
The same report* shows that on one sample the results of
twenty-nine determinations of citrate soluble phosphoric acid by
fourteen chemists, by the direct method of Ross, varied from
2.47 to 1.04 per cent., with an average of 1.52 per cent., the
extreme variation being 1.43 per cent., or nearly equal to the
average of all the determinations.
On the same sample, by the official method, the results of
twenty-three determinations by fourteen chemists ranged from
2.26 to 1. 18 percent., with an average of 1.46 per cent., the
extreme variation being 1.08 per cent., or over two-thirds of
the average determination.
Summing up. we have fifty-two determinations by fourteen
chemists working by two methods, ranging from 2.47 to 1.04
percent., and averaging 1.49 per cent., the extreme variation
being 1.43 per cent., or nearly equal to the average.
1 Ibid,^ P- 72.
8 14 FREDERIC P. DEWEY.
On another sample thirty-six determinations by fifteen chem-
ists by the direct method of Ross, range from 3.29 to 1.87 per
cent., with an average of 2.36 per cent., the extreme variation
being 1.42 per cent., or considerably over one-half of the average
determination.
On the same sample, twenty-four determinations by fifteen
chemists, ranged from 3.40 to 2.08 per cent., with an average of
2.60 percent., the extreme variation being 1.32 per cent., or a
little over one-half of the average determination.
Summing up, we have sixt}' determinations by fifteen chemists
working by two methods, ranging from 3.40 to 2.08 per cent.,
and averaging 2.44 per cent., the extreme variation being 1.32
per cent., or a little over one-half of the average determinations.
In the determination of the total phosphoric acid,' fort>'-five
determinations, by eighteen chemists, ranged from 20.67 to 19.74
per cent., with an average of 20.09 per cent., the extreme varia-
tion being 0.93 per cent. By a volumetric method, thirty deter-
minatiqns, by eleven chemists, ranged from 20.60 to 19.83 per
cent., with an average of 20.14 per cent., the extreme v*ariation
being 0.77 per cent. By another volumetric method, twenty-one
determinations by ten chemists, ranged from 20.45 ^o 19-27 per
cent., with an average of 19.96 per cent., the extreme variation
being 1.18 per cent.
Combining these results, we have ninety-six determinations
by eighteen chemists working by three methods, ranging from
20.67 to 19.27 per cent., with an average of 20.08 per cent., the
extreme variation being 1.40 per cent.
Similarly, on another sample, we have 120 determinations, by
twenty-two chemists, working by the same three methods, rang-
ing from 1.8. 15 to 16.25 per cent., with an average of 17.26 per
cent., the extreme variation being 1.90.
Again, on another sample, we have ninety-six determinations
by twenty-one chemists, working by the same three methods,
ranging from 2.85 to 2.20 per cent., with an average of 2.50 per
cent., the extreme variation being 0.65 per cent.
COPPER.
At the August meeting of the A. I. M. E., in 1882, Mr. W.
I Ibtd., pp. Si, S2. 53.
ACCURACY OF CHEMICAL ANALYSIS. 815
E. C. Eustis presented a paper entitled '' Comparison of Various
Methods of Copper Analysis.*'* For the purpose of this com-
parison a ver>' complex sample was made up, containing sul-
phides, oxides and metallic copper, a silicate, sulphides of iron
and zinc, arsenic and nickel. The paper reports forty-five
determinations by seventeen chemists, using some eight methods.
The results showed a wide variation, ranging from 53.34 to
43.92 per cent, and averaging 47.75 per cent. On throwing out
a set of six results from one concern, all of which were more
than two per cent, and two of them nearly five per cent, above
the nearest other result, as being manifestly too high, and two
results by one chemist and one method, which were more than
two per cent, below the nearest other result, the series still
rang^es from 48.72 to 46.24 per cent., with an average of 47.23
per cent., and a maximum variation of 2.48 per cent., which
cannot be considered very satisfactory.
The same paper reported seventeen determina^ions by seven
chemists on borings of pig copper. These ranged from 91.07 to
98.17 per cent, and averaged 94-25 per cent. On throwing out
two results that were nearly three per cent, higher than the
nearest other result, and four that were over three per cent.
below the nearest other result, the series ranges from 94.91 to
94.38 per cent, with an average of 94.^9 per cent. The extreme
variation of only 0.53 per cent, must be regarded as very good
work, especially when we consider the character of the material.
At the Florida meeting in March, 1895, the results of a sym-
posium on copper and copper matte, initiated bj' Dr. A. R.
l,edoux, of New York City, were presented.* Eight chemists
reported the copper in the matte, some in duplicate or more, as
determined by electrolysis, as ranging from 55.17 to 54.50 per
cent, and averaging 54.91 per cent. The extreme variation was
only 0.67 per cent ; and this must be regarded as satisfactory,
and very much better than the results on Mr. Eustis complex
mixture.
- Six chemists reported results by the cyanide method, ranging
from 54.8 to 50.55 per cent, all but one of the results being below
1 Trnii!». A. I. M. K., it. 120.
2 Trans. A. I. M. K.. as* ^5° <^"d io<^-
8l6 FREDERIC P. DEWEY.
the lowest electrolytic result. These cannot be regarded as sat-
isfactory.
A plate of copper made from melted anodes was drilled and
six chemists reported the copper in the drillings, as found by
the electrolytic method, as ranging from 98.46 to 97.04 per cent.,
and averaging 97.67 per cent, with a maximum difference of
1.42 per cent. These results are not as good as those previously
reported by Mr. Eustis.
GOLD AND SILVER IN COPPER MATERIALS.
The symposium above referred to was undertaken primarily
to test methods of assaying copper material for gold and silver.
Fourteen chemists reported the silver by scorification assay,
some entirely uncorrected, some partially corrected, and some
corrected for both loss in slag and cupel and presence of copper
in the silver button. The averaged results ranged from 135.38
to 122.88 ounces per ton and averaged 128.86 ounces per ton ;
the extreme variation being 12.5 ounces per ton, or nine and
seven-tenths per cent, of the average.
Nine chemists reported ten results by combined wet and scor-
ification methods, a few of them corrected for slag and cupel
absorption. The averaged results ranged from 130,68 to 123.03
and averaged 127.25 ounces per ton. The extreme variation
was seven and six-tenths ounces per ton, or 5.97 per cent, of the
average determination.
One chemist reported 123.6 ounces per ton by crucible method.
Another reported 126.2 ounces per ton by combined wet and
crucible method, corrected for slag and cupel.
Summing up, we have twenty-six results by twenty chemists
working by two main methods, but both of them modified in
various ways, and two methods, each by a single chemist, vary-
ing from 135.38 to 122.88 and averaging 127.94 ounces per ton.
The extreme variation was 12.5 ounces per ton, or 9.77 per cent,
of the average determination.
In the case of the silver assay of the copper borings, nine
chemists reported by the scorification method, with and without
corrections. The averaged results varied from 164.35 to 154.40,
and averaged 159.36 ounces per ton. The extreme variation
was 9.95 ounces per ton, or 6.24 per cent, of the average.
ACCURACY OP CHEMICAL ANALYSIS. 817
Fifteen chemists reported sixteen results by combined wet and
scorification methods, with and without corrections. The aver-
aged results varied from 161.40 to 148.50 and averaged 156.48
ounces per ton. The extreme variation was. 13. 9 ounces per
ton, or 8.88 per cent, of the average. A single chemist reported
161.35 ounces per ton by combined wet and crucible process,
corrected for slag and cupel.
Summing up, we have twenty-six determinations by twenty
chemists working by three methods, ranging from 164.35 to
148.5 and averaging 157.67 ounces per ton. The extreme varia-
tion was 15.85 ounces per ton, or 10.05 per cent, of the average
determination.
Twenty chemists working by the four methods reported twen-
ty-six results on the gold in the matte varying from 2.41 to 1.85
and averaging 2.245 ounces per ton. The extreme variation
was 0.56 ounce per ton, or 24.94 P^^ cent, of the average.
On the gold in the copper borings twenty chemists working
by two main methods, each one variously modified, and the com-
bined wet and crucible method by a single chemist, reported
twenty-six results varying from 0.501 to 0.205 ^^<^ averaging
0.307 ounce per ton. The extreme variation was 0.296 ounce
per ton, or 96.4 per cent, of the average determination.
POTASH.
In the determination of potash the 1894 report of the Associa-
tion of Official Agricultural Chemists' gives six determinations
of potassium chloride by six chemists by one method, ranging
from 97.79 to 99.32 per cent, with an average of 98.56 per cent,
the extreme variation being 1.53 per cent. By another method
on the same sample seven determinations by seven chemists
range from 97.21 to 98.86 per cent., averaging 98.16 per cent.
Combining these results we have thirteen results by seven
chemists, by two methods, ranging from 97.21 to 99.32 per cent.
and averaging 98.35 per cent., the extreme variation being 2. 11
per cent.
This report contains also a table of results on soil analyses'
which I quote entire.
I page M.
« paffc 41.
8i8
ACCURACY OF CHEMICAL ANALYSIS.
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REVIEW
ON THE DEVELOPMENT OF SMOKELESS POWDER.'
By Charles K. Munroe.
To intelligently present a sketch of what has been done in the
development of smokeless powder, it is necessary to first
briefly review the history of black gunpowder. Although
the place and date of its origin and the name of its inventor
are yet open to dispute, it is generally accepted that
it was employed as a propellent in cannon at the battle of
Cr&y in 1346, and in small arms for some time prior to this
date, and that it then consisted of a mixture of niter, charcoal
and sulphur. Considering the existing state of chemistry, it is
fair to infer that the making of gunpowder, like the manufac-
ture of guns, was for long an empiric art, and that, notwith-
standing that Tartaglia, Galileo, Newton, puygens, and many
others speculated upon and discussed the effects which gun-
powder produced upon projectiles ; that granulating was em-
ployed in 1445 ; that Cellini had observed the necessity of
adapting the grains to the piece ; that sizing was practised in
France in 1525, and that Hawksbee had in 1702 measured the
volume of gas resulting from a known volume of gunpowder,
the science of gunnery had no existence until Robins devised the
ballistic pendulum by which he measured the velocity of pro-
jectiles and with which he obtained the experimental data upon
which his ** New Principles of Gijnnery,*' printed in 1742, was
founded. The science of exterior ballistic was materially
improved when Hutton, in 1778, extended Robins' principle to
the use of the gun as the pendulum also, for it became then pos-
sible to not only measure the velocity of the projectile, but the
energy involved in the reaction, and this method was employed
for larger an4 larger calibers until it reached its practical limit
in the ver>' elaborate and precise series of experiments made at
the arsenal in this city (Washington) from 1842 to 1847, by
Major Mordecai, who succeeded in swinging cannon weighing
about 7,700 pounds and throwing 32-pound balls ; but this
necessitated the use of a pendulum weighing over 9,300
pounds, the center of gravity of which was over fourteen feet
below the axis of suspension. The weight and length of the
pendulum increases so rapidly with the increase of the projectile
that to determine by this method the velocity of the projectile
from a 100- ton gun, would require towers like those from which
the Brooklyn bridge is suspended, between which to swing the
pendulum.
1 Presidential addrees delivered before the Washing^ton Section of the American
Chemical Society. Feb. 21. 1896.
820 REVIEW.
Opportunely as this limit was approached, Dr. Joseph Henry
announced, in 1843, his invention of a method for the determi-
nation of velocities by interposing screens, which were electri-
cally connected with chronographs, in the path of a projectile
and at definitely determined distances from the gun, and this
method, which while possessing the merit of great simplicity, is
at the same time very precise and capable of being used for
determining the velocities of projectiles from -guns of every cali-
bre, is now universally employed with chronographs, such as the
Bouleng6, Schultz-Deprez, and Mahieu, while the principle has
been extended by Captain Noble to the study of interior ballis-
tics, in his very ingenious chronoscope by which the velocity of
the projectile can be determined at frequent intervals, even when
it is moving through the bore of the gun.
The ability to measure the velocities which it produced led to
active investigations into the properties of gunpowder and
resulted in the experiments of Lavoisier, between 1777 and 1778
on the deflagration of powder, of Berthollet, on the best propor-
tions for mixing the ingredients, of Gay Lussac, on the refining
of niter, of Violette, on the production, composition and pro-
perties of charcoal, of Gay Lussac and Chevreul, of Bunsen and
Schischkoff, of Linck, and of K&royli, on the composition and
volume of the products of the combustion of this substance, and
of many other experimenters on the effects resulting from differ-
ences in the density, hardness, size of grain and other physical
characteristics of the explosive. But notwithstanding the great
advance made through the invention of methods by which to
measure the velocity of the projectile and the recoil of the
piece, the science of gunnery was still incomplete without an
accurate knowledge of what was going on within the chamber
and particularly what pressures were produced and how this
pressure was distributed within the gun before the projectile
left its seat and while it was traveling through the chase ; yet,
although direct experimental determinations of the pressure
exerted by fired gunpowder were made by Count Rumford in
1797 in a somewhat rude device, and numerous indirect estima-
tions were deduced from the observations of Robins on the vol-
ume of the gases produced by its combustion and from the more
precise and detailed researches of Bunsen and Schischkoff and the
other experimenters previously referred to, no practical means
were at command by which to piake direct measurements
of the pressure developed within the gun itself until Captain
Rodman, in 1857, invented the pressure gauge, described in his
** Reports of Experiments,'* published in Boston, in 1861. which
in common with several modifications of it, such as the Noble
RBVIBW. 821
crusher gauge and the Woodbridge spiral gauge, came into gen
eral use in all experimental firing and in the proving of guns
and powders.
In estimating the pressure developed by powder from the data
obtained in their chemical analyses of its products, Bunsen and
Schiachkoff proceeded on the assumption that Piobert's conclu-
sion from his experiments, viz. , * * that the rate of combustion of
powder is not affected to any sensible degree by h%at or pres-
sure/' was correct; but their conclusions having been ques-
tioned by many authorities, among them by Vignotti, in 1861,
and by Craig about the same time, who showed that the pro-
ducts of combustion differs with the pressure, and their physical
data by F. A. P. Barnard, who submitted them to a rein-
vestigation in 1863, and arrived at a widely different result ; and
they having also failed of verification by the pressure gauge, the
matter was again experimentally attacke4 by Noble and Abel,
who employed as a firing chamber a hermetically closed steel
cylinder sufficiently strong to resist rupture by the explosion of
a charge of powder which completely filled it (such as Dr.
Woodbridge had previously used at the Washington navy yard
in 1856), in which pressure gauges were enclosed, and they fired
the charge by the electric method invented by Dr. Robert Hare
in 1832. In addition the apparatus was so contrived that the
gaseous and solid products could be collected, measured and
analyzed at will.
With this they found that whjen powder is fired in a confined
space the products of combustion are about fifty-seven per cent,
by weight of ultimately solid matter, and forty-three of gases,
which at o^ C. and* 760 mm., o(^cupy about 280 times the volume
of the original powder. That the temperature of explosion is
about 2,200'' C, and the tension of the products, when the pow-
der entirely fills the space in which it is fired, is about 6,400
atmospheres, or forty-two tons per square inch.
When fired in the bore of the gun it was shown that the work
on the projectile is effected by the elastic force resident in the
permanent gases, but the reduction of temperature, due to the
expansion of the permanent gases, is in a great measure com-
pensated for by the heat stored up in the liquid residue. The
total theoretical work of gunpowder when expanded indefinitely
(as for instance in a gun of infinite length) was deduced from
the data which they accumulated as about 486 foot tons per
pound of powder.
They further ascertained that the fine grain powders furnish
decidedly smaller portions of gaseous products than large grain
or cannon powders ; that the variations in the ' composition of
822 REVIEW.
the products of explosion, in a closed vessel, furnished by one
and the same powder, under different conditions as regards pres-
sure, and by two powders of similar composition, under the same
conditions of pressure, are so considerable that no chemical
expression can be given for the metamorphosis of a gunpowder
of a normal composition, and that the proportions of the several
constituents of the solid residue are quite as much affected by
slight accidental conditions of explosion of one and the same
powder in different experiments as by decided differences in the
composition or in the size of the grain.
The subsequent researches of Berthelot and Vieille, and of
Sarrau and Vieille showed that gunpowder was not singular in
that its combustion products varied with the variations in the
conditions prevailing in the firing chamber, but that this same
rule held for gun cotton, picrates and other explosives, also, and
that consequently the chemical reaction taking place and the
physical phenomena attending them were changed with these
varying conditions, and more particularly with variations in the
densit}' of loading.
Before the invention of the instruments of precision above
alluded to, guns were constructed largely on principles deduced
from obser\'ations of exterior phenomena, and powder was manu-
factured largely by rule of thumb. With the ability to determine
quantitatively their behavior, each has been studied in a scientific
manner and improved by rational methods.
By their use the real importance of uniformity in chemical and
physical composition was demonstrated for the powder, and the
means by which to ** prove powder" before issue were supplied,
while rational blending, by which to minimize the irregularities
incident to the best commercial processes was made possible.
At the same time greater uniformity in granulation was secured ;
the best form of grain was developed for g^eat guns through the
pebble to the mammoth, disk, pellet, sphere, cylinder, hollow
cylinder, hexagon and cube to the hexagonal prism, with one
canal, which is now generally adopted, and which is a modified
form of the grain invented by Rodman ; the size of the grain
best adapted for a given gun was ascertained, and the size rose
trom one-sixth of an inch, as used in the 15-inch S. B., to
fhe hexagonal prism one inch in height by 1.36 inches in diame-
ter ; the density of the grain rose from 1.60 to 1.86 ; the effect
of prearranged variations of density in grain's, as proposed by
Doremus and carried out in the Fossano powder, was deter-
mined ; and the important part which moisture played in the
reactions going on in the chamber with the necessity for introduc-
ing it into the grain in definite quantities and retaining it there
REVIEW. 823
wicbin very narrow limits was discovered. In fact these methods
of inspection have become so precise and the powder specifica-
tions so severe that the manufacture of military gunpowder is
now a most difficult art, and the maker must not only watch
the barometer and thermometer and hygrometer to determine
his action at each step of his process, but according to one
authority, he must "vary his treatment with each passing
cloud/* and notwithstanding all precautions, it is no uncommon
thing for the best makers to have their product rejected at the
proving ground.
Besides these improvements in black gunpowder, which have
resulted from our ability to accurately gauge its performance,
these instruments have shown us that it is possible to avail our-
selves of the energy stored up in underburned charcoal or carbo-
hydrates if we but modify the brusqueness incident to mixtures
containing them by adopting the proper size, form, hardness
and density for the grain, and this has resulted in the cocoa or
brown prismatic powders which have come into very extented
use since 1880.
The valuable properties of the compressed powder were then
applied for use in small calibers and enabled Hebler to realize a
marked increase in efficiency for his rifles, and in these forms
the limit of efficiency of gunpowder appeared to be reached.
But while this was being accomplished, progress was being
rapidly made along other lines which we will briefly point out.
Among the other inventions in gunnery which preceded the
invention of smokeless powder, and made its use possible or
essential, we may mention the introduction of rifling, by which
greater accuracy of fire and a higher velocity and penetrating
efiFect is obtained, and which, while invented by Gaspard Zoll-
ner, of Vienna, in 1480, did not come into vogue until 1850, or
general use until much later. Breech loading, which was
known among the Chinese as early as 13 13, but which has prac-
tically been developed since 1863, our civil war having been
fought chiefly with muzzle loaders. Percussion caps, invented
by Joseph Egg, in 18 18, and adopted, with the nipple, in France
in 1838. Self obturating metallic ammunition, which depended
on the preceding invention, and which we owe apparently to Flo-
bert, who introduced it for use, with a quick powder, in his parlor
rifle in 1845, though it did not come into use for larger caliber
for some years later, and then only after the discovery of a metal
having the necessary ductility and strength from which to
strike the shells and the perfecting of machinery for their eco-
nomic and rapid production. Magazine rifles and machine
guns, the earlier practical forms of the latter being the weapon
824 RBVIBW.
exhibited by Dr. Gatling in 1867, and the French mitraiUettse,
and which have now developed into the automatic machine guns,
such as Maxim, Colt, Hotchkiss, and others possessing an
almost incredible rapidity of discharge. Rapid fire large caliber
guns, which, like the foregoing, depend for their development on
the prior invention of the breech mechanism, and the metallic
ammunition and which have reached calibers of six-inch diame-
ter and throw lOO-pound shot at the rate of six per minute, with
a velocity of over 2,000 feet per second. Breech-loading, built-
up steel rifles, which, while embodying the ideas of a gun of equal
strength, as announced by Professor Treadwell, in 1843, the
mechanical devices of Chambers patented in 1849, and the prin-
ciples of initial tension, as expounded in Rodman's publication
of the same year, have been developed, at least in this country,
only since the appointment of the Gun Foundry Board by Sec-
retary Chandler, and whose manufacture was then rendered pos-
sible only through the perfection which our machine tools had
attained and the improvements achieved in the metallurgy of
steel. Small caliber rifles, with steel or german-silver mantled
bullets, which are sighted for about two miles, and whose projec-
tile will pierce six men, standing one behind the other in close
order, at 1,000 yards. And finally to the invention of range-
finders or telemeters, through which by trigonometric or
mechanical methods, the position of the far distant targets now
in range of new weapons may be located with precision.
For it is evident that to use these precise and powerful weap-
ons and instruments, with the accuracy and rapidity they
are capable of, the atmosphere must remain clear, and the
piece must remain clean, while at the same time the highest
attainable velocity must be imparted to the projectile without
an undue strain being brought upon the gun. Yet we have
seen that Noble and Abel found that military gunpowder
gives off, on combustion, fifty-seven per cent, by weight of
ultimately solid matter which is either thrown into the
atmosphere to produce smoke or left as a residue to foul the
bore. How considerable this smoke producing capacity of gun-
powder is maybe estimated if we take a Gatling firing 1200
rounds of small arm ammunition per minute (and this by no
means expresses the highest attainable speed to-day) and
assume that all the solid matter is driven out the gun, when we
shall find that each minute six and six-tenth pounds of finely
divided solid matter will be projected into the atmosphere. Add
to this, in a general engagement, the smoke from the great g^ns,
which, as with the iio-ton gun, can project 528 pounds of this
solid product at each discharge, and that coming from the rapid
REVIEW. 825
fire, and magazine rifles, and it is obvious that unless a favora-
ble breeze is blowing or other favorable atmospheric conditions
prevail, the force or ship will soon be enveloped in an opaque
cloud of smoke and be at the mercy of an invisible foe. It is, I
repeat, conditions such as these which have rendered smoke-
less powder, of good ballistic qualities, a great desideration,
if not an absolute necessity.
While the development of the projectile, the musket, the
machine gun« and ordnance ; the perfection in the composi-
tions, forms, and manufacture of gunpowder ; and the inven-
tion of the instruments and devices for gauging and controlling
their performance was going on, chemists were engaged in add-
ing their contributions to the fund of human knowledge in the
field of explosives. In 1788 Hausmann discovered ** picric
acid,** in 1800 Howard discovered mercuric fulminate, in 1845
Schonbein discovered gun cotton, in 1845 Sobrero discovered
nitroglycerin, in 1875 Nobel invented explosive gelatine, and
in the meantime, or subsequently, numerous allied nitro-substi-
tution compounds, nitric ethers and diazo-bodies, less generally
known than those above enumerated, were produced, and iden-
tified, and shown to possess explosive properties.
The earlier experimental tests of these bodies proved that not
only were some of them more powerful or more violent explo-
sives than gunpowder, but that no smoke accompanied their
explosion, since the products of their explosive decomposition
were gases or vapors at the prevailing temperatures and efforts
were put forth soon after their discoverj'^ to adapt them for use
as propellents. These, together with various organic solids,
and liquids to ser\'e as solvents and hardening agents and am-
monium and barium nitrates to serve as oxidizing aj^^ents were
know^n and at hand.
The earliest experiment with smokeless powder was probably
that made by Howard, in 1800, when he tested the properties of
his newly discovered mercuric fulminate and found that though
this violent agent produced little smoke, imparted a low velocity
to the projectile and but a slight recoil to th« piece, it burst the
chamber, and demonstrated its unfitness to compete wnth gunpow*-
der as a ballistic agent. Nevertheless this substance has since
found a limited use, when mixed with solid diluents which act
as restrainers, in ammunition for parlor rifles, and it is notice-
able that when firing this ammunition there is little smoke and
a scarcely audible report attending the discharge.
In 1806 Grindel carried out a somewhat extended series of
experiments with a view to substituting ammonium nitrate for
potassium nitrate as the oxidizing agent in gunpowder mix-
826 RBVIBW.
tures but the deliquescent character of the ammonium salt ren-
dered the powder made with it useless under the then existing
conditions, and has proven a formidable obstacle to its use in
many of the attempts subsequently made. The fact, however,
that the products of its combustion, at the prevailing tempera-
ture, are wholly gaseous rendered it a tempting material to
inventors of smokeless powders and it has been more recently
used, among others, by F. Gaens, who, in 1885, patented, in
Germany, his so-called ** Amide Powder,'* produced by mixing
eighty parts of ammonium nitrate and loi parts of potassium
nitrate, with forty parts of charcoal. He claimed that this mix-
ture was not hygroscopic and was practically smokeless, and he
held that by the reaction consequent on the ignition, a potass-
amine was formed which was both volatile and explosive.
Whatever the nature of the reaction, it appears from the reports
that an ammonium nitrate powder was produced about this time
in Germany and later in England, under the name of Chilworth
Special, which possessed remarkable ballistic properties and
3'ielded comparatively little smoke, which speedily dispersed,
and which bore exposure very well until the humidit)' of the
atmosphere approached saturation.
It is possible that the ammonium nitrate used may have been
produced by Benker's process, in which the salt is formed by
metathesis from solutions of sodium nitrate and ammonium sul-
phate exposed to a temperature of — 15*", or below, for it is
claimed that the ammonium nitrate which crystallizes out under
these circumstances is of extraordinar>' purity and not at all
hygroscopic.
It would appear that though these ammonium nitrate powders
are slightly hygroscopic, they may retain their good qualities
for long times in the hermetically sealed cases used in fixed am-
munition up to the six-inch rapid fire gun, but that we know that
the small amount of water necessarily present produces marked
changes during long periods of storage »yith var>'ing tempera-
tures and that the ammoniacal salts attack the copper of the
shells. Besides, too, we must remember that ammonium nitrate
in common with other ammonium salts gives off ammonia, when
heated or exposed to the air, and becomes acid so that we are
debarred from using it in the presence of any bodies affected b)'
the acid.
The next step toward the development of our modern smoke-
less powder was taken when, soon after the discovery of guncot-
ton, in 1845, attempts were made to use this material as a pro-
pellent. These experiments were made in Gennany, France,
and England, and a very extended series were carried on by
REVIEW. 827
Major Mordecai, at the Washington Arsenal, but the material,
owing to its form and the imperfection in its manufacture,
proved too brisant and too irregular in its action, and so unsta-
ble on keeping as to undergo decomposition in storage. The
material having been proved to possess many valuable qualities
was not wholly abandoned, but it continued to be the subject of
study by many chemists until in 1862, it seeming that Baron von
Lenck had so perfected the methods for its manufacture and
purification as to ensure stability and uniformity of composition.
Austria adopted it as a' propellent and supplied thirty howitzer
batteries with g^ncotton cartridges.
This is the first instance in which a really smokeless powder
was employed on any but an experimental scale and this pow-
der foreshadowed in its composition and many of its character-
istics, the best modem powders of the smokeless class. The
guncotton as then made retained the fibrous condition of the
original cotton and in the Austrian cartridges it was spun into
thread and woven into circular webs like lamp wicks, or
braided, or wound on wooden or paper bobbins, and so arranged
in the piece as to secure the desired air spacing as well as to
insure ignition from the front. As thus used, it was claimed to
be uninjured by dampness ; to require a charge of but one-
fourth to one-third of that of the powder previously employed ;
to be capable of being regulated so as to produce widely var^'-
ing effects at will ; to leave no residue to foul the piece ; and to
produce no smoke, while the gases evolved were less injurious
to both the piece and men serving it than those of gunpowder.
At the same time it produced less heating effect on the gun.
Unfortunately, about this time, the factory at Hirtenberg,
where the guncotton was made, blew up for some undiscovered
cause, and accidents having occurred with the guns, the use of
guncotton was abandoned by the Austrians.
Its fate seemed now to be sealed, but such was not the case,
for the scene of action then passed to England, where Abel not
long after succeeded in effecting a more complete purification of
the body by pulping it prior to the final washing processes, thus
cutting the tubular fiber into short lengths and rendering it pos-
sible to remove the last traces of acid retained within the tubes
by capillarity and which had been the occasion of its decomposi-
tion with time. Having thus obtained his pulped, purified gun-
cotton he compressed it into such forms as was desired, and in
1867 and 1868 he obtained with it some very promising results
when used with field guns. But although comparatively small
charges often gave high velocities of projection without any
indications of injury to the gun, the uniform fulfillment of the
828 RBVIEW.
conditions essential to safety proved then to be beyond control,
and the military authorities not being, at that time, alive to the
advantages that might accrue from the employment of a smoke-
less explosive in artillery, experiments were discontinued not
to be resumed for nearly twenty years, and use was found for
compressed guncotton in military and naval mining and espe-
cially in filling torpedoes, where it has been found the most
efficient and satisfactory explosive thus far applied to this pur-
pose.
But sportsmen, to meet whose wants and wishes many note-
worthy improvements have been made in the arts, did appreciate
the value, to marksmen, of smokelessness combined with high
velocities and absence of fouling, and the progress made during
the succeeding twenty years in the adaptation of organic nitrates
to use as propellents was under their patronage and in response
to their demands, and naturally, the first object sought was to
so restrain the violence of the explosive that rupturing explo-
sions, such as had occurred, could not be induced under the
conditions in which the powder was to be used.
One of the first to realize a considerable degree of success was
Captain Schultze, of the German artillery, who made a powder
from well purified and partly nitrated wood. For this pur-
pose he sawed the wood into sheets about one-sixteenth of an
inch in thickness, which were passed through a machine that
punched out discs or grains of uniform size. The grains were
then deprived of their resinous matter by being boiled in sodium
carbonate, washed, steamed, and then bleached with chloride of
lime, when finally, after drying, the cellulose was nitrated in an
acid mixture, such as is used for making guncotton. The
nitrated wood was then steeped in a solution of potassium and
barium nitrates, and when dry the powder was finished. By
this means a nitrocellulose was produced which was diluted
with unconverted cellulose and metallic nitrates, which were so
intimately mingled that a fairly even rate of combusition was
obtained though abnormal results were not wholly avoided.
The advantage of using nitrates and combustible organic sub-
stances as diluents was soon recognized ; and, as a consequence,
many powders of this nature were devised, some thirty of them
having been produced and many of these put on the market, in
which we find that potassium, sodium and barium nitrates, and
potassium chlorate were used as oxidizing agents and sugar,
cellulose, charcoal, sulphur, starch, dextrin, gums, resins, and
paraffine as combustible diluents and cementing agents. All,
however, approximated black gunpowder, as regards physical
REVIEW. 829
Structure and none attained to complete success as regards uni-
formity of fire and reliability of pressure.
In 1882 Messrs. Reid and Johnson patented the process for
making £. C. powder, in which the pulped nitrocellulose and
nitrates was agglomerated into grains by revolving the mois-
tened mass in barrels, drying the grains, moistening with ether to
harden them, and then coloring them with aurine.
About 1885 Messrs. Johnson and Borland produced the J. B.
powder, in which a new idea, as regards powder manufacture,
was introduced, though it had been used elsewhere for many
years. The inventors mixed nitro cotton with barium nitrate
and with or without charcoal or torrefied starch and granulated
the mixture in a revolving drum, while the water was admitted
in a fine spray. When granulated the grains were dried and
then moistened with a solution of camphor in petroleum spirit,
and after a time heated in a water jacketed vessel to evaporate
the benzine, and the bulk of the camphor. By this treatment
the grains were hardened and rendered more slowly inflamable.
As this method of treatment resembles in some particulars that
followed in the production of celluloid, though it differs in
details, and as several of the smokeless powders are made by
methods which are adapted from this art, you will pardon me if
I briefly describe it.
Celluloid is made from that form of cellulose nitrate known as
nitro-cotton or soluble guncotton, and which is produced by
immersing unsized and uncalendered tissue paper for a short
time in a comparatively weak acid, both being kept at a mode-
rately high temperature. This nitro-cotton is pulped in a rag
engine, dried and moistened with camphor spirits. If a con-
siderable portion of camphor spirits be added, and the mixture
be allowed to stand for awhile, the mass becomes converted into
a soft translucent amber gum ; with more of the spirit the nitro-
cotton will be completely dissolved ; but as carried out, the pro-
portion of spirit added is insufficient to produce a very apparent
change.
The mixture is now taken to incorporating rolls or ' ^grinders, ' '
(as they are called in the caoutchouc industry), where it is inti-
mately mixed and well pressed ; when the particles cohere and
the whole becomes converted into a plastic, translucent homo-
geneous mass which behaves like India rubber and resembles it
superficially in every particular but color. After incorporation,
by cutting the length of the roll, the mass may be stripped off
in one continuous, coherent sheet, which on exposure to the
atmosphere, through which the spirit and camphor are volatil-
ized, hardens to a hornlike mass.
830 REVIEW. •
■
In the manufacture of a smokeless powder by this means, it is
customary to mix with the nitro-cotton or mixed cellulose
nitrates, a small proportion of other nitrates in order to effect
complete combustion and a restrainer to assist in bringing the
rate of combustion within normal limits; and this mixing is
easily effected on the incorporating rolls. Barium nitrate is the
salt whibh is perhaps most largely used, and it is preferred
because it is very permanent, contains a fair proportion of
available oxygen which it j'ields with comparative readiness,
and possibly because the carbonate which is formed by the com-
bustion has so high a specific gravity that it settles with consid-
erable speed.
Other solvents besides camphor spirits are employed when the
higher cellulose nitrates are used in the manufacture of the
powder. Thus Engel takes a cellulose nitrate prepared from
wood, while Glaser employs that prepared from paper or card-
board and treats it, when dry, with ethyl acetate or acetone, the
action of the solvent being aided by mechanical kneading in a
suitable vessel until a viscid paste or gelatinous mass is
obtained with which the barium nitrate and a h5-drocarbon,
such sis naphthalene, is incorporated. The mass is then
formed into any desired shape and the solvent is allowed to
evaporate or is distilled off by any suitable means when the pow-
der is left as a dense horny material, with a glassy fracture,
which can be readily granulated.
The first military smokeless powder of the modem class was
made in France in 1886 by Vieille, and is said to have been
compounded of cellulose nitrates mixed with picric acid, but it
was soon abandoned m favor of the Poudre B., which consisted
of cellulose nitrates alone, or Poudre B. N., which consisted of
these nitrates mixed with barium nitrate and potassium nitrate
as oxidants, and sodium carbonate as a neutralizer. Both these
mixtures were condensed and hardened to a celluloid-like mass
by means of a solvent like ether-alcohol, ethyl acetate or ace-
tone.
Excellent ballistic results have been reported from France as
being obtained with these powders, and they have been adopted
by the French government. At the same time similar mixed
cellulose nitrate powders have been produced and used in Ger-
many, Austro-Hungary and Switzerland ; the Weteren, Trois-
dorf and Von Forster powders being of this class. Notwith-
standing that these have so long been known, our government
has, with regal graciousness, recently granted a patent to two
of its officers for a powder of this composition.
These are made by mixing the ingredients together with the
REVIEW. S3 1
solvent in a kneading machine of the Werner and Pfleiderer
class, in batches of one to two hundred weight, until it is con-
verted into a dough, when it is incorporated and the solvent
partly driven off by putting on the grinding rolls, by which
means it is also formed into continuous sheets, whose thickness
is fixed by the set of the rolls. It is preferable where thick
masses are desired to first roll into thin sheets so as to evaporate
the solvent as completely as possible from the gelatinized mass,
and then by piling the thin sheets on one another, weld them
together b}' running them through the rolls. They are then
granulated by passing them under a set of revolving circular
knives which cut them first into strips and then . into rectangles
of the desired size and shape. These powders are dense, hard
and hornlike in appearance.
Following Vieille by about two years,* Nobel invented ballis-
tite, which practicall}' is a modified explosive gelatine, differing
from it only in that while the gelatine consists of ninety-three
per cent, of nitroglycerin, and seven per cent, of nitro-cotton,
ballastite contains about forty per cent, of nitro-cotton and one
to two per cent, of anilin or diphenylamin, which is added to
the nitroglycerol nitro-cotton mixture as a neutralizing agent
to ensure stability. At first the solution of the gun-cotton and
gelatinization of the mixture was effected by means of camphor
and later by means of benzene, but it is now produced under
the English patent of Lundholm and Sayer of 1889. They dis-
covered that while dry nitro-cotton is but slightly soluble in
nitroglycerin even at moderately high temperatures, when mixed
^'ith warm water and stirred up by compressed air, gelatiniza-
tion sets in and solution may be completed by pressing out the
water and working in the grinder. Flexible, transparent rub-
ber-like sheets are formed, which may be cut into flakes in cut-
ting machines of the usual type, or in pastry cutters, or may be
squirted through spaghetti machines, as is done in It'ily, where
these cords or threads of ballistite are known as ** Filite."
It is curious to note how many of the machines devised for
bread making, pastry cutting and macaroni forming, have been
employed in the manufacture of smokeless powder.
In 1889 Sir Frederick Abel and Professor James Dewar
secured their patents on cordite, which like ballistite, contains
nitroglycerin and cellulose nitrate, but whereas ballistite is
made from nitro-cotton alone, cordite is made from ** gun-cot-
ton *' containing from ten to twelve per cent, of nitro-cotton, to
TThicli is added a little tannin, dextrin or vaseline to ser\''e as a
restrainer. The gelatinization is effected by means of acetone,
1 Engliflh PMent. Januar>' 31. iv>S.
832 REVIEW.
the mixture being kneaded to a dough in a water-jacketed
kneading machine,compacted in a mould in a preliminary press,
and the mould transferred to a spaghetti machine, where the
explosive is squirted into cords. As these cords issue, they are
reeled on bobbins, which are placed in the drying house to drive
off the acetone. Whe^ this is completed the product of ten
pressings is wound from ten one-strand reels on to one ten-strand
reel and then the cordite on six ten-strand reels is wound on one
drum, making a cord of sixty strands, which in short lengths
forms the thirty and one-half grains charge for the magazine
rifle. For the higher calibers the cords are cut in lengths as
they issue from the press, dried and made up into bundles.
Cordite is an elastic rubber-like mass with a light to dark brown
color.
Analogous to these in composition, in that they consist of
nitroglycerin with cellulose nitrates, are many powders, such
as amberite, Maxim's powder, Leonard's powder, P. P. G.,
Peyton's powder, German smokeless powder and others, and
they differ in but slight particulars. Thus Curtis and Andr6
blend different cellulose nitrates before incorporation so as to
secure a definite nitrogen content, and then cement by ether-
alcohol ; Maxim restrains his powder with castor oil ; Leonard
restrains his with l3xopodium, and adds urea crystals as a neu-
tralizer ; Walke claims to make P. P. G. from a nitro-cellulose,
which is not gun-cotton, and so on.
The employment of nitro substitution compounds as bases for
smokeless powders has been comparatively limited. Over twenty
years ago Designolle invented powders made by mixing potas-
sium picrate, potassium nitrate and charcoal in various propor-
tions. Borlinetto produced them from picric acid, sodium
nitrate and potassium dichromate. Abel and Brug^re from
ammonium picrate, potassium nitrate and charcoal, and more
recently Nobel from ammonium picrate, barium nitrate and
charcoal. Within a few years past a powder has been manu-
factured in this country and put upon the market as a sporting
powder, which was composed of ammonium picrate, potassium
picrate, and ammonium dichromate, but I understand it has
given such irregular and abnormal pressures that its manufac-
ture has been discontinued.
While these powders may have been smok€-weak as compared
with gunpowder, it is difficult to understand how, in the pres-
ence of such amounts of metallic radicles, they could have been
smokeless. A powder, however, which is made by Hermann
Gttttler, by dissolving nitro-lignin in molten dinitro-toluene and
which he calls Plastomentite, may well possess this property^
REVIEW. 833
and it is reported to have given good ballistic results at the
Bucharest tests of 1893.
The powder called Gelbite, and invented by Dr. Stephen H.
£mmens» was also smokeless. This was made by an ingenious
process in which paper in strips was nitrated to a moderate degree
of nitration, then fumed with ammonia to neutralize the acid,
and then treated with picric acid to neutralize the ammonia and
form ammonium picrate. These strips were then rolled up into
rolls as charges, but as might have been foreseen from a study
of the behavior of gunpowder in guns and the study of the his-
tory of gun-cotton, this powder was too brusque in action and
has been abandoned.
I began my own experiments with smokeless powder manu-
facture in 1889. At this time the remarkable results published
from France, and the announcement that that country had
adopted a smokeless powder, had produced their desired strate-
gic effect. All her rivals were seeking to be equally well
equipped and were hastening to adopt a powder even before its
qualities were thoroughly proven. The newspapers contained
remarkable accounts of their performances and alleged descrip-
tions of their methods of production, which while interesting as
news and conveying valuable suggestions, could not be relied
upon as to accuracy in details.
At the outset, being familiar with the impossibility of secur-
ing absolute uniformity and constancy of composition in phy-
sical mixtures like gunpowder, and realizing how important this
feature was with our precise modern weapons, and when employ-
ing an explosive possessing great energy, I determined to
attempt to produce a powder which should consist of a single
substance in a state of chemical purity. This was a thing
which I had not known of having been done, nor have I yet learned
that any one else has attempted it. Among the bodies at com-
mand, the nitric ethers seemed most available, and of these cel-
lulose nitrate seemed for many reasons the most promising.
There are. as you are aware, several of these nitrates (authori-
ties differ as to the number) which differ in their action towards
solvents, though all except the most highly nitrated are soluble
in methyl alcohol. In the commercial production of cellulose
nitrate certainly, and so far as I have observed under all cir-
cumstances, when nitrating cellulose the product is a mixture
of different cellulose nitrates. Even in the perfected Abel pro-
cess for making military gun-cotton, as carried out at the Royal
Gun Powder Factory, at Waltham Abbey, according to Gutt-
manu\ the product contains as a rule, from ten to twelve per cent.
of nitro-cotton.
1 Manafacture of Bzplosires. a, 259, 1&95.
834 REVIEW.
Consequently I began by purifying my dried pulped military-
gun-cotton, which was done by extracting it with hot methyl
alcohol in a continuous extractor, and when this was completed
the insoluble cellulose nitrate was again exposed in the drying
room. The highly nitrated cellulose was then mixed with a.
quantity of mono-nitro-benzene, which scarcely affected its ap-
pearance and did not alter its powdered form. The powder was
then incorporated upon a grinder by which it was colloidized
and converted into a dark translucent mass resembling India,
rubber. The sheet was now stripped off and cut up into flat
grains or strips, or it was pressed through a spaghetti machine
and formed into cords, either solid or perforated, of the desired
dimensions, which were cut into grains. Then the granu-
lated explosive was immersed in water, boiling under the
atmospheric pressure, by which the nitro-benzene was carried
off and the cellulose nitrate was indurated so that the mass
became light yellow to gra\', and as dense and hard as ivory,
and it was by this physical change in state, which could be
varied within limits by the press that I modified the material
from a brisant rupturing explosive to a slow burning propellent.
This is the powder which I styled indurite, and which has
been popularly known as the Naval Smokeless Powder.
I was satisfied that I was justified in starting on this new-
practice in powder-making when I found, on examination of the
samples of foreign military powders* which later began to reach
me officially, that they were heterogeneous mixtures as the old
gunpowder is and that they contained matter which was volatile
at ordinary temperatures, and when I learned that the nitro-
glycerin powders cracked from freezing.
I was still more satisfied when I learned the results of the
proving tests which were all made except the chemical stability
and breaking down tests by naval officers detailed for this pur-
pose at the Proving Ground and elsewhere, and who had no pre-
judice in its favor. All of the numerous publications which
have appeared about it have issued from headquarters, and I
present the matter myself here for the first time.
I have appended the data from these trials to this address
where, on inspection it will be seen, that after development, the
powder in use, in successive rounds, gave remarkably regular
pressures and uniform velocities. I was informed by the
Chief of the Bureau before the firing trials, recorded in the
tables began, that if I could produce a powder giving 2,000
feet initial velocity and but fifteen tons pressure, it would be
a complete success. Inspection of the tables show that this was
more than realized and that in two successive rounds in the
1 Table I.
REVIEW. 835
six-inch rapid fire gun, using twenty-six pounds of my pow-
der and a 100 pound projectile, the pressures were 13.96 and
13-93 tons, and the velocities 2,469 and 2,456 feet per second
respectively, while according to the Report of the Secretary
of the Navy, 1892, page 26, ** the powder manufactured for use
in the six-inch rapid fire guns was stored at Indian Head
proving ground, through a period of six months, covering a
hot summer, and at the end of the time showed no change
in a firing test.*'
On page 25 Secretary Tracy says, * ' It became apparent to
the department early in this administration that unless it was
content to fall behind the standard of military and naval progress
abroad in respect to powder, it must take some steps to develop
and to provide for the manufacture in this country of the new
smokeless powder, from which extraordinary results had been
obtained in Europe. With this object negotiations were at first
attempted looking to the acquisition of the secret of its composi-
tion and manufacture. Finding itself unable to accomplish this,
the Department turned its attention to the development of a
similar product from independent investigation. The history of
these investigations and of the successful work performed in
this direction at the torpedo station has been recited in previous
reports. It is a gratifying fact to be able to show that what we
could not obtain through the assistance of others, we succeeded
in accomplishing ourselves, and that the results are considera-
bly in advance of those hitherto attained in foreign countries."
From this survey we see that all of the smokeless powders
that have met with acceptance and proved of value as ballistic
agents with the exception of Indurite are mixtures of one or
more of the cellulose nitrates, or mixtures of these bodies, with
nitroglycerin or some other oxidizing agent, like barium
nitrate, and a restrainer or with a nitro substitution compound
and that all have been condensed or hardened into a rubber-like
or celluloid-like form, by which, even under the high pressures
which obtain in the gun, they are expected to undergo combus-
tion only and that at a moderate and regular rate.
In thus condensing the material, and in determining the
best form of grain, it wull be observed that we have been
guided by the experience gained in the compression of
g^unpowder, and we have been able to effect this as we have
by the experience gained in the development of celluloid, and
we have been able to manipulate our product and shape it into
grains only by adopting the methods and machines developed in
the manufacture of food, while we have been able to test our
product and check our results and thus ensure a more rapid and
836 RBVISW.
certain advance by the constant use of the pressure gauge and
velocimeter. In my opinion, if these resources had not been at
command and available the smokeless powder Industry wotild
not yet exist.
From what has been said it may properly be inferred that we
seek in these new powders all the virtues of the old gunpowder
with the addition that the new powder shall be smokeless, impart
higher velocities while producing no greater pressures and that
less of it shall be required to do the work. These requirements
may be summed up as follows :
The conditions that a smokeless powder suitable for a propel-
lent should fulfill are :
1. That it shall be physically and chemically uniform in com-
position.
2 . That it shall be stable and permanent under the varying con-
ditions of temperature and humidity incident to service storage
and use for all time.
3. That it shall be sufficiently rigid to resist deformation in
transportation and handling.
4. That it shall produce a higher or as high a velocity with
as low a pressure as the service charge of black powder for a
given piece.
5. That it shall be incapable of undergoing a detonating
explosion.
6. That the products of its combustion shall be nearly if not
quite gaseous so that there shall be no residue from it and little
or no smoke.
7. That it shall produce no noxious or irrespirable gases or
vapors.
8. That it shall not unduly erode the piece by developing an
excessive temperature.
9. That it shall be as safe as gunpowder in handling and
loading.
10. That it shall be no more than ordinarily dangerous to
manufacture.
Most of these requirements have been satisfied in several of the
powders, but time alone can determine the question of absolute
stability and especially as the comparison is instituted with gun-
powder which has oeen under observation for over 500 years.
We can and do apply tests whose results give us some confi-
dence as I did when I exposed Indurite wrapped in felt in an
iron vessel to a temperature of 208° F. for six hours without its
undergoing change, and again at a temperature of 212° F. for
twenty hours before any change was observed, and again to 5**
F. without its being affected.
REVIEW. 837
In fact from the outset I have advised the application of
most rigid tests and drew up the following scheme for the Navy
Department in July, 1891, by which to test Indurite.
** The most important requisite of powder, after passing the
proof test, is that it shall retain its characteristics under all the
conditions of storage or transportation which may obtain in the
service or that, if any change does take place, it shall not cause
the powder to develop under the ** proof*' conditions any greater
pressure than it did at the time of proving, and that such falling
off in velocity as may result from this change in the powder
shall not be relatively greater than that which obtains for ser-
vice black powder, and shall be uniform for the same conditions
of exposure.
"In providing for this test I would first prove a ten pound
lot to determine the maximum weight that will come within the
limits fixed for pressure and velocity, and then I would load 1000
Winchester 30.1 cal. and 1000 Mannlicher shell with a charge
some grains (say five) less than the maximum, so as to be
doubly safe in case the pressure should become increased through
the treatment to which the powder is subjected.
**The loading should be done with extreme care by skilled
workmen in an especially clean and uniformly heated and dried
room. The charges should be weighed on chemical balances
and with all the precautions surrounding an analytical opera-
tion. The balls should be weighed and gauged, and the shell
should be gauged so as to secure as nearly absolute uniformity
as possible, while the caps and priming (if used) and wads
should be identical for each shell of each 1000 lot.
**These being prepared, I would pack these ball cartridges pre-
ciselj' as if ready for issue to the service, and then I would store
385 Winchester's and 385 Mannlicher's in the regular magazine
at the Naval Torpedo Station, and the same number of the same
kind in the regular magazine at the Naval Ordnance Proving
Ground. I would then draw from the magazine at the Torpedo
Station tri'enty-five Winchester's and 25 Maunlicher's and fire
them, using the muskets and measuring instruments which are
to be used throughout the trials, and I would repeat this trial
every month for three years, firing ten rounds of each form of
ammunition and using the same muskets and instruments
throughout. At the same time I would have an identical set of
tests made at the Proving Ground, the same precautions being
taken there regarding the instruments and tools. Throughout
the tests a close watch should be kept on the magazines by
means of maximum and minimum thermometers so that if abnor-
mal results are obtained in firing it may be known whether or
838 REVIEW.
not any abnormal conditions have obtained in tbe magazine.
This series of tests will consume 1540 rounds. It would, in my
judgment, be of much value to store with these cartridges and
fire with them an equal number of charges of standard service
black powder, to be used as a standard for reference by which
any error in the observations, or defects in the instruments may
be detected.
'*I would take eighty rounds of the Winchester*s and eighty of
the Mannlicher's and place them in an oven heated to 140^ F.
or thereabouts. At the end of one month twenty of each are to
be drawn out and this to be repeated each month for four
months. One half of each form should be proved at the Torpedo
Station and the other half at the Proving Ground.
**I would take eighty rounds of the Winchester's and eighty of
the Mannlicher's and subject them for two weeks to the freez-
ing temperature, then for two weeks to a temperature of about
140"^ F., and then draw twenty of each, and this should be
continued until the last forty drawn out have been exposed for
eight weeks to freezing and eight weeks to the high tempera-
ture. The firing trials with these should be made as with pre-
ceding ones.
"The remaining shell should be stored in the regular magazine
to be used in any test case which may arise or in any manner
suggested by the results obtained in the tests described above.
"In the meantime tests could be made with the hand cutS. P.
for the capacity of the powder to resist crumbling and dusting
during transportation and the tendency of the fixed ammunition
to explode en masse by the impact of projectiles, or by the
explosion of a single cartridge in the midst of a box filled with
them. The first can be effected by taking a pound or a kilo-
gram of carefully sifted powder, placing in a copper vessel which
it only partly fills, and attaching it to a shaft so that it will be
continually and violently shaken, and allowing this to go on
every working day for a week. The powder can then be sifted,
using the same mesh as before, the weight of the dust found and
the percentage of dusting for the given circumstances deter-
mined.
"In the trials for tendency to explode ^;«wawtf fifty or forty -five
caliber ammunition can be used and the weights of charges need
not be very precise, but the ammunition should be packed in,
as nearly as possible, the same way as would obtain in service
practice."
We have seen that the development of smokeless powder has
been rendered necessary by the improvement in the gun. It
now appears that in consequence of the possession of the powder
REVIEW. 839
we must further improve the gun for we cannot in our present
guns utilize all the energy now available. Experiments look-
ing to this have been going on in France, where in a Canet ten
cm. gun of eighty calibers, withachargeof 12. 35poundsof powder
and a projectile weighing 28.66 pounds there was obtained the
extraordinary muzzle velocity of 3366 feet per second, while the
maximum pressure was 18.91 tons per square inch. Longridge,
an English authority, deprecates the lengthening of the gun as
it becomes too unwieldy and he advocates utilizing the energy
of the gun by strengthening it so it will endure greater pressures
and then using larger charges. He points out that if this Canet
gun were reduced to forty-five calibers, and strengthened, we
could obtain from it the same enormous muzzle velocity by
increasing the charge to thirteen and a half pounds, though the
pressure would rise to twenty-five tons per square inch.
What the result will be where authorities of standing
disagree is impossible to foresee, but the fact is demonstrated
that the powder is now more highly developed than the gun,
and that while seeking for smokelessness, we have secured a
propellent which is capable of producing much higher velocities
than gunpowder, with all the additional advantages of flat tra-
jectory, increased danger area, greater accuracy, and greater
range which follow as consequences.
•J
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ACIDITY OF niLK INCREA5E0 BY BORACIC ACID.
By B. H. PARRIIfOTON.
Receired July n, 1S96.
WHILE making some investigations with milk preserva-
tives, the writer noticed that sweet milk in which a
small quantity of boracic acid (preservaline) was dissolved «
required what appeared to be an abnormally large quantity of
one-tenth normal alkali to neutralize it and much more than
water in which the same amount of ** preservaline *' was dis-
solved. One-half gram of preservaline was dissolved in 500 cc.
water, and twenty cc. of this solution required one cc. of one-
tenth normal alkali to produce the pink color, when phenol-
phthalein was used as an indicator in titrating. Before adding
preservaline the water had a neutral reaction.
One-half gram preservaline was dissolved in 500 cc. of sweet
milk, and twenty cc. of it required eight cc. of one-tenth normal
alkali to give the pink color, although before adding the preserv-
aline twenty cc. of this same milk gave the pink color with onl}^
four cc. of one-tenth normal alkali.
The same amount of preservaline increased the acidity of a
given quantity of milk four times as much as it did the acidity
of the water.
The writer is unable to explain this reaction, but it gives a
simple means of detecting preservaline or boracic acid in milk,
as normal milk will smell or taste sour when it contains as much
natural acidity as is represented by eight cc. of one-tenth normal
alkali to twenty cc. milk. This represents 0.36 per cent, lactic
acid, and it can be safely stated that milk which contains over
three-tenths per cent, lactic acid and neither tastes or smells
sour, has been adulterated with some preservative, probably
boracic acid.
Dairy School,
Ukivbrsity op WiacoifsiN.
848 BOOKS RECEIVED.
CORRESPONDENCE.
United States Department of Agriculture,
Division op Chemistry,
Washington, D. C, July 23, 1896.
Editor Journal of the American Chemical Society,' Easion^ Pa,:
Dear Sir : — A majority of the Executive Committee has
decided to call the annual meeting of the Association of Official
Agricultural Chemists for Nov. 6, 7 and 9, 1896. These
dates immediately precede the meetings of the Association of
Agricultural Colleges and Experiment Stations, which will con-
vene in Washington, Nov. 10. The session will be held, as
heretofore, in the lecture hall of the National Museum, at
Washington, D, C.
The Ebbitt House offers to the Association entertainment at
the rate of 93.00 per day and the free use of its parlors for com-
mittee meetings, if desired. The Ebbitt House is on the cor-
ner of ** F " and 14th Sts., and can be reached from all stations
by the **F" St. or Avenue cars.
Respectfully,
H. W. Wiley.
Secretary A. O. A. C.
BOOKS RECEIVED.
Bulletin No. 42. Second Series. Horticulture. Louisiana State Ex-
periment Station, Baton Rouge, La. 1896. 44 pp.
Bulletin No. 123. Examination of Pood Products sold in Connecticut.
Connecticut Agricultural Experiment Station, New Haven, Conn. Jul^-,
1896. 79 pp.
Transactions of the American Institute of Mining Engineers. Vol.
XXV. February to October, 1895, inclusive. New York City : Published
by the Institute. 1896. xvii, 1068 pp.
Part III. Geology and Agriculture. A preliminary report upon the
Florida parishes of East Louisiana and the Blufif. Prairie and Hill Lands
of Southwest Louisiana. By VV. W. Clendeuin, A.M., M.S., Geologist.
Louisiana Experiment Station, Baton Rouge, La. 96 pp.
ERRATA.
On page 667, August number, 12th line from bottom, in equation, for
o.^b read o.^y.
On page 668, 2nd line from top, for Dividing read Multiplying,
Vol. XVIII. [October, 1896.] No. 10.
THE JOURNAL
OF THE
AMERICAN CHEMICAL SOCIETY.
SOriE EXTENSIONS OF THE PLASTER OF PARI5 nETHOD
IN BLOWPIPE ANALYSIS.
By W. w. Andrews.
Received August 7, i8s)6.
IN the years 1883 and 1884 two papers were published by Dr.
Eugene Haanel, of Victoria College, Cobourg, Ontario, now
of Syracuse University, in the Proceedings of the Royal Society
of Canada, in which he described the brilliant results he was
able to obtain in the production of the Bunsen iodide films on
the blowpipe support then proposed for the first time ; namely,
thin tablets of plaster 01 Paris made by casting sheets three-six-
teenths of an inch thick on panes of glass and scratching them,
before hardening, with ruled lines, so that when set they would
readily break into oblongs measuring two and one-half by one
and one-quarter inches. The pure white and highly polished
surface of these tablets and its great power of condensing heated
gases and exhibiting the true colors, their cheapness, thermal
and hygroscopic properties of the tablets, the ease with which
they may be prepared and carried, and the excellence of the
results when the sublimed iodides, bromides, oxides and sul-
phides are deposited as coatings upon them, make them an ideal
form of support in blowpipe work.
A small pit is made at one end of the tablet somewhat larger
than a pin's head, and in this the ore to be tested is heated.
The oxide coatings are produced by heating the substance per
se^ the bromides by adding to the substance a drop of fuming
hydrobromic acid, and the iodides by adding a strong solution
850 W. W. ANDREWS. PLASTER OF PARIS
of hydriodic acid (made by dissolving five ounces of metallic
iodine in seven ounces of water, by passing a steady stream
of hydrogen sulphide through the solution while the iodine is
slowly added). All who have experimented with this solution
will be ready to admit that it yields superb results, but thougli
easily renewable when one is near a hydrogen sulphide gener-
ator it is very unstable, takes a long time to prepare and is
troublesome to carry.
In 1890 Mr. F. A. Bowman read a paper before the Nova
Scotia Natural History Society, in which was described a search,
for a solid reagent to replace the hydrogen iodide solution. He
found that potassium hydrogen sulphide or any alkaline sul-
phate, which does not yield a coating of its own, mixed with
potassium iodide would do very well . He also found that microcos-
niic salt and potassium iodide gave good results. This mixture
i s a favorite one with some blowpipe experts . Tin is the only metal
in the three series of the periodic table, beginning with copper,
silver and gold, which does not yield a characteristic coating-
with this reagent.
The writer has not been able to find whether there have been
any other reagents besides these seriously proposed. Plaster of
Paris as a support is mentioned in Moses and Parsons' late work,
as an alternative to charcoal. This is, as far as known to the
writer, the only standard work, in which the colors of the films
on the tablets are described.
In the rapid development of other methods in chemical work
the blowpipe has fallen largely into disuse, and for many years,
besides the work outlined above and that of Col. Ross and some
valuable tests for individual elements proposed by Chapman,
little or no advance has been made. There are two possible
lines of future progress in blowpiping, one in the direction of
increased power and simplicity, so as to make the method more
valuable for the field work of the mineralogist, geologist and
prospector, and the other in the direction of increased range
and delicacy until the dry way tests rival the delicacy and dis-
tinctiveness of the wet tests, as they surpass them in expedi-
tiousness. It may not be amiss, therefore, to call attention
to the instrument of Plattner and Berzelius, which, in its mod-
METHOD IN BI^OWPIPK ANAI^YSIS. 85 1
em form as the hot-blast blowpipe and with the new support
and the new reagents and reactions now known to chemistry,
is an instrument surpassed by the electric furnace only.
The cleanliness of the method here described, as compared with
the charcoal method and the quickness with which sure results
can be obtained with very small amounts, should call the blow-
pipe back to the table of the chemist for preliminary and con-
firmatory tests, to class work as an accompaniment of the wet
methods, and to the lecture table for the purposes of illustration.
It is possible to detect five or six metals in presence of each
other on one tablet. Many of the coatings are permanent and
are all renewable on reheating with addition of a drop of the
reagent, so that a set of tablets carefully labelled with a pencil
forms a permanent record of a set of experiments. The value
of this to the practical chemist and to the student need not
be emphasized. It may be noted that blowpiping is so much of
an art that new methods are seldom well enough practiced, by
those who have become skillful in other methods, to reveal their
value.
The extensions of the plaster of Paris method here proposed
are : A set of new reagents, which yield some new reactions
which are of value in detecting elements in the presence of each
other, notably gold and copper in very small amounts in the
presence of all elements so far experimented with ; arsenic, tin
and antimony in presence of each other; sulphur in the presence
of selenium and tellurium, and chlorine, bromine and iodine in
the presence of each other ; a new set of film tests which are
found to be of great delicacy (the limits of delicacy are now
being measured, it being found that gold, one part in one mil-
lion, and copper, one part in four millions, are easily detectable) ;
a change in the composition of the tablets which does away with the
necessity for using platinum wire in the production of the colored
glasses with borax and metaphosphoric acid, these being formed
on the tablets with a decided gain in facility and deb'cacy; and
lastly several new methods of handling the tablets themselves.
It is evident that solid reagents will always be the more con-
venient to carry afield, but, in the laboratory, liquids are to be
preferred, since they are more readily applied, and when the
852 W. W. ANDREWS. PLASTER OF PARIS
assay is heated » tbe reagent, which has soaked into the tablet,
is fed steadily toward the hot portion of the tablet, so that the
heated assay is constantly enveloped in the vapor of the reagent.
For over two years the writer has used with satisfaction the
following reagents, which have been selected from a score of
experimental ones. They are stable and almost odorless, can
be carried to the field in a solid form and so used if need be,
while a few seconds suffice to prepare them in liquid form if it be
desired so to use them.
The chief reagent is a saturated solution of iodine in a strong
solution of potassium thiocyanate in water. The solution takes
place almost instantly and with great absorption of heat. The
bottleful now in use has been in use for over two years, a little of
one or other of the ingredients being added from time to time as
seemed to be required. Exact proportions are not necessary to
the efficiency of the reagent. It can be prepared on the field
from the solid chemicals at a moment's notice. The brilliancy
of the iodide films produced with this solution are not one whit
behind those possible with the pure solution of hydriodic acid.
Its coatings tend to form in definite bands of color. The spheres
of desposition of the iodide and the oxy-iodide are sometimes very
well defined. Some striking and important variations are pro-
duced by the presence of the potassium thiocyanate, for example,
with molybdenum, osmium, iridium, tin, antimony, lead, bis-
muth, cadmium and mercury.
Dr. Haanel showed in his second paper that by means of
hydrobromic acid, copper and iron could be detected at one oper-
ation in the presence of each other and in the presence of nickel
and cobalt and any other flux-coloring substances. Instead of
the fuming acid with its dangerous properties, a mixture in
molecular proportions of powdered potassium bromide and meta-
phosphoric acid, or potassium hydrogen phosphate or sulphate
may be used. This, suggested by Bowman's work, suggests
further a set of solid reagents, made by using potassium chlo-
ride, potassium fluoride and potassium iodide with metaphos-
phoric acid, and these form a valuable set for special tests.
They have the advantage of yielding at once the colored flux
and the coatings produced by any volatile matter in the assay.
METHOD IN BLOWPIPE ANALYSIS. 853
When heated, the reaction represented by the'following general
equation takes place : KX+ HPO, = KPO, + HX
These two reagents, the iodine solution and the bromide
mixture, suffice for the production of coatings. The following
which are used to differentiate them, are dropped upon the
oxide or iodide film and colored spots are produced, or the color
is discharged to white (technically, wiped), or the coating dis-
appears through solution and absorption by the tablet.
Dr. Haanel used ammonium hydroxide and yellow ammonium
sulphide for the purpose of testing the solubility of the films and
to produce the sulphide spots. Both of these are troublesome to
carry, and the latter is objectionable on account of its intolera-
ble odor, its instability and the fact that for its renewal the
hydrogen sulphide generator is required. It has been found that
a solution of potassium sulphide, strong enough to show a clear
amber color, made by dissolving the solid potassium sulphide in
water, or by boiling a strong solution of potassium hydroxide
with an excess of flowers of sulphur till the solution assumes a
blackish color, which on cooling will be amber yellow, fulfils all
the required conditions. If through the action of light it is
decomposed, all that is necessary for its renewal is to boil the
solution and perhaps add a little sulphur. We therefore have a
reagent which can be carried as a solid, can be renewed any-
where, is as efficient as the ammonium sulphide solution and is
almost odorless.
In the place of ammonium hydroxide a solution of potassium
cyanide is used, made a little more stable by the addition of a
little ammonium or potassium hydroxide. Besides these the
common acids of the laboratory are useful and a solution of
potassium thiocyanate.
The potassium thiocyanate solution is used in two ways. It
is either dropped on the coating to test its solubility and to note
the colors produced after heating, or it is dropped on the tablet
before the coating is deposited, and then the hot vapors sweep-
ing over the moist spot, give with some metals characteristic
reactions.
Those coatings which are pure white and therefore invisible
on the white tablet, are examined on a tablet which has been
854 W. W. ANDREWS. PLASTBR OF PARIS
smoked in a flame, or on one streaked up the middle by means
of a glass rod which has been dipped in a solution of boric and
metaphosphoric acids mixed with lampblack or bone charcoal.
In this way the coatings may be viewed on a white and on a
black surface at the same time.
In order that the colored fluxes may be made on the tablets, the
latter must be made more resistant to the dissolving effect of the
metaphosphoric acid and the alkali in the borax. If one teaspoonful
of boric acid be added to each quart of the water used in mak-
ing the tablets, they will be found to be denser and to have the
necessary quality. Borax can be fused on them without gath-
ering any impurities from the plaster and if metaphosphoric acid
be substituted for phosphor salt, we have a flux which will spread
upon the tablet and exhibit the colors of all degrees of satura-
tion at the same time. This reagent, first proposed by Ross,
who described its reactions, is preferable to microcosmic salt,
since, as it contains no volatile matter and melts readily to a clear
glass, it will show by effervescence the presence of water or car-
bon dioxide, or other gas in a mineral. With cobalt it yields a
fine violet when cold, which becomes blue on the addition of
any of the alkali metals, for which therefore it furnishes a ready
test. The only objection to this reagent is the tendency of the
sticks to deliquesce, but a piece can be kept in a corked test-
tube,* which can be readily dried over the flame, if dampness
should gather. In dry weather it causes no trouble. Its sol-
vent power is very great and the colors are fine. Ross asserts
that silica and zirconia are the onl}' oxides which are not
soluble in this flux. The whole operation may be completed in
the time usually required to form the bead in the platinum wire
loop and the volatile oxide films will be found on the tablet above the
glass, where they may be tested with potassium sulphide and
the other reagents. One operation, -therefore, suffices for the
determination of the volatile acid elements, the volatile metal or
metals, and flux-coloring metal. Metaphosphoric acid well re-
places potassium hydrogen sulphate in the operation as
1 1n this laboratory each student is supplied with a set of very small dipping tubes
and a wooden block into which holes are bored for the reception of a set of test-tubes
closed with paraffined corks, to hold the reagents.
METHOD IN BLOWPIPE ANALYSIS. 855
described in most text-books for the detection of carbon mon-
oxide, carbon dioxide, iron, chlorine, bromine, iodine, nitrogen
tetroxide, chlorine tetroxide, sulphur dioxide, h5'drogen sulphide,
hydrocyanic acid and acetic acid.
DESCRIPTIVE LIST OF REACTIONS OBTAINABLE ON THE
TABLETS.
Copper/^rj^ yields with diflBculty a coating of volatilized metal.
With the iodine solution it yields a white iodide coating and an
emerald g^een flame. The iodide treated with a drop of potas-
sium sulphide gives with gentle heat a blackish gray, which is
removed by greater heat. Potassium cyanide and nitric acid dis-
solve the sulphide; hydrochloric and sulphuric acids have no effect
till heated and then they remove the spot. Potassium thiocyanate
applied to the coating has no effect till heated, when a gray spot
is shown. Any part of the coating touched with the tip of the
flame shows the emerald green flame (Haanel). Metaphos-
phoric acid glass is greenish-blue when hot and a fine robin's
egg blue when cold. Metaphosphoric acid and potassium bro-
mide yield a splendid reddish violet coating of copper bromide
(compare osmium) . The bromide plus potassium sulphide shows
a brown, which if heated turns blackish and then green, not
affected by sulphuric acid, but immediately destroyed bj' a drop
of nitric acid.
Copper plus metaphosphoric acid and potassium chloride
yields a yellow brown cupric chloride, which, if treated with a
drop of potassium thiocyanate, gives a black ring, which, if
heated, becomes a black spot. If, before the assay is heated,
a drop of nitric acid be placed one-half inch from the assa}^ and
a drop of potassium thiocyanate be placed above that, on heat-
ing a fine and very volatile blue-black coating is deposited far
up the tablet. This blue-black is not affected b)' acetic acid, is
wiped off by sulphuric acid slowly, and immediately by hydro-
chloric and nitric acid. The formula of this compound will be
determined if some method be found, by which it may be col-
lected in quantity. (See chlorine.)
Silver gives /^rj^ a pinkish gray coating, which touched by
the blowpipe flame (flamed) becomes mottled brown. Reduced
856 W. W. ANDREWS. PLASTER OF PARIS
globules are often shown. Metaphosphoric acid yields the same
coating and a pearl-like glass. The iodine solution yields a pale
yellow, paler when cold, and around the assay forms a black,
which does not fuse into the tablet (compare lead). Flaming
with oxidizing flame yields a mottled brown anywhere on the
tablet. This is a very delicate test and as all qther coatings are
volatile, the flame drives them off and leaves the silver oxide.
Potassium sulphide produces a spotted blackish brown, proba-
bly potassium silver sulphide, the analogue of ammonium silver
oxide, for if treated with a drop of potassium cyanide it immedi-
ately disappears, but if it be first heated, the potassium cyanide
has no effect. If only one-half of the sulphide spot be touched
with the tip of the flame and then the potassium cyanide be ap-
plied, the untouched portion will disappear while the other half
will remain. Potassium thiocyanate on the iodide wipes it ofi;
when heated the spot turns black, which is not wiped oS by
potassium cyanide.
Gold is slightly volatile /^r se and more so if a solution of
iodine in potassium iodide be used as a reagent, and the result is
a fine rose-colored film of the metal. If potassium thiocyanate
be present, no volatility is noticed. Gold and the other ele-
ments which respond to the new tests will be the subject of
another paper.
Zinc per se yields a white coating, not very volatile and lumin-
ous yellow when hot. Potassium sulphide and potassium thio-
cyanate produce no visible change on zinc films. The iodide
film is a white, which treated in any part with cobalt nitrate
solution yields the well-known zincate of cobalt, which is quickly
decomposed by a drop of nitric acid (compare tin). This reac-
tion obtained in this way is decisive for zinc, as aluminum and
silicon do not volatilize and are therefore not present in the coat-
ing. In the metaphosphoric acid glass, zinc causes flashes of
light and detonations (Chapman). Metallic zinc sometimes
yields per se a black sublimate along with tlye white oxide
(compare arsenic.)
Cadmium /^r se yields one of the most beautiful of the oxide
films, which consists of a rich brown with black farther away
and somewhat iridescent near the assav. Acetic acid does not
METHOD IN BI^OWPIPE ANALYSIS. 857
afiect it ; potassium cyanide dissolves it at once (compare cad-
mium sulphide). Potassium sulphide and potassium thiocya-
nate 3rield a scarlet when hot, and bright yellow, cold. This cad-
mium sulphide is not affected by potassium cyanide, is quickl}'
destroyed by nitric acid, less readily by hydrochloric acid,
immediately by acetic acid (compare cadmium oxide) , and is
not affected by sulphuric acid (compare copper).
The iodide coating is white with well-defined borders, which
is easily distinguished in the presence of other white coatings
by the per se and sulphide reactions. In the assay and near it
the sulphide reaction will be seen caused by the potassium thio-
cyanate in the iodine solution (see sulphur). In metaphos-
phoric acid cadmium acts like zinc and yields at the same time
its oxide coating beyond the glass.
Mercury gives per se a very volatile film of mercur}* snow,
which, with a feather, may be swept into a globule. It is not
affected by the other reagents.
The iodide coating is a splendid combination of scarlet, yellow,
and velvety green. This is caused by the mixing of the green
mercurous iodide with the scarlet and yellow forms of the mer-
curic iodide. The reactions of each kind of iodide may be
obtained on the one tablet. The green and the scarlet are the
stable forms into which the coating changes on standing. A
drop of the reagent or some more of the vapor blown across the
coating changes all into the scarlet form. With mercurous
iodide, sulphuric acid gives a yellow spot (mercurous sulphate).
Potassium hydroxide gives a black ; so does ammonium hydrox-
ide, (iodomercurosamine, NH,Hg,I),and potassium sulphide.
With the mercuric iodide, sulphuric acid increases the amount
of the scarlet, potassium hydroxide yields a white, as does ammo-
nium hydroxide (iodomercurosamine) and potassium sulphide,
yield a white spot, quickly turning black. The sulphide spot,
strange to say, is partiall}*^ dissolved in nitric and hydrochloric
acid, while sulphuric acid turns it brownish. Potassium cyanide
yields a black and potassium thiocyanate a dark spot,and if
heated both are wholly volatilized (compare lead, bismuth, and
silver). Water has no effect on this coating (compare lead), nor
858 W. W. ANDREWS. PILASTER OF PARIS
have hydrochloric, nitric, or sulphuric acids. By the last the
coating is not readily wetted.
Gallium has not been experimented with. Indium yields a
pale yellow iodide coating and a blue flame.
Thallium per se yields a feathery brown with white farther
away and a green flame (compare arsenic and tellurium) . Potas-
siu 1 sulphide gives a terra cotta brown spot with a black ring.
Potassium cyanide and potassium thiocyanate have no effect upon
it. The iodide film is an ^^'g yellow with a purple black veil farther
away. Potassium sulphide gives a rich brown which potassium
cyanide darkens. Hydrochloric acid discharges it slowly and
yellow is left (compare bismuth and tellurium). Potassium
thiocyanate has no effect on the yellow or the black till heated,
when it yields a white (compare bismuth, tellurium, tin, and
lead). Potassium cyanide dissolves the black but has no effect
on the yellow. Sulphuric acid has no effect. A drop of the
reagent on the coating heated shows a spreading black and an
orange ring.
Carbon yields a sooty coating, which comes better if sulphuric
acid or metaphosphoric acid be used upon the assay. In the
case of the carbonates, boric oxide or metaphosphoric acid yield an
odorless effervescence (Ross, Chapman) . Organic acids blacken
the tablet when heated.
Silicon. An interesting reaction given by the silicates, espe-
cially the hydrous forms, is being investigated. Chapman dis-
solves a silicate in boric oxide and then precipitates the silica
by adding metaphosphoric acid.
Germanium will give a light yellow iodide film, but none has
been on hand to experiment with.
Tin gives a slightly volatile coating, showing a trace of brown
when hot. Potassium thiocyanate, if dropped on the oxide and
strongly heated gives a pale yellowish green, infusible (compare
lead) . The slight volatility of tin oxide suggests a scale of vol-
atility, of great use in describing the formation of the films on
the tablets. The scale runs in the order of increasing volatility :
tin, zinc, cadmium, and mercury. Anything less volatile
than tin might be classed as non-volatile.
The iodine solution yields a yellow, reddish brown when hot,
METHOD IN BLOWPIPE ANALYSIS. 859
the brown fading instantly. Potassium sulphide yields a black
with a brown edge, which darkens on heating. Potassium cyanide
discharges the color, which turns black on heating, and when
strongly heated shows the pale yellowish green (stannous thiocy-
anate, Sn(SCN),; compare lead, bismuth, arsenic, mercury and
zinc). Water decomposes the film with formation of oxy-iodide.
Cobalt nitrate gives the bluish g^een, which is not so readily
attacked by nitric acid as the zinc green.
Antimony tri- or pentachloride yields with all tin salts a fine
purplish blue-black coating, stable in the presence of acids.
Potassium thiocyanate decomposes it when heated and forms
the pale green.
These tests with iodine, antimony trichloride, and with
potassium thiocyanate remove tin from the list o^metals determin-
able with difficulty before the blowpipe. They can be depended
on through a wide range of mixtures.
Lead yields per se a white and yellow ; reddish brown when
hot. All lead salts fuse into the tablet with the formation of
lead plumbate, one of the constituents of glass. Potassium sul-
phide produces a brownish black, with reddish brown ring.
The iodine solution gives a film which is chrome yellow, with
a band of fainter yellow farther away (oxy-iodide?), and the
assay is black. Potassium sulphide yields a spot with the
reddish brown edge. Hydrochloric acid destroys the edge at
once. Nitric acid wipes the spot off slowly, and sulphuric acid
destroys the black and restores the yellow. The very volatile
paler yellow on the outer edges is turned to a brighter
color by the same treatment (compare mercury). Potassium
cyanide produces a slight paleing of the sulphide color. Potas-
sium thiocyanate on the iodide film gives a black ring, which
heated becomes a black spot (compare bismuth). Water wipes
off the coating (compare mercury, arsenic and silver).
The bromide film made by using potassium bromide and
potassium hydrogen sulphate presents some interesting difiFer-
ences. It is white with a trace of yellow, the yellow fusing into
the tablet. Potassium sulphide gives a spot, greenish for a moment
and then black, on which potassium cyanide and potassium
thiocyanate have no effect, but is partly destroyed by hydrochloric
86o W. W. ANDREWS. PLASTER OF PARIS
acid, niorerapidly by nitric acid, and completely by sulphuric acid.
Potassium thiocyanate, placed on the sulphide and heated, gives a
black ring ; with greater heat, a yellow, and still greater heat, a
greenish gray ring. Potassium cyanide on the iodide film has no
effect till heated ; then a white. Potassium thiocyanate has no
effect on iodide till heated ; then a yellowish spot appears (com-
pare tin). The sulphide heated becomes grayish black, on
which nitric acid and the other acids have no effect (compare
copper) .
It is a good illustration of Camelley'slaw of colorthatin general
the bromide film of any metal resembles the iodide film of an
element either in a higher series in its own family or in the same
series, in another family toward the left in the natural classifi-
cation. Thus the bismuth bromide film resembles the iodide
film of antimony and lead. Lead bromide resembles tin and
thallium iodide. Thallium resembles mercury, and meroury
resembles silver in the same way.
Nitrogen with metaphosphoric acid in the nitrates yields an
effervescence with the fumes, odor and reactions of nitrogen
tetroxide farther up the tablet, and in the cyanides, the odor of
hydrocyanic acid. Nitrates with carbonaceous matter j'ield
ammonia, which will cause white fumes to rise from a spot on
the tablet moistened with hydrochloric acid. Ross reports that
any nitrogen compound with boric oxide yields a tough trans-
parent bead, and with metaphosphoric acid, purple in the redu-
cing fiame with manganese dioxide.
Vanadium gives with metaphosphoric acid a pale yellow in the
oxidizing fiame, and in the reducing flame a green. (Ross).
Phosphorus. A great desideratum in blowpipe analysis is a
good test for this element and the phosphates.
Arsenic yields per se a brownish black w^ith a white film falling
farther away with odor of garlic and blue flame (compare
thallium and tellurium) . The iodide coat is white and pale yel-
low; the assay wholly volatile. Potassium' sulphide, with a
drop of hydrochloric acid, forms the yellow sulphide, little
affected by acids. If oxalic acid be applied to a sulphide spot and
then hydrochloric acid, no effect is noticeable. The yellow will
show up still better next day (compare antimony). If a drop
METHOD IN BLOWPIPE ANALYSIS. 86 1
of potassium thiocyanate be placed on the tablet about one inch
above the assay, and between them a drop of nitric acid and the
arsenical vapor be blown over them from the assay, there will
generally be formed in the edge of the potassium thiocyanate
spot a bright bluish green of unknown composition. All com-
mon acids except acetic destroy it. It shows well in the pres-
ence of salts of tin and antimony. When it does appear it is
decisive for arsenic. This iodide film exhibits a very marked
repulsive power for water, probably due to the arsenic oxide
which forms with it. Potassium iodide with metaphosphoric
acid yields more of the yellow than does the iodine solution.
Antimony per se yields a white and yellow band and white
fumes. Potassium sulphide yields on this an orange brown,
which is quickly destroyed by a drop of nitric acid.
The iodide film is a fine orange yellow far away with yellow
nearer the assay and abundant white fumes. Potassium sul-
phide yields, especially when heated, an orange red with a rich
brown and then a black beyond the spot. Hydrochloric acid
slightly heated destroys it ; nitric acid destroys it instantly ; so
also does its vapor. Potassium thiocyanate wipes the coating,
but heated it yields a fine brown, which is permanent when
exposed for months. Potassium cyanide wipes the coat. The
orange yellow sulphide spot, produced on the iodide film ob-
tained with potassium iodide and metaphosphoric acid, is not
so susceptible to the action of nitric acid and is more rapidly
destroyed by hydrochloric acid than the one described above.
If arsenic be present with antimony, there will be shown
inside the yellowish orange of the iodide film, a fine peachy pink,
which is hard to wet. Stannic chloride yields with antimony in
most combinations a purplish blue-black, which is remarkably
stable (Haanel). It is now being collected in quantity, with a
view to the determination of its formula. It will be seen that
with the blue with potassium thiocyanate, the rose pink, and the
reactions of the sulphide with hydrochloric, nitric and oxalic
acids, the presence of arsenic can be easily demonstrated in the
presence of antimony and, as far as experiment has gone, in the
presence of any other substances.
Bismuth yields /^r se a yellow ring near the assay and often a
862 W. W. ANDRBWS. PLASTER OF PARIS
brittle globule. Potassium sulphide gives on the white oxide a
brownish black which nitric acid destroys and on which hydro-
chloric acid has little effect till heated, when it removes it com-
pletely. Sulphuric acid has no effect. Potassium thiocyanate
on the oxide produces a yellow ring, and heated a yellow spot
turning black. (It is to be boted that potassium thiocyanate
itself when heated or treated with strong acids, shows on the
tablet a fine yellow, which further heating renders colorless.)
The iodide film is a splendid combination of chocolate black,
crimson and yellow, the assay turning black. Potassium sul-
phide forms a chocolate black, soluble in nitric acid and not
effected by sulphuric acid. The latter acid on the iodide film
produces a black and a dull red edge. This is probably the sul-
phide formed by the reduction of the acid by the decomposition
products of the potassium thiocyanate, which fall with the
iodides. It has been noticed, however, to happen with no other
metal than bismuth. This reaction is very useful in detecting
small quantities of bismuth in the presence of other metals giv-
ing dark colored films (compare tellurium). Potassium thio-
cyanate on the iodide wipes it off, forming a yellow ring, but
when heated it forms a black spot with a brown ring. Potassium
cyanide also wipes the iodide, but when heated forms a dark g^y
spot. Glacial acetic acid wipes off the yellow and the crimson,
but has no effect on the chocolate iodide.
Sulphur. In looking for a better test for sulphur than the
ordinary one with soda and a piece of silver, the stability at high
temperatures and the two brilliant and characteristic colors of
cadmium sulphide attracted attention, and the fact that it is
easily formed in the presence of potassium cyanide. To a solu-
tion of cadmium bromide, potassium cyanide was added till pre-
cipitation took place and then the solution of the precipitate as
potassium cadmium cyanide. This, dropped on a fragment of the
sulphide and heated, will show on the tablet near the assay a bril-
liant scarlet when hot, and bright yellow when cold. This is not
affected by potassium cyanide (compare cadmium oxide). One
great advantage of this is that selenium and tellurium do not
yield anything which can be confounded with these colors,
selenium giving a grayish brown and tellurium a yellowish
MBTHOD IN BLOWPIPE ANALYSIS. 863
brown. Sulphates may be reduced by potassium cyanide, orby
glycerol. A sulphide or sulphate fused with potassium cyanide
will, if touched with a drop of ferric chloride, show in the tablet
the pinkish red of ferric thiocyanate. The sulphur in the tab-
let causes no trouble.
Selenium and tellurium are further differentiated from sulphur
by their characteristic films, which are tests of great delicacy.
Twenty-seven varieties of complex sulphides, such as boumonite,
tetrahedrite, stannite, etc., and all of the common sulphides and
sulphates, were found to respond to this test at once.
Selenium yields/^ se with characteristic odor and-flame a fine
reddish brown, almost pure red on the outer edges and black on
the inner edges near the assay. Potassium cyanide wipes it off,
while potassium thiocyanate has no effect, except that, if it be
heated, a very stable red compound is formed (KSeCN ?).
The iodide film forms in color very similar to the per se coat,
bat more volatile. Potassium sulphide yields a yellow. Potas-
sium cyanide wipes the iodide film off instantly, and therefore
will reveal the presence of any other element not so affected,
whose film might be hidden by the pronounced hues of the sele-
nium film. Potassium thiocyanate has no effect, while it and
heat wipe off most other coatings, and therefore will reveal the
presence of selenium in obscuring associations, such as lead.
Sulphuric acid shows a slight tendency to make this coating
darker (compare bismuth).
Tellurium gives ^^r 5^ with flame and odor a brownish black
with a white film falling nearer the assay (compare arsenic).
Sulphuric acid-, if gently heated, shows an effervescent pink of
tellurium sulphate. Acetic acid wipes off this coat (compare
cadmium). So do the potassium cyanide and ammonia fumes.
The iodide film is brownish and purplish black, less brown than
ih^perse coat. Potassium cyanide wipes it off in the cold.
Potassium thiocyanate has no effect on the purple (compare
thallium), and slightly dissolves the brown, and if nitric acid
be added a yellow appears. Potassium sulphide darkens the
coating a little. Sulphuric acid acts as on per se film.
Chromium yields an assay which is dark green when hot and
864 W. W. ANDREWS. PLASTER OF PARIS
a fine g^een on cooling. This test can be made very delicate.
Metaphosphoric acid gives similar colors.
Molybdenum yields /^r se, and especially by flaming » an ultra-
marine coating. The oxide film, which forms when the iodine
solution is used, comes better by flaming of the film and in pres-
ence of vapors of sulphuric acid. A potassium thiocyanatespot,
over which the vapors from the assay have swept, exhibits a
splendid hyacinthine pink. Metaphosphoric and sulphuric acid
vapors aid its formation. It is probably molybdenum thiocya-
nate (Mo(SCN)J. If potassium thiocyanate be added to the
assay this color will spread all around the edges of the blue,
extending to a distance of two inches from the assay. This very
delicate reaction is of special interest, from the fact that it shows
that part of the potassium thiocyanate, or at least the radical
thiocyanogen travels undecomposed that distance over the tablet
and that all these films are formed in the presence of moist potas-
sium thiocyanate or thiocyanogen vapors, which will account for
the behavior of some of the films. This pink is decolorized by
ammonia, not restored by nitric acid. Sulphuric acid dropped
on the tablet will form a blue ring (MoSOJ. Metaphosphoric
acid yields blue or bluish green glasses according to the degree
of saturation (Ross).
Tungsten and uranium in metaphosphoric in the reducing
flame yield, the former a blue and the latter a green glass ( Ross) .
Fluorine. If a fluoride be mixed with phosphoric acid and a
piece of glass be laid on the tablet about two cm. away from the
assay, a fine etched semicircle will show itself after the heating
of the assay. The radius of the semicircle is about three cm.
long.
Manganese yields with metaphosphoric acid a glass, which
is \dolet hot and cold, colorless in the reducing flame, and
turning green on the addition of an excess of soda (Chapman,
Ross).
Chlorine . Chlorides, bromides and iodides of the alkali metals
yield per se white coatings, which may be distinguished from
other white coatings by their flames and by the action of a small
quantity of the coating scraped together and mixed with the
METHOD IN BI.OWPIPE ANALYSIS. 865
metaphosphoric acid cobalt glass, which will remain blue on
cooling.
A compound of chlorine if mixed with metaphosphoric acid
and heated, in the reducing flame (if oxy salt), will cause white
fumes to rise from a spot moistened with ammonia situated
about two cm. above the assay. If a copper salt be present in
the glass or near it, so that copper chloride vapors are formed
and these are allowed to sweep over a spot of nitric acid and then
over one of potassium thiocyanate, near the assay a yellowish
brown coating of cupric chloride will form with an azure blue
flame, and beyond the potassium thiocyanate spot a fine blue-
black, very volatile (see copper).
A bromide with potassium cyanide added to it and the fused
mass laid upon a copper glass and a drop of nitric acid added, a
fine red will show itself. Bromides with metaphosphoric acid
saturated with copper, upon blowing, yield a fine and very vola-
tile reddish violet coating. If a bismuth salt be exposed to the
hot vapors, it will yield a yellow coating. The spot on the
tablet moistened with starch paste, not too near the assay, will
turn yellow.
Similarly treated iodine compounds yield violet vapors, a vio-
let in the glass appearing with effervescence, and with copper
salt they yield a. white coating, with bismuth scarlet and choco-
late, and with starch a bluish black.
Iron gives an iodide film too delicate in color to show up well,
either on the white or the black surface. Its presence can be
shown by a red coloration after blowing hydrochloric acid vapors
over the tablet, to turn all ferrous compounds into ferric, and
then adding a drop of potassium thiocyanate to the coating. It
is difficult to obtain plaster of Paris sufficiently pure not to give
this reaction for iron. Such reaction can, however, be readily
distinguished from that given by an assay. Metaphosphoric
acid gives a luminous yellow when hot, which is perfectly color-
less when cold. A drop of acid on this to produce ferric com-
pounds, followed by a drop of potassium thiocyanate, will show
the red of ferric thiocyanate, which is decolorized by phosphoric
add, but not by hydrochloric acid. Made in this way this test
is not too delicate to show the iron of composition. An assay of
866 W. W. ANDREWS. PLASTER OF PARIS
iron treated with a drop of sulphuric acid and heated will show
on the tablet a film of Venetian red.
Cobalt yields a glass blue hot, and violet cold ; permanently
blue if alkali be present. Boron trioxide acts similarly. With
the iodine solution a spot around the assay turns pink, then deep
blue on heating, and then black.
Nickel with boron trioxide separates as green fragments,
which may be gathered by solution of the glass in water, and
then the separated nickel (as any nickel compound) will yield
in metaphosphoric acid, a reddish brown when hot and amber
yellow when cold (Ross).
Palladium gives a dull blue-black film with the iodine solu-
tion, which is very characteristic. The assay turns dull black.
Osmium yields ^^r se a greenish black. The iodide film is a
combination of olive green, dove and slate colors, with red
appearing around the lower edges. The edge of the coating
nearest the assay shows greenish brown and the assay itself will
be closely surrounded with an iridescent black film. Potassium
sulphide turns the coating somewhat darker, which heated,
becomes a brownish film, which is wiped off by hydrochloric and
nitric acids and not affected by sulphuric acid and potassium
cyanide. On the iodide films sulphuric acid has no effect;
potassium thiocyanate has none till heated and then it turns
brown. Hydrochloric and nitric acids remove the film. Potas-
sium thiocyanate dropped on the tablet over an inch from the
assay before the coating is deposited, will, when the vapors
sweep over it, turn to a fine brick red, destroyed by potassium
cyanide and the acids.
Potassium bromide and potassium hydrogen sulphate give a
pinkish brown (compare copper) . Potassium sulphide produces
a gray not affected, which turns darker on being heated,
destroyed by acids, and not affected by potassium cyanide.
Indium yields with the iodide solution an indistinct brownish
yellow coating and a potassium thiocyanate spot which in tint
resembles the molybdenum spot, but it is covered with dots of
darker pink.
Platinum gives an infusible gray film. Ruthenium and rho-
dium are being investigated.
METHOD IN BLOWPIPE ANALYSIS. 867
All these reactions have been obtained from a large number
of the compounds of each element except in the cases of osmium,
indium and iridium. The writer will be glad to hear of any
cases in which they fail and to receive specimens of combina-
tions which cannot be unlocked by this method. One gram
weight of any allby is sufficient. The next work to be under-
taken is to exhaustively determine the lowest percentage of
any metal which can be determined with certainty in the pres-
ence of one, two, or any number of other metals, to describe
the characteristic effect that one metal has on the coating
yielded by another when they are deposited together and to
determine the value of each metal as an interfering element.
COVERED TABLETS.
The tablets are easily cut with a knife and therefore they can
be used in various ways. Open tube work can be performed on
a tablet, if a groove be cut lengthwise of a tablet and laid upon
another, groove down. A small pit for the assay is cut in the
lower one about one centimeter from the end. The groove is
cut so that its narrowest part is just above the assay pit, and from
that point to the lower end it flares into a half funnel form and
into this the flame is blown. By regulating the size of the
groove at its narrowest part the amount of air which will flow
over the assay may be regulated. This method is of great use
when very small quantities of precipitates are to be tested. For
instance, five-tenths mg. of arsenious oxide gave in one experi-
ment a narrow coating one-half inch long on each tablet. This
gives ample opportunity for making confirmatory tests. Various
reagents may be placed along the groove to be acted on by the
vapors, gold leaf for mercury, potassium cadmium cyanide and lead
acetate for hydrogen sulphide fumes, starch, bismuth and anti-
mony solutions for iodine, copper sulphate for chlorine, etc.
If a coating be made, or a small piece of volatile salt be
placed in a small pit in the tablet and a thin tablet be placed
over it, it is found that if potassium sulphide, or potassium thio-
cyanate be dropped on the upper tablet and the flame be directed
upon the drop, they will pass through the tablet and reactions
will take place away from the air. After a few seconds blowing
the upper tablet will be found to be floating on a layer of hot
868 PLASTER OF PARIS METHOD IN BLOWPIPE ANALYSIS.
gas, which flows between the two smooth surfaces. Tin and
arsenic, and other substances easily oxidizing in the air, form
their sulphides very readily under these conditions. Potassium
thiocyanate forms sulphides. It is in this way possible, by-
using ammonium hydroxide or hydrochloric acid, to form the
sulphides in the presence of moist acid or alkaline vapors.
Other methods of using the tablets will be described later.
In teaching research methods, the plasterof Paris method is one
of the finest instruments to use with beginners. In the course
of an hour a student will have been able to make from twenty to
forty different tests and without any delay in preparing solu-
tions, or in waiting for filtration to take place, he will have pro-
duced the oxide, sulphide, chloride, bromide, and iodide of a
given metal, and will have noted their colors, manner of deposi-
tion, volatility, solubility in several reagents, and the behavior
of the assay itself at high temperatures and will have ransacked
his vocabulary to find terms to describe the phenomena in his
written notes. His skill in manipulation and his powers of
observation are kept in liveliest exercise and his independence
developed, for it is quite possible to give each student in a large
class his own problem. In no other laboratory work do the
compelled acts of judgment follow each other asrapidly. There
are many problems which may be set requiring reference to
standard chemical literature, and many simple and some very
diflBcult equations of reactions to be written.
Not the least valuable consideration from an educational
standpoint, is the aesthetic quality of the work. All the coat-
ings are symmetrical in form and beautiful in shading, and
many of them in brilliancy of hue and in delicacy of shading,
rival the most splendid colors of flowers. This gives added
interest to the work and is of great value since adult students are
so frequently found to be greatly deficient in the color-sense, as
children are not. There has not been opportunity to compare
the shades of these films with the descriptions given in the
Standard Dictionary. When this has been done, exact training
can be given in color language also.
Apology is offered for publishing the results of this research
at this stage, when so many unsolved problems stand along its
HYDROLYSIS OF STARCH BY ACIDS. 869
path, but this much is given in order that the practical
value of these reactions and methods may be put to the test.
UXIVmSITT OF MT. ALUSOlf COLLEOB,
SACKVILLB, N. B.
AN ANALYTICAL INVESTIQATION OF THE HYDROLYSIS
OP STARCH BY ACIDS.
By Gbo. W. Rolfb axtd Gbo. DBPHBif .
Received July 3. sSp6b
FEW problems of commercial analysis have been so compli-
cated and so discouraging as that of the determination of
the components of starch conversion products. The well-known
schemes of commercial analysis of worts and similar products of
the action of diastase are based on the assumption that but two
simple compounds are formed from the starch — maltose and
dextrin. In the case of glucose syrups and starch sugars,
which are the results of acid hydrolysis, it is known that the
reaction proceeds farther as dextrose is formed from the maltose
and dextrin.
Musculus and Gruber* decided that these reactions went on
together so that except at the very beginning or final stage of
hydrolysis all of these compounds must be present in solution.
The analysis of acid-converted starch products must therefore
take into consideration the presence of the third compound,
Much doubt» however, has been thrown on the accuracy of
such analyses, as during the past twenty years the researches of
O'SuUivan, Brown, Heron, Morris, Bondonneau, Herzfeld, Mus-
culus, Bruckner, Fischer, and other distinguished investigators,
have shown that not only the simple compounds referred to can
be isolated from starch products but also many others of quite'
distinct optical and chemical properties. Space will. not permit
a review of this work, which is in many points conflicting. The
recent conclusion of Lintner and Diill is that the following com-
pounds result from hydrolysis :'
1 Bull. Soc. Chim., s, 30.
S Ser. d. chtm, Ges., si, i52»-i53i.
870 GBO. W. ROLPE AND GBO. DSPRBN.
Hydrolysis with oulic scid. With disstsse.
Amylodextrin Amylodeztrin
Erythrodeztrin I Brythrodeztrin I
lla
Up
Achroodeztrin I Achroodeztrin I
II " II
Isomaltose Isomaltose
Deztrose Maltose
Others, as Brown and Morris,' deny the existence of the iso-
maltose of Fischer and Lintner and Diill, and mention another
compound, maltodextrin, an intermediate between dextrin and
maltose.
In 1885 Brown and Morris' discovered the remarkable laif7
that at any stage of the conversion of starch by diastase, the
total product, in its optical properties and relation to Fehling^
solution, behaved exactly as if made up of two components only,
maltose and dextrin, so that it was possible by taking the rota-
tory power to calculate at once the cupric reducing power if the
total carbohydrates were known. This law indicated that, how-
ever complicated the bodies isolated, they could be considered
as existing in solution as two simple compounds, and did much
to establish the validity of the principles of the usual commer-
cial analyses of beer-worts and similar products.
The method of analysis of glucose syrups and starch sugars
implies the assumption of a similar law, but the proof that this
law actually exists under varying conditions of hydrolysis appa-
rently has not been worked out.*
Our investigations have been made, first, to determine
whether there was any simple constant relation between the
optical rotation and the cupric reducing powers of starch pro-
ducts hydrolyzed under different conditions ; and, secondly,
whether any laws could be found affecting the three simple
bodies assumed to be formed and determined by the usual methods
of analysis.
Incidentally we have collected some data as to the speed of
hydrolysis, influence of carbohydrates on specific gravity of
I J. Chem, Soc., No. 393. Aug., 1893.
*Ann. Chem. (Uebigr). 331, 131.
• A very complete bibliography of the original pnblications on Uie carbohydntet is
in rollem*s Handbuch der Kohlenhydrate^ Vol. x, i88S^ 331-3^; Vol. XI, lifs^ 36^-396.
HYDROLYSIS OP STAKCH BY ACIDS. S71
solutions, and some looking to the adoption of a more rapid and
accurate mf^tliod of determining cupric reducing power by Feb-
ling solution.
Tbe latter data are included in a separate paper. The work
on specific gravities is not yet sufficiently complete for publica-
tion.
An autoclave of the usual construction was modified in the
following manner : The thermometer tube was taken out and in
its place was attached a specially constructed valve, by means
of which liquor cooking in a beaker in the interior could be
removed at any time during the progress of the experiment.
This superheated liquor was prevented from vaporizing by pass-
ing through a condenser. Excessive condensation into the
beaker was prevented in large part by a well fitting lead cap.
The illustration sufficiently explains the apparatus.
In most of the work about 100 grams of a good quality of
commercial com starch' was mixed with a liter of water con-
I AB aMl j^* of thli atanb by tbc anal conmercUl nctbod* can :
SUrcb B^is
(Ml 0.14
A*b 0.11
AlbumlBoid 0^
Water ■ "o-"
872 GEO. W. ROLFE AND GEO. DEFREN.
taining the hydrolyzing acid. Samples of from fifty to sevent5'-five
cc. of the liquor were removed at different stages of the conver-
sion and immediately shaken up with a few grams of marble
dust. Two drops of tenth normal sodium hydroxide solution
were then added to the sample, which was cooled and filtered.
This method of neutralization, except in cases of very low con-
verted samples, gave an absolutely clear filtrate, the filtration
being exceedingly rapid, and the removal of the albuminoids
being practically complete. Low-converted products often re-
quired to be heated with aluminum hydroxide before filtering.
The samples were tested as follows :
( 1 ) For specific gravity by Westphal Balance, corrected to a
temperature of 15.5® C.
(2) Specific rotatory power ( [«]d) by a Schmidt and Haensch
half-shade saccharimeter.
(3) Cupric reducing power by means of Fehling solution.
Total Solids — Total solids were calculated from the specific
gravity of the solution by the factor 6.00386, which was taken
to represent the influence of one gram of the mixed carbohy-
drates in 100 cc. of solution. Corrections were made when
necessary for the influence of other substances in solution, not
carbohydrates. This factor 386 is practically that of Balling
and Brix and has been found exact for approximately ten per
cent, solutions of cane sugar, and the balance of evidence seems
to be that it is correct for starch products.
We have made several determinations of this factor by drying
ten cc. of solution on rolls of dried paper at a temperature of
100-105® C. Our results point to the constancy of this factor
386 even in solutions of low rotatory power, but are not yet
complete enough to establish the value for all rotations.
Therefore, in this work we have adopted the expedient used
by Brown and Morris, and others, and calculated all optical and
copper reduction constants on the assumption that all three car-
bohydrates in solution affect the specific gravity like cane sugar
when the concentration is approximately ten per cent. Even if
subsequent investigations show that this view is not exactly cor-
rect, the relative values of the constant will not be appreciably
affected nor the truth of the laws as set forth.
HYDROLYSIS OF STARCH BY ACIDS. 873
To illustrate this method of calculation of constants we give
the following from our own determinations :
Ten grams of dextrose dissolved in 100 cc. of water gave a
rotation of 30.70® on the Schmidt and Haensch saccharimeter.
This gives [ajp as 52.8.* As the increase in specific gravity
per gram of crystallized dextrose in 100 cc. is 0.00381, [^jojedis
53.5.
9.751 grams of crystallized maltose anhydride in 100 cc. of
water gave a rotation of 76.40. This gives an absolute specific
rotatory power of 136.6. The specific gravity factor of maltose
being 0.00390, [«]d386 is 135.2°. No exact figure is known for
the influence of crj-stallized dextrin on the specific gravity of
its solution. O^Sullivan gives 0.00385, and the balance of evi-
dence seems to favor this. Hence 195 is probably correct for
In like manner the values for K have been reduced to a dex-
trose with the factor 386.
Specific Rotatory Power, — All readings were made as nearly as
possible at a temperature of 20** C. in 200 mm. tubes, the mean
of several readings being taken. Corrections for zero-error were
made frequently, and the instrument was carefully screened by
glass plates from the heat of the. lamps. Comparisons were
made with a Laurent polariscope to determine the value of the
division in terms of angular degrees for sodium light, the accu-
racy of the quartz wedges having being verified previously.
With standard quartz plates the usual factor 0.346 was obtained,
but solutions of commercial glucose of approximately ten per
cent, gave the figure 0.344, which agrees with the recent work
of Rimbach' and other investigators. We have taken, there-
fore, the latter factor in our calculation.
I Precautioas agrainst bi-rotation were taken in both examples cited,
s Brown and Heam: Ann. Chem. (Liebig), X99, 190-243.
t Ber. d. chem. Ges., 97. aaSz.
874
GBO. W. ROLPB AND GBO. DBPRBN.
TABIvB A.
Comparison op Schmidt and Habnsch Halp-Shadb Saccharimbtbr
WITH THAT OP LaURBNT PoLARISCOPB RBADING IN AUfGXJULK
Dbgrbbs.
Test
(t
Quartz A •
Reading.
20—22)
. 62.965
• 62.800
• 62.970
. 62.836
Glucose A-.. 77.510
B... 76.355
B . . . 76.355
c... 76.535
D-.. 76.110
(t = 25)
Hydroliz-") « «- -,i
products J ^' ^'^
8. and H. taccharimeter.
(Using batpwing burner and lens.)
Zero Corrected
error.
Laurent polariscope.
(Sodium flame.)
Zero Corrected
reading. Reading, error.
reading. Pactor.
II
II
II
i<
II
II
II
0.300
0.150
0.290
0.130
0.277
0.150
0.150
0.150
0.130
00
00
62.665
62.650
62.680
62.706
77.233
76.205
76.205
76.385
75.980
92.73
24.84
21° 40'
21° 40'
21° 40.2'
21° 40.7'
26° 35'
26° 15.3^
26° 14'
26° 18'
26° 10.3'
3»° 56'
8° 32'
o
o
0.6'
C.6'
o
o
.0
o
0.6'
-I'
—I'
21.666°
21.666°
21.660°
21.666°
26.582°
26.254°
26.233°
26.300°
26.162°
31.95?
8.55"
0.3457
0.3458
0.3458
0.3455
0.3442
0.3445
0.3442
0.3443
0.3443
0.3445
0.3442
Cupric Reducing Power. — Our method is practically that of
0'Sullivan» first published in 1876. The copper is weighed as
the oxide. We have found this method exact and rapid. An
anal3rtical investigation of this process has been made by one of
us and given in detail in a separate paper.
Plotted Results, — ^To show the relationship of the copper-re-
ducing power, and the specific rotator}" power of the products
formed during the progress of the hydrolysis of the starch, we
have plotted our results, taking as abscissae the decreasing
values of the rotatory power, from the amy lodextrin stage (195"*)
to that of dextrose ([^]dsk = 53*5^) i ^^^ as ordinates the cupric
reducing power (K^ ) taking that of an equivalent weight of
dextrose as 100.' [See Plate A.]
1 Using Welsbach burner.
SData given in Table B.
•«t-y
•98t °[»]
*appEO idddoD
<
<
Q
<
s
X
u
o
M
09
O
u
Q
s
'S-Si *jjl 'ds
'39 13)9 AL
•93 )anoiny
•pnni<
*ajns«Md
3p91|d90linV
*q9i«)v fvnuJ
'SnpiooD
'dfdiBvt )0 'OM
'vnn
HYDROLYSIS OF STARCH BY ACIDS. 875
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ddodooddddddodddddo'dddo'oodddo
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r^ OnnO iO«'>OOv)mOm On^ OsnO M9^r«.M M o ONt^tor«.^^0 M M
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rN.«^ioONO O O «o« r^- »o
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876
G£0. W. ROLFB AND GEO. DBPRBN.
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•nnn
HYDROLYSIS OP STARCH BY ACIDS.
877
W On f*:0O OnvD OnxO QQ O d\^r*rO«^0
ro «" ro^ 10 >0 to N OnoO vO vO ci O 00 I>
t«Hf0iO'n-*25S'»O
t^ ^ ONNO 10 I') VNVd
iOnO pi W "H «o »0
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M M H
« « «
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w w « «
so O CI M o\ r>> r*NO o for*»Ovpopi « rhnoo t>. rcoo w ^ ^ ^o 10 »o f> ^
• •••■•*■•••••••••••••■••*•• • • •
r>.>o ao «o •*> «o o^oo >o lo ^ ^ 00 r^NO 10 on>o rh ro »^no ^ f*5 »ooo 0 ^ fo »o
ON 10 O M so VO ^00 N 00 to r^vO 00Q*o000Q0^^»O »Q M M fp j^-OO
iAio^rN.r^O *• -^loio^o ^vB r*0 cs »*>eo«Oforo« p* pi f^oo on o 00 r^
I
8
8
8
8
cS
o
lO
o
»o
I 1%
o
o
c5
BZe
0
6
^■4
0
rf\
^■4
^■*
v^ ^^
9^
u
U3
0
u
oa
u
s
X
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s
re
XX
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NO
10 "PQ
PI
10
NO
PI
10
NO
eOM
^
NO NONO NO
0 fONO r* ON ^ ON »*500 M »OnO on W »0 ^ « r»5 ^vO M M CI M onoo pi on w
M MNHP4 (i^M MCIM
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878 GEO. W. SOLFE AND CEO. DEFREN.
HYDROLYSIS OP STARCH BY ACIDS. 879
The results point to the remarkable fact that the cupric reduc-
ing power of the total product bears a constant relation to the
specific rotatory power, even when the starch is hydrolyzed under
widely varying conditions. Hence, given the one, the value of the
other can be calculated. To a rotation of about 90'', the plotted
r^ults outline with extraordinary exactness the arc of a circle,
the equation of which is
•^* + y* + 46&r — 646^ + 1580 = o,
which exactly intercepts the ** zero'* and ** hundred** points at
195 and 53.5, respectively. The upper part of the curve is not
so well defined, the results showing more discrepancy at the
high conversion stages. This may be due to some decomposi-
tion and the formation of ** reversion** products as stated by
Wohl,* Maercker, Ost, and others. Wohl's figures show the
maximum amount of dextrose possible to be 92.7 per cent, of
the theoretical quantity. Others give ninety-six to ninety-seven
per cent., the missing dextrose being supposed to be converted
into dextrin-like bodies identical with those variously described
as •*gallisin,*' ** isomaltose,'* etc. We have experimented but
little along this line, having made but one hydrolysis with this
special object, using y^ hydrochloric acid at four atmospheres
pressure, with the following results :
Time of cooking. L^Jd*
60 minutes 55-24
90 ** 5309
120 ** 53.40
150 " 54.42
While several of our own results at the low rotations show a
cupric reducing power of only about ninety-six per cent, of that
of pure dextrose, we do not think that we are justified in arriving
at any definite conclusion with the data at hand.
That the solutions begin to color considerably at rotations
beyond 90*^ is, moreover, a strong indication of such decomposi-
tion. On the other hand, this accounts for much of the dis-
crepancy of the ploi at this part of the curve, as it is exceedingly
difficult to get accurate readings on the saccharimeter of these
highly colored solutions. Obviously, too, slight errors in the
iBer. d. ckem. Gts., 33, aioi.
880 GEO. W. SOLPE AND GEO. DEFREN.
readings afiect the calculations of the rotatory power the most at
these lowest rotations.
Quite as noteworthy are the curves' plotted by taking the
values of maltose, dextrin, and dextrose as computed for every
PCffCrNT^ or CAIfBOHYDRATCS
Plate B.
five degrees of rotation from the values of /C, as given by this
curve.
In this work we have figured constants for solids estimated
from the specific gravities of solutions by the factor, 386, and
calculated percentages by the well-known equations :
5-+OT+rf=I.OO
^ + o.6iwi = A"
Where g- is per cent, dextrose,
m is per cent, maltose,
and d is per cent, dextrin.
27. 82
> Sn platt B.
HYDROLYSIS OP STARCH BY ACIDS. 88l
HxamiDing these curves we see that the dextrin starting from
the maximum of loo per cent, gradually falls to zero near the
rotation corresponding to dextrose, while the maltose gradually
rises, reaches a maximum percentage of 44.1 at about 129°
rotation, corresponding to the usual state of conversion of com-
mercial glucose, and then falls, disappearing at 53.5^. The
dextrose, on the contrary, steadily mounts to 100 per cent. It
will be noted, too, that at the point of maximum maltose the dex-
trin and dextrose, as shown by the intersection of the curves,
are present in equal quantity.
Tests with phenylhydrazin acetate show the presence of the
dextrose distinctly at about 185°, and we had hoped to prove the
gradual rise of the dextrose percentage by means of the dex-
trosazon. While copious precipitates of this beautiful com-
pound were obtained, any attempt of ours to isolate it in any-
thing like quantitative amounts proved a failure, even in solu-
tions containing a known amount of pure dextrose. We hope
to take this* up more fully in a later investigation.
We have also calculated a table (Table C) from the curves
giving the value of maltose, dextrose, and dextrin within one-
tenth per cent, for successive stages of acid hydrolysis repre-
sented by each degree of rotation between 195 and 53.5. This
table, calculated for the factor 386, makes no allowance for pos-
sible decomposition of high-converted products.
TABLE C.
Cai^ulatbd Values op Cupric Reducing Powers and Parts op Mal-
tose, Dextrose and Dextrin per Unit op Carbohydrate por
Bach Degree op Rotation op a Normally Hydro-
lyzbd Starch Solxttion.
C«]i%...
-^is.*
^.1.-
£^%%%'
^.•f
195 >
0.000
0.000
0.000
I.OOO
194
0.01 1
0.017
O.OOI
0.982
193
0.022
0.033
O.OOI
0.966
19a
0.032
0.048
0.002
0.950
191
0.04.1
0.063
0.002
0-935
190
0.051
0.079
0.003
0.918
189
0.061
0.094
0.004
0.902
188
0.071
O.I 10
0.005
0.885
187
0.081
0.123
0.007
0.870
882 GBO. W. ROLPB AND GBO. DBFRBN.
[«]y.M.
^f'
^tM-
^ISC*
^•••*
i86
0.090
0.135
0.009
0.856
185
o.zoo
0.147
0.0x0
0.843
184
0.109
0.160
0.013
0.827
183
0.1 18
O.I7I
0.016
0.813
183
0.137
0.183
0.019
0.799
181
0.137
0.193
0.033
0.786
180
0.146
o.ao3
0.035
0.772
179
0.155
0.3I3
0.038
0.760
178
0.164
0.332
0.031
0.747
177
0.173
0.231
0.034
0.735
176
0.183
0.240
0.037
0.723
175
0.I9I
0.250
0.040
0.710
174
0.199
0.357
0.043
0.700
173
0.307
0.365
0.047
0.688
172
0.316
0.373
0.050
0.677
171
0.334
0.380
0.054
0.666
170
0.333
0.387
0.058
0.655
169
0.343
0.394
0.063
0.644
168
0.351
0.301
0.066
0.633
167
0.359
0.307
0.071
0.632
166
0.367
0.314
0.075
0.61 1
16S
0.37s
0.330
0.080
0.600
164
0.383
0.336
0.084
0.590
163
0.393
0.332
0.089
0.579
163
0.300
0.338
0.093
0.569
161
0.308
0.344
0.098
0.558
z6o
0.316
0.349
0.103
0.548
159
0.334
0.356
0.107
0.537
158
0.332
0.363
O.III
0.527
157
0.340
0.369
O.I 15
a5i6
156
0.348
0.373
O.I3I
0.506
155
0.3S6
0.378
0.136
0.496
154
0.36s
0.383
0.130
0.487
153
0.373
0.388
0.135
0.477
152
0.381
0.392
O.I4Z
0.467
151
0.389
0.397
0.146
0.457
150
0.397
0.401
O.I S3
0.446
149
0.404
0.405
0.157
0.438
148
0.413
0.408
0.163
0.429
147
0.419
0.413
0.164
0.420
146
0.427
0.415
0.174
0.41 1
US
0.43s
0.415
0.183
0.403
144
0.443
0.421
0.186
0.393
143
0.450
0.423
0.193
0.385
HYDROI«YStS OP STARCH BY ACIDS. 883
C«]«....
^w
^m-
^«at*
^.•.•
14a
0.458
0.4*5
0.199
0.376
HI
0.465
0.427
0.2Q5
0.368
140
0.473
0.428
0.212
0.360
139
0.481
0.431
0.217
0.352
138
0.488
0.432
0.22 J
0.344
137
0.496
0.434
0.231
0.335
136
■
0.503
0.436
0.237
0.327
135
0.510
0.437
0.243
0.310
134
0.517
0.438
0.249
0.313
133
0.524
0.439
0.256
0.305
132
o.53«
0.439
0.263
0.298
131
0.538
0.440
0.270
0.290
»30
0.546
0.440
0.277
0.283
129
0.553
0.441 .
0.284
0.275
138
0.560
0.441
0.291
0.268
127
0.567
0.440
0.298
0.262
Z26
0.574
0.440
0.305
0.255
"5
0.580
0.439
0.313
0.248
124
0.588
0.438
0.320
0.242
123
0.595
0.438
0.327
0.235
122
0.602
0.437
0.335
0.228
X2I
0.608
0.436
0.343
0.221
120
0.614
0.435
0.350
0.215
119
0.621
0.433
0.358
0.209
XI8
0.628
0.431
0.366
0.203
XX7
0.655
0.429
0.374
.).I97
X16
0.642
0.428
0.381
0.191
"5
0.649
0.425
0.390
0.185
114
0.656
0.422
0.398
0.180
113
0.663
0.420
0.408
0.174
112
0.669
0.417
0.414
0.169
III
0.675
0.414
0.423
0.164
no
0.681
0.408
0.432
0.160
109
0.687
0.407
0.439
0.154
108
0.694
0.403
0.448
0.149
107
0.700
0.400
0.456
0.144
Z06
0.707
0.396
0.465
0.139
105
0.713
0.392
0.474
0.134
104
0.719
0.387
0.483
0.130
103
0.725
0.383
0.492
0.125
102
0.732
0.379
0.500
0.121
ZOI
0.738
0.375
0.508
0.117
100
0.744
0.370
0.518
0.112
99
0.750
0.366
0.527
0.107
884 Ono. W. ROLPB AND GBO. DBPRBN.
[«]?....
^w
Jlf„^.
^«M*
^•M-
98
0.757
0.361
0.537
0.102
97
0.763
0.356
0.546
0.098
96
0.769
0.350
0.556
0.094
95
0.775
0.345
0.565
0.090
94
0.781
0.341
0.574
0.085
93
0.787
0*336
0.583
0.081
92
0.793
0.331
0.592
0.077
91
0.799
0.326
0.601
0.073
90
0.805
0.320
0.610
0.070
89
0.810
0.314
0.620
0.066
88
0.816
0.308
0.629
0.063
87
0.822
0.302
0.638
0.060
86
0.828
0.295
0.649
ao56
85
0.834
0.288
0.658
0.054
84
0.839
0.282
0.667
0.051
83
0.844
0.275
0.677
0.048
82
0.850
0.267
0.688
0.045
81
0.856
0.259
0.698
0.043
80
0.862
0.251
0.709
0.040
79
0.867
0.243
0.719
0.038
78
0.872
0.234
0.730
0.036
77
0.878
0.225
0.741
0.034
76
0.884
0.217
0.751
0.032
75
0.889
0.208
0.762
0.030
74
0.895
0.200
0.772
0.028
73
0.901
0.191
0.783
0.026
72
0.906
0.182
0.794
0.024
71
0.91 1
0.173
0.805
0.022
70
0.916
0.163
0.817
0.020
69
0.921
0.153
0.828
0.019
68
0.926
0.143
0.839
0.018
67
0.932
0.134
0.850
0.016
66
0.937
0.125
0.861
0.014
65
0.943
0.115
0.872
0.013
64
0.947
0.105
0.883
0.012
63
0.952
0.095
0.895
0.010
62
0.957
0.085
0.906
0.009
61
0.962
0.075
0.917
0.008
60
0.967
0.065
0.927
0.008
59
0.972
0.055
0.938
0.007
58
0.977
0.045
0.949
0.006
57
0.982
0.035
0.960
0.005
56
0.987
0.025
0.971
0.004
55
0.992
0.015
0.982
0.003
54
0.997
0.005
0.993
0.002
53-5
1.000
0.000
1. 000
0.000
HYDROLYSIS OF STARCH BY ACIDS. 885
It would seem obvious that we are now prepared to determine
whether a sample of glucose is a product of one hydrolysis ot is
a mixture of two separately converted products, by comparison
of the actual analytical results with those calculated from the
rotatory power.
For testing this method we have made a few analyses of com-
mercial glucoses obtained in open market.
In the manufacture of glucose syrup all the starch is not
hydrolyzed under strictly the same conditions, as the factory
practice is to pump the starch into the converter, which is under
steam pressure and already contains the hydrolyzing acid. As
the filling of a converter takes about one-third of the total time
of cooking, it is clear that there is a radical difference in the
time of hydrolysis of different portions of starch. Nevertheless,
we have found that samples known to have been made under
these conditions conform to the laws of our curve, and the evi-
dence seems strong that those which depart widely from these
conditions are mechanical mixtures.
The following determinations of four samples of commercial
glucose giving the cupric reducing power as found and as calcu-
lated for the corresponding rotation will illustrate the method :
Sample. ^»386. -^386 (obUincd). K^ (calculated).
I. C. PopeCo. (J) 131. f 0.566 0.537
II. C. PopeCo. (M) 125.4 0-578 0-578
III. Rockford Co 141 -9 0.454 0.457
IV. Chicago Co 137-2 0.505 0.495
Evidently II and III are normally hydrolyzed. IV is possi-
bly a mixture, while I is undoubtedly so. As this latter is a
sample of jelly goods which in factory practice are often made
by mixing two lots, our conclusion is strengthened.
From the results as a whole we have concluded that the evidence
is strong, ( i ) that in any homogeneous acid-converted starch prod-
uct, irrespective of the conditions of hydrolysis, the specific
rotatory power always represents the same chemical composition.
(2) That but three simple carbohydrates,* possible in molec-
ular aggregates, exist in the solution of a starch product hydro-
lyzed by acids.
^ Leaving: out of consideration the possible sm<(ll amounts of products formed by
ttrcrsion.
886 GEO. W. ROI«PE AND GEO. DEPREN.
DETERMINATION OP THE CONVERSION OP COMMERCIAL GlrU-
COSE.
In the manufacture of gluco^ it is obviously essential to have
a rapid means of determining the degree of conversion of the
starch during the cooking process. The usual factory practice
is to control the conversion by means of iodine color tests.
These tests are usually made by adding a definite number o£
drops of standard }odine solution to a te^t-tube of the cooled
glucose liquor. The tint at which the conversion is considered
complete varies in general practice from that corresponding to
[a]D = r28 to [«]d = 135, the variation being even grater in
some cases, depending on the ideas of the manufacturer and the
grade of goods desired.
By daily practice workmen become quite expert in making
these iodine tints, which are usually carried out by crude
methods and read off without comparison with any standard.
Nevertheless, the product, when examined by more refined
laboratory processes, shows wide variations from day to day,
which does not appear surprising when we examine into the
errors of such color tests.
Assuming that the test is carried out under uniform condi-
tions of concentration and proportion of reagent to liquor to be
tested, which is by no means always the case, the other condi-
tions affecting the color are (i) temperature, (2) turbidity, and
(3) illumination.
Uniform temperature can be obtained easily by some simple
cooling device as a stream of running water.
The acid converter liquors are always turbid when tested, as
filtration in this rapid testing is impracticable. The turbidity^
however, is fairly constant. It is the third condition, that of
illumination, which is constantly variable and which gives rise
to the greatest error. This source of error can be largely elimi-
nated by the use of a comparison standard, prepared of the same
volume as that used in the color test and hermetically sealed in
a glass tube of the standard size used in testing. Mixtures of
solutions of iron salts with finely pulverized glass giving the
requisite turbidity when shaken, can be easily made to exactly
match the iodine tint, and will preserve their intensity indefi-
HYDROLYSIS OP STARCH BY ACIDS. 887
nitely. When properly adjusted by means of polariscopic tests
such standards have served well to fix the point of conversion
within narrow limits and have done much to insure a uniform
product.
It is of course important that these should be in the hands of
the chemist or superintendent of the works, a much more exact
means of testing the degree of conversion. This is most natur-
ally accomplished by determining the specific rotator>' power.
We have arranged a table for quickly calculating specific
rotatory power, and found it so useful that we venture to publish
it. The following simple calculation will sufficiently explain
the principles on which the table has been worked out :
TABLE D.
Table for Determining Specific Rotatory Power of Solutions of
7.50^-10^ Brix by Reading of Ventzke Saccharimetbr.
Srix.
Sp. gr.
/r= grram
per 100 cc.
Log '7.20
Brix.
Sp. gT.
/r= gram
per xoo cc.
i^kCV^).
7.50
1.0298
7-724
0.3477
S.80
1.0352
9.1 10
0.2760
7.55
1.0300
7-777
0.3447
8.85
1.0354
9.163
0.2735
7.60
X.0302
7.829
0.341S
S.90
1.0356
9.217
0.2709
7.65
1.0304
7-883
0.33S8
8.95
X.035S
9.270
0.2684
7.70
1.0306
7.936
0.3359
9.00
1.0360
9324
0.2657
■■75
1.030S
7.0S9
0-3330
9.05
X.0362
9.378
0.2634
7.''«o
1.03x0
S.042
0.3301
9.10
io:M
9.430
0.2610
7.»5
1.0312
S.096
0.3272
9.15
1.0366
9.4S4
02585
7.90
1.0315
S.149
0.3244
9 20
1.036S
9.538
0.2560
7-95
1.P317
S.202
1
0.3216
9.25
1.0370
9-592
0.2536
S.00
1.0319
S.255
0.3187
930
1-0372
9.646
0.25x0
S.05
1.0321
S.30S
0.3160
9.^5
1.0374
9.690
0.2488
R.10
1.0323
S.361
0.3x32
9.40
1.0376
9.753
0.2464
8.15
1.0325
0.415
0.3104
945
1.0378
9.S07
0.2440
8.30
1.0327
S.468
0.3077
9.50
1.03S1
9.862
0.24x5
S.35
1.0329
8.522
0.3050
9.55
1.03S3
9.916
0.239X
S.50
1.033:
8.575
0.3022
9.60
10585
9.970
0.2368
».35
10.V3
S.629
0.2995
965
1.03S7
10.023
o.?346
R.40
1.0335
S.6S2
0.2969
9.70
1.03S9
X0.077
0.2323
8.45
1.0337
8.7.^5
0.2943
9-75
10391
X0.X30
0.2300
S.50
1.0339
S.7SS
0.2916
9. So
1.0393
10.185
0.2277
8-55
1.0341
$.842
0.2S89
985
1.0395
10.239
0.2252
R.60
10343
S.895
0.2S64
9.90
10397
10.293
0.223X
8.65
10345
8.9*9
0.283S
9.95
10399
10.347
0.2207
8.70
1.0347
9.002
0.2812
10.00
1.Q401
10.401
0.2x85
8.75
1.0350
9.056
0.2786
Taking the usual formula for the specific rotatory power,
«= ~, where a is the angle of rotation of the solution of w
Iw
888 GEO. W. ROI«PB AND GBO. DBPRBN.
gram of the active substance in v cc. of water observed through
a column / decimeters long. If we make a^=^ a it is plain 'w is
the weight of substance under standard conditions which will
give a direct reading of the specific rotatory power without calcu-
lation. In an instrument reading in angular degrees under the
usual conditions of v = loo and /= 2, w is therefore 50^.
If a is the reading of a saccharimeter with the Ventzke scale,
a^.:^ 50 X 0.344 =17.20, and the specific rotatory power of any
solution of known concentration of an optically active substance
will be -^ — . The easiest way of finding the concentration
w
of glucose solutions with sufficient exactness for this work is by
the Brix (or Balling) hydrometer, as this instrument is now
made of great accuracy.
Brix hydrometers are carried in regular stock of the larger
houses dealing in chemical apparatus for brewers and sugar
manufacturers, with scales having a range of about five degrees
and easily read to 0.05 per cent. Thermometers are attached
having corrections for temperature marked on the scale. Con-
centrations of about ten per cent, are mo.st convenient for polar-
izing ; hence a spindle will be needed reading from five to ten
per cent.
The method of determining rotatory powers is as follows : The
glucose is diluted to an approximately ten per cent, solution.
An exact Brix (or Balling) reading is taken, corrected for
standard temperature and the solution polarized in a 200 mm.
tube in any saccharimeter with the Ventzke scale. The loga-
rithm of the factor -^ — corresponding to the Brix reading is
w
then found in the table. Therefore, the calculation which is,
log [«]d "=■ log \— — ) + log a, simply requires finding the
logarithm of the saccharimeter reading and the number corres-
ponding to the sum of this and the logarithm given in the table.
This number is the required specific rotatory power.'
1 Obviously a table made on the scheme of the well-known Schmits table for cane-
sugrar aymps would do away with all calculation. Such a table is, however, rather
bulky for insertion here.
HYDROLYSIS OF STARCH BY ACIDS. 889
Thus a solution of 7.85 Brix having a reading of 51.7*,
Ventzke has the rotatory power of its anhydrous carbohydrates
determined as follow^ :
By the table, the corresponding logarithmic factor is 0.3272.
Log 51.7 = 1.7135
Factor 0.3272
2,0407 = log 109.8
which is the required rotatory power.
In this calculation no correction is made for ash, which, as a
rule, does not affect the results appreciably.
The errors due to the slight variations in the concentration of
the solutions used and changes in the temperature of the labora-
tory are too small to be taken into consideration in factory work
or in general commercial analysis. The method in practice is
^uite as rapid as the '* quotient of purity" determination of cane-
sugar syrups. We suggest that this, or some similar scheme,
be uniformly used for expressing the results of all polarimetric
investigations of honeys, syrups, and similar indeterminate mix-
tures of carbohydrates met with in commercial analysis, instead
of merely giving the polari2ations, or the specific rotatory powers
referred to the weights of the sample. The advantages are
obvious. Such analytical results would be close approxima-
tions to the exact specific rotatory powers of the mixed anhydrous
carbohydrates, and would be convenient of interpretation by
inspection as being directly comparable on what is for all prac-
tical purposes an absolute standard and the one used in all
strictly scientific work of the kind.
THE SPBBD OF THE HYDROLYSIS OF STARCH BY ACIDS.*
The laws of the speed of hydrolysis of the carbohydrates with
the exception of that of cane-sugar have been but little studied.
Solomon* has collected some data on the action of various acids
at boiling temperature. Welhelmy' showed in the case of the
catalytic action of hydrochloric acid on cane-sugar that if the
1 Wc are greatly indebted to Prof. A. A. Noyes* of this department, for valuable aid
in calculating the results of this work on speed of hydrolysis.
^J.prakt, Chem., (a). a6.
• Ber. d, chem. Gts,^ il, »xi.
890 GEO. W. ROI,FE AND GEO. DEFREN.
amount of acid and the temperature remained constant the rate
of the inversion at any specified moment is proportional to the
amount of unchanged sugar present at that moment.
That is, if A^ represent the amount of sugar originally pres-
ent, X the amount of this sugar changed over in any period of
time, /, and cthe reaction-constant, we have ~- =z c (A^ — x).
at
The relative values of the constant, c, of the various acids in
their action on cane-sugar have been determined by several
observers, notably Ostwald,* who has compared, by means of
their constants, the relative effect of chemically equivalent quan-
tities of a large number of acids, taking the constant of hydro-
chloric acid as a standard with the arbitrary value of 100.
Recent work shows that acids act on salicin,*one of thegluco-
sides, in a manner analogous to that of cane-sugar, the speed of
hydrolysis of this body by the different acids bearing the same
relation to hydrochloric acid.
The observations noted above suggested the possibility that
in the hydrolysis of starch the acids would show the same pro-
portional speed of reaction. This is an especially interesting
problem because the starch molecule is exceedingly complica-
ted, the molecular weight being undoubtedly very high. Starch
hydrolysis, however, must be considered as somewhat different
from that of cane-sugar or salicin. While these are easily solu-
ble in cold water, starch is totally insoluble at ordinary room
temperature. On the other hand, amylodextrin, the product of
decomposition of starch by boiling water, is somewhat soluble in
cold water, its solubility increasing with rise of temperature.
As by the customary procedure in determining speed of
hydrolysis, it would be necessary to ascertain the exact moment
when all the starch has been converted into the soluble form, a
point not conveniently determined, we have adopted a method
of measurement, based on the following principles :
The conversion products of starch, with the possible excep-
tion of those of very high rotatory power, are easily soluble in
water, and can be looked upon as mixtures of maltose, dextrose
and dextrin.
\J,prakt. Chem., 18S4, 401.
2 Noyes and Hall : ZUchr. phys. Otem.^ /SgtS^ MO-
HYDROLYSIS OP STARCH BY ACIDS. 89 1
The starch first changes to amylodextrin. The hydrolysis
then proceeds by successive stages through the so-called malto-
dextrin; maltose, and dextrose. ** Reversion," so-called, may
take place to some extent, a small amount of the dextrose form-
ing dextrin-like bodies, ** gallisin," ** isomaltose," etc., but this
point is not considered in this work. The dextrin may there-
fore be looked upon as the original substance hydrolyzed, and
maltose and dextrose as successive products of the reaction.
Further, we have shown that whatever the condition of
hydrolysis by acids, the specific rotatory power of any conversion
product corresponds to a definite chemical composition, tables
for determining which we have constructed.
Thus, for instance, a conversion product of i6o^ has been
proved to contain 54.8 per cent, dextrin, the remainder being
maltose and dextrose.
Hence, the time of taking any sample after the contents of
the autoclave has acquired constant temperature, which re-
quires about ten minutes, can be taken as the initial point for
determining speed of hydrolysis, and all subsequent samples
referred to this, as it is obvious that in any sample we can ascer-
tain the dextrin unacted upon at that stage of the hydrolysis.
The same holds true of maltose.
We have to deal with two reactions, the first being the hydrol-
ysis of dextrin to maltose.
If Ao is the amount of dextrin at the initial point taken, A^ — x,
the amount remaining at any time, /, and c the constant depend-
dx
ing on conditions of hydrolysis we get, -~- =c (A^ — x),
at
A I
This, on integrating, gives log ° = ci, or — log
A—^x t
=f f , which is the general equation of a first-order reac-
^0 — X
tion. The second decomposition is that in which maltose is
hydrolyzed to dextrose, and is peculiar in so far as it pro-
ceeds simultaneously with that by which the maltose is formed.
As a result of the hydrolysis of the dextrin the maltose increases
rapidly to' a maximum of 44.1 per cent, at a rotation of 129**.
892 GEO. W. ROLFE AND GEO. DEPREK.
It then gradually diminishes, while the dextrose percentage
always increases.
Consequently, the equation expressing accurately the rate of
change in the total amount of maltose present is quite compli-
cated, and we have therefore used an approximate formula,
which is sufficiently exact for the work in hand. The formula
is derived from the exact differential equation
which states that the amount of dextrose formed at each moment
is proportional to the amount of maltose present by replacing
the differential quantities by finite differences, which in applica-
tions of the formula must of course be taken small. In the
place of M the average amount of maltose present during the
interval of time considered is also substituted. That is, if M^
and M^ are the amounts of maltose present at the time, /. and /,,
and D^ and D^ the amounts of dextrose present at these same
times, and c^ is the reaction constant, we get as a result of the
above mentioned substitutions :
or,
1^. + ^, '
(^)
I
2
The results are contained in the following tables :
TABLE E.
Speed of Hydrolysis of Starch.
Time /.
(minutes)
[«]o...
A Q'~'X.
-4.
Ci.
2
c,.
Hydrochloric acid
: 0.02 normal ; aX2 A T= 135°
c.
io = 20\
c
"]'i?«..=
161 ; Wo
= 55.8.
10
137
35-5
0,2216
0.02216
0.3581
0.0358
20
IIS
20.3
0.4391
0.02196
O.3II8
0.0312
30
100
II. 2
0.6784
0.02261
0.3790
0.0379
40
88
6.3
0.9684
0.02421
0.3274
0.0327
50
76
32
I.24I5
0.02483
0.4638
0.0464
60
69
1.9
1.4678
0.02446
0.4162
0.0416
70
64
1.2
0.02344.
1-6674
0.02382
0.4264
C,= 0.0373.
0.04.36
HYDROLYSIS OP STARCH BY ACIDS.
893
40
70
100
X40
180
Snlphnric acid : 0.0a normal ; ata A T^ 135° C.
/o » ao ; [a] D ,M = 177° ; ^o —73.5.
to
X63
57.9
ao
15a
46.7
3«>
140
36.0
40
139
375
60
109
15.4
80
90
7.0
100
77
3.4
lao
66
M
azQ36
a3i48
0.3100
0.4270
0.6788
1. 021 3
1.3348
1.7103
O.OX(^
O.OII34
0.0x033
0.01068
0.0ZI3X
0.0x377
0.0133s
0.01434
01954
O.X436
O.X703
0.X678
a.36s6
0.4700
0.4809
0.6915
Cg ss o.oaxx.
aoz95
0.0x44
0.0x70
0.0168
0.0x88
ao335
0.0340
0.0346
Ci s 0.01x8.
Oxalic acid : 0.04 normal ; at 2 ^ T^t 135^ C.
/oa2o; [«]i?,„s=l8oO; -4«=s77.2.
30
157
51.6
O.X75O
0.00875
0.3147
0.0157
40
137
33.5
a ^36
0.00907
0.3890
0.0x45
60
X30
31.5
0.555a
0.00935
0.3738
aoi37
80
106
13.9
0.7446
0.0093X
0.3763
0.0x38
xoo
93
8.x
0.9791
0.00979
0.3334
* 0.0x61
130
83
4.5
1.2344
O.00039
0.3426
0.0x71
140
73
3.6
B 0.00957.
1.4726
0.01053
0.4149
Cn ss 0.0x59.
Sulphnrous acid : 0.02 normal ;At2A T^ 135^ C.
/o — 50; [«]d„.= i87^; ^0=87.
50
179
76.0
0.0587
0.00x17
O.X354
0.0035X
xoo
17a
67.7
O.X069
0.00x09
0.0907
o.oox8x
150
165
60.0
o.x6x3
0.00X0B
O.IOX3
O.OQ303
300
159
53.7
0.3095
0.00105
0.0799
0.00x59
ago
151
45.7
0.3796
O.0OXX3
o.xq36
300
144
39-3
0.3451
O.OOXX5
0.0978
0.00X96
350
137
335
0.4145
0.00X19
0.1053
o.ooaxx
400
131
39.0
0.4773
O.OOXX9
0.0893
0.00x79
C^
3S O.OOXX3.
c^
s 0.00x98.
Acetic acid
: 0.5 normal ;
at 2 ^ r«
« 135^ c.
/o — 50;
[«]"„. = «7o°; A
= 65.5.
50
143
38.5
a3307
O.OQ46X
0.3775
0.00755
100
I3X
33.x
0.4718
aoQ473
0.35x6
0.00703
ISO
103
X3.5
0.7193
aoo48o
0.3643
0.00739
300
86
5.6
1.0680
O.00S34
0^638
0.00938
350
74
3.8
1.3690
0.00548
0.4969
0.00994
C^
K 0.00449.
c.
s 0.00633.
Hydrochloric acid : 0.01 normal ; at i ^ 7"= I2Z^ C.
4«4o; [«]",„ =183°; ^0 = 81.3.
0.00373
0.00369
0.00369
350
168
158
149
137
136
130
107
63.3
52-7
43.8
33.5
25.5
31.5
14.4
10
!>»••'
0.1087
O.X883
0.3686
0.3851
0.5036
0.5777
0.7517
0.00375
0.00380
0.003S9
0.0030X
Cj SE 0.00279.
0.31X8
O.X358
0.1199
0.1764
0.1693
O.X038
0.2539
Ci s 0.00467.
0.00539
0.00453
0.00400
0.0044X
0.00423
0.005x4
0.00506
894 OBO. W. ROI«PE AND GEO. DBPRBN.
Hydrochloric acid : o.oi normal ; at 2 A Ts= 135^ C.
/os2o; [«]"„.= 176°; Wo«»7a-3-
10
163
56-9
0.1040
0.0104
O.X937
0.0x94
90
148
4a.9
0.3366
0.0x13
0.1877
0.0x88
40
138
36.8
0.4310
0.0x06
0.30x5
O.OI5X
60
XIO
16.0
0.6550
0.0x09
0.3*59
0.0x63
80
93
8.1
0.9506
0.0XX9
0.4x02
0.0305
100
81
4.3
X.3356
0.0x33
0.3830
0.0183
xao
70
3.0
0.0x15.
1.5581
0.0x30
0.4479
Cf as 0.0x87.
0.0394
5
X58 5a-7
xo
X40 36.0
15
X3S 14.8
ao
XIO x6.o
30
88 6.3
40
74 a.8
50
65 1.3
Ci = 0.03x4.
0.0347
0.3766
aQS53
0.0389
0.3538
0.0506
0.0300
0.3351
OXH70
0.0331
0.3756
OJ055X
0.0349
0.5544
0.0554
0.0350
0.5630
0.0563
0.0344
0.6349
C« 9:0.00548.
0.0640
Hydrochloric acid : 0.01 normal ; at 3 y^ T^at 145^ C.
/o«io; [«]i?,M — 174°; ^0 = 70.
O.X333
a3888
0.4506
0.64x0
1.0458
1-3979
1.73X3
Hydrochloric acid : o.oi normal ; at 4 yf 7^=: 153^ C.
/o =* 10 ; [a] *D ,„ = 147° ; Ao = 42.0.
5 XX7 X9.7 0.3387 0.0657 0.4900 0.0980
xo 96 94 0.650X 0.0650 0.467X 0.0934
15 79 3-8 1.0434 0.0696 0.5443 0.X088
30 68 X.8 X.3679 0.0684 0.6060 0.13X3
25 61 0.85 1.6938 0.0678 0.7x57 O.X43X
30 57 0.5 X.9343 0.0641 0.7818 0.X564
Cj = 0.0668. Ci SSO.X303.
Hydrochloric acid : 0.04 normal ; At ^ A T= 145^ C.
3
XX5 X8.5
0.383X
O.X377
0.5736
0.X9X3
5
95 9.0
0.696X
0.1393
0.4541
0.3370
7
80 4.0
X.048X
O.X497
0.4833
0.34x6
xo
66 X4
1.504a
0.1504
0.8083
0.3694
X3
58 0.6
1.8731
0.1440
1.0350
0.3450
«5
66 0.4
C| s 0.14x3.
3.0482
0.X365
c.
0.6385
s 0.3648.
0.3143
Hydrochloric acid : 0.02 normal ; At ^ A Tss 145^ C.
/o = 10 ; [«] D „a« 148" ; Ao =?42.9.
5
xx6 19. X
0.3515
0.0703
0.5346
0.X019
xo
96 9.4
0.6594
0.0659
0.4478
0.0896
X5
80 4.0
1.0304
0.0687
0.5075
0.X015
30
69 1.9
1.3537
0.0677
0.5889
0.XX78
15
6x 0.85
X.7031
0.0681
0.7739
0.X548
30
56 0.45
Cj =0.0678.
1-9793
0.0660
X.0600
C, = 0.1304.
0.3x60
HYDROI^YSIS OP STARCH BY ACIDS. S95
Hydrochloric acid : o.ox normal ; at 3 yl Tss 145° C.
^— s; Wd,„ = i74°; a— 70.
5
158
Sa.7
0.XJ33
0.0147
0.3766
0.0553
10
X40
36.0
o.a888
0.OS89
0.3538
0.0506
15
185
H.8
0.4506
0.0300
0.335X
0.0470
ao
txo
x6.o
0.64x0
0.0331
0.3756
0.0551
3»
88
6.3
X.Q458
o.<^J49
0.5544
0.0554
40
74
3.8
X.3974
0.0350
0.5^
0.0563
50
65
Ci
u 0.03x4.
x.yaxa
0.0344
0.6349
C,s 0.0548.
0.0640
Hydrochloric acid :
0.005 normal ; at
ZAT^ 145°
c.
/o = ao ;
[«]V...-
172° ; Ao
= 67.7.
ao
Ua
37.6
o.a554
o.oxaB
0.4370
o.oax4
40
1x3
17.4
0.590X
0.0148
0.0345
60
9X
7-3
0.9673
o.oi6x
0.5336
0.036X
80
77
3-4
x.a99X
0.0163
0.5083
0.0354
xoo
66
M
1.6845
0.0x68
0.7439
0.0371
190
59
0.7
=E 0.0x55.
X.9855
0.0x65
0.8X73
C| TT 0.0379.
0.0409
At the head of each table are given data as to the concentra-
tion and nature of the acid, the temperature corresponding to
the steam pressure given in atmospheres and [^]d386 at the initial
time period /« with the corresponding value of A^, Time values
are expressed in minutes, and the constants c^ for the hydrolysis
of dextrin, c^ for that of maltose, are calculated according to the
formulas given above.
The results show that the constants in general are satisfac-
tory, and that therefore the reaction like the sucrose inversion
follows the law of the first order. It will also be seen that the
values c^ are much more uniform than those of c^, which is to be
expected since c^ is absolute and c^ only approximate. Devia-
tions of c^ may be fairly ascribed to variations in temperature
which, though slight, are significant, owing to the high temper-
ature coe£Gicient of the reaction.
The dextrin values in Table C are consequently correct within
the hmits of error of analysis. It will be seen that the values
of c^ are much more constant in those determinations in which t
is larger and the values of [^]d decrease slowly. This was to
be expected from the conditions of the approximate formula
given above for the decomposition of maltose, these requiring
that the amount of substance changed in a period of time must
be small. The question of reversion may possibly have some
896 GEO. W. ROLFB AND GBO. DBPRBN.
influence on the values of r, but as yet we are not prepared to
express ourselves definitely on this subject.
The relative effects are shown in the following tabic : Table
I shows the influence on the speed of hydrolysis of various acids
at the same temperature, 135® C.
Table II shows the influence of temperature on the speed of
hydrolysis when the same amount of acid is used.
Table III gives the influence of varying amounts of acid.
The mean value of constants are given in column II. Column
III gives the relative value of the constants referred to that of
y^A^ hydrochloric acid at 135° taken as 100. Column IV
gives the velocity constants determined by Ostwald' for cane-
sugar inversion by the same acids at half-normal concentration.
Tablb I.
Acid. Concentration. II. III. IT.
Hydrochloric 0.02 N 0.02344 100 100
Sulphuric 0.02 N 0.0118 50.35 53.6
Oxalic 0.04 N 0.00957 40.83 ....
( *' ) (0.02 N) (0.00479) (20-42) 18.6
Sulphurous 0.02 N 0.00113 4.82 ....
Acetic , 0.5 N 0.00499 21.29 *"■
( ** ) (0.02 N) o.oo(i20 0.8 0.4
Tabi«b II.
Acid. Concentration. Temp. I. II.
Hydrochloric o.oi N 121 0.00279 11.91
** 0.01 N 134 0.0115 49-07
** 0.01 N 145 0.0314 13.40
'* 0.01 N 153 0.0668 28.50
Tablb III.
Acid. Concentration. II. III.
Hydrochloric 0.04 N 0.1413 602.9
*' 0.02 N 0.0678 289.3
'* O.OI N 0.0314 134.0
" 0.005 N 0.0155 66.13
It is seen that the corresponding numbers of columns III and
IV agree fairly well. The relative influence of the various acids
upon the hydrolysis of starch, sucrose and salicin are therefore
nearly identical. It should be noted however that the chemical
activity of hydrochloric acid on starch, as in the case of salicin
1 Loc, ciU
HYDROLYSIS OF STARCH BY ACIDS. 897
and cane-sugar, increases in a greater ratio than the concentra*
tion, while the electrical conductivity increases more slowly.
The influence of temperature can be explained graphically by
a curve approximating a parabola.
89S GEO. W. ROLPE AND GEO. DEFREN.
Plate II shows the influence of the various acids.
HYDROLYSIS OP STARCH BY ACIDS. 899
Plate III shows the tnflaeoce ot the conceDtration, or amount
of acid used.
900 HYDROLYSIS OF STARCH BY ACIDS.
Plate IV shows the relative curves due to temperature.
NICKELO-NICKELIC HYDRATE, Ni,0,.an,0.
By William L. Dudlby.
Received Aufust ttf, M»gii.
IN Studying the action of fused sodium dioxide on metals, I
have obtained interesting crystalline compounds, some of
which, at least, have never been described. Only one of them
has been carefully investigated and it proves to be nickelo-
nickelic hydrate, having the formula Ni,0^.2H,0.
It is prepared by fusing sodium dioxide in a nickel crucible
with metallic nickel at a cherry-red heat. The action of the
oxide upon the nickel proceeds with moderate rapidity, and in
a few minutes scaly crystals appear floating in the fused mass.
The crystals multiply steadily until, in the course of an hour,
the contents of the crucible is thick with them, and comparatively
little liquid remains. After cooling, the crucible is submerged
in a beaker of distilled water and the undecomposed sodium
dioxide together with the sodium oxide dissolves out, leaving
the crystals which rapidly settle to the bottom of the liquid.
The crystals should be washed several times with boiling water
by decantation, and finally thrown in a filter. It is quite diffi-
cult to wash out all of the alkali, which adheres with unusual
persistence. Probably the best plan to adopt is to put the crys-
tals in a Soxhlet extraction apparatus and wash with water until
no coloration is obtained with phenolphthalein. This requires
about fifty hours of continuous washing. The crystals should
then be dried at iio^ C. and a magnet passed carefully through
them to remove ^ny particles of metallic nickel which may have
eroded and not been completely acted upon.
The crystals are lustrous and almost black, with a slight brown-
bronze hue. They are soft, and grind in a mortar much like
graphite. The crystals seem to be hexagonal plates, but meas-
urements of the angles have not been made. They dissolve
slowly in acids, forming uickelous salts. Hydrochloric acid
evolves chlorine ; sulphuric and nitric acids, oxygen. They are
insoluble in water and in solutions of the alkalies. The com-
pound is not magnetic. The specific gravity is 3.41 15 at 32** C.
At 130* C. the compound does not undergo decomposition, but
at about 140* C. it begins to lose weight ; at 240'' C. the weight
902 NICKBU>-NICKBUC HYDRATE.
remains constant. At a red heat further loss is sustained and
the residue remaining is nickelous oxide. The loss, from 130** C.
to 240^ C. is due to water driven off, and at a red heat this loss
is due to the evolution of oxygen.
The compound proved to be Ni,0«.2H,0, as is shown by the
results of the analysis :
Loss of H,0 on heating from 130® C. to 240* C. :
Per cent.
First determination 13.00
Second ** 13.13
Theory for Ni,04.3H,0 13.06
The residue remaining after heating to 240** C. is Ni,0^.
On heating this residue to redness the loss of oxygen was found
to be:
Per cent.
Loss of oxygen 6.63
Theory 6.67
The total loss of water and oxygen obtained on heating the
compound from 130^ C. to redness was :
Per cent.
First determination 18.91
Second •* 18.88
Theory for NijO^.aHjO 18.86
The oxygen given off on heating to redness was determined
by calcining the compound in an atmosphere of carbon dioxide
and collecting in Schiff's apparatus over potassium hydroxide
solution. The result gave :
Per cent
Oxygen 5.93
Theory for NijO*. 2HiO 5 .84
The nickel was determined and found to be :
Per cent
Nickel 63.67
Theory 63.72
In all of the calculations the atomic weight of nickel was taken
to be 58.56 and oxygen 16.
The compound made in a nickel crucible of commerce is not
perfectly pure, as the sample obtained was found to contain 0.71
per cent, of cobalt, the presence of which, however, would make
no appreciable difference in the results of the analyses. No
method has been found for freeing the compound from this im-
TABLE OF FACTORS.
903
purity, and it appears at present as if the only plan would be to
use a chemically pure nickel crucible in making it, forno crucible
will withstand the action of fused sodium dioxide. Porcelain,,
iron, silver, gold and platinum crucibles are rapidly attacked.
The presence of water in this compound seems curious, but it
may be due to the presence of sodium hydroxide in the sodium
dioxide. Again it may be due to the water added to dissolve
the soluble residue from the crystals. The first explanation
seems to be the more plausible since the crystals are formed in
the mass while it is fused, and they are not produced upon the
addition of the water. If such is the case it would seem that
the water driven off between 130** C. and 240** C. is from the
breaking down of a true hydrate, rather than the expulsion of
water of crystallization.
A cobalto-cobaltic hydrate, Co,0,.2H,0, has been described,'
but it was obtained by exposing to moist air, Co,0^, prepared
by heating cobalt carbonate. Ni,0^, prepared by heating nickelo-
nickelic h3'drate to 240*^ C. is hygroscopic and absorbs about
seven and four- tenths per cent, of water from the air at 30® C,
which is completely lost at iio^ C, showing that no hydrate is
formed under these conditions.
The study of the action of fused sodium dioxide on the metals
will be continued here, and it is' hoped that some more data
can be contributed soon.
Vandbrbilt university.
TABLE OF FACTORS.
By Edmund H. Miller and J. A. Mathews.
Received August 6, xt96.
ATOMIC masses^ based on 0= i6, taken from an article by
F. W. Clarke, this Journal, March, 1896.
AIPO4
Sb,04
Sh,S,
A8,S,
Mg,As,OT
AgiAsOf
BaSO*
Required.
Al.
A1,0,.
Sb.
Sb.
As.
As.
As.
BaO.
PRCtor.
0.221976
0.418489
0.790067
0.714570
0.609522
0.483268
0.162234
0.657088
IpOSTftrithm.
I.346307I
I.6216835
1.8976643
i.8540446
i.7849890
1.6841870
I.2101418
r.8i 76234
I Gentta and Gibbs : Am. J. Set',, S3, 257.
904
TABLE OF FACTORS.
Required.
Factor.
Logarithm.
SO,.
0.342912
".5351829
s.
0.137342
i.1378121
Bi,0,
Bi.
0.896600
1.9525990
CaCO,
CaO.
0.560296
1. 7484173
CaSO,
CaO.
O.411899
1.6147904
CaCO,.
0.735145
1.8663731
CO,
C.
0.272893
1-4359916
Cr,0,
Cr.
0.684791
f.8355581
3K,S04.2CoS04
Co.
0.1415"
1. 1507892
CuO
Cu.
0.798995
j. 9025440
Cu,S
Cu.
0.798644
1.9023531
Fc,0,
Fe.
0.700076
i.8451446
Fe
Fe,0,.
1.42842
0.1548554
FeO.
1. 28561
O.IO91100
Fe,04.
1.38082
O.I401359
PbCrO*
Pb.
.640500
I. 8065 193
PbSO^
Pb.
.682927
1.8343742
Mg,PA
P.
.278681
1. 445 1076
PA.
.638038
1.8048465
MgO.
.361962
"•5586631
MgCO,.
.757343
1.8792934
MnjO^
Mn.
.720490
1.8576283
MnjPjO^
Mn.
.387226
£.5879648
CNH,),PtCl.
Pt.
.439205
1.6426669
N.
.063281
2.8012744
NH,.
.076911
2.8859881
NH,C1.
.241235
I 3824396
Pt from
f N.
.144081
1. 1 586075
(NH,),PtCl,
NHj.
.175114
1. 2433212
I NHjCl.
.549253
1.7397727
KjPtCl,
KCl.
.306951
1.4870695
KjO.
.193944
i. 2876767
KCl
K,0.
.631840
1.8006072
K,SO,
K,0.
.540593
1.7328706
SiO,
Si.
.470199
1. 6722814
AgBr
Br.
.425560
i. 628961 1
Agl
I.
.540313
1.7326479
AgCl
CI.
.247262
i393i579
Ag.
.752738
1.8766436
NaCl
Na,0.
•530769
1.7249057
Na,SO,
Na,0.
.436801
1.6402836
SnO,
Sn.
.788150
i. 8966087
TiO,
Ti.
.600749
1.7786928
ZnO
Zb.
.803464
1.9049663
ZdjPjOt
Zn.
.429115
1.6325737
ZnNH^PO*
Zn.
.366438
1. 564001 1
RAPID MEASURING PIPETTE.
Bv Bdward L. Smith.
RocelTad August 4, 1896.
THE apparatus described below is a device for rapidly meas-
uring and discharging a definite volume of liquid. It
may be well to state at this point that the principle is not appli-
cable in all, or in even the majority of cases, where it is desired
to measure and discharge liquid reagents in the laboratory. Where
extreme accuracy is essential, the ordinary pipette or a burette
must still be used. Perhaps the best way to explain the utility
of the apparatus will be to state the exact use to which it is put
in our laboratory. In the course
of some experiments with sand fil-
ters, samples of the different efflu-
ents as well as of the applied sew-
age were taken daily, treated with
a small quantity of a concentrated
sterilizing agent, and an analysis
made each week of the combined
daily samples.
It was to measure and discharge
this sterilizing solution that the
appsCratus was devised . The quan-
tity added in each case was five cc.
Of course a variation from that
amount of one- or two- tenths cc.
would not materially affect the re-
sults and the great advantage in con-
venience and rapidity over the use of
the common pipette for the same
purpose is admitted by ail who have
seen the apparatus work. A large
bottle forms the reservoir. The stopper of this bottle carries
two tubes. One simply serves to admit air and contains a loose
plug of cotton to exclude dust, etc. The other tube is bent to
form an ordinary siphon and the end of the longer limb is
attached to a short glass tube by means of a rubber connection.
906 CHARLES H. HBRTY AND J. G. SMITH.
provided with a pinch-cock. The short glass tube to which ref*
erence was just made passes through a stopper inserted into the
mouth of an ordinary test-tube. Through a hole blown in the
side of this tube another glass tube, bent to form a siphon, is
inserted and fastened in place by a piece of rubber tubing of the
proper size, slipped on over the tube. The leg of the siphon
inside the test-tube is of such a length that when the pinch-cock
above is opened and the liquid allowed to enter the test-tube,
five cc. will be automatically discharged when the level of the
liquid has reached a mark on a line with the top of the bend in
the siphon tube.
The apparatus can be constructed in a few moments in any
laboratory, and for purposes to which it is adapted, it will, I am
sure, be found satisfactory. It may be asked, what is the
advantage of the form suggested over the ordinary burette with
supply tubes ? The answer is, it does away with the necessarily
oft-repeated filling of the burette, and there is but one mark to
watch in making the measurement — ^that previously mentioned,
on the test-tube. The tubing used is of such size that a rapid
discharge is insured, the time required being less than would be
the case were a burette employed.
MERCURIC CHLOROTHIOCYANATE.
By Chaklbs H. Hbrty and J. G. Smith.
Received August 8. it96.
IT has been shown by one of us' that the so-called compound
lead iodochloride, PblCl, is not a true chemical compound,
but a mixture of lead iodide and lead chloride.
It has seemed advisable, therefore, to study more fully the
nature of the compound mercuric chlorothiocyanate, HgCl(CNS),
described by McMurtry.* To this end a series of solutions was
prepared, in one of which was used the exact proportions of
mercuric thiocyanate and mercuric chloride given by McMurtry
for the preparation of mercuric chlorothiocyanate ; in the other
members of the series, arbitrarily taken quantities of the one
salt were replaced by equivalent quantities of the other. The
^Am. Ckem.J.^ i8, 290.
sy. ckem. Soc., 1889, 50.
MERCURIC CHLOROTHIOCYANATB. 907
mixed salts were completely dissolved in hot water and the solu-
tions allowed to cool and crystallize. The quantities actually
used were :
Mercuric Mercuric
Name. thiocyanate. chloride. Water.
Grams. Grams. cc.
A 9-5000 3*1439 20cx>
B 6.7500 65.5004 750
C 5-5000 6.5715 550
Z>(McMQrtry) 5.0000 7.0000 450
E 4-5000 7-4285 350
F' 3-5000 8.2853 300
G i.oooo 10.4296 200
On cooling, crystals separated from all of the solutions except
G, The crystals from Ay B, C, and D were fern-shaped, while
those from E and /^were prismatic.
By evaporating the solution G one-half, quite a good crop of
prismatic crystals was obtained. The crystals from all of the
solutions were separated from the mother-liquor by filtration
and rapid pressing between folds of drying paper.
From the mother-liquor of D two crops of prismatic crystals
were obtained by evaporating to one-half and then to three-
fourths of original volume. These were designated D^ and
D\
The character of the various crops of crystals was determined
by estimating the mercury present in each. This was done by
reducing the compounds with sodium peroxide, as recommended
by Schuyten,' and weighing the mercury. Analysis showed :
Mercury calculated for
Mercury Mercuric Mercuric Mercuric
found. thiocyanate, chlorotbiocyanate, chloride,
per cent. per cent. per cent. per cent.
A 62.72 63.28 68.12 73-85
B 62.76
C 62.74
D 63.91
E 68.24
F 68.67
G 72.59
I> 68.45 —
Z>" .... 72.41
These results show that the various crops of crystals fall into
three classes, mercuric thiocyanate, mercuric chlorotbiocyanate,
and mercuric chloride. This was confirmed by inspection with
1 Chem, Ztg.t so, 339.
• • a... •••■
*• ••*■ ...
.• .... .*•
.... .... ..
• .
.« .... ....
a .
...
908 MBRCURIC CHU>ROTHIOCYANAT9.
the microscope. Further, the three successive crops of crystals
from solution D are seen to be the first mercuric thiocyanate,
slightly contaminated by mercuric thiocyanate, as proved both
by the high analytical result and by microscopic inspection, the
second crop is mercuric chlorothiocyanate, and the third mer-
curic chloride.
The low results in the case of the pure salts is undoubtedly
due to the fact that the filters containing the reduced mercury
were dried at the ordinary temperature with consequent slight
volatilization of mercury.
The effect of crystallization upon the salt mercuric chloio-
thiocyanate was next tried. A portion of the salt was dissolved
in hot water just sufficient for complete solution. On cooling
crystals separated, which, under the microscope, were seen to be
only mercuric thiocyanate. The mother-liquor from these, on
evaporating one-half, yielded only mercuric chlorothiocyanate.
On evaporating the mother-liquor from this last two-thirds the
crystals formed are seen to be a mixture of crystals of mercuric
chlorothiocyanate and mercuric chloride. Finally, on evapora-
ting this mother-liquor to dryness spontaneously, only crystals
of mercuric chloride were obtained. The substance therefore
undergoes dissociation when dissolved in water.
From all of the above it would seem that mercuric chlorothio-
cyanate is a true chemical compound, and further, that the only
compound which can be prepared from solutions of mercuric
chloride and mercuric thiocyanate is that represented by the
formula Hg<^5^g or HgCl,.Hg(CNS)..
These results varying so widely from those obtained in the
case of lead iodochloride suggest the question: is the difference
due to the fact that in the one case we have the more closely
related groups, iodine and chlorine, while in the other we have
the more different groups, thiocyanogen and chlorine, or is the
difference due to the fact that in the one case we have a lead
compound while in the other a mercury salt ? To test this point
work will be begun at once on mixtures of lead chloride and
lead thiocyanate.
University of Gborgia.
[Contributions prom the Chbmical Laboratory op Ca»b School op
Applied Science.]
XXIV — COMPOSITION OF AHERICAN KAOLINS.
By Charx,bs p. Mabb&y andOtzs T. Ki.ooz.1
Received July ae, 1^96.
ALTHOUGH great advances have been made in recent years
toward a better knowledge of American clays and suita-
ble methods for the manufacture of ware from them, much more
extended investigation is necessary, both concerning the com-
position of the great clay deposits and in the details of manufac-
ture. The first and most essential information is a correct
knowledge of the composition of all clays available for use. Of
scarcely less importance is masterly skill in the purification of
crude materials, shaping the ware and burning. In the prepa-
ration of materia Isit is questionable whether American manufac-
turers can wait patiently several months for the slow processes
of lixiviations and kneading that European porcelain makers
have found indispensable in the production of the finest porce-
lain. The great porcelain factories in Europe are founded on
the application of scientific skill and a personality in shaping
and burning, handed down by lineal descent through many
generations. Is it possible to procure for American factories
scions for those ancient families, or must we wait for its perfec-
tion by our own ready facility and ingenuity ?
As already mentioned, the porcelain manufacturer must be
perfectly familiar with the composition of all materials within his
reach. In making suitable mixtures he must have before him
as one of the most essential features of composition, the propor-
tions of free and combined silica, as well as the percentages of
lime, iron, alkalies and water.
Having at hand a collection of clays, including representa-
tives of American deposits, as well as several specimens from
famous factories in Germany, it seemed of interest to compare
the composition of clays from different sources. For the manu-
facture of the finest porcelain, the kaolin used in the Royal Ber-
lin factory, at Charlottenburg, may be accepted as a standard of
comparison. As every one knows who is familiar with the
1 This work was offered by Mr. Klooz in a thesis for the degrree of Bachelor of
Science.
9IO CHARLBS P. MABBRY AND OTIS T. KLOOZ.
qualities of true porcelain, the products from this factory are
approached by no other in the world. The composition of the
kaolin used in the manufacture of this ware is shown by the fol-
lowing analysis of the clay, two specimens selected at different
times, from great quantities within the Berlin factory.
I. 11.
Combined water 6.00 7.65
Silica 72.16 65.70
Alumina 20.05 24.49
Iron o.io 1.03
Lime 1.14 0.60
Magnesia 0.02 0.26
Sodium oxide 0.12 6.23
Potassium«ozide 0.41 0.03
Free silica 49-84 44*93
The different percentages in these analyses indicate that some
latitude is permissible, although a high percentage of silica is
evidently essential. These analyses show nearly the same com-
position as is given in the numerous analyses of the most cele-
brated clays of the German factories, especially in the low per-
centages of lime, iron and alkalies, and the large proportion of
silica. An analysis of biscuit ware from the same factor)' shows
nearly the same composition. Apparently the clay has the
required proportion of silica without further addition :
Silica 68.24
Alumina 29.16
Iron 0.10
Lime 1. 18
Magnesia o. 12
Alkalies 0.17
Free silica 57«50
Of the American clays, analyses showed that some contained
a considerable excess of silica above the amount required for the
oxygen ratio of silica to that of the alumina, 2 : i, or the formula
Al,0,.3SiO„ which is accepted in the manufacture of the best
German ware ; others only a small excess of silica. Of the high
silica clays, a specimen from a deposit in Maryland gave the
following results :
COMPOSITION OF AMERICAN KAOLINS. 9II
Combitied water 11.23
Silica 47.60
Alumina 37'38
Iron 1.66
Lime 1.50
Sodium oxide 0.22
Potassium oxide 0.34
Free silica 17.10
Another clay of this class is a Missouri kaolin which was
analyzed :
Combined water 4.15
Silica 82.64
Iron 12.41
Lime • 0.05
Magnesia 0.1 1
Sodium oxide 0.08
Potassium oxide 0.53
Free silica 69.45
The following analysis represents another high silica clay
from Black Rock, Arkansas:
Combined water 3.98
Silica 84.24
Alumina 11.50
Iron 0.08
Lime 0.52
Magnesia 0.02
Sodium oxide trace
Potassium oxide 0.42
Free silica 69.93
Another high silica clay is from Milton Hollow, Middlesex
Co., N. J. :
Combined water 5.52
Silica 75.06
Alumina 18.32
Iron 0.08
Lime 0.80
Magnesia 0.14
Potassium oxide 0.25
Free silica 59»7i
A specimen of clay from a deposit in Washington, Middlesex
Co., N. J., also showed a high percentage of silica :
912 CHARLBS F. MABBRY AND OTIS T. KLOOZ.
Combined water 2.00
Silica 89. 16
Alumina 5.77
Iron 0.07
Lime 0.70
Magnesia o. 12
Potassium oxide 1.29
Sodium oxide 1.31
Free silica 80.30
A clay having nearly the same composition as the specimen
from the Berlin factory, is from a deposit at Hockessen, Dela-
ware :
Combined water 6.55
Silica 71.46
Alumina 21.02
Iron 0.08
Lime 0.54
Magnesia 0.14
Potassium oxide 0.33
Sodium oxide 0.36
Free silica 53.13
It should not be inferred from the foregoing analyses that all
American clays are high in silica. Some of the largest and most
important deposits contain very little free silica. One of the
purest kaolins is found in large quantities in Indiana, and the
following analysis shows its composition :
Combined water I5»09
Silica 44.23
Alumina - 40.56
Iron 0.07
Lime 0.13
Magnesia o.io
Potassium oxide o.io
Sodium oxide 0.15
Free silica 2.41
A clay of somewhat similar quality is found in Northampton
Co., Pa. :
COMPOSITION OF AMERICAN KAOLINS. 913
Combined water 11.20
Sil ica 48 . 1 6
Alumina 37-24
Lime 2.00
Magnesia 0.29
Iron 1. 16
Potassium oxide 0.25
Sodium oxide 0.08
Free silica 2.8s
A paper clay from South Amboy, N. J., Middlesex Co., gave
the following results on analysis :
Combined wflter I3'35
Silica 43-30
Alumina 42.45
Iron 0.09
Lime 0.34
Magnesia o- 10
Potassium oxide 0.44
Sodium oxide • 0.08
Free silica 3.55
A washed clay used in the manufacture of china, from New
Castle, Del., gave the following composition :
Combined water 12.95
Silica 47.42
Alumina 38.42
Iron 0.08
Lime 0.70
Magnesia 0.12
Potassium oxide 0.30
Sodium oxide 0.12
Free silica - 4.79
A clay in Woodbridge, Middlesex Co., N. J., also used in the
manufacture of ware, is nearly pure kaolin :
Combined water 14-34
Silica ' 44.34
Alumina 38.09
Iron 0.15
Lime 0.96
Magnesia o.io
Potassium oxide i.oo
Sodium oxide 0.79
Free silica 1.33
914 COMPOSITION OF AMERICAN KAOLINS.
It is interesting to compare the composition of American kao-
lins with a standard kaolin used in England :
Combined water 13.00
Silica 46.00
Alumina 40.00
Iron » 0.33
Lime 0.33
Magnesia 0.33
Several of the clays analyzed are used in the manufacture of
ware. From some of these deposits specimens have been ana-
lyzed, and the results given in the " Chemistry-' of Pottery," by
K. Langenbeck, are not essentially different from those given in
this paper.
It is evident that the wide differences in the proportions of clay
and silica in American kaolins render it imperatively necessar>'
that they be taken into account in the selection of materials for
the manufacture of ware. It is also evident that the United
States is not wanting in an abundance of material for the manu-
facture of ware equal to the best foreign production .
DISCUSSION.
IVm . McMurtrie : It is an interesting fact not brought out here,
that in many of the clays of New Jersey, and I think particu-
larly from some of the deposits represented in the tables. Prof.
Geo. H. Cook reported appreciable quantities of titanic oxide
amounting to one-half per cent, more or less. The same con-
stituent has been found in clays from other localities which I do
not now exactly remember, but I have been led to believe that
the existence of titanic oxide may be expected in a good many
American clays.
W. A, Noyes : I have analyzed a number of Indiana clays and
have found titanic oxide with but one exception. The Indiana
clay given corresponds closely with one I analyzed last fall, and
that particular one is free from titanic oxide, or practically so.
All the other claj's, and I feel safe to say that all these clays
must contain titanic oxide.
The President : Does anyone know the effect of titanium on
the ware ?
COMPOSITION OF CERTAIN MINBRAL WATERS. 915
A, A, Brenema7i : My impression is that Seger says there
seems to be a connection between the peculiar light gray of
salt-glazed stoneware, a color which is unique, and the presence
of titanium. That is a very interesting statement, because that
peculiar form of whitish or bluish gray stoneware is very char-
acteristic, and I see nothing in the presence of iron alone in the
clay sufficientlj' to account for it.*
[Contributions from thb Chemicai, Laboratory of Case Schooi« of
Appukd Science. ]
XXV. COMPOSITION OF CERTAIN MINERAL WATERS IN
NORTHWESTERN PENNSYLVANIA.*
By a. K. Robinson and Charles P. Mabery.
Received July a6, 1896.
THE therapeutic qualities of mineral springs throughout
northwestern Pennsylvania have long been recognized,
and recently some of these springs, notably those at Saegertown
and Cambridgeboro, have come into prominence through the
enterprise of persons interested in hotels and sanitariums. The
desirable qualities of these waters are doubtless dependent on
INOTE ov Titanium xn Clays.— In the course of a discussion of Prof. Mabery's
paper on American clays at the Buffalo meeting I alluded to the peculiar color of salt-
glazed stoneware, and ascribed to Seger the suggestion that it was due to the presence
of tiUnium. On referring to Seger's article (Wagner's Jahresbericht, 1883. p. 625). I
find that he says that titanic acid (13.3 per cent.) heated with a very pure kaolin to a
temperature between the melting points of wrought iron and platinum fuses, and that
titanic acid is, under similar conditions, more of a flux for clay than silicic acid is. In
the proportion of 6.65 per cent, of TiOt, the mass became only semi-fused, and exhibited
a dark-blue gray color. He says this color suggests the tint given by many clayp
when strongly heated.
Horgenroth (Wag. Jahr., 1884, 638) says, however, that rutile gives to clay ware a gray
color under the glaze when impure ferruginous clays are used, but a yellow, ivory-like
tint with pure clays. As rutile was used in the proportion of only 0.4 per cent., the
minute proportion of iron which it carries (1.5 to 3.4 per cent. Pe,0|) would have little
effect.
The interpretation of these facts to explain the peculiar gray color of salt-glazed
stoneware, was probably a suggestion of my own, made at the time of reading these
articles a dozen years ago. It was ascribed in the course of the discussion to Seger, as
my " impression."
Nevertheless, in view of the peculiarity of this color, the gray of salt-glazed ware
which is uniform throughout the body and becomes more bluish in overbumed pieces,
and in new also of the presence of iron in the rather crude clays used for the ware, and
the (act that iron alone tends to escape as volatile chloride in presence of the salt used
for glazing, the suggestion is worthy of note. A. A. BRBXRMAif ..
* This work, with a study of the methods of analysis, was offered by Mr. Robinson
in a thesis for the degree of Bachelor of Science. Read at the Buffalo Meeting. August,
X896.
9l6 A. £. ROBINSON AND CHARI^BS F. MABERY.
iron and certain other salts, especially on the bromides, and it is
a popular view that lithium salts sometimes present impart
valuable medicinal qualities. A quantity of water was col-
lected from one of these surface springs at Conneautville by one
of us (Robinson) audits composition as shown by analysis may
serve as a representative of the springs in this region. The
total solids in this water is equivalent to 6.586 grains per
imperial gallon, or 9.83 parts per 100,000. Evidently the com-
bination of bases and acids is to a certain extent arbitrary, but
this distribution accounts for the total quantities of the various
elements given by analysis :
Grains
per gallon.
Potassium carbonate * 0.985
Lithium carbonate 0.002
Sodium chloride 0-925
Calcium bicarbonate • 2.879
Calcium sulphate 1.291
Magnesium chloride 0.204
Ferrpus carbonate 0.743
Silica 0.233
Hydrogen sulphide trace
The specific gravity of this water was foitnd to be i .0002 at
20°. Evidently the analysis shows the composition of a good
potable water. Any medicinal qualities it possesses must be
referred to the iron and perhaps to a less extent to the lithium.
At greater depths in this section of Pennsylvania and in cer-
tain portions of Ohio, water may be found that partakes in a
greater degree of the qualities imparted by the constituents of
bittern. Wells sunk to depths of 1,000 to 3,000 feet have pene-
trated strata enclosing, frequently under great pressure, large
quantities of bittern waters. While in general conforming in
composition to the salts contained in bittern, occasionally these
wells have yielded peculiar results on analysis. Such an aque-
ous stratum was reached several years ago at Conneautville,
Crawford County, Pa., in an endeavor to obtain oil or gas. The
drill penetrated the formation enclosing water at a depth of 2,667
feet and the drilling tools were forced upwards to a height of
1,800 feet by the water which prevented further drilling. This
COMPOSITION OF CERTAIN MINERAL WATERS. 917
level was maintained notwithstanding vigorous attempts to clear
the well by pumping. A slight examination then showed that
this water possessed peculiar qualities, but the well received no
further attention until within a few months ago when it was cleared
and a quantity of the water was procured for a more thorough
examination. The total solids is equivalent to 21,334.34 grains
per gallon or to 30,536 parts per 100,000. The specific gravity
of the water is 1.205 at 15®. Its composition as shown by the
results of analyses is as follows :
Grains per Parts per
gallon, 100.000.
Potassium chloride 528.577 755-6
Lithium " 56.432 80.3
Ammonium *' 151*879 216.6
Soilium •* 9902.57S 14430.0
Potassium bromide 137.010 345*7
*' iodide 2.078 2.96
Magnesium chloride 2172.499 3096.0
Calcium '* 8335.537 1 1880.0
sulphate 7.886 11. i
Ferrous carbonate 1 14.836 163.5
Aluminum chloride 21.816 31. i
Silica 3.220 4.6
Hydrogen sulphide 0.033 0.05
There are certain features of this water that deserve especial
mention. The large proportion of ammonium chloride is quite
unusual in waters from such depths. Lithium chloride is fre-
quently found in surface springs, and in brines from deep wells,
but rarely, if ever, in such quantities as this water contains.
If lithium salts impart to spring water the therapeutic qualities
claimed for them, it is not difficult to account for the beneficial
effects that have been observed in the use of this water. No
doubt the large proportion of potassium bromide has much to do
with the marked sedative effect. The large percentage of potas-
sium iodide is also phenomenal, and it must intensify the min-
eral characteristics of the water. Besides the characteristics of
a bromo-lithia water the large percentage of iron assures the
desirable qualities of an iron water. The peculiar composition
of this water, especially in the large quantities of the rarer ele-
ments, offered a favorable opportunity to ascertain whether these
9l8 B. B. ROSS.
bittern deposits contain also the elements, cesium and rubid-
ium, which are rarely found in springs. Forty-five liters of
the water were evaporated to a small volume, removing the great
quantities of salt as they separated. When the volume was
reduced to less than fifty cc. this solution as well as the lixivia-
ted salts that had separated during evaporation were carefully
examined in the spectroscope. But not a trace of rubidium nor
cesium could be detected. It is therefore safe to conclude that
the bittern deposits from the ancient sea do not contain these
rarer elements.
It may not be out of place to remark that the chemical com-
position of this water explains the remarkable therapeutic quali-
ties especially for rheumatism and nervous diseases that it has
been found to possess.
SOriE ANALYTICAL HETHODS INVOLVING THE USE OF
HYDROGEN DIOXIDE.'
Bv B. B. Ross.
Received Au);ust 31. i8g6.
THE use of hydrogen peroxide as a laboratory reagent,
although originally restricted to a few operations of
minor importance, has within recent years met with a m\ich
wider extension, and its numerous applications in both qualita-
tive and quantitative analysis, render it at present almost indis-
pensable in every well-equipped analytical laboratory.
Among the more interesting applications of this substance in
quantitative estimations are those which are based on the reac-
tion which takes place when an excess of hydrogen dioxide is
brought in contact with an acid solution of chromic acid, and
Baumann' several years since described quite fully a number of
analytical processes growing out of the reaction referred to.
In the process for the estimation of chromic acid in soluble
chromates as outlined by Baumann, the substance under exami-
nation is first brought into a state of solution, and the not too
concentrated liquid is transferred to a generating flask of special
construction.
iRead at the Buffalo meeting^, Augrust 23, 1S96.
3 Ztichr. anal. CMem., 31, 436.
USE OF HYDROGEN DIOXIDE. 919
Ten cc. of dilute sulphuric acid are next added, after which
from five to ten cc. of commercial hydrogen peroxide are run in
from a small closed vessel connected with the generating flask,
while the oxj'gen which is evolved, after the vigorous shaking
of the contents of the flask, is collected over water in an azotom-
eter.
The following equations given by Baumann illustrate the
chemical changes connected with the above described reaction :
K.Cr,0, + H,0, + H,SO, = k,SO, + 2H,0 + Cr A ;
CrA + 3H,SO, + 4H A = Cr,{SO J, + j^fi + O..
From these equations it will be seen that for two molecules of
chromic acid or one molecule of potassium dichromate, there are
evolved eight atoms of oxygen, giving an equivalent of 445.3 cc.
of oxygen (measured at 0° C. and 760 mm. pressure) for each
gram of. chromic acid which may be present.
The writer, soon after the appearance of the original article
by Baumann, made a number of experimental tests of this method
with a view to applying it to some other analytical processes,
and still more recently has conducted a series of tests for the
purpose of determining the adaptability of Baumann's method to
the indirect volumetric estimation of iron.
In the dichromate method for the volumetric determination of
iron, as commonly employed, the end point of the oxidation
process is ascertained b}* the reaction with potassium ferricy-
anide.
As the end of this reaction is almost invariably difficult to
determine particularly if zinc has been employed as a reducing
agent, the dichromate process has met with but limited applica-
tion.
In order to apply the principle of the chromic acid method of
Baumann to the estimation of iron, an excess of dichromate
solution was employed in all of the tests and experimental deter-
minations, the amount of the excess of chromic acid being deter-
mined by the volume of oxygen evolved upon treatment with
hydrogen dioxide.
The mode of procedure adopted was as follows :
A dichromate solution was prepared by dissolving 4.913 grams
920 B. B. ROSS.
of C. P. crystallized potassium dichromate in water and dilu-
ting to a bulk of one liter.
The iron solution employed in standardizing the dichromate
and permanganate solutions was obtained by dissolving iron
wire in dilute sulphuric acid, the solution being reduced vrith
metallic zinc, as usual, previpus to titration.
The dichromate solution was also titrated against a freshly
prepared solution of ammonium ferrous sulphate, the strength of
which had been determined ' by titration with permanganate
solution, which had also been carefully standardized by means
of iron wire.
In order to ascertain the strength of the dichromate solution
by the hydrogen dioxide method, about fifteen cc. of the
dichromate solution is run into the generating flask above
referred to, and there is also added an amount of ferric sul-
phate solution (free from ferrous sulphate) equivalent to about
0.06 to o.io gram of iron. The object of employing the ferric
sulphate in this standardization is to supply approximately the
same conditions as obtain in the process for the actual deter-
mination of iron.
The amount of oxygen given off from chromic acid in the
presence of ferric sulphate is slightly less than thate\'olved when
ferric sulphate is absent, but the amount of ferric iron present
may vary considerably without affecting the volume of oxygen
liberated.
To the contents of the generating vessel about ten cc. of dilute
sulphuric acid are now added, and the flask is then connected
by means of a rubber tube with a Schulze's azotometer, which
has been filled with water to the zero point.
From five to ten cc. of hydrogen dioxide are next run in from
a small closed vessel connected with the generating flask and the
mixed liquid is then shaken, at first gently, and afterwards vig-
orously. The tube leading from the flask to the azotometer
should be provided with a stop-cock, which should be closed
before and opened immediately after each shaking.
The last trace of the oxygen liberated will not be disengaged
until after the lapse of about five minutes, but it is notnecessj'r>'
to continue the shaking during the whole of this period. After
USE OP HYDROGEN DIOXIDE. 921
*
eqaalizing the height of the water in the two tubes of the
azotometer, the volume of oxygen is noted and is easil}' cor-
rected for temperature and pressure by reference to proper tables.
In order to test the strength of the dichromate solution by
means of iron wire, a given weight of the wire is dissolved in
dilute sulphuric acid, the solution reduced with zinc, as usual,
and rapidly transferred to the generating flask (filtering, if
necessar>0 .
An excess of dichromate solution is now run in, hydrogen
dioxide is added, and the oxygen is set free and collected as
belore described.
If a large excess of dichromate has been used in the prelimi-
nary test, duplicate tests should be made with employment of a
small excess, say from two to three cc, of the dichromate.
The strength of the solution can then be readily calculated by
difference, and, if necessary, the results can be checked by still
further tests.
In the determination of iron in ores by this process, the solu-
tions of ferric iron are reduced by zinc, as in the common per-
manganate method, and the remainder of the process is con-
ducted just as described for the standardization of the dichro-
mate b}' means of iron wire.
In addition to numerous tests of solutions of pure iron, several
estimations of iron in iron ores were made by this process, the
results obtained being compared with those secured by the per-
manganate method.
The following are the results of the tests of the iron ores
referred to :
Permaiigauatc method.
Mean of several deter mitiatiotis. Dichromate method.
Iron ore No. i 40.92 f ?'5?
41-23
55-35
Iron ore No. 2 54.71 55.43
55-50
In the determination of iron in ores b}' this process, it is best,
as in the case of the tests with iron wire, to employ only a small
excess of the dichromate solution, after making a preliminary
determination, as the results are much more accurate with a
small than with a large excess of chromic acid.
922 USE OF HYDROGEN DIOXIDE.
While a sufficient number of determinations have not been
made to ascertain the probable value of this method as an inde-
pendent process for the estimation of iron, nevertheless some of
the results secured would seem to warrant the conclusion that it
might prove of utility as a check method, it being easy of execu-
tion and not at all time-consuming.
The following equation represents the changes which take
place when the dichromate is brought in contact with the iron
solution after reduction :
6FeS0, + K,Cr,0, + yH^SO, =3Fe.(SOJ. + K.SO,+
Cr.(SO,). + jH^O.
The writer has also attempted to apply the principle of the
chromic acid method above described to the estimation of invert
sugar, or rather to the determination of the amount of cuprous
oxide thrown down from Fehling's solution in the process com-
monly employed for estimating reducing sugars.
The following equation represents the changes which take
place when cuprous oxide is brought in contact with potassium
dichromate in the presence of dilute sulphuric acid :
3Cu,0 + K,Cr,0, + ioH,SO, = 6CuS0, + K.SO, +
Cr,(S0j3-|- ioH,0.
The cuprous oxide thrown down from the sugar solution
under examination is brought upon an asbestos filter connected
with a filter pump and thoroughly and rapidly washed with hot
water. The filter and contents are next transferred to the gen-
erating flask of the apparatus before described, and after the
addition of dilute sulphuric acid, an excess of dichromate is
run in.
Very thorough and long continued agitation of the contents of
the flask is necessary in order to effect the complete oxidation
and solution of the cuprous oxide, and the hydrogen peroxide
must not be added until the solution is complete.
The oxygen liberated on the addition of the hj-drogen dioxide
is collected and the volume noted as before described. The
equivalent amounts of chromic acid, cuprous oxide and invert
sugar can be easily calculated from the data thus secured.
This method, while apparently satisfactory from a theoretical
INTERNATIONAL CONGRESS OF APPLIED CHEMISTRY. 923
standpoint, has so far failed to give sufficiently uniform results,
one of the chief objections to the process being the difficulty
attendant upon the solution of the cuprous oxide.
With improvements in the details of manipulation of the pro-
cess, however, it is quite po.ssible that more satisfactory results
could be obtained.
SECOND INTERNATIONAL CONGRESS OF APPLIED
CHEniSTRY.
By H. W. Wiley.
Rece«\e«l September 15. 1S96.
At the first congress held in Brussels, in 1S94. it was decided
to hold the meetings bi-annually and Paris was selected as the
mo.st desirable place for the reunion this y/ear. As has already
been announced to the readers of the Journal, the present con-
gress is organized under the patronage of the French govern-
ment and under the immediate direction of 1' Association des
Chimistes de Sucrerie et de Distillerie de France et des Colonies.
The late Professor Pasteur had accepted the honorary presidency
of the congress, and all delegates from foreign countries have
felt an especial regret that his death has prevented them from
listening to his words of welcome and from forming his personal
acquaintance.
To promote the interests of the congress, committees were
organized in most countries. The personnel of the one in the
United States has already been published in this Journal.
Through the French Foreign Office all the principal govern-
ments were invited to send delegates to the congress. Official
representatives were present from Belgium, Germany, Italy,
Russia, Switzerland, Austria, Portugal, Denmark, and the
United States. So far as I can learn, and the fact is worthy of
remark, there is no representative in attendance from England,
either official or otherwise. The official delegate from the
United States is Mr. C. A. Doremus, of New York, while the
writer has a commission as a delegate from the Department of
Agriculture, and one from the American Chemical Society,
sent through the courtesy of the president and council. Bel-
gium has the largest representation of any foreign country, and,
since these gentlemen are all French in their language, the con-
gress, as is natural, is essentially French.
The congressrwas formally opened July 27, at 10 a. m., in the
grand amphitheater of the Sorbonne. Perhaps there is no other
spot in the whole world so well suited by its history and tradi-
924 H. W. WILEY. SECOND INTERNATIONAL
tions for the seat of a scientific congress, especially of chemistr>'.
In or near the Sorbonne were made those advances in chemical
science which have made famous the names of Lavoisier, Chev-
reul, Dumas, Deville, Wurtz, Pasteur, Berthelot, and maii3'
others scarcely less renowned. The address of welcome was fitly
made by Mr. Berthelot, rendered, by the death of Pasteur, the
head and front of French science. The response was pronounced
by Mr. Lindet, provisional president. After these addresses, the
provisional secretary of the congress presented a report showing
the activity of the French and other committees and giving the
number of chemists who had become members of the congress.
The congress is organized with ten sections, as follows :
r* Section. — Sucrerie.
2* Section. — Industries de la fermentation : alcools, vins,
bieres, cidres, vinaigres.
3* Section. — Industries agricoles : laiterie, fromagerie, f6cu-
lerie, amidonnerie, glucoserie, mati^res alimentaires.
4' Section. — Chimie agricole : engrais, terres, eanx residu-
aires ; alimentation du b6tail.
5* Section. — Analyses officielles et commerciales des matieres
soumises k Timpot. — Appareils de precision.
6* Section. — Indu.stries chimiques : produits chimiques, phar-
maceutiques ; corps gras, caoutchouc, matieres colorantes,
papiers, tannerie, verrerie, cferamique, etc.
7' Section. — Photographie.
8* Section. — M^tallurgie, mines, explosifs, etc.
g"" Section. — Chimie Appliqu6e a la medecine, k la toxicologic,
k la pharmacie, k I'hygiene et k Talimentation. Matiferes ali-
mentaires : alterations et falsifications.
lo* Section. — Electricity : 61ectro-chimie.
The meetings of the congress are held in the Hotel de la So-
ci^tfe d* Encouragement del' Industrie Nationale, 44 rue de Rcn-
nes, opposite the church of St. Germains des Pr6s and in the
H6teldesSoci6tesSavantes, situated in rue Serpente, opposite rue
Danton. Only four or five of the sections are in session at any
one time, thus affording an opportunity to the members of the
congress of attaching themselves to several sections.
In the afternoon of the first day visits were made to the Gobe-
lin tapestries, the Museum of Natural Histor}-, botanical gardens,
the National Tobacco Factory, and the Eiffel tower, the latter
being reached by boats on the Seine. At the end of these visits
a banquet was served on the first floor of the tower and from the
tables a pleasing vision of Paris by night was obtained.
On the second day of the congress, an interesting paper was
read by Mr. Moissan on the electric furnace. A large number
CONGRESS OF APPLIED CHEMISTRY. 925
of samples of tlie typical compounds obtained at the intense heat
of the furnace was exhibited and a description of their physical
and chemical properties given. The possibilities of the electric
furnace in the near future were outlined. Mr. Moissan described
in some detail the construction of the furnace. It is best made
by carving a block of quicklime into the proper shape. The
high infusibility of the quicklime and its non-conducting power
are points in its favor. The electrodes should be of the purest
carbon and there should be no deflection of the arc into the cru-
cible. The control of the current is of the greatest importance.
For instance, in the case of titanic oxide it is reduced to tiianous
oxide with a current of thirty amperes ; at 300 amperes tita-
nium nitride is produced and at 3,000 amperes titanium carbide.
Many metallic carbides, as, for instance, calcium, yield a gas
when moistened, but the gases are not identical. In addition to
acetylene, hydrogen, marsh gas, and petroleum have been
obtained, the latter from uranium carbide. This fact is of great
interest in respect of the origin of natural gas and petroleum,
which, by many, are supposed to be of organic derivation. In
the furnace, molybdenum and manganese are capable of form-
ing compounds similar to cast iron. Fine samples of chromium
obtained in the furnace were shown and many specimens of
various nitrides, carbides, and borides. Chromium oxide was
reduced to metal before the audience and silica was sublimed.
In addition to Mr. Moissan's paper, a general discussion of
electrolytic problems was held including electrolytic methods of
preparing chlorine, chlorinated soda, and calcium carbide.
Mr. Moissan has accepted an invitation to attend the Prince-
ton College celebration in the autumn and has made arrange-
ments to give some lectures in the United States. Our chem-
ists, therefore, will have an opportunity in the near future to
bear him and to note the great progress which the elec-
tric furnace has made possible in the line of discoveries in min-
eral chemistry.
Another discussion of unusual interest was devoted to the
official graduation of instruments of precision. It was the
general consensus of Opinion that a uniform 100 gram weight of
platinum should be adopted by all countries, and that all instru-
ments and utensils for w^eight and volume should be referred to
this standard. The ofRcial meter was regarded by all to be the
ultimate standard of instruments to measure length. Some of
the members favored a standard of brass coated with gold or
platinum, in order to have an ultimate standard of greater volume
than the one made of platinum. The difficulty of securing brass
of uniform and definite constitution was considered as an insu-
perable objection to this proposition.
926 H. W. WILEY. SECOND INTERNATIONAL
Among the man}' papers of special interest read on this day
only a few can be mentioned here by title, viz,. Application of
Electro-Chemistrj' to the manufacture of Chemical Products, by
M. Joly ; The Difficult Digestibility of Sterilized Milk, by M.
Laurent ; Determination of Soil Elements Assimilable by Plants,
by M. Garola ; Plan and Installation of an Agricultural Experi-
ment Station, by M. Soillard.
At 4 p. M. the sections were adjourned to visit the new city
hall (Hotel de Ville), which has finally been completely restored
from its destruction by the Commune. There the members were
.received by the mayor of the city (Prefet de la Seine), the chief
of police and the chief of the fire department. After enjoying a
delightful collation, such as the city of Paris knows so well how
to prepare, we were conducted b}' the mayor throughout the
building and had described to us the mural decorations and the
various groups of statuary- In the opinion of experts, the new
Hotel de Ville is quite equal in its artistic decorations to the
magnificent structure so wantonly destroyed by the Communists
in 187 1.
On the third daj- of the congress sessions of the sections were
held only in the morning. A communication was presented to
the second section by Mr. Chas. J. Murphy, describing a new
process of fermenting maize and showing the way to a more
extended use of this product in the European distilleries.
Before the third section was read several papers giving the latest
European processes for the manufacture of starch. Mr. Grau-
deau, an agronomist well known in the United States, presented
a communication to the fourth section on the assimilability of
phosphates. Methods of analysis of phosphates, especially those
applicable to phosphatic slags were discussed by Mr. Class, of
Halle, and by many others. The Wagner method of solution
in ammonium citrate, of a definite constitution, was advocated
by nearly all those taking part in the discussion. A paper on
the official German method of determining iron and alumina in
phosphates, was presented by Dr. von Grueber. The method
of E. Glaser, as modified by Jones, is the one which the German
chemists regard as the most reliable. This method has already
been described in the Jownial of Ayialytical and Applied Chemis-
try, 6, 671. It was pointed out that analysts had received an
impression that E. Glaser had acknowledged that this method
was unsound. This, however, is not the case, but the impres-
sion arose by reason of a critique of the method by C. Glaser, of
Baltimore. Mr. E. Glaser died soon after publishing his method
and it devolved on Dr. Grueber to continue his work. The
modifications of the original method, as proposed by E. Glaser,
CONGRESS OF APPLIED CHEMISTRY. 927
which have been accepted by the German chemists are princi-
pally those made bj- Jones and with which American chemists
are quite familiar. The process, as conducted by the German
official chemists, is as follows :
Ten grams of the sample are dissolved in twenty-five cc.
hydrochloric acid, sp. gr. 1.20, and the volume completed to a
half liter. Fifty cc. of this solution, corresponding to one gram
of the substance, are evaporated to half that volume in a beaker,
ten cc. of sulphuric acid (one part to four of water) added and
the mixture shaken. 150 cc. of absolute alcohol are added,
shaken, and the beaker placed aside for three hours. The
deposited calcium sulphate is separated by filtration and washed
with absolute alcohol. The washing is finished when ten drops
of the filtrate, diluted with the same volume of water, does not
become red when a drop of a solution of methyl orange is added.
The alcohol from the filtrate and washings is recovered by dis-
tillation, and the residue oxidized by bromine and hydrochloric
acid, a slight excess of ammonia added and heated until the
excess is expelled. This operation is very important to prevent
the incorporation of magnesia in the precipitate. The residual
precipitate is separated by filtration, any remaining on the walls
of the beaker being washed off with cold water and a rubber-
tipped tube. The whole is washed on the filter with boiling
water until all traces of sulphuric acid have disappeared. The
precipitate is dried, ignited and weighed and consists of the
phosphates of iron and alumina. One-half of the weight of the
precipitate consists of the oxide of iron and alumina.
The quantity of iron is determined by reducing the iron in fifty
cc. of the first solution made, by means of zinc, and titrating the
amount reduced by a solution of potassium permanganate in the
usual way. The quantity of iron having thus been determined,
it is calculated to oxide and subtracted from half the weight of
the iron and aluminum phosphates. The difference is the alumina.
The members of the photographic section were provided with
an interesting program, but the writer was not able to be present,
and the total absence of any reports of the meetings in any of
the daily papers, or in any other accessible form, makes it impos-
sible to give even a summary of what was accomplished. I do
not think it advisable to encumber the pages of the Journal with
a complete list of the papery presented, inasmuch as the present-
ing of the titles of the papers would fill many pages and give
but little idea of the proceedings. Moreover the published pro-
ip-am, although extensive, does not include perhaps more than
half the titles of the papers presented, and I am not sufficiently
acquainted with the French way of doing things to be able to
928 H. W. WII.EY. SECOND INTERNATIONAL
complete the list. Only one program of papers and proceedings
has been printed, and that evidently is to serve for the whole
congress. The French in this particular might well imitate the
practice of the American Association for the Advancement of
Science in providing daily programs.
Interesting communications were presented to the ninth sec-
tion on food adulteration, and Mr. Doremus read a paper on the
nature of the gases contained in canned goods. He showed that
these gases were chiefly hydrogen and probably the hydrogen is
produced by galvano-electric action in the metals of the can.
In all cases where much gas was found, the sides of the can were
found deeply corroded. There was no evidence in these cases
of the. action of ferments and in every case the sterilization of
the canned goods was perfect. Mr. Thomas Taylor sent to the
section a communication on the crystals of butter fat embodying
the results of his observations while chief of the Division of
Microscopy of the Department of Agriculture. Mr. F. Jean read
a communication on the distinction between butter and marga-
rine as determined by his instrument, the oleorefractometer.
This instrument has been carefully tested in the Chemical Divi-
sion of the Department of Agriculture, and while it has been
found to give valuable indications it is by no means so definitely
diagnostic as its inventor claims.
Before the eighth section were presented memoirs on the
methods of determining sulphur, phosphorus, nickel and carbon.
The afternoon of the third day (Wednesday) was given over
to a visit to the celebrated agricultural school and experiment
station at Grignon. The members of the congress traveled by
railway to Versailles where carriages were provided to conduct
us to Grignon. Passing the palace and garden of Versailles,
we entered the forest and after two miles reached a stretch of
fields which for beauty and fertility are scarcely equaled in the
world. The wheat and oats harvests were going on and I was
impressed with the primitive methods employed. The cradle and
the sickle are almost universally used, only one reaping machine
being seen in a drive of ten miles. At Grignon the tourists were
received by Mr. Philippar, the principal of the school, and by Mr.
Deherain, the director of the station, whose name and fame are
well known to all chemists, especially those engaged in agricul-
ture in the United States.
The experimental plots of thestatibnwej-e explained by Mr. De-
herain, and thereafter, in his laboratory, he gave a brief explanation
of the charts representing the results of the experiments for many
years. After leaving the experiment station, the members of
the congress were driven over the farm connected with the
CONGRESS OF APPLIED CHEMISTRY. 929
school and. they also inspected the barns, stables, horses and
herds of sheep and cows. I noticed that much of the agricul-
tural machinery, especially the reapers, hay-rakes and plows, were
of American manufacture. The college buildings are part of an
old chateau which, under the first empire, belonged to one of the
marshals of France. The school at Grignon is the largest and
most important of the three national colleges of agriculture.
The other two are established at Montpellier and Rennes respect-
ively. Three classes of pupils are admitted; viz., internes, who
pay $240 a year, demi-internes, who pay $120, and externes,
who pay $80. Others known as free auditors are also admitted
to all the lectures and pay $40 a year. The course of instruc-
tion lasts two years and a half and includes zoology, botany,
mineralogy, agricultural geology, physics, meteorology, general
and agricultural chemistry, agriculture, horticulture, arboricul-
ture, viticulture, sylviculture, rural economy, entomology, seri-
culture, apiculture, technology, agricultural legislation, hygiene
and military exercises. The number of pupils admitted to each
class is fixed annually by ministerial decree, and is limited also
in the class of internes by the number of beds. The total num-
ber of pupils, excluding the free auditors, is about 250. On the
completion of the course and passing a satisfactory examination,
which shall merit at least sixty-five out of a possible 100 points,
the pupil receives the diploma of the National School of Agricul-
ture, and four-fifths of the whole number thus graduating, com-
prising those who have received the highest marks, are excused
in time of peace from all military service, except one year.
Examinations for admission to the school are competitive and
include arithmetic, algebra, geometry', trigonometry, elementary
physics, chemistry, zoology, botany and geology. The chem-
ical instruction is given by Mr. Deherain and his assistants and
consists of lectures and demonstrations in general and agricul-
tural chemistry, including the chemical study of plants, soils
and fertilizers. It is evident, however, that in the short time at
their disposal the students can not acquire great efficiency in
chemical manipulations and in fact it is not the object of the
school to train agricultural chemists, but rather to provide young
men with that character of instruction which will enable them to
manage with intelligence and in harmony with the most
advanced teachings of science, large landed estates.
Those members of the congress who did not desire to visit
Grignon were offered an alternative excursion to the nickel
works of Messrs. Christofle, Bouilhet and Cie., at Saint Denis..
I have not been able to secure any reports of this visit.
The fourth day of the congress, July 30, was devoted exclu-
930 H. W. WILEY. SECOND INTERNATIONAL
sivelj' to the honor of the late M. Pasteur. At 9.30 in the
morning, the members assembled in the chapel of Notre
Dame and placed a memorial wreath on Pasteur's coffin. The
body of the illustrious savant lies in an alcove near the middle
of the north side of Notre Dame, the coffin scarcely visible
beneath a mountain of wreaths and crowns. Not onl}* is the
alcove in which the coffin rests full of these offerings, but they
have been stored, in cart-loads, in all the adjoining alcoves.
They come from individuals and learned societies from all parts
of the world and from nearly every municipality in France.
The coffin rests here temporarily until the tomb and monument,
to be erected by popular subscription from all parts of the world,
are ready. The final resting place of the body of Pasteur is to
be in the court of the Pasteur Institute. With bowed heads the
members of the congress marched by the coffin holding onlj- the
motionless brain whose activity has done so much to advance
knowledge and benefit mankind. Thence the carriages con-
veyed us to the Pasteur Institute where the laboratories were
inspected. A collection of many compounds of historical inter-
est, prepared by Pasteur, was on exhibition, among which were
all the tartaric acids and tartrates used b}' Pasteur in demon-
strating molecular asymmetry as displayed by the ^ame chemical
substance having opposite relations to polarized light. A large
collection of original cultures of the ferments leading to the dis-
covery of antidotes for rabies was also on exhibition. A large
number of microscopes showing the specific microbes of phthisis,
cancer and diphtheria attracted g^ieral interest. In the clinical
rooms we were permitted to see one of the daily inoculations
with antirabic serum. About thirty patients were treated in less
than half that number of minutes. About two or three cc. of
serum are administered by hypodermic injection to each patient.
The serum is inserted in the skin on the right or left side of the
abdomen, the most convenient place on account of the infre-
quency of nerves. Each patient receives from ten to fifteen
injections on successive days. About 150 patients are received
monthly, and the treatment is entirely gratuitous. Those who
are able, however, usually give generously to the funds of the
institute. A large collection of rabbits, guinea pigs and dogs,
serving for experimental purposes, was also inspected. We were
next driven to St. Cloud and through its beautiful gardens and
forests to Garches, where a delightful breakfast was served at
one o'clock. After breakfast a visit was made to the stables
containing the horses used to furnish the anti-diphtheritic serum.
There are 120 of these and all seemed to be in perfect health.
Each one of these horses has been inoculated with the diphthe-
CONGRESS OF APPLIED CHEMISTRY. 93 1
ritic poison and the blood thereafter serves as the source of the
serum. Two horses were operated on as an illustration of the
method of work. A large vein in the neck of the animal is
opened, a tube inserted and the blood collected in a sterilized
jar. So skillfully is this accomplished that scarcely a drop of
blood is lost. From four to six liters of blood are collected from
each animal, when the vein is closed and the horse returned to
his stall. In three or four weeks he is ready to supply another
quantity of blood. The jars containing the blood are placed in a
cupboard for about forty-eight hours, when, if the horse has been
properly inoculated, their contents will be found sharply separated
into clots and serum. The serum, which is of a light yellow
color, is removed by decantation and by an ingenious appara-
tus, which prevents all danger of infection, is bottled in vials
containing ten cc. each. One horse was shown us that had fur-
nished in the past few years several hundred liters of serum. He
appeared to be good for many hundred more. The serum thus
prepared is used directly by subcutaneous injection on patients
suffering from diphtheria. Every appointment in these stables
was such as to impress the visitors with a new and a noble idea of
science, ministering thus directly to saving life and especially
the lives of children. No wonder the body of him who did
so much to establish the lines of investigations which, under his
immediate direction, if not by his own hands, have led to such
ameliorations in the sufferings of men, lies to-day in honor in
one of the most magnificent churches in the world, buried under
flowers and wreaths, while the piemory of his work lives immor-
tal in the hearts of the people it has blessed.
Next was inspected the national porcelain works at Sevres,
reached after a pleasant drive from Garches. The officials of
the factory received the guests at the entrance and dividing the
visitors into small parties each was personally conducted through
the works. Beginning with the crude materials, kaolin, quartz,
etc., the methods of grinding and mixing were first explained.
The character of the mixing is of course suited to the nature of
the object in view, the massive urns and vases having a different
proportion of the several ingredients from the delicate cups and
saucers. The molding of the objects was shown in detail in its
three forms; viz., by carving the solid moist mass, by allowing it
in a pasty state to flow into moulds, and by turning the waxy
mass on a table and imparting the desired form by the hands of
the operator. The urns and vases are made by the first and
third methods, while the thinner vessels, such as cups, etc., are
made by the second method. After drying, the glaze is applied
by dipping the objects in a creamy bath of the silicates serving
932 H. W. WILEY. SECOND INTERNATIONAL
to form the glaze. After the glazing is fixed by firing, the
objects are passed to the decorating room to receive their final
colorings. After each color is applied, it is fixed by firing.
The ingenious hoods used to secure an even firing of the objects
were exhibited and the manner of using them shown. The con-
struction of the large furnaces where hundreds of vases and other
objects are fired at once, was described, and the furnaces cold
and in action exhibited. The visit concluded with an inspec-
tion of the museum and salesrooms with their artistic and costly
contents. These are known to all visitors, but the process of
manufacture which was so minutely shown us is not open to the
public in general. The day was finished by a drive back to
Paris through the parks of Meudon and Boulogne.
Having taken the whole of the fourth day for the interesting
and instructive excursions which have just been briefly
described, the fifth day, Friday, July 31, was wholly devoted to
the scientific work of the congress. Sections i, 2, 4, 5, 9, and
10 held morning sessions, and 2, 3, 5, 6, 8, and 9 met in the
afternoon. The time of Section i was devoted to a discussion
of the crystallization of sugars and the methods of suppressing
the molasses in the manufacture of sugar from canes and beets.
The papers presented and the discussions thereon were more
technical than chemical.
In the second section, the difficulties attending the detection
and estimation of the higher alcohols, aldehydes and ethers in
brandies and whiskies were set forth and Mr. Tavildaroff, of St.
Petersburg, gave a rfesumfe of the best methods of procedure.
In the third section the methods of determining phosphoric
acid in soils and fertilizers were again the subject of discussion
and papers on this subject were presented by Messrs. Garola
and Sidersky. Mr. Lasne presented a rfesumfe of his work on
the detection and estimation of iron and alumina in phosphates.
In section 5, papers on the analysis of fats, estimation of acetic
acid in pyroligneous acid, a new method of estimating alcohol
by means of the ebuUioscope, and a rapid method of analyzing
denaturalized alcohol were presented by Messrs. Jean, Kestner,
Wiley, and Guillier, respectively.
In the ninth section, the application of the spectroscope in
medico-legal cases was discussed. In connection with a discus-
sion of the influence exerted by ptomaines on the detection of
alkaloids in medico-legal cases, Mr. Dorenius presented a paper
entitled *' Recovery of Morphine from a Cadaver Embalmed
with Arsenical Solution .''
The subject of the possible detection of toxines in potable
CONGRESS OF APPLIED CHEMISTRY. 933
waters was also discussed and the influence exerted on them by
organic matters in process of decomposition pointed out.
In the afternoon, in section 2, a paper was presented by Mf.
Kayser on the properties of yeasts of different origin. A sub-
ject of interest to the wine growers of our southern states and
California was a paper on the vinification in warm climates, by
Mr. Dugast. The pasteurization of wines was discussed in a
paper by Mr. Malvezin. Other papers of interest to wine makers
were presented and discussed.
To chemists and bacteriologists engaged in the manufacture
and study of butter and cheese, the proceedings in section 3 were
of great interest. The best methods of disinfecting stables and
creameries by chemical means were presented by Mr. Bordas. A
rteum6 of our knowledge concerning the influence of food on the
composition and character of milk and butter was presented by
Mr. Martin. A general discussion of the best means of provi-
ding cities with pure milk was led by Mr.*Saillard. The impor-
tance of selecting ferments in the manufacture of butter and
cheese was discussed by the section, but the work done by Conn
and others in the United States did not seem to be appreciated.
In section 3 a paper on the effect of impurities on the proper-
ties of metals was presented by Mr. Le Verrier, and the methods
of micrographic and photomicrographic examination of metals
and alloys were described by Mr. Osmond.
In section 5, Mr. Jobin presented a paper giving the data for
comparing the different saccharimetric scales in use in the deter-
mination of sugar by the polariscope, and the method of secur-
ing a uniform scale was discussed by Mr. Sidersky. It was
voted that a quartz plate of exactly one millimeter thickness was
the most scientific standard by which to measure or fix a sac-
charimetric scale. The most probable value of this standard
at the present time is expressed by an angular rotation of
21** 40'.
In section 8, papers were read by Mr. Lasne on the phosphate
industry, by Mr. Th. Schloesing on the condensation of vapors
at a high temperature, on the ammonia industry by Mr. Truchot,
and several other papers of less importance.
In section 9, the subject of the analysis of urine and the
determination of urea was discussed by Messrs. Monfet, Taffe,
Hodencq, Vicario, Hugnei, Barthe, Girard, and Doremus, the
latter describing an apparatus for the purpose, invented some
time ago by himself, and also the use of bromine dissolved in
sodium bromide, as proposed by Rice.
In the evening a lecture was given to the congress in the
amphitheatre of the Sorbonne on color photography by Mr.
934 H. W. WII.EY. SECOND INTERNATIONAI,
Lippmann, who has achieved an international reputation by his
researches into this important process. The principles of color
photography were described and illustrated by apt experiments
in conjunction with a projecting lantern. The process developed
by Lippmann is based on the well known properties of thin films,
as, for instance, a soap bubble to show colored bands due to the
relation between the thickness of the film and the length of the
waves of light. Mr. Lippmann has succeeded in depositing on
a glass plate superimposed films of silver of extreme tenuousness
and each of these films differs in thickness for each variation of
color in the object producing the photograph. When the photo-
graph is thus constructed it happens that when it is viewed by
reflected light, every color of the object photographed is exactly
reproduced. A large number of these photographs, representing
paintings, flowers, landscapes and persons, was projected by
reflection with the most vivid verisimilitude. Perhaps the most
interesting of these was the spectrum of argon, in which the blue
bands were shown in perfectly natural colors and clearly defined.
The photographic effect is secured by exposing a perfectly trtins-
parent sensitive plate, backed by metallic mercury, in contact
with the film. The sensitive surface of the plate is turned
away from the object to be photographed. The plate holder
for this operation was shown and is remarkable alike for
its ingenuity and simplicity. The importance of color photog-
raphy, as a means of fixing objects for study, is as great as its
usefulness will prove to be in preserving with all the tints of
vitality' the faces of friends and the beguilements of beauty.
Mr. Lippmann kindly granted to Mr, Doremus and myself a
private interview after the lecture, where we had a better oppor-
tunity to examine the negatives. They resemble the daguerreo-
types of forty years ago and a distinct view of the image is only
obtained by inclining the plate in the proper manner to secure
the reflection of the light. Unfortunately, these negatives are
not capable of being reproduced as positives as in the case of
ordinary photography, and we are apparently as far away as
ever from multiple printing color photography.
Sixth day, Saturday, August i. Sessions of the sections were
held only in the morning and those meeting were i, 2, 4, 6, 7,
8 and 10.
In the fourth section Mr. Kjeldahl gave a brief statement of
the present methods of conducting his process for the determina-
tion of nitrogen by moist combustion. Papers on methods of
detecting and preventing frauds in the sale of commercial fertil-
izers were presented by Mr. Petermann. A paper on the
importance of international agreement in methods of agricultural
CONGRESS OF APPLIED CHEMISTRY. 935
analysis was presented by the writer. A general discussion of
official methods of analyzing fertilizers was carried on, and at
the end it was voted that the congress collect and publish in
German and French the official methods of France, Germany
and the United States. Mr. Sidersky was selected as editor of
this brochure,
Messrs. Roy and Jean gave a paper in section 6 on tannins,
their nature and analysis. It contained little that is new to
American chemists and showed a lack of familiarity with the
American publications on that subject.
In section 7 Mr. Vogel presented a paper on photograph}' in
colors, and one on the same subject was presented by Mr. Vidal.
These papers gave in detail the points given en risumi in Mr.
Lippmann's lecture.
In section 9, Mr. Guichard read a paper on alcohol from a
hygienic point of view.
The employment of aluminum in the construction of cooking
utensils arid its influence on the wholesomeness of food prepared
therein was the subject of a paper by Mr. Boronia. It was shown
that with proper precautions aluminum could be safely used,
but that it presented few if any advantages over copper or other
metals in common use.
So widely has aluminum come into use for cooking utensils
that a brief abstract of our present knowledge concerning its
merits may be presented. The utility of an aluminum dish, in
respect to its fitness for culinary vessels, depends on the purity
of the metal. A pure aluminum dish is almost if not quite as
resistant to solvent effects of ordinary foods as any common
metal. The impurities which do the most harm are sodium and
carbon. When the aluminum contains carbon an electric cur-
rent is at once set up when a suitable liquid is applied. In such
cases after water, especially if it be saline, has stood in the dish
for one or two weeks, the surface will be found dotted with bril-
liant rings, and on scraping off the aluminum the particle of car-
bon will be disclosed. If a strong solution of salt be used, the
action may be sufficient to cause a perforation of the metal.
The aluminum of commerce, unfortunately, is not very pure, and
it is for this reason that so many aluminum dishes have shown
a rapid deterioration. The French troops in Madagascar have
been supplied with 15,000 sets of aluminum dishes, and, when a
soldier has to carry his kitchen with him, the importance of
lightness is not to be despised. But even granting that in cook-
ing in aluminum dishes a small amount of alumina is introduced
into the food, it has not been shown that it exercises the least
harmful action on the digestion. The experience of two men
93^ H. W. WILEY. SECOND INTERNATIONAL
may be cited who lived for a year on food prepared exclusively
in aluminum dishes without the slightest impairment of their
health.
In the afternoon the members were driven in carriages to
Gennevilliers, where they inspected the irrigation works, lately-
constructed to supplement those at Asni^res in disposing of tbe
sewage of Paris. It has now been more than a quarter of a
century since the city of Paris has been using its sewage for irri-
gation. The fact that in the light of that long experiment it has
recently more than doubled the area under irrigation, shows that
the process is considered a practical success. The sewage of
Paris consists mostly of the water used for washing the streets.
Water-closets are, to a large extent, connected with vaults
whose contents are removed by means of wagons, pumps and
closed tanks during the night. The sewage, therefore, is not so
highly polluted nor so rich in fertilizing materials as might have
been supposed. For summers like the present one, which has
been excessively dry, the disposal of the sewage by irrigation is
easily accomplished. But in summers of excessive rainfall and
in the winter, the problem is much more complex.
We first were shown a plan on a large chart of the system of
sewers and the distribution of the waters. Next the pumping^
house was visited where the sewage is raised to a sufficient
height to carry it under the Seine by a siphon aqueduct and dis-
tributed to the irrigated fields. The fields which were inspected
are only a part of the vast system of irrigation now in operation.
They contain 799 hectares, a part of which was once covered by
the old forest of St. Germain. The city of Paris spent 200,000,000
francs in the purchase of the grounds, the building of the aque-
duct, erecting the pumping machinery and building the irrigating
canals. The work on the aqueduct of Ach6res was commenced in
1893 and the whole work was completed in 1895. The aqueduct is
eleven kilometers long and is three meters interior diameter, and
it crosses the Seine, which below Paris forms a loop, twice. For-
tunately, the soil, forming the basin of the Seine in this locality,
is of a sandy nature and permits a somewhat rapid filtration.
A clay subsoil would render the whole process inapplicable.
The gardens, though only two years old, presented a scene of
almost tropical exuberance. Many dwarf fruit trees were
already in bearing and older trees showed the existence of
orchards before the present system was inaugurated.
The methods of irrigation are exactly those practiced in
the arid regions of the United States. The water is conducted
in furrows on the surface between the rows of growing crops.
Aside from a slightly unpleasant odor arising from the sewage,
there is nothing in the scene to cause the observer to look on
CONGRESS OF APPLIED CHEMISTRY. 937
the perfect vegetables and flowers with suspicion. In harmony
with the French devotion to art, the borders of all the plots are
planted in roses and other flowers and these, at the time of our
visit, were all in full bloom, recalling in their floral exuberance
the gardens of California. Here, as a result of the applications
of science, tj-phoid fever is turned into turnips, dysentery dances
in the dew on the dahlias, and cholera comes chortling as cab-
bage. The one unpleasant reflection is found in the fact that
this extensive harvest is sold exclusively in the Paris markets
and one can hardly avoid thinking in the restaurants over his
cauliflower and artichoke of the long race they may have run in
the aqueduct of Ach^res. At the end of the experimental field,
next to the river, the sewage which has passed through the soil
reappears as a large stream of pure water, absolutely colorless
and bright. Glasses of the attractive fluid were offered the
visitors, many of whom, unmindful of miasm and microbes,
drank, willing martyrs to science or curiosity. The number
of micro-organisms, which is many millions in the sewage, is
diminished to 2,500 in each cubic centimeter of the filtered water.
Seventh day, Sunday, August 2. An excursion was offered
to the members of the congress on Sunday to Comp^igne. On
reaching the station, a band of music welcomed the excursion-
ists. They were driven through the gardens and forests in car-
nages and at one o'clock a breakfast was ser\'ed.
Eighth day, Monday, August 3. In section i papers were
presented on the methods of determining water in organic vis-
cous liquids, by Mr. Pellet. The process recommended is by
absorption with pumice stone and subsequent drying, first at
60° to 80° and finally at 100°. Molasses and solids should first
be dissolved in water to promote absorption by the pumice. A
dr>'ing dish was exhibited with a circular depression in the cen-
ter, into which the body is weighed and mixed with enough
water to make it flow easily. The fragments of pumice are
placed on the flat bottom of the dish, exterior to the depression,
and the dissolved mass is absorbed by the pumice on inclining
the dish. The dish and cover are made of aluminum. The
diameter of the dish is about seven and its depth two cm. The
composition of molasses derived from the sugar cane was dis-
cussed at some length. Raffinose, to the extent of three per
cent., has been detected in samples of cane molasses of Egyptian
origin. The reducing sugar, in cane molasses, according to the
statement of Pellet, is composed solely of invert sugar, a con-
clusion which he has reached by applying the method of esti-
mating levulose described by the writer in this Journal a few
months ago.^
1 Vol. z8. No. X. p. 81.
938 H. W. WII^EY. SECOND INTERNATIONAL
An interesting paper by Mr. Herzfeld, of Berlin, gave a
r6suni6 of the best methods of separating sugars in mixtures.
In section 3 , the session was devoted to the chemical study of pro-
cesses of bread making, and especially to the methods of analysis
of moist and dry gluten . The processes presented are al most iden-
tical with those in use in the United States. Mr. Lindet, the
president of the congress, read a communication on the methods
of determining starch in grains and flours, in which the separa-
tion by a ferment or by water under steam pressure was recom-
mended as the best. These are the processes which we have
preferred for several years in the agricultural laboratory at
Washington.
In section 6, papers were presented on gutta percha, paper,
and paint used to prevent corrosion of ship bottoms.
In section 9 a paper on the analysis of wines and vinegar was
presented by Mr. Leroy. The detection of glucose in beer was
discussed by Mr. Pad6. The question of fermentation and the
germicidal methods of controlling it by means of fluorides was
discussed by Mr. Effront.
An interesting exhibition was given of the workings of the
latest form of bomb calorimeter for the determination of the ther-
mal equivalents of foods.
Among the more interesting papers presented in the afternoon
may be mentioned one by Mr. Fernback, director of the labora-
tories of the Pasteur Institute, on the utilization of the carbon
dioxide arising from fermentation, in section 2 ; the influence of
culture on the chemical and physical properties of the soil, by
Mr. Deherain, in section 4, and the estimation of lactose and
sucrose in condensed milks, by Mr. F. Dupont, the general sec-
retary of the congress, in section 5.
In the evening a banquet was given to the chairmen of com-
mittees of organization and to the delegates of foreign govern-
ments, in theSalledesgrandesF^tesof the Grand Hotel, under the
presidency of Mr. Cochery, Minister of Finance, at which nearh'
500 sat down. An orchestra rendered beautiful music during
the repast, giving among other things the national airs of the
various governments represented. '* Yankee Doodle'' doubtless
was heard with equanimity, but one can imagine the feelings of
the Frenchmen present when '*Die Wacht am Rhein" was
given. Short addresses were made by Mr. Lindet, the presi-
dent of the congress, by Mr. Doremus, on the part of the foreign
delegates, and a rather long one by the Minister, who greeted the
chemists for many reasons, and especially, he said, ** because you
are the precious auxiliaries of my department in promoting the
production of articles that can be taxed." Mr. Doremus intro-
duced his address by quoting one of the inscriptions on the statue
CONGRESS OP APPLIED CHEMISTRY. 939
of Danton : '* Apres le pain reducation est le plus grand besoin
du peuple." He alluded to the addresses of Berthelot, Moissan,
and Lippmann, as illustrations of a few of the accomplishments
of applied chemistry, and said the congress had shown in a
striking manner the necessity of a close alliance between applied
and research science. Pasteur will owe his immortality to the
great faculty he possessed of finding a practical application for
his discoveries. He concluded as follows : ** Hon. Minister of
Finance, representing the French Republic, M. Berthelot, the*
illnstrious president of honor of this congress, M. Wndet, the
president of the congress, M. Dupont, the secretary, I wish to
thank you in behalf of the foreign delegates, for the hospitality,
friendship, and good fellowship with which we have been
received. In the name of the foreign delegates, I propose this
toast, the French Republic, patron not only of this congress, but
also of science, art and industry, the mother of men famous in
each science, but especially, in chemistry.'*
The strangers present were given a very favorable opportunity
to understand the heartiness of French hospitality and the excel-
lence of French cooking. We might learn more things than
good cooking from a French banquet and among others the art
of limiting the post prandial speeches. At ten o'clock the
guests left the table and assembled in the grand salon, where
coffee and liqueurs were served and an hour or more spent in
social intercourse.
Ninth day, Tuesday, August 4. I have already used so much
space in giving even a few of the details of the congress that it
is not advisable to mention even the more important communi-
cations presented to-day. Morning sessions only were held. In
the afternoon the Conservatoire des Arts et Metiers was
visited, where the congress was received by Mr. Aim6 Girard,
the professor of applied chemistry, and shown through the
laboratories and museums. In the latter alone are enough
objects of interest to employ the time of a scientist for a month
for a careful study. We can only mention /asiigta rerum. The
pendulum used by Foucault in his classical experiments is still
swinging and showing by its deflections the rotation of the earth.
All the important apparatus used by Lavoisier is collected here.
The globes employed by him for determining the composition of
water are remarkably well made and even to-day would be
regarded as entirely convenient. But they have their chief value
as the remains of those era-making investigations, cut short by the
guillotine, which laid the foundation of modern chemistry. A
wooden wheel, preserved by the copper sulphate in an aban-
doned copper mine since the fifth century, illustrates in a most
940 NOTE.
Striking way one of the best methods of preventing decay in rail-
road ties. The standard measures of all nations make an inter-
esting collection, but, unfortunately,wewere not permitted to see
the original meter, which is preserved from view in the vaults of
the building. In the courtyards are bronze statues of Le Blanc,
who made the fortunes of so many and committed suicide by
reason of his own poverty, and of Boussingault, the contem-
porary of lyiebig and the father of French agricultural chemis-
try. A photographic view of the congress was made on the
steps of the \yest facade of the building.
Tenth day, Wednesday, August 5. In the morning the sec-
tions held their final sessions for hearing papers and discussions.
In the afternoon the closing meeting of the congress was held in
the grand amphitheatre of the Sorbonne under the presidency of
Mr. Henri Boucher, Minister of Commerce and Industry.
Addresses were made by Mr. Lindet and the Minister and a
report of the proceedings of the cot^ress presented by the sec-
retary, Mr. Dupont. Turin and Vienna were placed in nomina-
tion as the places of meeting of the congress in 1898. Vienna
was selected by a large majority. An invitation was extended
by Mr. Lindet to hold the congress of 1900 in Paris during the
World^s Exhibition, and that invitation will doubtless be
accepted at Vienna.
After the adjournment of the meeting, the new laboratories of
organic chemistry, constructed by Friedel, were inspected by-
Mr. Doremus and myself. In the confusion of the summer
cleaning, we could hardly form any favorable judgment of their
points of excellence. The ultra impressionist painting of Para-
dise Lost, a mural ornamentation back of the professor's lecture
table, was the most original and inexplicable feature of the lab-
oratory.
Paris, August lo. 1896.
NOTE.
The fourteenth annual report of the Committee on Indexing
Chemical Literature was presented to the American Association
for the Advancement of Science at the Buffalo meeting, August
24. A large amount of work has been done in this field during
the year. The committee is an active one and has done a val-
uable work in encouraging and recording biographical under-
takings. Copies of the report may be obtained of the chairman,
Dr. H. Carrington Bolton, Cosmos Club, Washington, D. C.
Vol. XVIII. [November, 1896.] No. 11.
THE JOURNAL
OF THE
AMERICAN CHEMICAL SOCIETY.
A NEW FORM OF POTASH BULB.*
By M. Gomberg.
Received August aS, 1896.
THE potash bulb most frequently used at present in elemen-
tary organic analysis is that known as Geissler*s bulb.
"While neat and compact, it still has the same drawback as pos-
sessed by other forms of potash bulbs; namely, that even with
tlie most careful handling it is not unfrequently broken. Some
two years ago I drew up a design for a different form of bulb,
^wherein all the connections should be enclosed. Several attempts
to have it made in this country have proven unsuccessful. The
design was then sent to Greiner & Friedrichs, of Thtiringen,
and I have recently received from them samples of such bulbs.
Meanwhile, it came to my notice that a bulb based on similar
principles has been put upon the market by Bender & Hobein,
of Miinchen. A comparison of the two bulbs shows them, how-
ever, to be sufficient!^ different to justify me in presenting a
description of the one made according to my design, without
claiming priority as to the principle of construction.
The arrangement and working of the bulb will appear clear
from the subjoined diagram, which presents the apparatus re-
duced to one-half its actual size.
The potash bulb is divided into three compartments, /f, ^
and C, B and C contain the potash solution for the ab-
sorption of the carbon dioxide, while A serves as a safety res-
ervoir in case of backward suction. The bulb is filled by dipping
a into the solution, and applying suction at ^, until the two com-
I Communicated by A. B. Prescott. Read at the meeting of the American Chemical
society, Buffalo, N. Y., August 32, 1896.
942
CHARLBS BASKERVILLB. REDUCTION OP
partments B and C contaia as
much of the solution as would
completely fill A^ which is
about thirty-five to forty grams
of a 2 : 3 solution. />, which
is fastened to the bulb by
means of a ground-glass joint,
contains solid potassium hy-
droxide, or soda-lime, sup-
ported by a plug of glass-wool.
The liquids in^ and Ccan be
easily mixed when desired,
by applying suction at a.
The bulb, when filled and
ready for use, weighs from
sixty-five to seventy grams,
and undoubtedly can be made
even much lighter.
The total number of compartments is thus reduced from five
in Geissler's form to three in the form here presented, while the
absorbing chambers are reduced only from three to two. The
construction of the bulb is such that C can never get overfilled
by the solution from B.
This form of a potash bulb possesses the advantages first,
that it can be easily handled and wiped, presenting the out-
side surface of an ordinary small flaslc, and second, that it
can be set without any support, and can be weighed without
suspending it if so desired.
I wish to express my thanks to the firm of Greiner & Fried-
richs, of Thiiringen, who have kindly made the bulb for me in
a most satisfactory manner.
CBBMICAI. LABOKATORV, UNrVBRSITY OP MICHIGAN.
REDUCTION OF CONCENTRATED SULPHURIC ACID BY
COPPER.
I
Bt Charlbs Baskervillb.
Received August 97, 1890.
KCCVITCU August S7( I«9P.
N a previous communication* the writer noted that copper was
acted upon by concentrated sulphuric acid (i.84sp. gr.) not
1 This Journal. 17, 90.
r-
CONCENTRATBD SULPHURIC ACID BY COPPER. 943
only at the ordinary temperatures of the air » 20^-30'* C . , but at zero
as well. Andrews' states that the assertion is ihcorrect and that
it does not occur until the temperature 86^ C. has been reached,
or a point above the dissociation temperature of the concentra-
ted sulphuric acid I 67* C, according to him. Andrews further
says that the author's statements were based "not upon any
demonstrations of the formation of sulphurous acid, but solely
on the formation of copper sulphate," which, he says, occurs
only '* in consequence of the presence of the air.** It is to be
regretted that Dr. Andrews did not note carefully the statements
of the author in his previous communication, as no reason what-
ever exists for any such conclusions, because it was distinctly
stated that not only the copper as sulphate, but as sulphide was
determined, as well as sulphurous acid, and moreover, that the
experiments were carried out when the air had been replaced by
a neutral gas, either hydrogen or carbon dioxide.
The author, although confident of the correctness of his for-
mer statement, carried out further experiments to correct the
error, if committed or to establish, beyond question, the fact that
concentrated sulphuric acid of 1.84 sp. gr. is reduced b}' copper
below 86® C, the limit postftve/y .set by Dr. Andrews.
The fact that these experiments but confirmed the former
statement of the author allows the incorporation of the results in
this paper.
As far back as 1834 the fact that copper is acted upon by
concentrated sulphuric acid at ordinary temperatures, if suffi-
cient time be given, was made known by Barruel.* Calvert and
Johnson,' however, failed to obtain any action below 130® C. and
considered that none took place. Pickering/ however, stated
that " sulphuric . acid attacks copper at all temperatures from
19** C, (and probably even still lower) upwards.*'
Ftrs/ Experiment. — Copper ribbon in strips, i x 3-4 cm., was
submerged in concentrated sulphuric acid in a clean glass stop-
pered flask for a month. At the end of that time not only were
there white crystals of anhydrous copper sulphate clinging to
1 This Journal, i8» 353.
sy. depkarm.^ 90, 13, 18J4.
•y. Chem. See., 19, 438, iS66.
«y. Oum. Soc., Trans., 1878, 115.
944 CHARLES BASKERVILLE. REDUCTION OP
the sides of the containing yessel, but there was a very appre-
ciable amount of brownish black cuprous sulphide and sulphur
dioxide was easily detected by its strong odor when the vessel
was opened.
Andrews' states *' that in the presence of air sulphuric acid is
attacked by copper at ordinary temperatures, but without reduc-
tion of the acid. The reaction must take place according to the
equation,
2CU + O, + 2H,S0, = 2CuSO,+ 2H.O.''
Formerly the author* stated that the presence of the oxygen
of the air when it comes into contact with the copper in the acid
has great influence on the reaction. Fifty years ago, Maumen^'
proved that when a current of oxygen gas was passed through
the boiling acid, the amount of insoluble residue, e, g,^ cuprous
sulphide, was diminished, that is, less than there would be
formed if the experiment were carried out with a current of car-
bon dioxide. The copper must be directly exposed to the oxy-
gen by only partial submersion or the bubbling of the air against
or around the submerged copper ; but the air in a confined
space, not at all in contact with the copper, but separated by a
thick layer of concentrated sulphuric acid, has little or.no effect.
Yet grant that the oxygen of the air (volume of air about 200
cc.) confined in the flask, had been utilized in the formation of
the copper sulphate produced. According to the formula given
above, the oxygen would be absorbed and no corresponding
amount of any other gas would be eliminated; consequently
there should be a greater external pressure at the close than at
the beginning of the experiment. When the smoothly fitting
glass stopper was removed, not only no extra internal pressure
was noticed, but in fact a pressure from within. This was evi-
dently produced by the sulphur dioxide generated. The sulphur
dioxide was swept out by a current of air through a dilute solu-
tion of potassium permanganate, which was quickly bleached.
The presence of sulphur dioxide was further proven by the addi-
tion of barium chloride to the bleached potassium permanganate
^ This Journal, i8, 252.
a Ibid, 17. 912.
^ Attn, chim, phys., 1B46, [3I, il, 311.
CONCENTRATED SULPHURIC ACID BY COPPER. 945
solution. Nor does the formula given above account- for the
cuprous sulphide which is always produced.
Second Experiment. — Realizing the possibility of some organic
matter or dust remaining in the flask, although it had been care-
fully cleansed, the first experiment was repeated with the great-
est precaution to ensure the absence of dust. The flask was scoured
with boiling concentrated pure sulphuric acid containing potas-
sium bichromate and carefully cleansed with distilled water.
The last traces of water were removed by four subsequent wash-
ings with the same kind of concentrated acid used throughout
the experiments. The experiment was carried out in the same
manner as the first, the same results l)eing obtained.
A blank experiment was carried out at the same time. The
flask was rendered dust free in the manner just mentioned
and fifty cc. of the same acid allowed to remain in the flask for
six months. At the end of that period not a trace of sulphur
dioxide could be detected in the blank, therefore the sulphur
dioxide produced when the copper was inserted could not be due
to the reduction of the sulphuric acid by an extraneous sub-
stance, but solely by the copper. The conclusion is that sul-
phuric acid is reduced by copper when air is present at the ordi-
nary temperatures, 2o**-30° C.
Third Experiment,— Kxi ordinary Kjeldahl digestion flask was
made dust free by the treatment noted above. 100 cc. sul-
phuric acid, 1.84 sp. gr., were placed therein and clean dry
strips of copper ribbon were completely submerged in the acid.
Now air-free carbon dioxide was passed through the flask for
three hours. The inlet tube was just dipped into the acid.
The flask was then attached to a suction pump, with a sulphuric
acid dr>'ing flask intervening to prevent a possible return flow of
gas or air which might carry moisture or dust into the flask.
The flask was exhausted of the carbon dioxide present for three
hours at a pressure of 150 mm. It was then sealed with the
blast lamp and placed aside in a darkened cupboard. Obser\'a-
tions were made every few days to note any reaction taking
place. Within two days it could be easilj' seen that copper sul-
phate had been formed and the liquid was somewhat clouded by
very finely divided suspended cuprous sulphide. Continued
94^ REDUCTION OP CONCBNTRATBD SULPHURIC ACID.
observations extending over a period of seven weeks showed
only an increase in the amounts of both of these substances.
The temperature of the cupboard had at no time risen above 20*
C, and was for most of the time much lower. The flask was
then opened as any other sealed tube, and instead of an external
pressure inward, which had been sufficient to heavily dent the
tube in sealing, there was a strong internal pressure outward.
The gas evolved was sulphur dioxide, easily detected by its
strong odor and bleaching effect upon a dilute solution of potas-
sium permanganate. The sulphuric acid produced by the oxi-
dation of the sulphur dioxide by the permanganate was precipi-
tated by barium chloride. All solutions and apparatus were
proven to be free from traces of sulphur dioxide and sulphuric
acid by a blank experiment.
Coficlusian, — Concentrated sulphuric acid, 1.84 sp. gr., is
reduced by copper when air is absent and at temperatures far
below 86^ C, in fact at the ordinary atmospheric temperatures
with the formation of copper sulphate and cuprous sulphide and
the production of sulphur dioxide.
Finally. — Apparatus similar to that made use of by Andrews*
was employed with the modification of having three drying
flasks containing concentrated sulphuric acid instead of one, and
a Meyer absorption tube was substituted for a single small flask.
These served merely as extra precautions against dust and
insured an intimate mixing of the outgoing gases with the per-
manganate. Within twelve hours the permanganate was
bleached. Andrews' experiment lasted only fifteen minutes.
The presence of the sulphur dioxide produced was easily
detected by the odor when the apparatus was opened, and in the
bleached permanganate solution by barium chloride. Copper
sulphate and cuprous sulphide were also formed.
Concentrated Sulphuric Acid is Acted upon by Copper at Zero, —
Quantitative experiments were carried out by the author when
the concentrated sulphuric acid in which the copper was sub-
merged was practically at zero.' In stating the results, how-
ever, the author gave the temperature as * * o'-io' C. " The flask
1 This Journal, xl, 251.
a Ibid. 17, 908.
SEPARATION OP THORIUM. $47
containing the acid was buried in an ice-bath and the tempera-
ture of the liquid noted by a thermometer inserted through a
rubber stopper. The apparatus was air-tight. A stream of
hydrogen gas was continued through the apparatus in one
experiment for six Weeks and in another two months. On two
occasions when the ice in the bath had melted in going over
Sunday, the temperature rose to lo** C. The temperature could
not possibly have remained that high for over twelve hours, which
would have had small influence when the experiments lasted
through a number of days. The temperature was reported
o'^-io^ C, however. Not only copper sulphate, but cuprous sul-
phide and sulphur dioxide had also formed. Copper, therefore,
decomposes concentrated sulphuric acid (sp. gr. 1.84) practi-
cally at zero.
From my own experiments and from experiments performed
with apparatus similar to that used by Andrews and under the
same conditions, except with regard to the important element,
time, which consideration is necessary for all chemical reac-
tions, the author must adhere to his former statement.
UifrvBRSiTY OF North Carolina.
THE SEPARATION OF THORIUfl FROil THE OTHER RARE
EARTHS BY MEANS OF POTASSIUfl TRINITRIDE.
By h. M. Dennis.
Received Scptenber 4. 1896.
SOME time ago the author and F. L. Kortright* briefly
described the action of a solution of potassium trinitride
upon a neutral solution of the rare earths. It was found at that
time that the flocculent precipitate which is produced was most
probably thorium hydroxide, but our supply of potassium trini-
tride having been exhausted it was impossible to further inves-
tigate the reaction or ascertain the completeness of the separa-
tion. The immediate continuation of the work was prevented
by unexpected difficulties which were encountered in the prepa-
ration of pure hydronitric acid on a large scale. These difficul-
ties have since been removed, and it has been possible to prepare
an amount of the reagent sufficient for the investigation
described below.
> Xtschr. anoirg. Ckem., 6, 35 ; Am. Chem.J., x6, 79.
94^ L. M. DENNIS.
The solution of potassium trinitride which was used was pre-
pared by careful!}' neutralizing a dilute solution of hydronitric
acid with a dilute solution of pure caustic potash and then add-
ing hydronitric acid sufficient to give to the solution a distinctly
acid reaction. The solution first employed contained about
three and two-tenths grams of potassium trinitride to the liter.
Before studying the separation of thorium from the other rare
earths, the reaction between potassium trinitride and pure tho-
rium chloride was first investigated. The thorium employed
was from a sample of thorium oxalate, which had been very
kindly presented to me by Dr. Theodor Schuchardt, of Goerlitz.
It was found to be of a very high grade of purit}', but to guard
against the possible presence of other rare earths, the oxalate
was converted to the oxide b}' ignition, treated with concentra-
ted sulphuric acid, the anhydrous sulphate dissolved in distilled
water at a temperature of o°, and this solution was precipi-
tated with pure oxalic acid. The precipitated thorium oxalate
was thoroughly washed with hot water containing one per cent.
hydrochloric acid, and was then dropped into a hot, concen-
trated solution of ammonium oxalate. It dissolved completely
and no precipitate formed when the solution was diluted and
cooled. From this solution the thorium was again precipitated
as oxalate by means of strong hydrochloric acid and was then
brought into solution as thorium sulphate in the manner
described above. It was then precipitated by ammonium
hj-droxide and the precipitate thoroughly washed with water.
The thorium hydroxide was then dissolved in hydrochloric acid,
ammonium hydroxide was added until a faint but permanent
precipitate remained, and this was then removed by filtration.
There was thus obtained a neutral solution of thorium chloride
containing a very small amount of ammonium chloride.
The strength of this solution of thorium chloride was ascer-
tained by precipitating portions of ten cc. each with ammonium
hydroxide, filtering, washing, igniting, and weighing as ThO,.
Two determinations gave, for thorium oxide in ten cc., 0.0591
gram and 0.0595 gram. The mean of these results is equivalent
to 0.00521 gram thorium in one cc.
Upon adding to this thorium solution a few cc. of the solution
SEPARATION OP THORIUM. 949
of potassium trinitride, the precipitate which, in the previous
work with Dr. Kortright, had formed at once, failed to appear ;
upon heating the solution to boiling, however, there was quickly
formed a white, flocculent precipitate, closely resembling in
appearance aluminum hydroxide, but settling rapidly when the
flame was removed. In the first determinations the solution
was boiled for five minutes, but it was later found that boiling
for one minute is sufficient. During the boiling the odor of
hydronitric acid was distinctly noticeable. The precipitate was
washed by decantation with hot water, transferred to the filter,
ignited, and weighed as ThO,. Twenty cc. of thorium chlo-
ride, containing, according to the determination with ammo-
nium hydroxide, 0.1186 gram thorium dioxide gave, by precipi-
tation with potassium trinitride, 0.1183 gram thorium dioxide,
equivalent to 0.00520 gram thorium in one cc. instead of 0.00521
as obtained with ammonia.
It is apparent, therefore, that thorium can be quantitatively
precipitated by potassium trinitride.
The pre\^ious work of Dr. Kortright showed that the thorium
is probably precipitated as the hydroxide, but the tendency of
the precipitate to absorb carbon dioxide rendered the analyses
unsatisfactory. If, however, the thorium is precipitated as the
hydroxide, then all of the hydronitric acid of the potassium salt
first added must reappear in the filtrate from the thorium
hydroxide and in the gas evolved during the boiling. To ascer-
tain whether this took place the precipitation was made in a
round bottomed flask. In the neck of the flask there was
inserted a two hole rubber stopper, through one opening of
which a current of purified air was admitted, the other opening
carrying an upright condenser. The condenser was connected
at the upper end with two absorption vessels containing neutral
silver nitrate solution. As the hydronitric acid was to be deter-
mined by precipitation with silver nitrate, a neutral thorium
nitrate solution, containing 0.0075 gram thorium in onecc, was
substituted for the thorium chloride. The thorium nitrate solu-
tion was placed in the flask, potassium trinitride was added, and
after starting a current of air through the apparatus, the con-
tents of the flask was heated to boiling and kept boiling for two
950 h. M. DENNIS.
minutes. Soon after the heating began a white precipitate of
silver hydronitride formed in the first absorption flask contain-
ing the silver nitrate ; by the time the reaction was complete
this precipitate had become quite voluminous. The absorption
of the gas by silver nitrate seems to be both rapid and complete^
for nothing more than a slight opalescence ever appeared in the
second absorption flask. After the apparatus had become cool
the thorium hydroxide was filtered off and the filtrate was pre-
cipitated by silver nitrate. The silver trinitride thus obtained,
together with that in the absorption flasks, was washed by
decantation with cold water, the washings being passed through
a hardened filter. When the wash water gave no further reac-
tion for silver the funnel with the filter was placed in the neck
of the flask containing the main part of the precipitate, and
quite dilute, hot nitric acid was poured upon the paper. The
silver trinitride on the paper dissolves almost immediately.
After washing the paper with water, the funnel was removed
and the contents of the flask was boiled until all of the silver tri-
nitride had dissolved. The silver was then precipitated by
hydrochloric acid and weighed as silver chloride. Ten cc. of
thorium nitrate and ten cc. of potassium trinitride were used.
The silver chloride resulting weighed o. 1447 gram, equivalent
to 0.0434 gram hydrpnitric dcid. The strength of the potas-
sium hydronitride, which was a different solution from the one
first employed, was then determined in the same manner.
5 cc. gave 0.0744 AgCl = 0.02232 HN,,
5 cc. gave 0.0745 AgCl = 0.02235 HN,.
Using the mean of these results, it appears that 0.0446 gram
of h3'dronitric acid was used in the precipitation of the thorium
nitrate, of which 0.0434 gram was recovered from the filtrate
and distillate. That this latter result is somewhat low is doubt-
less due to the loss of hydronitric acid by volatilization during
the filtration of the liquid in the flask. These results, together
with those given in the preceding article • already referred to,
enable us to represent the reaction by the equation
Th(NO,), + 4KN. + 4H.O = Th(OH), + 4KNO, + 4HN..
This reaction is interesting not only because of the quantita-
SEPARATION OP THORIUM. 95 1
tive precipitation of thorium by this means, but also because 6f
the peculiar behavior of the potassium hydronitride. As Ost-
wald has stated, hydronitric acid is but slightly stronger than
glacial acetic acid, and the above equation reminds one of the
behavior of acetates towards ferric iron, the solution of ferric
acetate being fairly stable in the cold, but breaking down upon
heating, into acetic acid and ferric hydroxide.
The experiments detailed below were then made to ascertain
whether thorium could be quantitatively separated from the
other rare earths by means of the above reaction. A neutral
solution of pure lanthanum chloride was first prepared and its
strength determined by precipitating with ammonium hydroxide
and weighing the lanthanum as La^O,. The solution contained
0.00431 gram lanthanum in one cc. This solution gave no pre-
cipitate when boiled for some minutes with potassium trinitride.
Fifteen cc. of this solution and fifteen cc. of the thorium chloride
solution were placed in an Erlenmeyer flask, twenty-five cc. of
potassium trinitride (three and two-tenths grams to the liter)
was added and the solution was boiled 'or one minute. The
precipitate was filtered ofiF and washed with hot water, ignited,
and weighed. To the filtrate five cc. more of potassium trini-
tride was added and the solution boiled for two minutes.
No further precipitation resulted. The solution was then pre-
cipitated with ammonia and the lanthanum weighed as the
oxide. The results were :
Taken. Pound.
Thorinm 0.0781 0.0777
Lanthanum 0.0646 0.0642
A mixture of the rare earths in Brazilian monazite was then
freed from thorium by repeatedly digesting the mixed oxalates
with a hot, concentrated solution of ammonium oxalate. The
residual oxalates were then transformed into chlorides and dis-
solved in water. The solution showed the pink color and
absorption bands of didymium and gave a strong reaction for
cerium when treated with hydrogen peroxide and ammonia.
When boiled with potassium trinitride it gave a very faint pre-
cipitate which was filtered off. By precipitation with ammonia
this solution of cerium, lanthanum, didymium, etc., free froni
952 SEPARATION OF THORIUM.
thorium, was found to contain 0.0166 gram of the mixed oxides
in one cc. The precipitation was made as in the separation
from lanthanum and an excess of potassium trinitride was used
in each case.
Taken. Found.
I. Thorium... 0.1300 0.1294
Ce, t^a, Di oxides 0.0332
II. Thorium 0.0785 0.0783
Ce, La, Di oxides 0.0830 ....
III. Thorium 0.0535 0.0526
Ce, La, Di oxides 0.2490 ....
IV. Thorium 0.0535 0I0531
Ce, La, Di oxides 0.2490 ....
V. Thorium., r 0.0550 0.0541
Ce, La, Di oxides 0.4980 . . • .
VI. Thorium 0.0555 • 0.0550
Ce, La» Di oxides 0.5810 ....
VII. Thorium 0.0570 0.0558
Ce, La, Di oxides 0.8300
• a
The recovery of the thorium is in all cases fairly exact and the
variation in the relative amounts of thorium and the other earths
does not influence the sharpness of the separation. That tho-
rium alone is precipitated by potassium trinitride is to be
explained by its weak basicity. It is the weakest base in the
whole group of the rare earths with the possible exception of
cerium in the eerie condition, and this higher form of cerium is
probably incapable of existence in the presence of hydronitric
acid.
We have, then, in potassium trinitride a reagent which can be
used both for the qualitative detection of thorium and for its
quantitative determination either alone or in the presence of
other rare earths. So far as the author is aware, this is the
only method as yet devised by which one of these earths can be
quickly and accurately separated from the others, and that in a
single simple operation.
Cornell University, Augrust, 1896.
NOTES ON REIN§CH'S TEST PORARSENIC AND ANTIMONY.
By Jas. I«bwx6 Howe and Paul S. Mertin s.
Received September la. 1896.
THAT Reinsch's test for arsenic possesses, in point of con-
venience, marked advantages over that of Marsh, is gen-
erally acknowledged, but it has been questioned both as to deli-
cacy and as to accuracy in distinguishing between arsenic and
antimony. As to the former point, Reinsch, in his second arti-
cle on the test,* states that arsenic may be detected in a solution
of one part per million. In his original description* of the test
he placed the accuracy about one-third of this. Our own
experiments show that this accuracy is not overstated. The
fact that arsenious oxide and antimonous oxide (Sb.O.) are
isomorphous in their crystallization has led to the conjecture that
antimonous oxide subliming from the copper in the closed tube
might appear in the brilliant octahedra, characteristic of arsenic
in the test.
Experiments bearing on this point were made as follows :
Reinsch's test was applied to the different compounds of arse-
nic in this laboratory and in each case several sublimation tubes
were used. The test was carried out by boiling the substance
with sixteen per cent, hydrochloric acid, in which several strips
(2.5 X 0.5 cm.) of thin, pure copper were placed. After fifteen
minutes (except in cases to be mentioned later) the strips of
copper were removed, washed and dried, and after rolling or
folding to small compass, placed in open tubes five cm. long and
not over five-tenths cm. diameter. These tubes were held in an
inclined position in the lowest possible flame of a Bunsen burner
until the arsenic sublimed ; a second or two usually sufiices.
The test was similarly carried out with compounds of anti-
mony and also with various organs of two cats, one killed by
six grains of tartar emetic, dying six hours after administration,
and the other dying in three days after the administration of the
first of six small doses given every twelve hours. Each dose was
two grains, but much of this was probably not taken into the
system. A perceptibly higher degree of heat was necessary to
1 H. Reinsch : De 1* Bssai de 1' Arsenic par le Cuivre : /. pharm. Chim., 2, 361, {1842).
s H. Reinsch : Ueber das Vetlialten des metallischen Kupfers xu cinigcn M etall-
MhiiBgeB: /,prakt. Chem., 24, 244, (/^).
954 reinsch's test for arsenic and antimony.
sublime the antimony than was the ca^e with arsenic;
altogether 185 tests were made, most of them furnishing good
sublimation tubes. Each tube was numbered as made, and
later the whole number were mixed and sorted for arsenic and
antimony by examination with a microscope of low power.
Reference to the note book showed that in no case had a mis-
take been made, in fact in every case the arsenic sublimation
could easily be distinguished from that of antimony by the naked
eye. In no case did the sublimate of antimonous oxide show a
trace of crystallization under the microscope used, nor did the
arsenious oxide fail in any case to show the characteristic bril-
liant octahedral crystals.
The evidence that the antimonous oxide cannot appear in
crystals which might be mistaken for arsenic is of course nega-
tive, but owing to the variety of forms used it must be con-
sidered to have the weight of positive evidence.
As regards the substances tested, the following may be re-
corded :
All arsenious compounds soluble in hydrochloric acid gave
the deposit on copper immediately on heating.
Commercial ** metallic '* arsenic gave the deposit readily.
Freshly sublimed ** metallic'* arsenic (bright crystals) gave
no deposit.
Arsenates gave a deposit only after several minutes boiling.
In the presence of nitric acid or chlorates no test is obtained
owing to the solution of the copper.
Whenever aqua regia or potassium chlorate is necessary for
solution of an arsenic compound, the solution should be evapo-
rated to dryness with hydrochloric acid. The test can then be
carried out as with arsenates.
The presence of organic matter in the arsenic solution does
not affect the test, hence it can be applied directly to any organs
without any previous destruction of tissue. If much arsenic is
present it is best to use but a small portion of the substance, since
if much arsenic is deposited on the copper, it will not adhere
with firmness.
Antimony is not precipitated on the copper as rapidly as arse-
PHOSPHORUS IN STEBL AND CAST IRON.
955
nic, and the deposit has a decidedly violet tint, very distinct
from the iron gray deposit of arsenic.
The following distribution of antimony in the two cats may
be added :
Acnte poisonins: (6 hours}.
Stomach, — Heavy deposit and sub-
limate. Good test with ^\^
of stomach.
Liver, — Not so heavy deposit as
stomach. Good sublimate.
Heart. — Good deposit after sev-
eral hours boiling. Good sub-
limate.
I^ncreas, — Faintdeposit. No dis-
tinct sublimate.
'Spleen, — Paint deposit. No dis-
tinct sublimate.
JCidney. — Faint deposit. No dis-
tinct sublimate.
Intestine, — Good deposit and sub-
limate.
Muscle.— VeXvX deposit on two
days boiling. No sublimate.
£rain, — No deposit.
Spinal Chord, — No deposit.
V/ASH1NCTON AND LBE UNIVERSITY.
Lbxinoton, VA.
Slow poi!M>utug (73 hours),
Good tests.
Heavy deposit and good subli-
mate.
Good deposit on ninety minutes
boiling. Good sublimate.
Good deposit and sublimate.
Good deposit and sublimate.
Good deposit and sublimate.
Slight violet tinge to copper. No
sublimate.
Marked violet tint to copper. No
sublimate.
NOTES ON THE DETERMINATION OF PHOSPHORUS IN
STEEL AND CAST IRON.
By George Auchv.
Received August 97, 1196.
OF the many improvements made in recent years in the
method of determining phosphorus in steel, that of Jones
— ^the use of the **reductor'* — is not the least. There has been,
however, some difference of opinion as to the completeness of
the reduction accomplished by its use. Quoting from three
most recent pu'blications on the subject: Doolittle and Eavenson
consider the reduction of the molybdic acid to be to a point cor-
95^ GEORGE AUCHY.
responding to the ratio of 89.16 iron to molybdic acid ; Noyes
and Royse, by special precautions, obtain a reduction completely
to Mo,0, (factor 85.71) ; and Blair and Whitfield find the ratio
88. i6, a reduction to Mo,^0„ only, even with the precautions of
Noyes and Royse observed. Doolittle and Eavenson heat the
solution before passing it through the reductor. Noyes and
Royse do not. The first named chemists do not use the pre-
cautions of Noyes and Royse. It appears from a result by
Prof. Noyes given in this Journal, 10, 759, that he does not
invariably get a reduction to Mo,0, by his method, his result
there given corroborating Blair and Whitfield's hypothesis of a
reduction to Mo„0„ only.
It was thought by the writer that perhaps the reduction to Mo,0,
could invariably be accomplished by combining the precautions
of Noyes and Royse with the practice of Doolittle and Eavenson
of passing the solution through the reductor hot. The following
results were obtained « using yellow, phosphomolybdate precipi-
tate dried six hours at 150** C.
Phosphomolybdate
taken.
Gram.
Phosphorus
present.
Per cent.
Phosphorus found.
Noyes' factor.
fPcr cent.
Phosphorus foui
Blair's factor.
Per cent.
O.OIOO
1.63
1.63
1.68
O.OIOO
1.63
1.63
1.68
0.0200
1.63
1.59
1-63
0.0300
1.63
1.63
1.68
0.0300
1.63
1. 61
1.65
0.0200
1.63
'•55
1-59
0.0400
1-63
1.59
1.63
0.0500
1.63
1.62
1.67
0.0500
1.63
1.63
1.68
0.0600
1.63
1.63
1.68
0.0700
1.63
1.61
1.65
0.0700
1.63
r.6o
1.64
O.IOOO
1.63
1.63
1.68
0.0400
1.63
1.59
1.63
0.0400
1.63
1-59
1.63
0.0200
1.63
1.58
1.62
0.0400
1.63
1.56
1.60
0.0300
1.63
1.59
1.63
0.0900
1.63
'•57
1. 61
0.0400
1.63
1.60
i6i
0.0500
1.63
1.61
1.65
PHOSPHORUS IN STEEL AND CAST IRON. 957
Passing the solution through the reductor hot does not seem
to insure an invariable reduction to Mo,0,, and perhaps adds
nothing to the effectiveness of the process. The following tests
were made in the cold :
Phosphomolybdate
taken.
Gram.
Phosphorus
present.
Per cent.
Phosphorus found.
Noyes* factor.
Per cent.
Phosphorus found.
Blair's factor.
Per cent.
0.0500
1.63
1.58
1.62
0.0400
1.63
1.59
1.63
0.0300
1.63
1.59
1.63
0.0400
1.63
1-57
I.61
0.0500
1.63
1.63
1.68
But in these last tests, and also in the first series of tests in
nearly all cases where the result calculated by Noyes' factor
came low, the point of the reductor had been washed off, and the
sides of the flask ivashed down by the jet. Noyes warns against
any dilution of the reduced solution before titration, but it was
thought that such a slight dilution would do no harm. For a
test of this the following determinations were made (cold) and
without washing down :
»homolybdai
e Phosphomolybdate
Phosphorus found.
Phosphorus found.
taken.
present.
Per cent.
Noyes' factor,
rer cent.
Blair's factor.
Gram.
Per cent.
0.0500
1.63
I.61
1.65
0.0900
1.63
1.60
1.64
0.0300
I. .63
I.61
1.65
0.0300
1.63
1.63
1.68
0.0400
1.63
1.60
1.64
0.0400
1.63
1.63
1.68
0.0300
1.63
1.63
1.68
0.0400
1.63
1.60
1.64
0.0400
1.63
1.63
1.68
0.0500
1.63
1.62
1.67
Comparing these results with those of the preceding series it
is seen that a complete avoidance of any dilution, however slight,
after reduction, will bring higher results than if this precaution
be neglected. But it is further seen that the observance of this
precaution does not invariably assure a result agreeing with a
reduction to Mo,0„ although it generally does so. Of the
eleven results in the^ first series of experiments (solution passed
through the reductor hot), obtained by an observance of this
precaution, seven, calculated by Noyes' factor, are over 1.61 ;
95^ GEORGB AUCHY.
and of the ten results of the last series (reduced cold) , seven
are 1.61 per cent, or over. On the other hand» of the thirteen
results obtained by washing down the sides of the flask after
leduction, ten fall short of the theoretical f.63 per cent, by more
than 0.02 per cent., calculated by Noyes* formula, and do bring
1.63 per cent, calculated by Blair*s factor. The inability of
Messrs. Blair and Whitfield to accomplish a reduction to Mo,Og
by an observance of the precautions given by Messrs. Noyes
and Prohman, and also the still higher factor found by Messrs.
Doolittle and Eavenson, may perhaps be due to the fact that
the zinc in each case used differed in reductive power from that
of the others. The writer had on one occasion zinc which when
used in the reductor with all care and precautions, never gave a
/eduction of more than one-half ; and in his opinion it is safer
and more accurate to use the old Emmerton method of reduc-
tion and filtration, but with the modifications and precautions
described later in this article.
The phosphomolybdate employed in the above tests, was, for
part of them, made by precipitating from sodium phosphate
solution ; for another part of the tests, made by precipitation
from pig iron solution, exactly as is done in the determination
of phosphorus in pig iron. Messrs. Blair and Whitfield have
shown the constancy of the composition of phosphomolybdate
made under varying circumstances.
The volume of the solution passed through the reductor in
each of the above experiments was 100 cc, as recommended by
Blair and Whitfield. Noyes and Frohman use 200 cc, but this
seems an unnecessary bulk. Fifteen cc. of sulphuric acid (2:1)
was used for acidifying.
For washing 100 cc. of hot water was used containing ten cc.
of sulphuric acid, ( 2 : i ), followed by 100 cc. cold water, and
again by fifty to seventy-five cc. of cold water.
The reductor was of the form described b)' Blair and Whit-
field,* except that it was considerably wider at the top than the bot-
tom— in shape like a common tinhorn. This shape holds more
zinc for the given height (ten inches) of the column, and so
makes the necessity of filling less frequent.
1 This Journal. 17. 74-
PHOSPHORUS IN STEEI, AND CAST IRON. 959
The redactor may be used without refilling till the column of
zinc falls to five or six inches without any diminution of effective-
ness. AH of the results of the two preceding series, and some of
the last results in the first series were obtained by the use of five
to seven inches of zinc in the reductor.
It adds somewhat to the facility of the working of the apparatus
to have the beaker containing the phosphorus solution above
the level of the zinc in the reductor so that the connecting tube
may work as a siphon. And the last washing may then con-
veniently be made by diminishing the force of the suction of the
pump, loosening the stopper of the reductor, and allowing the
water to be siphoned over and fill up the vacant space in the
reductor above the zinc column.
The passage of the solution through the reductor was not pre-
ceded by the passage of dilute sulphuric acid, and in many of
the tests some little air was accidentally drawn over into the
reductor at the time of washing, although care was uniformly
taken to allow no air to enter at the first washing.
Messrs. Noyes and Royse direct that the reductor should be
rinsed with dilute sulphuric acid before using, even if it has
stood but a few minutes. This is some little trouble, and to test
the necessity of it, the following tests were made :
Ptaotptaomolybdate
Phosphorus
taken.
Phosphorus
Uken.
found.
Reductor
Grmm.
Per cent.
Per cent.
stood.
0.03CX>
1.63
I.61
one hour
0.0700
1.63
1.60
all night
O.IOOO
1.63
1.63
six hours
0.0300
1.63
1.63
all night
0.0300
1.63
1.63
three hours
0.0300
1.63
1.63
two days
0.0300
1.63
1.63
two days
0.Q500
1.63
1.63
two days
0.0500
1.63
1.62
two days
These results seem an indication that this precaution is not
absolutely necessary. But if the reductor stand nearly a week
or more, the sulphuric acid will take up considerably more of
the impurity of the zinc than ordinarily. Zinc, for instance,
which ordinarily will require a deduction of two-tenths cc. from
the amount of permanganate used in the titration, will require
960 GBORGB AUCHY.
a deduction of four-tenths if the reductor has stood that length
of time unused.
It is necessary to remove the zinc from the reductor at
intervals for cleaning, best done by stirring up in a capacious
dish with hot water, adding a little sulphuric acid to
clear the liquid, pouring ott, washing by decantation and. drying
in the dish on the hot plate. But after such a treatment the
zinCi after being replaced in the reductor, should be rinsed with
dilute sulphuric acid before being used in analysis, as much
more than the ordinary impurity of the zinc will be taken up by
the sulphuric acid the first time it is used.
Perhaps a more convenient way of cleaning the zinc is to soak
it (in the reductor) in water for a day (conveniently over Sun-
day) , plugging up the ends of the reductor to retain the water.
After such a treatment the reductor will go a long time without
becoming clogged up with zinc oxide.
Instead of using the reductor, it is a trifle quicker and more
convenient,, especially when the phosphorus present is consider-
able as in pig iron, to use the following slight modification of
the old Bmmerton method of reduction and filtration.
The yellow precipitate in a seven cm. filter paper is dissolved
in as little ammonia as possible, allowing to run into the eight-
ounce Erlenmeyer flask in which the precipitation occurred;
washed five minutes with hot water ; the solution acidified with
twenty-five cc. of sulphuric acid (two parts water to one part
acid) ; a mustard spoonful of granulated zinc added (five grams),
and the flask heated gently on the hot plate for five minutes, or
until the zinc is nearly dissolved (ten minutes is required for
some zinc). The flask is removed from the plate, a little dry
sodium carbonate added, and when effervescence has nearly
ceased the flask is corked tightly and cooled in cold water with-
out agitating the contents any more than can be helped. The
solution is then filtered from the undissolved zinc through a
little cotton wool in a Hirsch funnel, smallest size, using the
pump, and the flask rinsed out with cold water three times and
the rinsings drawn through the cotton wool. The sides of the
sixteen-ounce gas flask which receives the liquid are washed
down with the jet, and the solution titrated in the flask without
further dilution.
PHOSPHORUS IN STBBL AND CAST IRON.
961
If the zinc is of the sort not dissolving very readily, thirty-five
cc. of sulphuric acid should be used for acidifying the phos-
phorus solution instead' of twenty-five cc.
The reduction is to Mo„0,,. Factor of iron to molybdic acid
90.76. More correctly speaking, the reduction is to Mo,0,,
which filtering and dilution oxidizes to M0j,0„.
It will be found upon trial that this way of reduction and fil-
tration is somewhat easier and more rapid than the usual reduc-
tor method, as the filtration through cotton wool in a Hirsch
funnel and with aid of the pump is performed as easily and
quickly as merely pouring and rinsing from one vessel into
another. While the zinc is dissolving in one determination^
the yellow precipitate of the next determination may be filtered
off.
The following results show that the reduction and filtration
through cotton wool, as described, brings the molybdenum oxide
to the form Mo„0„.
Considerable phosphomolybdate (four-tenths to eight-tenths
gram) taken for each test.
Phosphorus
present.
Phosphorus
founcf. Fac-
tor 90.76.
Phosphorus
present.
Phosphorus
founa. Fac-
tor 90.76.
Per cent.
Per cent.
Per cent.
Per cent.
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.62
1.63
1.62
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.62
Small amounts of phosphomolybdate taken.
Phosphomolyb-
date taken.
Phosphorus
present.
Phosphorus
found.
Factor 90.76.
Phosphorus
present, reck-
oned as if
from 1.8333
grams steel.
Phosphorus
found if
from i.8a33
grams
steel.
Gram.
Per cent.
Per cent.
Per cent, in
the steel.
Per cent, in
the steel.
0.2000
1.63
1.63
0.179
0.179
0.2000
1.63
1.63
0.179
0.179
0.2000
1.63
1.65
0.179
O.181
0.2000
1.63
1.63
O.I 79
0.179
0.1500
1.63
1.64
0.134
0.135
0.0890
1.63
1.62
0.071
0.071
0.0700
1.63
1.64
0.062
0.063
0.0700
1.62
1.63
0.062
0.063
962
GEORGE AUCHY.
Phoftphotnolyb-
date taken.
Phosphorus
Phosphorus found,
present. Factor -90. 77.
Phosphorus
present, reck-
oned as if
from x.823^
firrams steel.
phosphorus.
found if
fr»m X.8933
fframs
steel.
Gram.
Per cent P«
ir cent.
Per cent, in
the steel.
Per cent. in.
the steel.
0.0600
1.63
r.64
0.054
0.054
0.0600
1.63
r.63
0.054
0.054
0.0500
1.63 ]
[.61
0.045
0.044
0.0400
1.63 :
t.64
0.036
0.036
0.0300
1.63 1
[.64
0.027
0.027
0.0300
1.63 ]
[.64
0.027
0.027
0.0300
1.63 ]
[.61
0.027
0.027
0.0300
1.63 1
t.6o
0.027
0.026
0.0400
1.63 :
[.62
0.036
0.036
0.0400
1.63 ]
[.63
0.036
0.036
0.0400
1.63 :
t.63
0.036
0.036
0.0350
1.63 ]
[.62
0.031
0.031
0.0380
1.63 ]
^63
0.034
0.034
0.0250
1.63 J
[.6z
0.022
0.022
0.0230
1.63 ]
r.6i
0.020
0.020
0.0200
1.63 ]
C.55
0.018
0.017
0.0200
1.63 :
t.51
0.018
0.017
0.0200
1.63 ]
1.64
0.018
0.018
0.0200
1.63 ]
r.50
0.018
0.017
0.0200
1.63 1
.60
0.018
0.018
0.0200
1.62 ]
^55
0.018
0.017
0.0200
1.63 ]
t.57
0.018
0.017
0.0180
1.63 1
1.55
0.016
0.015
0.0150
1.63 1
.55
0.013
0.013
0.0150
1.63 1
.55
0.013
0.013
0.0130
1.63 ]
^51
0.012
0.01 1
0.0120
1.63 ]
r.63
O.OIO
0.010
O.OIOO
1.63 1
^51
0.0089
0.008
O.OIOO
1.63 ]
t.55
0.0089
0.0085
O.OIOO
1.63 ]
[.46
0.0089
0.008
O.OIOO
1.63 1
[.64
0.0089
0.0089
O.OIOO
1.63 ]
[.64
0.0089
0.0089
The figures in the last two columns were obtained by reckon-
ing as though 1.8233 grams of steel had in each case been taken
for analyses. In other words, these percentages in the last two
columns are what they would have been had the phosphomolyb-
date taken been, in each case, obtained from 1.8233 grams of
steel, in the regular course of analysis, for phosphorus.
It will be noticed that when the amount of phosphomolybdate
PHOSPHORUS IN STEEL AND CAST IRON. 963
taken is very small (equivalent to 0.008 to 0.017 per cent, in
steel) there is frequently some oxidation, the percentage of
phosphorus in the yellow precipitate thus falling short of 1.63
by as much as 0.17 per cent, in one case. But, as will be seen
by reference to the last two columns of results, this affects the
result in steel but slightly.
This proneness to oxidation when very little phosphorus is
present in the solution indicates that the stability of the Mo^.O,,
solution is greater when concentrated than when dilute. And
the solution should therefore be in as small bulk as possible.
Other necessary precautions are : to have a large excess of sul-
phuric acid present, to avoid a boiling temperature when dis-
solving the ^inc, to cool the liquid before filtering from the un-
dissolved zinc, to exclude air while cooling, and to filter rapidly
through cotton wool in a Hirsch funnel, with aid of the pump.
But where considerable phosphorus is present, as in pig irons,
these precautions may be neglected, except the cooling before
filtering. That is, the liquid may be cooled, after the reduction
with zinc, without the addition of sodium carbonate, and with
free access of air, and the filtration may be made through a
seven cm. coarse paper (instead of cotton wool) by aid of the
pump. The results given under the head * ' considerable phos-
phomolybdate taken for each test'* were obtained in this way,
air not excluded, and filtered through paper instead of cotton
wool.
The advantage of making the reduction and filtration in this
way in the case of pig iron is very marked when, as frequently
happens, the yellow precipitate separates out when its solution
in ammonia is acidified with sulphuric acid. For if the reduc-
tion be made as described, this separation may be ignored as in
contact with the zinc and sulphuric acid the yellow precipitate
becomes reduced and goes into solution. This is shown by the
following tests, in which no ammonia was used at all. That is,
the yellow phosphomolybdate precipitate was weighed directly
into the reducing flasks, and thirty-five cc. of sulphuric acid
(2:1) poured over, a mustard spoonful of zinc added, heated
gently, etc.
964 GBORGB AUCHY.
Phosphomolybdate Phosphorus Plosphorus
taken. present. found.
Gram. Per cent. Per cent.
About 0.4000 1.63 1.63
** 0.4000 1.63 1.62
** 0.4000 1.63 1.63
" 0.4000 1.63 1.62
•* 0.4000 1.63 1.63
In experimenting with this process some interesting results
were had. The port wine Mo„0,, solution is apparently not so
stable, especially in dilute solution or with small amounts of
phosphorus present, as Emmerton supposed, and certain precau-
tions are necessary.
In the first place considerable amounts of phosphomolybdate
were taken, dissolved and reduced as described, and filtered
through seven cm. filter papers by aid of the pump. The re-
sults showed 1.63 per cent, phosphorus, the theoretical amount.
Several tests were then made in the same way and with the
same weights of yellow precipitates, but not waiting for the solu-
tions to cool before filtering from the undissolved zinc. Instead
of the theoretical 1.63 per cent., 1.57 per cent., and 1.58 per
cent, were obtained, showing the necessity of filtering cold.
Next the stability of the reduced solution was tested.
Before filtering from the Phosphorus Phosphorus
undissolved zinc. present. found.
Per cent Per cent.
Stood two hours 1.63 1.59
" ** ** and poured back and
forth four times i .63 1.55
Stood one hour 1.63 1.59
** one-half hour 1.63 1.61
The flasks were not corked while standing.
Smaller weights of phosphomolybdate precipitate were then
taken. The results obtained fell very much short of the theo-
retical, 1.63 per cent., and varied considerably. It was at first
thought that the filtration by aid of the pump oxidized the
solutions more than by the original Emmerton way of filtering
through a large ribbed filter. But, upon making four tests and
filtering in that way (Emmerton's) the results gave 1.51 per
cent., 1.52 per cent., 1.46 per cent., and 1.48 per cent., respect-
ively, instead of the theoretical, 1.63 per cent., although about
PHOSPHORUS IN STBEL AND CAST IRON. 965
four-tenths gram yellow precipitate, was in each case taken ;
an amount of yellow precipitate which, when taken for the
foregoing tests made by filtering through a seven cm. filter paper
by aid of the pump, never failed of bringing a result equal to
the theoretical. In filtering through a seven cm. filter by the
pump the oxidation of the solution is therefore considerably less
than the oxidation by filtering through a large ribbed filter.
An article by Blair and Whitfield' contains a description of an
experiment made by reducing the phosphorus solution by boiling
with zinc, keeping an atmosphere of hydrogen continually in the
flask, and boiling till the zinc was completely dissolved ; then
cooling (maintaining the atmosphere of hydrogen in the flask)
and titrating, the result falling considerably below the theo-
retical. In the case of the writer's low results just spoken of,
obtained by filtering through a seven cm. filter paper by suction,
the reduction had also been effected by boiling with the zinc,
though not in an atmosphere of hydrogen, and not to complete
solution of the zinc. Remembering the experiment of Blair and
Whitfield, above quoted, it was thought that the reason for
the^ low results in both cases lay, perhaps, in the boiling of
the phosphorus solutions while being reduced, the sulphuric
acid having an oxidizing effect perhaps in that case. No
otheri reason could be offered at least for the low result in
Blair and Whitfield's experiment, since, in that experiment, air
had been so carefully excluded from the flask during the solu-
tion of the zinc and the cooling of the liquid. To test the mat-
ter, Other determinations were made, exactly as before, except
that the zinc was dissolved at a gentle heat instead of by boiling.
Results were much better, as will be seen in the following table.
Hence the necessity for the precaution of avoiding a boiling tem-
perature while dissolving the zinc.
Phosphorus present — 1.63 per cent.
1 This Journal, 17, 757.
966
GBORGB AUCHY.
Phosphosnolybdate
Uken.
Gram.
Zinc dUtoWed
by boiling.
Pbosphoma fonnd.
Zinc diMoIved at
a gentle heat.
Phoaphorui found
O.OIOO
1.37
1.55
0.0200
1-37
1-50
0.0200
1.37
1. 41
0.0300
1. 31
1.46
0.0300
1.37
■ • ■ •
0.0400
1.46
1.55
0.0500
0.0600
1-39
1.28
1.57
1.60
0.0700
1.52
1.57
0.0700
0.0800
1.53
1.16
a a ■ •
1.57
0.2000
1.58
1.63
O.IOOO
1-59
1.64
In the second column of results, the third and fourth results
are considerably lower than the rest of them. But it had been
noticed that in these two determinations the green color of the
reduced phosphorus solution had faded to the port wine shade
during the cooling of the liquid and before the filtration from
the undissolved zinc, while in all the other determinations the
green color had persisted till the moment of filtration. This
pointed to the necessity of excluding air during the cooling of
the liquid, preparatory to filtration, from the undissolved zinc,
and the precaution was accordingly adopted of corking the flask
while cooling,first adding a little sodium carbonate to fill the
flask with carbon dioxide. Results by this procedure follow.
As the flask is already filled with hydrogen gas from the solu-
tion of the zinc, and vapor from the heating of the liquid, it is
perhaps unnecessary to add the sodium carbonate at the end of
the reduction. In that case the flask should be corked with a
one-hole cork with drawn-out glass jet» during the solution of
the zinc ; and the jet closed when the reduction is completed.
It was thought that results agreeing more closely and uni-
formly with the theoretical might be obtained by filtering
through cotton wool instead of paper, as the filtration can be
considerably more quickly accomplished in that way, even when
much suction is used in the latter way. Results showed
this to be the case, and are also given below in comparison with
results by filtering through paper.
PHOSPHORUS IN STBBI« AND CAST IRON.
967
Phosphomolyb-
date taken.
Gram.
O.OIOO
O.OICX)
O.OIOO
0.0100
O.OIOO
o.oaoo
0.0200
0.0200
0.0200
0.0200
0.0200
0.0300
0.0300
0.0300
0.0300
0.0400
0.0400
0.0500
0.0600
0.0600
0.0700
0.0800
Piltration
through paper.
Through cot-
ton wool.
Phoaphorua
present.
Phosphorus
found.
Phosphorus
found.
Per cent.
Per cent.
Per cent.
1.63
1. 41
X.55
i.63
• • a .
1.64
X.63
• . • ■
1.46
1.63
• • • ■
1.64
1.63
• . ■ •
1.46
1.63
1.46
1.50
1.63
1.48
1.60
1.63
1.48
1.64
1.63
• • a •
1.63
1.63
• • a a
1.55
1.63
m » » •
1.57
1.63
1.58
1.64
1.63
1.57
1.63
1.63
• • • •
1.64
1.63
■ • • •
I.61
1.63
1.55
1.64
1.63
• • • •
1.62
1.63
1-57
I.61
1.63
1-57
1.64
1.63
1.60
1.63
1.63
1.60
1.63
1.63
1.62
a • • a
Prom these results it is seen that cotton wool is much better
for use in filtering from the undissolved zinc than paper. Very
little pressure is required with the former and very little cotton
wool is required. A small Hirsch funnel is necessary. But the
cotton wool should not be pressed down with the finger after it
is wet, but sucked down by the pumpa In the above experi-
ments the filtrations through paper were also accomplished by
a Hirsch funnel, smallest size. (Paper size, seven cm.)
Using cotton wool, no oxidation of the port wine, Mo,,0,„
solution need be feared where the amount of phosphorus pres-
ent is that which in a sample of steel (one and eight-tenths
grams) would be equivalent to 0.020 per cent, or over ; while
with percentages under 0.020 the oxidation is never greater than
will make a difference of o.ooi per cent, in the result.
All the foregoing experiments were made with the use of zinc,
requiring about ten minutes for solution. This supply becom-
968 GEORGE AUCHY.
ing exhausted, new zinc was procured which happened to dis-
solve much more freely in acid, and experiments were therefore
made as before but using only fifteen cc. of sulphuric acid for
solution of the zinc instead of thirty-five cc. as before with the
first lot of zinc. Results were noticeably lower, pointing to the
inference that a large excess of sulphuric acid present is neces-
sary as favoring the stability of the Mo,,Oj, port wine solution.
Other determinations were then made, using twenty-five cc. of
acid.
Phosphorus present, 1.63 per cent.
Phosphomolybdate
taken.
Gram.
0.0400
0.0380
0.0350
0.0320
0.0300
0.0280
0.0250
0.0230
0.0230
0.0200
0.0200
0.0180
0.0180
0.0150
0.0150
0.0160
0.0140
0.0130
O.OIOO
This shows the necessity for the precaution of using plenty
of sulphuric acid for solution of the zinc.
As before pointed out, results by the foregoing procedure,
using all precautions, never fail of the theoretical, 1.63 per cent.,
or a reasonable approximation thereto, except when the amount
of phosphomolybdate taken is only 0.0200 gram (equivalent to
0.018 per cent, in all steel determinations) or less, and the
error in that case in a steel never amounts to more than o.ooi
per cent, with about two grams of steel taken for analysis ; and
Fifteen cc. sul-
phuric acid.
Phosphorus found.
Per cent.
1.63
1.63
1.62
Twenty-five cc. sul
phunc acid.
Phosphorus found
Per cent.
« • ■ *
« ■ • •
• • • •
I-5I
• • • •
1-55
1.60
1-53
1.50
• • • •
1. 61
1.50
^.55
1.48
■ • • •
I.61
1. 51
1.55
1.55
1.47
1.48
1.46
1.55
• • • •
1.55
• ■ * •
1.55
• • • •
• • • •
1.54
1.56
1.40
I.5I
1.40
I-5I
PHOSPHORUS IN STBBL AND CAST IRON. 969
the writer therefore, on the sc«re of accuracy, prefers this
method to the reductor method.
A convenience in phosphorus determinations is a Mohr
burette for the sulphuric acid, attached to the sulphuric acid
bottle by tubing reaching just to the zero mark of the burette
according to the well known plan. The bottle should stand
high, and the tubing be wide so that too much lung power will
not be required to fill the burette. The delivery tube of the burette
should also be of a good width, so that the acid may run quickly
into the phosphorus solutions. The apparatus is also, conve-
nient for Blliott sulphur determinations, using sulphuric acid for
acidifying the caustic soda sulphur solution instead of hydro-
chloric acid.
There is some difference of opinion among chemists as to the
advisability- of using sugar for reducing the manganese precipi-
tate formed by the addition of permanganate to the boiling nitric
acid solution of the steel. Sugar was originally recommended
by Dr. Drown, but Mr. Clemens Jones, obtaining varying
results which he attributed to its use, substituted ferrous sul-
phate with very satisfactory results. Dr. Dudley also states that in
using sugar a different result is obtained than when ferrous sul-
phate is used. On the other hand. Handy and others have
claimed that sugar has no harmful effect. The following tests
were made by the writer :
Usinf ferrous sulphate. Using sugar.
No. Phosphorus. Phosphorus.
Per cent. Per cent.
Steel 618 0.017 0.018
*' 690 0.018 0.018
Gray pig iron 0'7i9 0.720
Test bar 0.016 0.016
Steel 684 0.049 0.049
Phosphate solution o. 123 0.121
Thes^ results were considered sufficient evidence that sugar
does not interfere with the precipitation of the phosphorus. Its
use is more advantageous in several respects : it is cheaper than
ferrous sulphate ; less of it is required ; it may be added to the
boiling solution without fear of the solution boiling over ; and it
never contains phosphorus.
970 I«. M. DENNIS, MARTHA DOAN, AND A. C. GILI«.
The merest pinch of sugar will suffice to reduce a very abun-
dant precipitate of manganese peroxide if the boiling be con-
tinued for some time after its addition to the liquid.
For the filtration of the yellow phosphomolybdate precipitate
with the aid of the pump, it is the writer's experience that noth-
ing succeeds so well as two seven cm. Schleicher & Schtill
No. 579 filter papers, folded and placed in the funnel together.
The filtration may be made very rapidly, yet without any of the
precipitate going through the paper.
After the solution of the yellow precipitate on the filter paper
in ammonia and washing, the same filter may be used (without
removal from the funnel) for another phosphomolybdate filtra-
tion, and so on for a number of consecutive determinations.
No. 579 is a very loose and porous paper. No. 589 black rib-
bon also serves.
50nE NEW COMPOUNDS OF THALLIUM.
By L. M. DBNms and Maktha Doam, with Crystallogrnpbic NoCeft, by A. C. Gill.
ReoeiTcd September 4. iflQ^
THAI.i:X>US TRINITRIDE, TIN,.
WHEN a concentrated solution of potassium trinitride con-
taining a little free hydronitric acid is added to a solu-
tion of thallous sulphate, a white, finely crystalline precipitate
is formed. This compound is soluble in hot water, and when
recrystallized from a hot aqueous solution, it separates in ortho-
rhombic needles of a light straw color.
The thallium in this salt was determined volumetrically by
means of a standard solution of potassium permanganate, accord-
ing to the method of Willm.'
In the case of the hydronitric acid, a volumetric method also
was first attempted. A weighed portion of the salt wasdissolved
in water and placed in a Hempel distilling bulb, which was con-
nected by fused joints to a condenser. A separatory futoel was
inserted in the neck of th^ distilling bulb. The hydronitric acid
was set free by the addition of an excess of dilute sulphuric acid
and was distilled into an Erlenmeyer flask containing a known
amount of ammonia, the excess of ammonia being then deter-
1 Ann. chtm. phys.^ (4), 5, 79.
SOMB NBW COMPOUNDS OP THALUUM. 97 1
mined by titration. It was at first difficult to drive over all of the
hydronitric acid, the results being uniformly low with one excep-
tion, and in that case the distillate gave a reaction for sulphuric
acid. The results continued poor in spite of various modifica-
tions which were tried, so that finally recour^ was had to the
gravimetric method, this not having been used before because of
the explosive character of the silver trinitride. A weighed por-
tion of the salt was dissolved in water and precipitated with a
neutral silver nitrate solution. The silver trinitride was thor-
oughly washed by decantation with cold water, the washings
being passed through a Schleicher and Schtill hardened filter
No. 575. The precipitate was then transferred to the paper, the
point of the filter carefully perforated and the precipitate
washed through into a weighed porcelain crucible. Hydro-
chloric acid was then added to the contents of the crucible and
the whole evaporated to dryness. By this treatment the
silver trinitride is decomposed and * the hydronitric acid
expelled, together with the excess of hydrochloric acid. The
silver chloride remaining in the crucible was then weighed, and
from its weight the amount of nitrogen in the salt was computed.
The results were :
Calculated for
T1N|. Pound.
Thallium 204.18 82.9 82.87
Nitrogen 42.09 17.1 17.2
246.27 loo.o 100.07
The prism angle could be measured on the goniometer, but
the end faces were too small to give good reflections. The trace
of the macrodome on the prism face was measured repeatedly on
the microscope stage, giving an angle of 51® 30' with the vertical
edge. The prism angle, no : 110=^79" 50'. Hence the axial
ratio :
a : b : c = 0.8366 : i : 1.2407.
The crystals were composed of many fine needles, sometimes
twinned on the prism face (no), but more frequently in parallel
growth. The double refraction was strong, and the plane of
the optical axes is at right angles to the long direction of the
needles, i. ^.,= o.ooi.
972 I<. M. DENNIS, MARTHA DOAN, AND A. C. GILL.
Thallous trinitride is somewhat soluble in cold water and is
easily soluble in hot water. It is not explosive, resembling in
this particular the trinitrides of potassium and sodium. It melts
without decomposition when heated in an atmosphere of carbon
dioxide. Its melting point was determined by placing some of
the crystals in a small glass tube in the top of which was inserted
a cork with two holes. Carbon dioxide was passed into the
tube through one of these openings, and a small exit tube was
inserted in the other. The tube was heated by immersing it in
a bath containing an easily fusible alloy, and the temperature
was measured with a carbon dioxide filled thermometer corrected
by the Physikalisch-Technische Reichsanstalt of Charlotten-
burg. The corrected temperature at which the crystals
melted was 334"*.
When exposed to the sunlight, the crystals of thallous trini-
tride assume a dark brown appearance, which is probably due
to the formation of thallous oxide. This change must be very
superficial, however, as no change in weight could be detected
in a sample which had been in a southern exposure for two
months.
When heated in a current of dry nitrogen, thallous trinitride
was easily reduced. The hydrogen on leaving the combustion
tube, in which the boat containing the thallous trinitride was
placed, was passed through two bulbs containing water. The
aqueous solution thus obtained had a very distinct odor of ammo-
nia, turned turmeric paper brown, and when neutralized with
hydrochloric acid and allowed to spontaneously evaporate over
sulphuric acid and caustic potash, it yielded crystals which
under the microscope were identical with those of ammonium
chloride. The ammonia found in two of the reductions in hydro-
gen was titrated with standard acetic acid, this acid being used
in order that only the free ammonia might be neutralized and
any ammonia which might be present combined with hydronitric
acid would remain as such.'
In one case 29.83 per cent, of the nitrojg^en in the trinitride
acid was converted into ammonia ; in the other 27.37 per cent.
of the nitrogen was thus changed.
1 HN3 is somewhat stronger than glacial acetic acid. /. prakt. Chem.^ (2), 4s, 207.
SOME NEW COMPOUNDS OF THALLIUM. 973
Hydroiiitric acid was tested for in the aqueous solution by
addition of silver nitrate to the solution in which the ammonia
had been neutralized, and in each case only a trace was found.
It was thought that perhaps the formation of the acid might be
due to the presence of a small amount of moisture in the hydro-
gen, so a reduction was made with hydrogen which had been
passed through a piece of moist cotton. In this case 21.55 per
cent, of the nitrogen was converted into ammonia, and as before
only a small amount of hydronitric acid was formed.
The highest results for the nitrogen converted into ammonia
approximate one-third of the total nitrogen present, and inas-
much as only a trace of the nitrogen is found to exist in the form
of hydronitric acid, it is possible that the molecule of the acid
breaks down thus :*
II )N— H + 5 = N,+ N— H.
N^ ^ \H
THALLOUS THALLIC TRINITRIDK, T1N,.T1N,.
It was thought .that thallic trinitride might be obtained by the
solution of freshly precipitated thallic hydroxide in hydronitric
acid. The hydroxide when .treated with hydronitric acid and
warmed, dissolved to a clear straw-colored solution, but when
the solution was allowed to stand at ordinary temperature,
hydronitric acid escaped and thallic hydroxide was precipitated.
Concentration of the solution was tried by placing it in a freezing
mixture and removing the water as ice. Prom the liquid thus
concentrated, bright yellow crystals separated, yet so much of
the salt solution was occluded in the ice that this method proved
wasteful. The best yield of crystals was obtained by dissolving
the thallic hydroxide in a one and six-tenths per cent, solution
of hydronitric acid and allowing the solution to stand at a tem-
perature of about zero in a Hempel desiccator which was
exhausted by means of a common suction pump. Glistening,
yellow, needle-shaped crystals appeared. They were removed
in five fractions, which under the microscope seemed to be alike
and homogeneous.
1 The further investigation of thin reaction is now being carried on in this labora-
tory. D.
974 ^- ^' DBNNIS, MARTHA DOAN, AND A. C. GII,I<.
These sharply outlined crystals verged toward a brown color
in the larger specimens. On the stage of a microscope they
showed either parallel extinction, or an extinction of 42^. That
is, the long direction of the crystals varied in different individuals.
The crystals were probably triclinic, though there is a possibility
that they furnished a case of flattening, parallel to the face of
the orthorhombic pyramid. An optical axis emerged obliquely
from the tabular face, showing that it was not really, as would
otherwise appear, the pinacoid of an orthorhombic crj-stal. The
plain angles were 132**, 132** and 96**. The double refraction
was not very strong.
The thallium was determined by dissolving some of the crj's-
tals in dilute hydrochloric acid, reducing the thallium to the
thallous condition by sulphurous acid, driving off the excess of
the latter acid by heating the solution and then titrating with
potassium permanganate. The nitrogen could not be determined
by the method used for thallous trinitride, because the salt
could not be dissolved either in water or dilute acids without
evolution of hydronitric acid. For this reason the absolute
method was used. We had already found that the salt was
highly explosive, but the behavior of the thallous trinitride, when
heated in an atmosphere of carbon dioxide, led us to attempt the
decomposition of a small portion of this substance in a similar
manner. A few milligrams were, accordingly, spread over the
bottom of a long porcelain boat, which was placed in a combus-
tion tube containing granular copper oxide. The tube was con-
nected at one end to a carbon dioxide generator, and at the other
to a Schiff nitrometer. The exit end of the tube was heated to
redness and the heat was then run back very carefully toward
the boat. Gradual decomposition of the compound, however,
was not attained, for when the temperature in the neighborhood
of the boat had risen but slightly, the salt exploded violently,
shattering the boat and tube. Another portion of the hydroni-
tride was then mixed with granular copper oxide and heated as
before. The decomposition in this case was quiet and gradual.
The nitrogen in the nitrometer amounted to 27.32 per cent, of
the salt taken. It seemed possible, however, that in mixing the
hydronitride with the coarse copper oxide, some of the salt
SOME NEW COMPOUNDS OP THALLIUM. 975
might have been decomposed by the friction, and that conse-
quently the above per cent, of nitrogen might be too low. To
ascertain if this were true, a fresh portion of copper oxide was
ground very fine and was then carefully mixed with a small por-
tion of the salt. In this way higher results were obtained.
The analysis gave :
Thallium 304.18
Nitrogen 84.18
Calculated for
TIN,.
Pound.
70.81
70.70
29.19
^.3
288.36 100.00 100.00
If this were a simple compound, the thallium would seem to
be in the bivalent condition, but as this is at variance with the
nsual behavior of the element, it seemed more probable that the
compound is a double salt containing thallium in both the thal-
lous and thallic condition. This supposition was confirmed by
the behavior of the crystals when treated with hot water. Brown
thallic hydroxide separated, and upon filtering this off and add-
ing potassium iodide to the filtrate, a precipitate of thallous
iodide resulted. Instead, however, of finding only fifty per
cent, of thallium in the thallous condition, as would be required
by the formula TIN,. TIN,, there was obtained 63.7 per cent.
This excess of thallous thallium is doubtless due to the reduc-
tion of some of the thallic hydroxide by the hydronitric acid set
free when the salt is treated with hot water.
Thallous-thallic trinitride is highly explosive, the decomposi-
tion being accomplished by a sharp report and a vivid flash of
green light. The explosion can be brought about by heat, per-
cussion or even gentle friction.
THALLOUS TELLURATE, Tl,TeO,.
In 1878 p. W. Clarke prepared what he supposed to be thal-
lous tellurate by precipitating a thallous nitrate solution with
ammonium tellurate.* The amount obtained was so small that
no analysis was made.
To avoid the presence of other salts in the solution, we used a
solution of thallous hydroxide and precipitated that by adding a
1 Ber.d. dUm. Ges.^ xi, 1507.
976 L. M. DENNIS, MARTHA DOAN, AND A. C. GILL.
solution of pure telluric acid. The white, flocculent precipitate
which formed was washed with cold water, transferred to a fil-
ter and dried over calcium chloride.
In the analysis of this substance, the thallium was determined
by the method above described. Considerable difficulty was
encountered in the determination of the tellurium, the presence
of thallium making it impossible to use either the potassium per-
manganate titration or the method recently described by Gooch.*
The thallous tellurate was soluble in water, but the amount of
water required for its solution was so great that the telluric acid
could be precipitated by neither lead nor barium solutions. For
these reasons the method of Kastner* was used, the tellurium
being precipitated in alkaline solution by means of grape sugar.
As some thallium separated with the tellurium, the precipitate
was treated with nitric acid and the acid then driven off by
evaporation. The thallous nitrate was removed by washing the
residue with water and the tellurous oxide was filtered in a Gooch
crucible, dried and weighed. The results were :
Calculated for
TljTc04. Found.
Thallium 408.39 68.13 68.17
Tellurium 127.00 21.19 21.19
Oxygen 64.00 10.68 (diff . ) 10.64
599-36 100.00 100.00
Thallous tellurate is slightly soluble in water, and it was
hoped that there might be obtained from the aqueous solution
crystals sufficiently well defined to admit of a comparison of
them with those of thallous sulphate and thallous selenate.
Unfortunately, however, it was found impossible, in spite of
many and varied attempts, to obtain anything but a white amor-
phous powder. Even when a solution saturated at 40** was
allowed to slowly cool to 15" through a period of eight days, no
cr>'stals resulted.
THALLOUS CYANPLATINITE, Tl,Pt(CN)^.
Carstanjen prepared what he reported to be thallous cyanplat-
1 Ztichr, anorg. Chem.y 7, 132.
a Ztschr. anal. Chem., 14, 142.
SOME NEW COMPOUNDS OF THALLIUM. 977
inite by neutralizing cyanplatinousacid with thallous carbonate.'
The compound was given the formula TlCN.PtCN, although no
analytical results were given.
The cyanplatinous acid used by us in the preparation of the
thallium cyanplatinite was obtained according to the method of
Schafarik.' It was neutralized by thallous hydroxide, which
was prepared by precipitating a thallous sulphate solution with
the calculated amount of baryta water. The crystals separated
out in the form of thin plates.
A determination of the thallium and cyanogen gave the follow-
ing results :
Calculated for
Tl>Pt(CN)4. Observed.
Thallium 408.36 57.73 57.7
Platinum I9S'(^ 37>S6
Cyanogen 104.12 14.71 14.5
707.48 100.00
The crystals are nearly colorless plates, usually very thin and
occurring irregularly grown together on the flat sides. The
crystal system was not positively determinable from the material
at hand, but is probably triclinic, possibly monoclinic with
crossed dispersion. In converged polarized light, a bisectrix is
seen nearly or quite normal to the large face of the plates, and
the dispersion of the planes of the optic axes is remarkably
strong, so that the crystals simply change color without becom-
ing dark on rotation between crossed Nicols. The double
refraction is high. The plates are bounded by crystal faces,
giving them a six-sided outline, but on the material used no
goniometric measurements could be made.
Cornell Univbrsity,
AUGUST 1896.
1 J.prakt. Ch€m.^ xoa, 144.
s/^uf.. 66,401.
NOTES ON THE ESTIHATION OF CAFFEIN.
By w. a. Puckker.
Received September a. 1896.
SOME time ago Gomberg published a method for the estima-
tion of caffein, by means of Wagner's reagent/ wherein
appear certain statements from which is to be inferred the
superiority of this method over such where the caffein is shaken
out of an aqueous solution by means of chloroform, and which,
if true, would show that most methods now in use, give low
results since but an imperfect separation of caffein is attained.
Thus Spencer* is said to have demonstrated the diflSculty with
which the alkaloid is abstracted from watery solutions, he
, directing that at least seven portions of chloroform be used for
this purpose, but offering no proof of the necessity for this
departure from the usual direction of shaking out the liquid
with three or four portions of the solvent. Spencer is at vari-
ance with Allen/ who investigated this matter and found that
from a solution, slightly acidulated with sulphuric acid, one
treatment with chloroform removed seventy to eighty-five per
cent, of the amount present, while four usually effected com-
plete extraction, especialh' if toward the end the solution is
rendered faintly alkaline.
This agrees well with the results of my own experiments,
where anhydrous caffein, in quantities from one-tenth to four-
tenths gram, dissolved in fifty cc. one per cent, sulphuric acid,
was shaken successively with twenty-five, ten and ten cc. chloro-
form, the united chloroform solution evaporated at a gentle
heat and the residue dried over sulphuric acid to constant
weight. In each case the solution was shaken with a further
quantity of ten cc. chloroform and the weight of the caffein so
extracted ascertained as before.
Caffeiti
Residue from first, secon
d Residue from
taken.
and third extraction.
fourth extraction.
Total percent
Gram.
Gram.
Gram.
recovered.
0. 1 285
0.1277
0.0004
99.69
0.1852
0.1820
0.0026
99.67
0.1988
0.1980
0.0002
99.69
0.201 I
0.1977
0.0025
99-55
0.2559
0.2552
0.0005
99,92
0.4416
0.4355
0.0043
9958
1 This Journal,
18,
331.
-
iy. AnaL Chem
.4i
300.
8 Com. Org.
Anal.
.3, Part 11. 485-
ESTIMATION OP CAPPBIN. 979
This shows that the extractioil of ca£Fein from an aqueous
solution presents no difficulties since, even when the solution is
quite acid, practically the entire amount is obtained when four
portions of chloroform are used ; while, even if the fourth be
omitted the results will be sufficiently correct for most purposes.
In the article referred to we are also told, although it is
usually stated caffein may be shaken out of an acid solution,
since its salts are broken up by water, that this is but relatively
true; as a proof thereof the following is offered :
•* 1.0085 grams of caffein were dissolved in sixty cc. of sul-
phuric acid (i.io), and this solution was repeatedly shaken with
chloroform, twenty-five cc. at a time :
m
Ten consecutive portions of chloroform gave a total of 0.3514 gram caffein.
Three additional " •* '* made *' "0.4859 "
Three more " *' " ** " '* "0.5034 '* " •»
Since the degree of dissociation of caffein salts is inversely
proportional to the acid strength of the solution, it is to be
expected that it will be extremely difficult to shake out the alka-
loid from a solution containing so great a quantity of free acid ;
but while at times it may be advantageous to extract caffein
from a solution having an acid reaction, in no instance would
there seem need of a sufficient amount to render the method
inapplicable ; further, according to Knox and Prescott' Gom-
berg*s method becomes uncertain under similar conditions.
Ill the experiments just quoted ten extractions with chloro-
form yielded but 34.85 per cent, of the total caffein, or on an
average each treatment removed only 3.485 per cent., while the
three subsequent treatments removed an additional 13.33 per
cent, of the whole, or 4.44 per cent, for each extraction, i, ^.,
although the total substance in solution had been decreased by
more than one third the average amount given up to chloroform
increased in the nth, 12th and 13th treatment; while in the
14th, 15th and i6th but 1.735 per cent., or on an average of
0.578 per cent, for each shaking was obtained.
Although the writer had never attempted a caffein determina-
tion under the conditions mentioned, he was, from theoretical
considerations, inclined to question the figures given, and
accordingly made the following experiments.
1 Proceedings Am. Pharm. Ass., 1896.
980 ESTIMATION OF CAPPEIN.
1. 0137 gi'ain caffein, rendered anhydrous by keeping in a
desiccator over sulphuric acid until its weight remained con-
stant, was dissolved in sixty cc. ten per cent, sulphuric acid and
shaken successively with nine portions of chloroform, twenty-
five cc. each ; the chloroform solutions evaporated sit a gentle
heat and the residue dried 6ver sulphuric acid to constant
weight.
1st portion of twenty-five cc. yielded a residue of 0.5525 gram.
and
3rd
4tli
5th
6th
7th
8th
9th
(i (< li
tt if If
tt t< it
ft f< <(
«i ii ((
<( (• II
II <i <i
0.2514 "
It 11 i< « 0.1155 "
II I* 0.0535 **
II II II II
11 II 0.0114 •*
It II II li M <^nfiQ (I
0.0237
o.oi 14
0.0058
n II II II 0.0029 "
II .1 II II 0.0015 "
I.Ol82» **
In the second experiment i.oooi gram anhydrous ca£Fein in
sixty cc. ten per cent, sulphuric acid, extracted as before, with
chloroform in proportions of twenty-five cc. each :
I St, 2d and 3rd portions gave a total residue of 0.9086 gram.
4th, 5th and 6th ** •• ** ** " ** 0.0854
7th, 8th and 9th " '* ** " '* " 0.0134
II
II
1.0074' •*
The sulphuric acid used in Gomberg*s experiments was
designated as '* ( i: 10) '' by which it is presumed an acid contain-
ing ten per cent, by weight of sulphuric acid was meant ; since,
however, it was possible that sulphuric acid 1:10 ^ volume
was the strength of the acid used, a determination was made
with an acid with such concentration, t. e., ten cc. concentrated
sulphuric acid mixed with water enough to make when cold,
100 cc. In sixty cc. of this were dissolved 0.9790 gram caffein
and extracted with chloroform in portions of ti^'enty-five cc. each
as before.
1st, 2nd and 3rd portion yielded a total residue of 0.6484 gram.
4th, 5th and 6th '* " '• ** " "0.2222
7th, 8th and 9th " ** " " " "0.0756
loth, nth, 1 2th, 13th, 14th, 15th and i6th *' ** 0.0379
It
II
It
II
0.9841*
1 No explanation is offered to account for the plus error in the at>ovc. Contamina-
tion with sulphuric acid was suspected, but disproved.
RUTHENOCVANIDE. 98 1
As was to be expected, this confirms in a general way, the
statement relative the difficulty with which caffein is shaken out
of solutions containing a large proportion of sulphuric acid ; in
no way, however, does it agree with the data given by
Gomberg, who by ten successive treatments with chloroform
removed only 34.85 per cent., while my figures show that when
a ten per cent, sulphuric acid was used, with but three extrac-
tions, fully ninety per cent, was recovered, and even with a still
stronger acid (1 + 9 by volume), three portions of chloroform
removed about sixty-five per cent.
UiriVB&SITY OF ILLIVOI8. SCHOOL OP PHiRMACY.
CONTRIBUTION TO THE KNOWLEDGE OF THE
RUTH ENOC Y AN I DES.
By J as. I<bwib Howb.
Received August 97. 1996.
POTASSIUM ruthenocyanide was described by Claus, in
1854, in his *• Beitrage zur Chemie der Platinmetalle."
The salt was formed by fusing ammonium rutheninitrosochlo-
ride' (tetrachloride of Claus) with potassium cyanide. The
attempt was also made to form it by fusing potassium ferrocya-
nide with ruthenium, but it was found impossible to separate
the ferrocyanide and ruthenocyanide. It is probable that some
of Claus' experiments were carried out with a ruthenocyanide
cx>ntaminated with ferrocyanide, from the fact that he describes
copper ruthenocyanide as brown, whereas, when free from the
ferrocyanide, it is pale green. Potassium ruthenocyanide in
reactions and crystallization resembles ver>' closely the ferro-
cyanide, except that when pure it is white. Its crystallography
as well as that of the isomorphous ferrocyanide and osmocya-
nide are described by A. Dufet.*
Preparation of potassium ruthenocyanide for the purpose of
carrying out experiments upon it not yet completed, gave occa-
sion to the work recorded in this paper.
In the Claus method of preparation, a large proportion ol the
ammonium rutheninitrosochloride is decomposed with separa-
tion of metallic ruthenium, and while a part of the ruthenocya-
1 Joly : Compi. rend., 108, 854, 1889 ; Howe : J. Am. Ckem. Soc., 16. 38S. 1S94.
* Compt. rend., (189$)* *ao. 377.
982 JAS. I.EWIS HOWE.
nide formed crystallizes out from a solution of the melt, in large
square pseudorhombic plates, much is left in the solution and
cannot be directly separated from the potassium cyanide and
other salts present. Attempts were therefore made to use other
methods of formation with the following results :
1. Potassium rutheninitrosochloride, K,RuCl^NO, fused with
potassium cyanide, gave rather better results in ruthenocyanide,
there being rather less decomposition than was the case with the
ammonium salt.
2. Ruthenium trichloride, RuCl., fused with potassium cya-
nide gave a fair product of ruthenocyanide.
3. Metallic ruthenium, fused with potassium cyanide, was
slightly acted upon, giving a trace of ruthenocyanide.
4. Metallic ruthenium, fused with potassium cyanide and a
little potassium hydroxide, gave rather stronger reaction than
case 3, but the amount of ruthenocyanide formed was very
small.
5. The melt formed by fusion of ruthenium in potassium
hydroxide and nitrate, containing potassium ruthenate, K.RuO^,
was dissolved in water and boiled with potassium cyanide. The
deep orange-red solution was quickly decolorized and the ruthe-
nium was converted into ruthenocyanide with little loss. A
considerable proportion could be obtained in the usual square
crystals. This process could, by modiQcation, probably be
made the most satisfactory method of forming the ruthenocya-
nide, presenting one decided advantage that metallic ruthenium,
or oxides, can be used, thus avoiding the necessity of preparing
the nitrosochloride or chloride.
6. Ruthenium trichloride was boiled with a strong solution of
potassium cyanide. The ruthenocyanide, crystallizing in the
usual square form, was obtained, but very much contaminated
with a greenish by-product not yet investigated, probably
analogous to Prussian blue.
7. Potassium rutheninitrosochloride was boiled with a strong
solution of potassium cyanide. The solution was slowly decol-
orized, considerable of the greenish by-product being formed.
From this solution there crystallized thick straw-coh>red hexago-
RUTHENOCYANIDE. 983
nal plates, which will be considered further on. The quantity
of the product is not satisfactor>\
8. The Weselsky method* of forming double cyanides was
tried. Hydrocyanic acid was led into a solution of the nitroso-
chloride, in which barium carbonate was suspended, until effer-
vescence ceased. The solution gave no reaction for ruthenocya-
nide. Its color had changed to the brown-yellow of the trichlo-
ride, but gave no reaction for this with potassium thiocyanate,
or with ammonia and sodium thiosulphate. On warming, the
solution gelatinized to a firm hydrogel, insoluble in hot aqua
regia, but soluble in boiling potassium hydroxide. This last
solution was unchanged on acidification with hydrochloric acid,
and gave the potassium ferrocyanide reaction for nitrosochlo-
ride, but no reaction for trichloride. The dried jelly was easily
explosive on heating. It presents an interesting analogy to
Jackson's* hydrogel of cobaltocyanide and is being further
studied.
9. The Weselskj' method was also applied to ruthenium tri-
chloride. The merest trace of ruthenocyanide was formed, and
the solution, little changed in color, no longer gave reactions for
the trichloride.
10. The nitrosohydroxide of Joly, formed by the precipitation
of the chloride by potassium carbonate, is easily soluble in potas-
sium cyanide and converted into ruthenocyanide by prolonged
boiling.
The following reactions of ruthenocyanide may be noted :
No precipitates are formed with the caustic alkaline earths,
their ruthenocyanides being soluble in water.
Lead acetate gives a fine white precipitate, soluble in nitric
acid.
Silver nitrate gives a white curdy precipitate, insoluble in
both ammonia and in nitric acid.
Ferric chloride gives a rich purple precipitate, closely resem-
bling Prussian blue in its chemical properties. In pure water it
is soluble, but is precipitated from this solution by salts or alco-
hol. It forms a very beautiful and intense dye, adhering with
1 WeseUky, Sitzber. Akad. Wien., 60, ii. (/870), 36t : Ber. d. chem. Ges., 2, 588, 1869,
s Jackson : Ber. d. chem. Gef., 39, 1020, iB^.
984 JAS. LEWIS HOWE.
great persistence to cotton fiber, on which it has been precipi-
tated. It is decomposed very readily by alkalies with precipita-
tion of ferric hydroxide, re-forming, however, on the addition of
acids, unaffected by dilute acids, but permanently decomposed
by strong acids. It is a most delicate reaction for the detection
of ruthenocyanide.
Ferrous sulphate gives a pale blue precipitate, which gradually
changes to the purple above mentioned, and instantly if bromine
water is added.
Copper sulphate gives a very pale green flocculent precipitate
(not brown as given by Claus).
With salts of the following metals precipitates are formed
insoluble in hydrochloric acid : Cadmium, white (soluble in hot
acid); zinc, white; tin (both stannous and stannic) , white ;
mercury, white ; bismuth, white (insoluble in nitric acid) ;
nickel, dirty green (changing to blue with hydrochloric acid) ;
cobalt, pale red ; platinum, yellow-green ; manganese gives a
white precipitate soluble in hydrochloric acid. With gold there
is no immediate precipitate, but a gradual darkening and sepa-
ration of a dark precipitate, the solution becoming green.
Bromine water changes the solution to a dark red, which does
not give the trivalent ruthenium reaction. Iodine also seems to
alter the solution.
No reaction with hydrogen sulphide, ammonium sulphide, or
thioacetic acid.
Nitric acid has no effect in the cold, but when heated slightly
reddens the solutions. It then shows no signs of a reaction
analogous to that of the nitroprussides.
It is acted on by potassium nitrite with sulphuric acid, and
when neutralized gives a fugitive rose red with ammonium sul-
phide.
It gives no apparent reaction with ruthenium trichloride or
nitrosochloride.
Two methods of purification, applicable to such portions of the
ruthenocyanides as cannot be separated by crystallization, may
be used. The most satisfactory is the precipitation in dilute
solution by lead acetate and thorough washing with hot water
to remove any lead chloride present. Suspension of the lead
RUTHENOCYANIDE. 985
ruthenocyanide (carbonate, cyanide, etc.) in much water and
decomposition with dilute sulphuric acid. Filtration and addi-
tion of baryta water till nearly neutral and then of barium car-
bonate in excess ; warming, filtration, and' evaporation to crys-
talUzation of the barium ruthenocyanide from which other ruthe-
nocyanides may be formed by double decomposition.
The other method of purification which is applicable especially
to all residues, is precipitation with ferric chloride in slightly
acid solution, washing with acidified water, as far as possible
(the purple begins to dissolve as the salts are washed out) and
decomposing with baryta water. This method, while very use-
ful for recovery of residue, does not give so pure a product as
the first method. n
The hexagonal crystals described above, in process 7, pre-
sented points of interest, in that it seemed not impossible that
they contained the nitroso group of the nitrosochloride from
which they were formed. When dissolved in water they showed
every reaction of the ordinary square crystals of the ruthenocya-
nide, but they could not be converted into the square form by
recrystallization nor could their yellowish tint be removed. The
crystals are anhydrous while the white crystals contain three
molecules of water of crystallization. On heating they explode
with considerable violence while the square crystals decompose
very gently. On recrystallization they show prismatic forms, with
many twins resembling staurolite crosses, and others resembling
aragonite twins. Though perfectly hexagonal in form, they do
not seem to belong to the hexagonal system. After conversion
into the lead, hydrogen, barium, and back into the potassium
salt by the first method of purification described, and further
precipitation of this potassium salt by alcohol and recrystalliza-
tion from water, crystals were obtained which were square,
white, and in every respect, crystallographically as well as
chemically » resembled the ordinary potassium ruthenocyanide.
This was verified by analysis of the barium salt and partial analy-
sis of the potassium salt.
It is evident that the hexagonal crystals are not a nitrosocya-
nide, and it seems possible that the form may be conditioned by
986 JAS. LEWIS HOWE.
some trace of impurity. They are being further studied at pres-
ent.
ANALYSIS OF POTASSIUM AND BARIUM RUTHENOCYANIDES.
Potassium ruthenocyanide, K^Ru(CN),,3H,0, formed by boil-
ing a solution of potassium rutheninitrosochloride with potassium
cyanide ; purified by conversion through lead, hydrogen, and
barium salts.
Per cent.
I. Loss of water in four days standing over sulphuric acid. 10.84
II. " •* " at 120^ 10.90
III. " " ** in 30 hours standing over sulphuric acid . 11.25
Theory for K4Ru(CN)e,3H,0. 3H,0 = 11.53
The crystals, especially when small, are so efflorescent that it
is difficult to obtain uneffloresced salt for analysis, and the fol-
lowing are calculated for the dehydrated salt.
Theory for
K4Ru(CN),.
Potassium 37-76
Ruthenium 24.53
This corresponds to the potassium ruthenocyanide described
by Claus.
Barium ruthenocyanide, Ba,Ru(CN)„6H,0, (new) formed
from the ordinary form of the potassium salt.
Pale straw-colored, diamond-shaped (up to one-half cm. long)
monoclinic crystals, or larger crystal rosettes, slightly soluble
in cold, more easily in hot water, slowly lose water of crystalli-
zation over sulphuric acid, lose five and a half molecules of
water at 100° but retain one-half molecule to nearly 200*", thus
resembling barium ferrocyanide. The barium ruthenocyanide
from the hexagonal form of the potassium salt was similar, but
was not obtained in well enough defined crystals to identify pos-
itively with the preceding, but analysis shows the constitution
to be the same.
The method of analysis was the following : The salt was
heated in a platinum boat (in two cases porcelain was used and
attacked, so that the ruthenium was contaminated by silica —
Analyses I and V) in an oxygen current, and the carbon
I.
37.22
Found.
XL.
38.32
in.
37.28
23.90
34.22
24.44
RUTHENOCYANIDE.
987
dioxide evolved collected in an absorption apparatus. The pro-
portion given off was variable, but usually a little more than five
atoms. The boat was then heated in a hydrogen current, to
reduce the oxide of ruthenium formed. The boat was then
placed in a carbon dioxide apparatus and treated with hydro-
chloric acid and the remainder of the carbon dioxide collected.
The barium chloride was then filtered off from the ruthenium and
determined as sulphate ; the ruthenium, after burning the filter
paper and heating in a hydrogen current in a porcelain boat,
was estimated as the metal. It was not found possible to arrive
at any agreement in different analyses as to the loss on heating
the barium salt in air, or oxygen, or subsequently in hydrogen.
While most of the carbon of the cyanogen is burned to carbon
dioxide, a part remains as barium carbonate. The remainder
of the barium seems to fluctuate between oxide and peroxide,
while a variable portion of the ruthenium is oxidized. The
analyses show conclusively that six atoms of carbon are present
in the salt derived from the nitrosochloride, hence one cyanogen
group cannot be replaced by the nitroso group.
The results of several analyses are as follows :
Theory From
for RuCli
Ba«Ru and
(CN),. KCN
6M,0. sol.
Found.
From
RuClaNO
fusion.
From •
RuCIsNO
by
solution.
I. 11.
Barium 42.90
Ruthenium 15.86 16.41 15.67
(with SiO,)
5JH,0 (ioqO) 15.67 15.67 15.63
6H,0 (200°) 16.83 16.68 16.85
5C 9.37
6C 11.23
C from combustion
^ in residue ••••••• •■•• •■•• ■•
xotsl csroon ••>••■ •••■ •••« ••
WaSHINGTOIT and LEB UKIVBRStTV.
I«BXiifCTON, Va., June. 1896.
III. IV. v. VI.
— 42.46 43.32 42.27
.... 15.72 17.92 15.80
(with SiO,)
• • • • X ^ • Oo ••■• ••••
... 16.69 16.71 16.56
VII.
42.54
1560
15.53
16.68
9.91 9.16
2.65 2.03
12.56 1 1. 19
9.96
9.98
2.30
12.28
DIPYRIDINE METHYLENE IODIDE AND THE NON-FOR-
MATION OF THE CORRESPONDING MONOPYRIDINE
PRODUCTS.'
By S. H. Babr and A. B. Prbscott.
Received Sepceniber % i4p6.
THE addition compound of pyridine and methylene iodide
was formed in different ways, varying the conditions of
mass, temperature, pressure, and time, as follows. The method
of preparation recommended is that of No. V.
Preparation I, — Pyridine and methylene iodode in equimolec-
ular proportions, reacting at laboratory temperature, for two
days, form a dark-red crystalline mass. This was washed in
cold alcohol, which does not dissolve it.
Preparations 11 and III, — The same proportions (those of a
monopyridine product) were taken in reaction at 120° C. The
methyl iodide for I and II was colored with free iodine, that for
III was obtained colorless by distillation in vacuum. In each
case the crystals, washed with cold alcohol, were dark-red. This
color was not afifected by treating the crystals with thiosulphate
solution, and therefore not due to free iodine or to periodides.
Preparation IV, — By reaction of colorless methylene iodide,
in the same proportions, with the pyridine, but without heat, an
orange precipitate settles slowly . This was washed as the others.
Preparation V, — Pyridine of boiling point 118* C, and
methylene iodide either colorless or tinged with iodine, in abont
equal molecular quantities, are placed in a flask, alcohol in
volume equal to the two reacting materials is added, a return-
condenser adjusted, and the heat of a water-bath applied for an
hour. On cooling, long yellow needles separate out. To purify
further, dissolve in hot fifty per cent, alcohol, cool, and add a
little ether, when fine crystals are formed.
So obtained, the product is in fine needles, of yellow color,
decomposing, not melting, at 220"* C. ; soluble in water, from
which it crystallizes at 0° C. ; insoluble in cold alcohol, spar-
ingly soluble in hot alcohol ; insoluble in ether, or chloroform,
or benzene, or amyl alcohol ; sparingly soluble in methyl alcohol.
Analysis gave us percentages as follows :
Calculated for Found.
(C»H|N),CH«I,. I. II. III. IV. V.
I 59.61 58.95 58.91 57.98 58.4 59.6
N».« ^'57 •••• .... .... ..• 0.73
1 Rend at the Buffalo meeting of the American Asaociation for the Advancement of
Science.
DIPYRIDINE METHYLENE IODIDE. 989
The product, therefore, not quite pure in the first four experi-
mental preparations, is substantially the same under the differ-
ent conditions employed, and with whatever excess of the diiodo-
methane, is always the dipyridine addition compound. And its
formula, agreeing with those of its bromine homologues,* maybe
confidently written, to express the relations of the methylene
group and the halogen atoms :^
^CH— CH. .CH,. ^CH=CH.
^CH=CH^ ^I V ^CH— CH^
Kleine found* that trimethylamine, in combination with dihalo-
gen substituted hydrocarbons, forms both the monammonium
and the diammonium products, the former prevailing, especially
when there are not more than two atoms of carbon in thehalide.
It seemed now desirable to subject pyridine to various condi-
tions of additive reaction with various dihalides, in order to
know whether it can in au}*^ case form such monamine com-
pounds as the fatty amines sometimes form.' Pyridine and
ethylene bromide, in equal molecular proportions, were digested
together in a sealed tube for two weeks, when the entire content,
a crystalline mass, was dissolved in hot alcohol of ninety-five per
cent., and. fractionally crystallized in successive crops, washing
each with cold absolute alcohol. These crops of crystals gave,
of bromine, respectively, 46.15, 46.15, 46.18, and 46.03 percent.,
the calculated per cent, in (C^HfcN),C,H^Br, being 46.21.
Next pyridine with excess of ethylene bromide was digested
in a pressure flask, in water-bath, with agitation. T^e crystal-
lized product gave 46.26 per cent, of bromine. Finally dipyri-
dine ethylene bromide was heated with excess of ethylene bro-
mide in a sealed tube to 170*" C. . There was some charring in
the mixture. By recrystallizing from it a product was obtained
which gave 45.84 per cent, of bromine.
Dipyridine ethylene bromide crystallizes in colorless plates,
insoluble in ether, and melting with decomposition at 295° C.
UitiVERSiTV OP Michigan.
1 The ethylene bromide, (Hofmann) Davidson, 1861 : Proc, Roy. Soc.^ pa?e a6i ; The
trimethylene bromide, Plintennann and Prescott, 1895 :J, Am. Chem, Soc., i8. 28.
*G. Kleine, 1894: Chem. Centrdi., page 161.
s This in continuation of the inquiry of Plintermann and Pretcotti 1895: J. Am. Chem.
Sof., 18, 33.
[Contribution prom thb John Harrison Laboratory of Chemistry.
No. 13.]
DETERMINATION OF THE ATOMIC HASSBS OF SILVER.
HERCURY AND CADMIUM BY THE ELECTRO-
LYTIC METHOD.'
By Wzllett Lbplby Hahdin.
Received September a6, 1896.
INTRODUCTION.
A glance at the literature on the determinations of the
atomic masses of silver, cadmium and mercury will show
that, with the exception of cadmium, the electrolytic method has
not been tried. A^ide from the fact that certain errors involved
in the washing and drying of the precipitates are eliminated by
this method, its simplicity at once gives it preference over the
usual methods of gravimetric determinations. Inasmuch as
these three metals are completely precipitated from certain of
their solutions by the electric current, and as it is desirable to
determine the atomic mass of any element by different meth-
ods, it was thought advisable to apply this method in a redeter-
mination of the atomic masses of these elements.
GENERAL CONSIDERATIONS.
Before taking up the different metals separately, the following
general considerations may be mentioned :
1. A careful preliminary study was made in the selection of
compounds. Some compounds, which from a theoretical stand-
point seemed to offer certain advantages, were found by experi-
ment not to meet the requirements of exact determinations.
Salts which can be sublimed were used whenever possible ; and
in all cases only those salts were used which form well defined
crystals.
2. All reagents used were either prepared or purified by my-
self and carefully tested for impurities.
3. The metals were deposited in platinum dishes of about 200
cc. capacity and about sixty-five grams in weight. When the
precipitation was complete, before interrupting the current, the
1 Prom the author's thesis presented to the Faculty of the Uaiversity of Pennsylvt-
nia for the degree of Ph.D., 1896.
ATOMIC MASSES OP SILVERi MERCURY AND CADMIUM. 991
solution was siphoned from the platinum dish, pure water being
added at the same time ; this was continued until the solvent
used was completely removed from the dish. The current was
then interrupted and the deposit washed several times with boil-
ing water, with the hope of removing any occluded hydrogen.
After drying, the dishes were placed in a vacuum desiccator
over anhydrous calcium chloride and allowed to remain in the
balance room until their temperature was the same as that of the
room. Atmospheric dust was excluded from the platinum
dishes during the process of deposition by means of two glass
plates which formed a complete cover ; the moisture which col-
lected on this cover was washed back into the dish from time to
time. The dishes were handled with nickel tongs tipped with
rubber.
4. The balance used was made expressly for this work by
Henry Troemner, of Philadelphia. The beam and pans were
made of aluminum, the beam being about twenty centimeters
long. The framework was plated with gold to prevent corro-
sion. The sensibility for different loads and the ratio of the
length of the two arms were carefully determined. The balance
is sensitive to the fortieth of a milligram, and the sensibility is
almost independent of the load up to seventy-five grams. The
difference in the length of the two arms is so slight that no cor-
rection need be applied. The balance was kept in a large quiet
room of nearly constant temperature.
The larger weights used were made of brass and the fractions
01 a gram made of platinum. The weights were all previously
compared against each other and standardized with reference to
the largest weight. The small corrections found in comparing
them were tabulated and applied to all results. The weighings
were made by the method of oscillations. The temperature and
barometic pressure were noted at the time of each weighing,
and all weighings were reduced to a vacuum standard. As the
density of the atmosphere at the time of weighing the empty
platinum dish was different from that at the time of weighing
the dish and deposit together, the following formula was applied
to obtain the weight of the deposit in vacuo :
992 WII.LETT LEPtEY HARDIN.
weight of dish ( i + -^ 7~)
Weight of (dish + deposit) ^l ii —
I A- A
' + — /
I + -^ j\ = weight of deposit in vacuo.
Where X = density of air at the time of weighing the empty
dish.
A.' = density of air at the time of weighing the dish +
deposit.
J = density of platinum dish.
J' = density of metallic deposit.
/ = density of weights.
As the weights were all standardized with reference to^ the
hundred-gram brass weight, it is evident that they must all be
calculated as having the same density, equal to that of brass.
5. The atomic masses of the different elements involved in
the calculation of results were taken from Clarke's latest report.^
PART I.
DETERMINATION OF THE ATOMIC MASS OF SILVER.
The mean of all the earlier determinations, as calculated by
Clarke, gives 107.923 for the atomic mass of silver; a result
almost identical with the mean (107.93 ; O = 16) of the deter-
minations of Stas.
PREPARATION OF PURE METALLIC SILVER.
The silver used in this work was purified by the Stas method.
Two hundred grams of silver, about ninety-nine per cent, pure,
were dissolved in dilute hot nitric acid. The solution was
evaporated to dryness, the nitrate heated to fusion and main-
tained in a fused condition until the oxides of nitrogen were no
longer evolved. The residue, after cooling, was dissolved in as
little cold water as possible, and after standing forty-eight hours
the solution was filtered through a double filter to remove any
suspended matter. The clear solution was then diluted with
thirty times its volume of distilled water, and to it was added an
ly. Am. Chem. Soc., x8, 197.
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. 993
excess of pure hydrochloric acid. The silver chloride which
separated was allowed to subside and was then thoroughly
washed by decantation, at first with water containing a little
hydrochloric acid, and finally with pure water. The precipitate
was then collected on a cheese cloth filter, pressed strongly and
allowed to dry. When perfectly dry, the silver chloride was
powdered finely and digested for three days with aqua regia ; it
was then thoroughly washed by decantation with distilled water.
After obtaining the pure chloride of silver, it was necessary to
purify the caustic potash and milk sugar used in reducing the
chloride to the metallic state . The caustic potash was heated to the
boiling point and to it was added a concentrated solution of po-
tassium sulphide to precipitate any heavy metals which might be
present. The solution was filtered and the filtrate digested for
some time with freshly precipitated silver oxide and again fil-
tered to remove the excess of potassium sulphide. The milk
sugar was purified in a similar manner. The silver chloride was
then placed in large porcelain dishes and covered with a solution
of caustic potash and milk sugar. The dishes were placed on a
water-bath and heated to a temperature of yo'^-So® until the
reduction to finely divided metallic silver was complete. The
alkaline solution was then poured off, and the gray metallic sil-
ver was washed with distilled water until the alkaline reaction
disappeared. The metal was then digested with pure dilute
sulphuric acid, and finally washed with dilute ammonia water.
The silver thus obtained was mixed, when dry, with five per
cent, of its weight of fused borax containing ten per cent, of pure
sodium nitrate. The mixture was fused in a clay crucible and
the silver poured into a mold. The metal obtained in this way
was almost snow white in appearance, and dissolved completely
in nitric acid to a colorless solution.
PREPARATION OF PURE NITRIC ACID.
To obtain pure nitric acid, one-half liter of the commercial
C. P. acid was mixed with an equal volume of concentrated C.
P. sulphuric acid and distilled from a retort provided with a
knee tube and condenser. The first portion of the dis-
tillate Was rejected. The process was stopped when half of the
994 WII^LETT LEPLEY HARDIN.
nitric acid present had been distilled over. The distillate was
mixed with an equal volume of pure sulphuric acid and redis-
tilled. The second distillate was collected in a flask, the mouth
of which was closed with glass wool. When the process was
complete, the flask was closed with a doubly perforated cork
and placed in a water-bath at a temperature of 40**. A current
of pure dry air was then conducted through the acid to remove
any oxides of nitrogen. The acid was kept in a dark place.
EXPERIMENTS ON SII^VER OXIDE.
If pure, dry silver oxide could be prepared, the atomic mass of
silver could be compared directly with that of oxygen. A large
number of experiments were made on this compound with the
hope of determining the ratio of the atomic masses of these two
elements.
PREPARATION OF SILVER OXIDE.
A portion of the pure metallic silver was dissolved in pure
dilute nitric acid and the solution evaporated to crystallization.
The crystals of silver nitrate were dissolved in pure water and to
the solution was added a solution of pure sodium hydroxide,
prepared by throwing pieces of metallic sodium on distilled
water in a platinum dish. The twenty-five grams of silver
oxide prepared in this way were washed by decantation with
twenty liters of water. The material was then dried at the
ordinary temperature, after whicn it was finely powdered and
dried for twenty-four hours in an air-bath at 100°. The oxide
was kept in a weighing tube in a dark place.
Several analyses were made by dissolving a weighed portion
of the material in pure potassium cyanide, electrolyzing the solu-
tion and weighing the resulting metallic silver. The observa-
tions invariably gave less than ninety-five for the atomic mass of
silver. The oxide was redried at a temperature of 125* and
analyzed as before, but the quantity of silver obtained was far
below that calculated for the compound Ag,0. Observations
were also made on material dried at 140® and 150**. The results
showed that it was impossible to prepare the silver oxide in a
pure, dry condition.
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. 995
After making these observations, my attention was called to
an article by M. Carey Lea,* in which were given the results of
a series of analyses of silver oxide dried at different tempera-
tures varying from lOO** to 170°. These observations prove con-
clusively that oxygen is given off at a much lower temperature
than that required to remove the last traces of moisture. From
these observations and the results obtained by myself, it was
evident that any further attempt to determine the atomic mass
of silver from the oxide would be useless.
Although no careful study was made as to the nature of this
compound, it might be added that, from my own observations,
it seems very probable that the oxide contains some hydrogen in
the form of hydroxyl.
FIRST SERIES.
EXPERIMENTS ON SILVER NITRATE.
The nitrate of silver seems to fulfil the conditions necessary
for accurate analyses, inasmuch as it is stable and crystallizes
in well defined crystals which can be fused without decomposi-
tion.
PREPARATION OF SILVER NITRATE.
The material used in these experiments was prepared by dis-
solving pure silver in pure aqueous nitric acid in a porcelain
dish. An excess of silver was used, and after complete satura-
tion the solution was poured off from the metal into a second
dish and evaporated to crystallization. The perfectly transpar-
ent, rhombic plates of silver nitrate which separated were dis-
solved in pure water and recrystallized. The crystals were then
carefully dried, placed in a platinum crucible which rested in a
larger platinum dish and gradually heated to fusion. After
cooling, the perfectly white opaque mass was broken up and
placed in a ground-glass stoppered weighing tube and kept in a
desiccator in a dark place.
MODE OF PROCEDURE.
The platinum dish in which the deposit was made was care-
^ Am.J. Set'., 44. 240.
99^ WILLBTT I^EPtEY HARDIN.
fully cleaned with nitric acid and dried to constant weight. It
was then placed in a desiccator over anhydrous calcium chloride,
and this, together with the desiccator containing the tube of
silver nitrate, was placed in the balance room, where they were
allowed to remain until their temperatures were the same as that
of the room. After weighing the platinum dish, the tube of sil-
ver nitrate was weighed and part of the salt removed to the dish,
after which the tube was reweighed. The difference in the two
weighings, of course, represented the weight of silver nitrate
used in the experiment. Enough water to dissolve the nitrate
was added to the dish, and then a solution of potassium cya-
nide, made by dissolving seventy-five grams of pure potassium
cyanide in one liter of water, was added until the silver cyanide
first formed was completely dissolved. The dish was then filled
to within a quarter of an inch of the top with pure water and the
solution electrolyzed with a gradually increasing strength of
current. The following table will show the strength of current
and the time through which it acted :
Time of action. Strength of current.
2 hours N.Djgo = 0.015 amperes.
4 " N.D,oo = o.030
6 " N.Dioo = o.o75
4 *• N.D,oo = o.i5o
4 " N.Dioo = o.4oo
By gradually incre^ing the strength of current in this way
the silver came down in a dense, white deposit. When the depo-
sition was complete, before interrupting the current, the liquid was
siphoned from the dish, pure water being added at the same time.
This was continued until the cyanide was completely removed.
The dish with the deposit was washed several times with boiling
water and carefully dried. It was then placed in a desiccator
and aHowed to remain in the balance room until its temperature
was the same as that of the room, when it was reweighed.
Weight of platinum dish = 71.27302 grams.
Weight of silver nitrate = 0.31 198 grams.
Temperature, 22*^.
Barometric pressure, 770 mm.
Weight of platinum dish + silver deposit = 71.47104 grams.
(I
<<
ATOMIC MASSES OF SILVSR, MERCURY AND CADMIUM. 997
Temperature, 22".
Barometric pressure, 760 mm.
Density of silver nitrate = 4.328.
** brass weights = 8.5.
" platinum dish = 21.4.
** metallic silver = 10.5.
*' atmosphere at the time of weighing the empty dish
and silver nitrate = 0.0012 12.
*' atmosphere at the time of weighing the platinum
dish + silver deposit = 0.001196.
Computing on this basis we have the following :
^ / , 0.001212 0.001212 \ . , <
o.3ii98^iH -— g — — j = 0.31202 = weight of
AgNO, in vacuo.
cc
( I
CI
i(
C (
71.27302
_ , O.OOI2I2 O.OOI2I2_
n + n
21.4 8.5
, O.OOII96 O.OOII96
L I +-
= 71.27291 = weight of
21.4 8.5
platinum dish at 22^ and 760 mm.
71.47104 — 71.27291 = 0.19813 = weight of deposit at 22** and
760 mm.
^ / , 0.001196 o.ooii96\ - • u^ / J
0.198131 iH r — ^— ) =0.19812 = weight of de-
^ *^\ 10.5 8.5 / **
posit tn vacuo.
Taking 0= 16 and N = 14.04, the atomic mass of silver =
0.19812 X 62.04 = , .
(31202 — I98I2)
Ten observations on silver nitrate computed in the foregoing
manner are as follows :
Atomic mass
WeiflTbt of AgNO*. Weight of Ag. of silver.
Gram. Gram.
1 0.31202 O.I9812 107.914
2 0.47832 0.30370 107.900
3 0.56742 0.36030 107.923
4 0.57728 0.36655 107.914
5 0.69409 0.44075 107.935
6 0.86367 0.54843 107.932
7 0.8681 1 0.55130 107.960
99^ WItLETT LEPI^EY HARDIN.
Weight of AgNOt.
Weight of Ag.
Atomic mass
Gram.
Gram.
of silver.
8
0.93716
0.59508
107.924
9
1.06170
0.67412
107.907
TO
1. 19849
0.76104
107.932
Mean
= 107.924
Maximum
— 107.960
Minimum
= 107.900
Difference = 0.060
Probable error = ±0.005
Computing the atomic mass of silver from the total quantity
of material used and metal obtained, we have 107.926.
SECOND SERIES.
EXPERIMENTS ON SILVER ACETATE.
The fact that silver forms well crystallized salts with a num-
ber of organic acids makes the comparison of the atomic mass of
silver with the combined atomic masses of carbon, hydrogen,
and oxygen, a matter of no great difficulty. From certain pre-
liminary experiments, the acetate of silver seemed to fulfill the
conditions necessary for accurate determinations.
PREPARATION OP SIIyVER ACETATE.
The purest commercial sodium acetate was dissolved in water,
the solution filtered and recrystallized. After three crystalliza-
tions the material was dissolved in pure water, and to the rather
concentrated solution was added a solution of silver nitrate, pre-
pared in the manner already indicated. The white curdy pre-
cipitate which separated, after washing with cold water, was
dissolved in hot water, the solution filtered and evaporated to
crystallization. The silver acetate separated in brilliant sword-
shaped crystals. After pouring off the solution the crystals
were quickly rinsed with cold water and placed between filters
to remove the adhering moisture. The material was allowed to
remain in contact with the filters only for a short time. It was
then placed in a platinum dish, and when apparently drj' the
crystals were broken up into a finely divided condition and dried
forty-eight hours in a vacuum desiccator. This work was car-
ried on in a darkened room, and the silver acetate obtained was
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. 999
placed in a weighing tube, and kept in a desiccator in a dark
place.
MODE OP PROCEDURE.
The method of operation was similar to that described under
silver nitrate. After weighing the silver acetate, its aqueous or
cyanide solution was electrolyzed and the weight of the result-
ing metallic silver determined. The results obtained from the
aqueous solution were sometimes vitiated by the separation of
silver peroxide at the anode. To prevent this, potassium cya-
nide was sometimes added. The results, however, from the two
solutions were practically the same when no peroxide separated.
Prom the aqueous solution the silver was deposited in a crystal-
line form. The strength of current and time of action were the
same as for silver nitrate.
Ten observations on silver acetate reduced to a vacuum stand-
ard on the basis of
3.241 = density of silver acetate,
10.5 = ** metallic silver,
24.4 = '* platinum dish,
8.5 = *' weights,
and computed for the formula AgC,H,0„ assuming the atomic
masses of carbon, hydrogen and oxygen to be 12.01, 1.008 and
16, respectively, are as follows :
Weight of ARCfHsO,.
Weif bt of Ag.
Gram.
Atomic mass of
Grams.
silver.
I
0.32470
0.20987
107.904
2
0.40566
0.26223
107.949
3
0.52736
0.34086
107.913
4
0.60300
0.38976
107.921
5
0.67235
0.43455
107.896
6
0.72452
0.46830
107.916
I
0.78232
0.50563
107.898
0.79804
0.51590
107.963
9
0.92 lOI
0.59532
107.925
10
1.02495
0.66250
107.923
Mean
= 107.922
Maximum
= 107.963
Minimum
= 107.896
Difference = 0.067
Probable error = ± 0.005
Computing from the total quantity of material used and metal
obtained we have 107.918 for the atomic mass of silver.
lOOO WILLETT LEPLEY HARDIN.
EXPERIMENTS ON SILVER SUCCINATE.
Silver succinate was prepared in a manner similar to that of
silver acetate. The commercial C. P. succinic acid was recr>'s-
tallized three times ; the ammonium salt was then prepared and
its aqueous solution precipitated with a solution of pure silver
nitrates. The precipitate of silver succinate was thoroughly
washed bj* decantation with pure water and carefully dried.
After drying for several hours in an air-bath at 50**, the material
was ground in an agate mortar to a finely divided powder, and
was then redried for twenty-four hours in an air-bath at a tem-
perature of 60**. The white powder obtaine;d in this way was
placed in a weighing tube and kept in a desiccator.
The method of analysis was similar to that of silver acetate.
A weighed portion of the material was dissolved in a little potas-
sium cyanide in a platinum dish. After diluting wath pure
water, the solution was electrolyzed and the resulting deposit
weighed. The strength of current and time of action were the
same as for silver nitrate. The results computed for the formula
C^H^O^Ag, were not constant, and were invariably from one to
two units lower than those obtained from silver nitrate and sil-
ver acetate. The material was then dried at a temperature of
75®, but the results obtained were not satisfactor>^
The two most probable causes for these low results are :
First, the difficult j"^ of removing the last traces of impurities
from a precipitate like that of silver succinate. The experience
throughout this work has been, that, to remove all the impuri-
ties from a finely divided precipitate by washing is almost impos-
sible.
Second, the difficulty met in drying material of this kind.
This same difficulty was met in the experiments on silver oxide
which, as shown by Lea, retained moisture up to 165**.
THIRD SERIES.
EXPERIMENTS ON SILVER BENZOATE.
The preceding work on silver acetate and silver succinate
shows the necessity of selecting compounds which form well
defined crystals. Perhaps no organic salt of silver fulfils the
ATOMIC MASSES OP SII^VER, MERCURY AND CADMIUM. lOOI
conditions necessary for accurate analyses better than silver
benzoate.
PREPARATION OP SILVER BENZOATE.
The purest commercial benzoic acid was resublimed thfee
times from a porcelain dish into a glass beaker. The product
thus obtained was dissolved in pure aqueous ammonia and the
solution evaporated to crystallization. The ammonium salt was
then dissolved in distilled water and to the solution was added a
solution of pure silver nitrate. The white precipitate of silver
benzoate which separated was washed with cold water ; it was
then dissolved in hot water, the solution filtered, and evaporated
to crystallization. The salt separated in fine needles, which
clung together in arborescent masses. After removing the
liquid from the beaker, the crystals were quickly rinsed with
cold water and placed between filters to remove the adhering
moisture. When apparently dry they were broken up into small
fragments and dried forty-eight hours in a vacuum desiccator.
The material was then placed in a glass stoppered weighing tube
and kept in a dark place.
MODE OP PROCEDURE,
The details of the method of operation are the same as those
given under silver nitrate. A weighed portion of the material
was dissolved in a dilute solution of potassium cyanide in a plat-
inum dish. The solution was then electrolyzed and the result-
ing metal weighed. The strength of current and time of action
were the same as for silver nitrate.
Before the results could be reduced to a vacuum standard it
was necessary to determine the specific gravity of silver ben-
zoate. This was done by means of « specific gravity bottle,
the liquid used being chloroform. The mean of two determina-
tions gave 2.082 for the specific gravity of silver benzoate.
Ten results on this compound, reduced to a vacuum standard
on the basis of
2.082 = density of silver benzoate,
10.5= ** *' metallic silver,
21.4= ** ** platinum dish,
8.5 = •* '* weights,
I002 WILLETT LEPLEY HARDIN.
and computed for the formula C^H^AgO,, assuming 12.01, 1.008,
and 16 to be the atomic masses of carbon, hydrogen and oxy-
gen, respectively, are as follows :
Atomic masi
of silver.
107-947
107.976
107.918
107.918
107.964
107.935
107.936
ro7.9i4
107.908
107.962
Weight of CyHsAkO,.
Weight of Ag.
Gram.
Grams.
I
0.40858
0.19255
2
0.46674
0.21999
3
0.48419
0.22815
4
0.62432
0.29418
5
0.66496
0.31340
6
0.75853
0.35745
7
0.76918
0.36247
8
0.81254
0.38286
9
0.95673
0.45079
10
1.00840
0.47526
Mean
= 107.938
Maximum
= 107.976
Minimum
= 107.908
Difference = 0.068
Probable error = ±0.005
Computing from the total quantity of material used and metal
obtained we have 107.936 for the atomic mass of silver.
SUMMARY.
In discussing the work on the atomic mass of silver, two pos-
sible sources of error suggest themselves.
First, the hydrogen which is continually being set free in the
process of electrolysis may, in part, be occluded by the metallic
silver. As already pointed out, the metallic deposits were
washed several times with boiling water, with the hope of remov-
ing any occluded gases ; but whether this effected a complete
removal of all the occluded gases was not determined.
Second, the condensation of moisture on the platinum dish
might be urged as a possible source of error. But it must be
remembered that the dish was dried in the same manner each
time and kept for several hours in a desiccator, and that the
atmosphere inside the balance was kept dry by means of several
beakers of anhydrous calcium chloride, and that the temperature
of the balance room throughout the work was almost constant.
Under these conditions there is but little chance of error irom
r
ATOMIC MASSES OP SILVER, MERCURY AND CADMIUM. IOO3
different amounts of moisture condensed. Moreover, the varia-
tion in the different weighings of the same dish was very
slight.
The advantages of the method are evident.
First, the great advantage of the method is its extreme sim-
plicity.
Second, the nature of the compounds used and of metallic sil-
ver renders them well adapted to weighing.
Third, the method was such as to eliminate the errors inci-
dent to the ordinary gravimetric methods of analysis.
Of the three series, the first is probably entitled to the greatest
weight. That the silver nitrate was pure and free from moisture
seems beyond question. However, the close agreement of the
last two series with the first indicates that the acetate and ben-
zoate of silver were also free from moisture.
Giving equal weight to each of the three series, we have the
following as the general mean computed from the separate obser-
vation :
Atomic mass of silver.
First series 107.924
Second '* 107.922
Third *' 107.938
General mean ^ 107.928
Computing the general mean from the total quantities of
material used and metal obtained we have :
Atomic mass of silver.
First series 107.926
Second ** 107.918
Third '* 107.936
General mean = 107.927
Combining this with the first general mean we have 107.9275
as the final result for the atomic mass of silver.
PART II.
DETERMINATION OF THE ATOMIC MASS 6F MERCURY.
From all the earlier determinations Clarke gives 200 as the
I004 WILLETT I^EPLEY HAKDIN.
most probable value for the atomic mass of mercury, assuming
oxygen equal to i6.
EXPERIMENTS ON MERCURIC OXIDE.
A large number of experiments were made with a view of
determining the ratio of mercury to oxygen in mercuric oxide.
The method proved to be unsatisfactory, although, apparently
very good results were obtained in some preliminary experi-
ments. The cause of this close agreement of results will be
explained in the details of the work.
PREPARATION OF PURE MERCURIC OXIDE.
The purest commercial mercuric chloride was carefully sub-
limed from a porcelain dish into a glass funnel. The sublimed
portion was dissolved in water, the solution filtered, and evap-
orated to crystallization. The crystals were then thoroughly
dried and carefully resublimed. The product obtained in this
way consisted of white crystalline leaflets which dissolved com-
pletely in water. Pure sodium hydroxide was then prepared by
throwing pieces of metallic sodium on pure water contained in a
platinum dish. To the pure sodium hydroxide was added a
solution of mercuric chloride, the former always being in excess.
The yellow mercuric oxide which separated was washed for
several days by decantation with hot water. The material was
then dried twenty-four hours in an air-bath at 105**.
MODE OP PROCEDURE.
In a series of 'preliminary experiments made in the spring of
1895, a weighed portion of mercuric oxide prepared in the above
manner was dissolved in a dilute solution of potassium cyanide
in a platinum dish. The solution was then electrolyzed and the
weight of the resulting metallic mercury determined. Inasmuch
as the results obtained in these preliminary experiments were
not reduced to a vacuum standard, it was thought advisable to
weigh the empty platinum dish after removing the metallic
deposit in order that the two weighings might be made under
approximately the same conditions. The results for the most
part agreed very closely and differed very little from the results
obtained by other methods. Six observations computed for the
formula HgO, assuming the atomic mass of oxygen to be 16, are
as follows :
ATOMIC MASSES OP SII^VER, MERCURY AND CADMIUM. IOO5
Atomic mass
Weight of HfirO.
Weight of Hg.
of mercury.
Gram.
Gram.
I
0.26223
0.24281
200.05
2
0.23830
0.22065
200.02
3
0.23200
0.21482
200.06
4
0.14 148
O.13100
200.00
5
0.29799
0.27592
200.03
6
O.I9631
O.18177
200.02
Mean ss 200.03.
These results were selected from a larger series. After ma-
king the above observations it was noticed that the platinum dish
had gradually decreased in weight throughout the work. This
decrease in weight indicated that the mercury deposit had
formed an amalgam with the platinum dish, which was soluble
in hot nitric acid. To ascertain whether such was the case or
not the platinum dish, after weighing* was filled with a solution
of the double cyanide of mercury and potassium and the solu-
tion electrolyzed. On dissolving the mercury deposit in cold
nitric acid a dark colored film remained on the sides of the dish.
The dish was then carefully washed, dried and reweighed, and
found to be heavier than at the beginning of the operation, show-
ing that the mercury had not been completely removed. The
dark film was then dissolved in hot nitric acid and the dish
again weighed. This last weight being less than that at the
beginning showed that some of the platinum had been dissolved
from the dish. The nitric acid solution of the dark film was
evaporated to dryness and ignited to remove the mercury. The
residue was dissolved in aqua regia, the solution evaporated to
dryness, and enough water added to dissolve the small residue.
A little concentrated ammonium chloride was then added to the
solution, and the double chloride of ammonium and platinum
separated as a yellow crystalline powder. This proved conclu-
sively that the mercury deposit had united with the platinum
dish to form an amalgam which was soluble in hot nitric acid.
Hence the results given for mercuric oxide are of no value in
determining the atomic mass of mercury.
A series of careful experiments was then made on the oxide
dried at different temperatures. To avoid any error from the
ICX)6 WILLETT LEPLEY HARDIN.
amalgam which formed with each deposit, the platinum dish was
weighed at the beginning of each observation, the temperature
and barometric pressure being noted at the same time. The
results obtained from the oxide dried at a temperature of 105**
gave from 180 to 185 for the atomic mass of mercury. The mate-
rial was then dried at a temperature of 125'', but the increase in
the amount of mercury obtained was very slight. Finallj- with
material dried at 150**, the results obtained for the atomic mass
of mercur>' were all below 195**.
The most probable causes for these low results are :
First, the difficult^' of removing the last traces of alkalies from
the mercuric oxide.
Second, the difficulty met in the complete removal of the
moisture from an amorphous precipitate. This difficulty as well
as the first was referred to in the experiments on silver oxide.
Third, mercuric oxide does not form a clear solution with
potassium cyanide. There seems to be a slight reduction of the
oxide to the metallic state. It is difficult to determine whether
this reduced portion unites completely with the metallic deposit
or is partially removed in the process of washing. The latter is
probably true, and it may be that a dififerent method of analysis
would give more accurate results for this compound.
FIRST SERIES.
EXPERIMENTS ON MERCURIC CHLORIDE.
The material used in this series of experiments was prepared
from the commercial C. P. mercuric chloride. The productwas
first dissolved in water, the solution filtered and evaporated to
crystallization. The crystals were dried and carefully sublimed
from a porcelain dish into a glass funnel. The sublimed portion
was dissolved in water, the solution filtered and evaporated to
crystallization. These crystals were dried as before and care-
fully resublimed. The material was then placed in a weighing
tube and kept in a desiccator.
'MODE OF PROCEDURE.
The method of operation was similar to that already described
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. lOOy
under the different compounds of silver. A weighed portion of
the mercuric chloride was dissolved in a little potassium cyanide
and the solution electrolyzed. The deposit was washed and
dried and handled in every way like the deposits of silver. The
strength of the current and time of action were as follows :
Time of action. Strength of current.
4 hours N.Djoo = 0.02 amperes.
6 " N.Dioo = o.05
6 " N.D,oo = o.io
6 ** N.Dioo=o.30
A current of gradually increasing strength deposits the mercury
in extremely small globules, which can be washed and handled
more easily than the larger globules obtained by using a strong
current at first. In cases where more than one-half gram of
metal was deposited the strong current was allowed to act two
hours longer.
Ten results on mercuric chloride reduced to a vacuum stand-
ard on the basis of
5.41 = density of mercuric chloride,
13.59=: *' •* metallic mercury,
21.4 = *' ** platinum dish,
8.5 = ** •' weights,
and computed from the formula HgCl,, assuming 35.45 to be the
atomic mass of chlorine, are as follows :
Weight of Hgd,. Weight of Hg. Atomic mass of
Grams. Grams. mercury.
1 0.45932 0.33912 200.030
2 0.54735 0.40415 200.099
3 0.56002 0.41348 200.053
4 0.63586 0.46941 199-947
5 0.64365 0.47521 200.026
6 0.73281 0.54101 199-988
7 0.86467 0.63840 200.838
8 1.06776 0.78825 199-946
9 1.^7945 0.79685 199-917
10 1. 5 1402 1. 1 1 780 200.028
Mean = 20o.cx)6
Maximum = 200.099
Minimum 3=5 199.917
Difference ss 0.182
Probable error s= ±0.011
I008 WILLETT LEPLEY HARDIN.
Computing from the total quantity of material used and metal
obtained we have 199.996 for the atomic mass of mercury.
SECOND SERIES.
EXPERIMENTS ON MERCURIC BROMIDE.
The bromine used in these experiments was prepared by dis-
tilling the commercial C. P. bromine twice over manganese
dioxide. Any trace of chlorine which might be present would
be removed by this method.
PREPARATION OP MERCURIC BROMIDE.
Fifty grams of metallic mercury were placed in a beaker and
covered with water. Pure bromine was then added until the
mercury was completely saturated. The contents of the beaker
were then digested with hot water until the mercuric bromide
dissolved ; the solution was filtered and evaporated to crystalli-
zation. The white cr^-^stals of mercuric bromide which sepa-
rated were thoroughly dried and carefully sublimed from a por-
celain dish into a glass funnel. Only the middle portion of the
sublimate was used in the experiments. The product obtained
in this way consisted of brilliant crystalline leaflets which dis-
solved completely in water. The material was kept in a weigh-
ing tube in a desiccator.
MODE OP PROCEDURE.
The method of analysis was exactly like that described under
mercuric chloride. A weighed portion of the mercuric bromide
was dissolved in dilute potassium cyanide in a platinum dish.
The solution was then electrolyzed and the resulting metal
weighed. The strength of current and time of action were the
same as for mercuric chloride.
Ten results on mercuric bromide reduced to a vacuum stand-
ard on the basis of
5.92 = density of mercuric bromide,
13.59 = ** '* metallic mercury,
21.4 = ** *' platinum dish,
8.5 = ** ** weights.
ATOMIC MASSES OP SILVER, MERCURY AND CADMIUM. IOO9
and computed for the formula HgBr,, assuming 79.95 to be the
atomic mass of bromine, are as follows :
Atomic mass of
mercury.
199.898
199.876
199938
199-832
199.814
199.91 1
199.869
199.840
199.899
199952
Weight of HgBr,. Weight of H
Grams. Grams.
I
0.70002 0.58892
2
0.56430 0.31350
3
0.57142 0.31750
4
0.77285 0.42932
5
0.80930 0.44955
6
0.85342 0.47416
7
I.I 1076 0.61708
8
1. 17270 0.65145
9
1. 36186 0.70107
10
1. 40142 0.77870
Mean = 199.883
Maximum = 199.952
Minimum = 199.814
Difference ^ 0.138
Probable error = ±0.010
Computing from the total quantity of material used and metal
obtained, the atomic mass of mercury is 199.885.
THIRD SERIES.
EXPERIMENTS ON MERCURIC CYANIDE.
A series of observations was made on several organic salts of
mercury with a view of selecting a compound suitable for atomic
mass determinations. Mercuric acetate and other similar salts
were found to be unstable in the air and unsuited for accurate
analyses. Mercuric cyanide, on the other hand, was found to
be perfectly stable and to form well defined crystals.
PREPARATION OF HYDROCYANIC ACID.
Five hundred grams of potassium ferrocyanide were placed in
a two liter retort connected with a condenser. A cooled mixture
of 300 grams of pure sulphuric acid and 700 cc. of distilled water
was then poured into the retort and the mixture carefully heated
until the hydrocyanic acid was distilled over into the receiver.
The product obtained was redistilled and used immediately in
the preparation of mercuric cyanide.
lOIO WILLETT LEPLEY HARDIN.
PREPARATION OF MERCURIC CYANIDE.
Fifty grams of mercuric oxide, prepared as already described
in the experiments on mercuric oxide, were dissolved in pure,
warm hydrocyanic acid. The solution was then filtered and
evaporated to crystallization. The transparent crystals of mer-
curic cyanide which separated were dissolved in pure water and
recrystallized. The product obtained by the second crystalliza-
tion was quickly rinsed with cold water and dried for six hours
in an air bath at a temperature of 50**. The crystals were then
ground to a finely divided powder in an agate mortar and redried
for twenty-four hours in an air bath at a temperature of 55**. The
dry, white powder was then placed in a weighing tube and kept
in a desiccator.
MODE OF PROCEDURE.
The mode of procedure with mercuric cyanide was somewhat
different from that of the preceding experiments, in that no po-
tassium cyanide was used in preparing the solution for electroly-
sis. A weighed portion of the material was dissolved in pure
water in a platinum dish. When the crystals had completely
dissolved, the dish was filled to within a quarter of an inch of the
top with water, after which one drop of pure sulphuric acid was
added. The solution was then electrolyzed and the resulting
metal weighed. The strength of the current and the time of
action were the same as for mercuric chloride. In the last four
experiments, where rather large quantities of mercury were
deposited, the strong current was allowed to act from two to six
hours longer.
The results of ten experiments on mercuric cyanide, reduced
to a vacuum standard on the basis of
4.0 = density of mercuric cyanide,
13.59 z= *' ** metallic mercury,
21.4 = " " platinum dish,
8.5 = *' ** weights,
and computed for the formula Hg(CN)j, assuming 12.01 and
14.04 to be the atomic masses of carbon and nitrogen, respect-
ively, are as follows :
ATOMIC MASSES OP SILVER, MERCURY AND CADMIUM. Id I
Weight of Hg(CN),.
Grams.
Weight of Hg.
Grams.
Atomic mass
of mercury.
I
0.55776
0.44252
200.063
2
3
4
0.63290
0.70652
0.86241
0.50215
0.56053
0.63663
200.092
200.038
200.075
5
6
7
8
9
0.65706
0.81678
1.07628
1. 22615
1.66225
0.52130
0.64805
0.85392
0.97282
I.31880
200.057
200.103
200.077
200.071
200.057
lO
2. 1 1 170
1. 67541
200.077
Mean
= 200.071
Maximum
= 200.103
Minimum
= 200.038
Difference = 0.065
Probable error = 0.005
From the total quantity of material used and metal obtained,
the atomic mass of mercury is 200.070.
FOURTH SERIES.
According to Faraday's law the quantities of different metals
deposited from their solutions by the same current are propor-
tional to their equivalent weights. In this series of experi-
ments an attempt was made to determine the ratio of the atomic
mass of mercury to that of silver by passing the same current
through the solutions of the two metals and weighing the two
resulting deposits. If the proper conditions could be obtained,
this would certainly be the simplest and most direct method for
comparing the equivalent weights of different metals. But so
many difficulties were met that the method on the whole was
not satisfactory.
In the ** Revision of the Atomic Weight of Gold,*'* Mallet
made use of this method, and in a series of careful preliminary
experiments determined the conditions most favorable to its
application. From a number of experiments made by passing
the same current through two different solutions of copper sul-
^ Am. Chem.J., la, 182.
IOI2 WILLETT LEPLEY HARDIN.
phate, using pure electrot)rpe copper for both anode and cathode
in each solution, Mallet found :
First. — Other conditions being the same, the difference in the
quantities of metal deposited from solutions of unequal concen-
trations was very slight and somewhat variable, but the ten-
dency was toward a slightly larger quantity from the more con-
centrated solution.
Second. — With equal quantities of metal in the two solutions
and unequal quantities of free acid, the difference in the results
obtained were almost insignificant and somewhat variable in
direction, the tendency being toward a slightly larger quantity
from the less acid solution.
Third. — Other conditions being the same, a difference in the
temperature of the two solutions invariably caused a slightly
larger deposit from the cooler solution.
Fourth. — Other conditions being the same, a difference in the
size of the copperplates, and hence a difference in the ** current
density," caused a slightly greater deposit on the smaller plate.
Fifth. — A difference in the distance between the two plates did
not produce a constant difference of result, but the tendency was
toward a slightly larger deposit on the cathode plate farther
separated from its anode.
From the foregoing experiments it is evident that the condi-
tions most favorable to this method are, that the two solutions
should be equally concentrated, of the same temperature, and
should contain equal amounts of free acid, or when the double
cyanides are used, equal quantities of free potassium cyanide.
And, moreover, that the two cathodes and also the two anodes
should be of the same size, and that the distance between the
anode and cathode should be the same in both solutions. These
conditiohs were closely observed throughout this work.
ARRANGEMENT OP APPARATUS.
The deposits in this series of experiments were made in two
platinum dishes of equal capacity and equal internal area. The
anode in each case consisted of a coil of rather large platinum
wire, the two coils being of the same shape and size. The dishes
were insulated from each other by means of two glass stands.
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. IOI3
The platinum coils were completely immersed in the solutions and
the portion of the wire near the surface of the liquid was covered
with paraffin to prevent surface contact. The current, after
passing through the two solutions, was allowed to pass through
a hydrogen voltameter in order that its strength might be
observed at any time.
In the second arrangement of apparatus the platinum dishes
were made the anodes, and two pieces of platinum foil of the
same shape and size were used for the cathodes. The results,
however, from this second arrangement were not as satisfactory
as from the first.
MODE OF PROCEDURE.
A solution of the double cyanide of silver and potassium was
placed in one of the platinum dishes and a solution of the double
cyanide of mercury and potassium in the other. The quantities
of silver and mercury present in their solutions were approxi-
mately proportional to their equivalent weights. Each solution
contained a slight excess of potassium cyanide. The dishes
were placed in their positions and the anodes immersed some-
time before the current was allowed to act. When the tempera-
ture of the two solutions was the same as that of the room, the
connection was made and the same current allowed to pass
through the two solutions. The quantity of metal deposited
was never allowed to exceed one-half of the metal present in the
solution at first. Before interrupting the current, the solutions
were siphoned from the two platinum dishes at the same time
with two siphons of the same bore. The deposits were then
washed several times with boiling water, carefully dried and
their weights determined. Experiments were made with cur-
rents of different strength and with solutions of various
degrees of concentration. The results obtained were far from
being satisfactory. The strength of current which seemed best
adapted to the work was that which deposited about one-tenth
of a gram of silver per hour.
From a large number of experiments, only seven results were
obtained which seem of any value in determining the atomic
mass of mercury. And it must be added that many others were
IOI4 WILLETT LEPLEY HARDIN.
rejected, not because they were known to be vitiated in any way,
but because the results obtained for the atomic mass of mercury
differed from those obtained by other methods. It is possible
that, in a large number of experiments, the condition would be
more favorable in some than in others, but whether the close
agreement of the results selected was due to this or to the bal-
ancing of errors, could not be determined.
Seven results computed on the basis of 107.92 for the atomic
mass of silver are as follows :
Atomic mass
Weight of Ug. Weight of Ag. of mercury.
Gram. Gram.
1 0.(16126 0.06610 200.036
2 0.06190 0.06680 200.007
3 0.07814 0.08432 200.021
4 0.1036 1 O.I 1 181 200.011
5 O.1520I 0.16402 200.061
6 0.26806 0.28940 199-924
7 0.82808 0.89388 199929
Difference = 0.137
Computing from the total quantities of mercury and silver
obtained, we have 199.971 for the atomic mass of mercury.
Although the cause of the large variation in the rejected
observations could not be definitely determined, several sources
of error suggest themselves.
First, small quantities of hydrogen were undoubtedly set free
in the process of electrolysis, and unless these quantities were
always equal in the two solutions, which is not probable, an
error would be introduced.
Second, in some solutions an error might easily be introduced
by a change in the atomicity of mercury, but in a solution of
the double cyanide of mercury and potassium this change is
hardly probable.
Third, the occlusion of hydrogen by the two metallic deposits
would also be a possible source of error ; but only small errors
could be introduced in this way.
To account for the difference of several units in the results,.
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. IOI5
the source of error first mentioned seems by far the most proba-
ble.
SUMMARY.
In the discussion of the results obtained in the different series
of observations on the compounds of silver, the probable sources
of error and likewise the advantages of the method were pointed
out. The same discussion applies equally well to the observa-
tions on mercury.
It is evident that the first tliree series of observations on mer-
cur>- are entitled to more weight than the last series. Just why
the results on mercuric bromide should be lower than those on
mercuric chloride is not clear. Both compounds are certainly
well adapted to atomic mass determinations, inasmuch as they
can be purified by both crystallization and sublimation.
The most probable impurity in mercuric bromine would be mer-
curic chloride, but that would tend to increase rather than lower
the results. The series of observations on mercuric cyanide
have, perhaps, one advantage over the others, in that no potas-
sium cyanide was used. The results obtained in this series are
still higher than those obtained from mercuric chloride and
almost two-tenths of a unit higher than those obtained from
mercuric bromide. However, as the same care was exercised
in the purification of the material for each of the three series,
and as there was no apparent error in either case, equal weight
must be given to each of the three series in determining the
most probable value of the atomic mass of mercury. And, as
the mean of the last series is almost identical with the mean of
the first three, equal weight can be given to this series without
introducing any error.
Computing the general mean from the separate observations,
we have :
Atomic mass of mercury.
First series 200.006
Second •' 199.883
Third " 200.071
Fourth ** 199*996
General mean ^ 199-989
IOl6 WILLETT I^BPLEY HARDIN.
Prom the total quantities of material used and metal obtained,
the general mean is :
Atomic mass of mercury.
First series - 199.996
Second ** 199.885
Third " 200.070
Fourth** Z99>97i
General mean = 199.981
Combining this with the first general mean we have :
Atomic mast of mercuty.
First general mean ^ 199.989
Second ** ** = 199.981
Most probable mean of all the results =s 199.985
or 200 for the atomic mass of mercury.
PART III.
DETERMINATION OP THE ATOMIC MASS OF CADMIUM.
Nine experimenters have determined the atomic mass of cad-
mium by many different methods, but the large variations in the
results given by different chemists leave the true value of this
constant still uncertain.
Stromeyer' gave no details of his method of operation, but
found that 100 parts of cadmium combined with 14,352 parts of
oxygen. On the basis of O = 16, this ratio gives 11 1.483 for
the atomic mass of cadmium. This result is mucji lower than
those obtained by other experimenters and is perhaps only of
historical interest.
In a series of nine experiments, Von Hauer' determined the
ratio of cadmium sulphate to cadmium sulphide. The sulphate
used was purified by repeated recrystallizations and was finally
dried at a temperature of 20Q**. After weighing the sulphate
was always dried a second time and reweighed. The two
weighings never differed as much as one milligram. The sul-
phide obtained was in each case tested for sulphate. The reduc-
tion of the sulphate to sulphide was accomplished by heating
1 Berzelius' Lehrbuch, 5th Ed., 3, 13x9.
^J.praki. Ck€m., 7a, 350.
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. IOI7
the sulphate in a current of dry hydrogen sulphide under pres-
sure. The mean of nine observations computed on the basis)
0= 16 and S = 32.06 gives 11 1.93 for the atomic mass of cad-
mium. Considering the large quantity of material used each
time and the precautions taken to insure accuracy, there seems
to be little objection to the method.
Dumas' determined the ratio of cadmium chloride to metallic
silver by titrating a solution containing a weighed quantity of
cadmium chloride with a silver nitrate solution of known
strength. The cadmium chloride was prepared by dissolving
metallic cadmium in boiling hydrochloric acid. The solution
was evaporated to dryness and the chloride fused for six hours
in a current of hydrochloric acid gas. The mean of six deter-
minations gives 1 1 2. 24 for the atomic mass of cadmium (0= 16).
Maximum result, Cd = 112.759
Minimum '* Cd = 1 11.756
DifFerence = 1.003
This large variation in the results obtained indicates the pres-
ence of impurities in the material used. In the first three ex-
periments the cadmium was not purified ; the mean of these
three is Cd = 112.476. The metal used in the last three exper-
iments was considered by Dumas to be absolutely pure ; the
mean of the last three results is Cd = 112.007. From the
degree of purity of the cadmium chloride used in the different
experiments, Dumas was inclined to reject the higher results
and concluded that the true atomic mass of cadmium was about
112.
Lensen* prepared pure cadmium oxalate by precipitating a
solution of cadmium chloride, purified by repeated crystallization,
with pure oxalic acid. The precipitate was washed and care-
fully dried at a temperature of 150**. The mean of three results
obtained by converting a weighed portion of the oxalate to oxide
gives 112.06 for the atomic mass of cadmium (O = 16). The
small quantity of material used in the different experiments is
somewhat objectionable.
1 Ahh. cAim.phys.t [3], 55, 158.
ij.^akt. Ckem., 79, 281.
IOl8 WILLETT LEPLKY HARDIN.
Huntington/ under the direction of Cooke, determined the
ratio of cadmium bromide to silver bromide and also the ratio of
cadmium bromide to metallic silver. The bromide used was
prepared by dissolving cadmium carbonate^ which had been
carefully purified, in pure hydrobromic acid. The product
obtained was dried at a temperature of 200^ and finally sublimed
in a porcelain tube in a current of dry carbon dioxide. In the
first series of experiments the silver bromide corresponding to
the cadmium bromide used was weighed. The mean of eight
determinations computed from the total quantity of material
used and silver bromide obtained, on the basis of Ag = 107.93
and Br = 79.95 is Cd = 112.24. In the second series of experi-
ments the quantity of metallic silver required to precipitate a
known quantity of cadmium bromide was determined. The
mean of eight determinations computed as in the first series
gives 112.245 for the atomic mass of cadmium. The separate
determinations in both series agree very closely.
Partridge* made three series of determinations. The first
depended upon ttie conversion of cadmium oxalate into oxide,
the second, on the reduction of the sulphate to sulphide, and the
third, on the conversion of the oxalate into sulphide. The cad-
mium used in these experiments was purified by distilling twice
in vacuo. Ten observations on the conversion of the oxalate
into oxide, computed on the basis of 0= 16 and C = 12, give
1 1 1. 801 as a mean for the atomic mass of cadmium. Recalcu-
lated by Clarke,' on the basis of 0= 16 and C= 12.005, the
atomic mass of cadmium becomes 11 1.8 18. The mean of ten
results obtained by reducing the sulphate to sulphide, computed
on the basis of O = 16 and S = 32, gives 11 1.797 for the atomic
mass of cadmium. Recalculated by Clarke on the basis of 0 =
16 and S = 32.074, the atomic mass of cadmium is 111.711. In
the third series the oxalate of cadmium was converted into sul-
phide by heating in a current of dry hydrogen sulphide. The
mean of ten determinations, computed on the basis of O = 16
and S=32, gives in. 805 for the atomic mass of cadmium.
1 Proc. Amer. Acad., 17, 28.
^ Am. J. Set., r3].40, 377-
^ Am. Chem.J., 13, 34..
ATOMIC MASSES OF SILVEP., MERCURY AND CADMIUM. IOI9
Recalculated by Clarke on the basis of O = 16 and S = 32.074,
the mean becomes 1 1 1 .589. Partridge gives 11 1 .8 for the atomic
mass of cadmium, as a mean of the three series. If the higher
values for carbon and sulphur be introduced this value becomes
somewhat lower.
Jones* determined the atomic mass of cadmium by two differ-
ent methods. The first was based on the conversion of the
metal into oxide, and the second on the conversion of the oxa-
late into oxide. The cadmium used was distilled six times in
*
vacuo. The last distillate was tested spectroscopically and found
to be free from impurities. In the first series of experiments a
weighed portion of the pure metal was dissolved in pure nitric
acid in a porcelain crucible. The solution was evaporated to
dr3mess and the resulting cadmium nitrate , ignited to oxide.
The final decomposition was accomplished by means of a blast
lamp. Reducing gases were carefully excluded from the crucible
during the process of ignition. The weighings were all made
against a tared crucible. The mean of ten observations, com-
puted on a basis of O = 16 gives 112.07 for the atomic mass of
cadmium. The different determinations agree very closely. In
the second series of experiments cadmium oxalate, prepared by
precipitating pure cadmium nitrate with pure oxalic acid, was
converted into oxide. The material was carefully ignited until
the oxalate was decomposed ; it was then treated with nitric acid
and again ignited in a manner similar to that described in the
first series. The mean of five determinations computed on the
basis of O = 16 and C = 12.003 is Cd = 1 11.032. From all the
observations, Jones concludes that 112.07 represents very closely
the atomic mass of cadmium (O = 16).
Lorimer and Smith' determined the ratio of the atomic mass
of cadmium to that of oxygen by dissolving pure cadmium oxide
in potassium cyanide and electrolyzing the solution. To obtain
pure material, the commercial cadmium was dissolved in nitric
acid and the solution evaporated to crystallization. The crys-
tals of cadmium nitrate were removed from the liquid, dissolved
in pure water and recrystallized. The product obtained by the
I Am, Chem.J,, 14, a6i.
9 Ztsckr. anorg. Chem., x, 364.
I020 WII^LETT LEPLEY HARDIN.
second recrystallization was dissolved in a little water and treated
with a slight excess of potassium cyanide in a platinum dish.
From this solution the metallic cadmium was thrown out by
means of the electric current. The nitrate obtained by dissolv-
ing the electrolytic cadmium in pure nitric acid was tested spec-
troscopically and found to be free from impurities. The pure
cadmium nitrate was digested with ammonium hydroxide and
ammonium carbonate and the resulting cadmium carbonate
ignited to oxide in a platinum crucible. The method of opera-
tion was very simple, a weighed portion of the oxide was dis-
solved in pure potassium cyanide, the solution electrolyzed and
the resulting metallic cadmium weighed. The mean of nine
observations computed on the basis of O = i6 gives 112.055 for
the atomic mass of cadmium.
Bucher* made six series of experiments. The cadmium used
was purified by nine distillations in vacuo. The weighings were
all reduced to a vacuum standard and computed on the basis of
0=16. 8 = 32.059, C= 12.003, CI = 35.45, Br =79.95, and
Ag = 107.53-
In the first series cadmium oxalate, dried for fifty hours at
150*", was ignited to oxide. The mean of eight observations
gives 1 1 1.89 for the atomic mass of cadmium.
In the second series, cadmium oxalate was converted into
sulphide by heating in a current of dry hydrogen sulphide. The
mean of four determinations is Cd = 112. 15.
In the third series a weighed quantity of cadmium chlo-
ride, dried at a temperature of 300* in hydrochloric acid gas,
was precipitated with silver nitrate and the resulting silver
chloride weighed. The mean of twenty-one determinations is
Cd= 112.39. The separate observations in this series agree
very closely.
The fourth series was similar to the third, except that cad-
mium bromide was used instead of the chloride. The mean of
five determinations is Cd= 112.38, a resuft almost identical
with that obtained from the chloride.
In the fifth series a weighed portion of metallic cadmium was
converted into sulphate, which was dried at 400' and weighed.
1 Thesis, Johnn Hopkins University, iSg4.
ATOMIC MASSES OP SII«VBR, MBRCURY AND CADMIUM. I02I
The excess of sulphuric acid which remained with the sulphate
was estimated and its weight deducted. The only result given
isCd = 115.35.
In the last series metallic cadmium was converted into oxide
by dissolving in nitric acid and igniting the resulting cadmium
nitrate. The mean of two determinations made by igniting the
material ip a porcelain crucible gives 112.08 for the atomic mass
of cadmium. Three similar determinations made with a plati-
num crucible gave. as a meanCd= 11 1.87. Prom a series of
experiments on cadmium oxide, Bucher concluded that a cor-
rection should be applied to the last and also the first series.
By making this correction, the results in these two series would
be very close to those obtained from the chloride and bromide.
Prom all the preceding determinations Clarke gives 11 1.93 as
the most probable value for the atomic mass of cadmium. The
large variation in the results of different experimenters has not
been fully explained. Some chemists think that the larger
values are due to a higher degree of purity in the metallic cad-
mium used, and hence regard these values as being more nearly
correct. But it must be remembered that the reverse is true in
the experiments of Dumas. From material which had not been
purified, Dumas obtained results ranging from 112.32 to 112.76
for the atomic mass of cadmium, while from material which he
considered absolutely pure, the results were from 11 1.76 to
112. 13.
PREPARATION OF PURE CADMIUM.
The metallic cadmium used in these experiments was purified
by distillation in a current of hydrogen which had been passed
through solutions of caustic potash^ lead nitrate, potassium per-
manganate, and sulphuric acid. A hard glass combustion tube
was heated to redness and the walls of the tube indented at two
points with a three-cornered file. This divided the tube into
three parts. Commercial cadmium was placed in one end Of the
tube and connection made with the hydrogen generator. After
complete removal of the air, the tube was carefully heated in a
combustion furnace until one-lialf of the metal had distilled over
into the middle portion of the tube. The metal was cooled in a
I022 WILLETT LEPLEY HARDIN.
current of hydrogen. The tube was then broken and the metal
removed. The portions in the first and last sections of the tube
were rejected. The middle portion was placed in a second com-
bustion tube, similar to the first, and the distillation repeated.
After three distillations the metal was examined spectroscop-
icallj' and found to be free from impurities.
FIRST SERIES.
EXPERIMENTS ON CADMIUM CHLORIDE,
Dumas and Bucher have both determined the ratio of cadmium
to chlorine in cadmium chloride. The results given for the
atomic mass of cadmium by the latter experimenter are almost
four- tenths of a unit higher than those given by the former.
PREPARATION OF CADMIUM CHLORIDE.
Hydrochloric acid was purified by first passing chlorine
through the commercial C. P. acid to remove any sulphur diox-
ide ; the excess of chlorine was removed by a current of carbon
dioxide. The acid was then distilled from calcium chloride and
the hydrochloric acid gas collected in pure water. Pure metal-
lic cadmium was then dissolved in the acid and the solution
evaporated to crystallization. The crj^stalsof cadmium chloride
were removed from the liquid and thoroughly dried. The
material was then placed in a hard glass combustion tube, simi-
lar to that used in the distillation of metallic cadmium, and care-
fully sublimed in a current of dry carbon dioxide. The first
and last portions of the sublimate were rejected. The middle
portion, which consisted of pearly leaflets, was placed in a
weighing tube and kept in a desiccator. As only a small quan-
tity of the material could be sublimed at a time, the different
analyses were made from different sublimations.
MODE OF PROCEDURE.
A weighed portion of the cadmium chloride was dissolved in
a little water in a platinum dish. A slight excess of potassium
cyanide was added and, after diluting to 200 cc. with pure water,
the solution was electrolyzed. Before interrupting the current,
the liquid was siphoned from a dish in a manner already outlined
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. IO23
in the experiments on silver. The metallic deposit was washed
several times with boiling water and carefully dried. The
strength of the current and time of action were as follows :
Time of action. Strensrth of current.
labours N.D,oo = o.i amperes.
4 •* N.Dioo=o.i5
4 " N.Dioo = o.30
The cadmium was thrown down as a dense white deposit.
Ten results on cadmium chloride reduced to a vacuum stand-
ard on the basis of :
3.3 = density of cadmium chloride,
8.55 = ** ** metallic cadmium,
21.4 = *' ** platinum dish,
8.5 = •* '' weights,
and computed for the formula CdCl,, assuming 35.45 to be the
atomic mass of chlorine, are as follows :
•
Weight of CdClf. Weight of Cd. Atomic mass of
Grams. Gram. cadmium.
1 0.43140 0.26422 112.054
2 0.49165 O.30112 112.052
3 0.7175a 0.43942 112.028
4 0.72188 0.44208 1 12.021
5 0.77264 0.47319 112.036
6 0.81224 0.49742 112.023
7 0.90022 0.55135 112.041
8 1.02072 0.62505 112.002
9 1.26322 0.77365 112.041
10 1.52344 0.93314 112.078
Mean = 112.038
Maximum = 112.078
Minimum = 112.002
Difference = 0.076
Probable error = ±0.005
From the total quantity of material used and metal obtained,
we have 112.040 for the atomic mass of cadmium.
SECOND SERIES.
PREPARATION OF CADMIUM BROMIDE.
The bromine used in this series was purified as outlined in the
experiments on mercuric bromide. The cadmium bromide was
prepared by allowing bromine water to act on metallic cadmium
for several days at the ordinary temperature. When the action
I024 WII^LETT LEPI^EY HARDIN.
was complete, the solution was filtered and evaporated to crys-
tallization. The crystals of cadmium bromide were removed
from the. liquid and thoroughly dried. The material was then
placed in a hard glass combustion tube and carefully sublimed
in a current of dry carbon dioxide. The first and last portions
of the sublimate were rejected. The middle portion was removed
from the tube, placed in a weighing bottle and kept in a desic-
cator. The product obtained in this way consisted of a crystal-
line, pearly leaflet which dissolved immediately in water with-
out leaving' a residue.
MODB OP PROCEDURE.
The method of operation was the same as for cadmium chlo-
ride. A weighed portion of the material was dissolved in a little
water in a platinum dish. A slight excess of potassium cyanide
was then added and after diluting to 200 cc. the solution was
electrolyzed and the resulting metal weighed. The strength of
current and time of action were the same as for cadmium chlo-
ride.
Ten observations on cadmium bromide reduced to a vacuum
standard on a basis of :
4.8 = density of cadmium bromide,
8.55= ** •* metallic cadmium,
31.4 = ** '* platinum dish,
8.5 = ** ** weights,
and computed for the formula CdBr,, assuming 79.95 to be the
atomic mass of bromine, are as follows :
I
2
3
4
5
6
7
8
9
10
Weight ol CdBr,.
Weight of Cd.
Gram.
Atomic masfl of
Grams.
cadmium.
0.57745
0.23790
1 1 2.03 1
0.76412
0.31484
112.052
0.91835
0.37842
112.067
1. 01460
0.41808
112.068
1.15074
0.47414
112.053
1. 2475 1
0.51392
II2.OI9
I.25051
i.5i«>5
O.SI905
112.087
0.62556
1x2.076
1.63543
0.67378
112.034
2.15342
0.88722
1 12.041
Mean
= 112.053
Maximum
= 112.087
Minimum
= II2.OI9
Difference
3= 0.068
Probable error
= ±0.005
ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM. IO25
From the total quantity of material used and the metal obtained,
Cd = 112.053.
THIRD SERIES.
In these experiments an attempt was made to determine the
ratio of the atomic mass of cadmium to that of silver by allowing
the same electric current to pass successively through solutions of
the two metals and weighing the resulting deposits. The arrange-
ment of apparatus and the details of the method were described
under the mercur^*^ silver series. The results were not as satisfac-
tory as the corresponding results obtained for mercury-. A large
number of determinations were made with currents of different
strength and solutions of different concentration, but the results
were, in most cases, far below those obtained in the first two
series. A current which deposited about twelve hundredths of a
gram of silver per hour seemed to give the best results. From
all the observations, five results were selected which differed
only about one-tenth of a unit from those of the first two series.
Results selected in this way are entitled to but little weight, and
perhaps should not be used in determining the general mean of
all the observations.
Computed on the basis of 107.92 for the atomic mass of silver,
the only admissible results are as follows :
Atomic mass
of cadmium.
1 0.24335 0.12624 II 1.928
2 0.21262 O.IIO32 III.99I
3 0.24515 0.12720 1 1 1.952
4 0.24331 O.12616 1 1 1. 916
5 0.42520 0.22058 1 11.971
Weight of Ag.
Weiflrht of Cd.
Gram
Gram.
0.24335
0.12624
0.21262
0. II 032
0.24515
0.12720
0.24331
O.I 2616
0.42520
0.22058
Mean
=s III.952
Maximum
= 111.991
Minimum
=s III.916
Difference
— 0.07s
This method was discussed under mercury. The probable
sources of error pointed out there apply equally well in the case
of cadmium. Until the large variations can be accounted for
I026 ATOMIC MASSES OF SILVER, MERCURY AND CADMIUM.
and the difficulties overcome, the method must be regarded as
unsatisfactory.
SUMMARY.
Inasmuch as but one method of analysis has been used
throughout this work, it is useless to discuss it here. The
advantages and objections pointed out under silver apply also to
cadmium.
In summing up the work on cadmium, equal weight must be
given to the first two series. The last series must be considered
alone and all that need be said of it is, that the results obtained
for the atomic mass of cadmium never exceeded 112. In the
corresponding series on mercury, the variations were in both
directions from 200.
The general mean of the first two series calculated from the
separate observations is :
Atomic mass of Cd.
First series = 112.038
Second series = 112.053
General mean = 11 2.1)455
From the total quantity of material used and metal obtained
we have:
Atomic mass of Cd.
First series =s 112.040
Second series = 112.053
General mean =112.0465
Combining this with the first general mean we have 112.046 as
the most probable result of all the work, for the atomic mass of
cadmium. This result is lower than those obtained by Hunt-
ington and Bucher, but agrees very closely with the results
obtained by von Hauer, Dumas, I^ensen, Jones, and Lorimer
and Smith.
I wish here to express my sense of gratitude to Professor
Edgar F. Smith, at whose suggestion this work was undertaken
and under whose personal supervision it was carried out.
BOOKS RECEIVED.
Bulletin No. 128. Pests of Grain Crops. Issued by the North Caro-
lina Agricultural Experiment Station, Raleigh, North Carolina. July i,
1896. II pp.
Bulletin No. 45. Varieties of Apples. University of Illinois Agricul-
tural Experiment Station, Urbana, Illinois. July, 1896. 52 pp.
The Solvay Process Alkali ; Its Various Forms and Uses, with Notes on
Alkalimetry and Chemical and Commercial Tables, conveniently arranged
for the Use of the Consumer. The Solvay Process Company, Syracuse,
New York. 39 pp. 7 plates.
Special Bulletin, Second Edition. Commercial Fertilizers. Purdue
University, Lafayette, Indiana. August, 1896. 8 pp.
The University Scientific Monthly. Published by the Engineering
Society of the University of Tennessee, Knoxville, Tennessee. August,
1896. 43 pp.
Bulletin No. 127. Parasites of Domestic Animals. Issued by the
North Carolina Agricultural Experiment Station, Raleigh, North Caro-
lina. May 15, 1896. 42 pp.
Chemistry in Daily Life. Popular Lectures by Dr. Lassar-Cohn. Trans-
lated by M. M. Pattison Muir. Philadelphia: J. B. Lippincott Co.
With 21 wood cuts in text, x, 324 pp. Price, $1.75.
Bulletin No. 40. I. Analyses of Manurial Substances Sent on for
Examination. II. Analyses of Licensed Fertilizers Collected by the Agent
of the Station during 1896. Hatch Experiment Station of the Massa-
chusetts Agricultural College, Amherst, Mass. July, 1896. 19 pp.
Bulletin No. 41. The Application of Tuberculin in the Suppression of
Bovine Tuberculosis. Hatch Experiment Station of the Massachusetts
Agricultural College, Amherst, Mass. August, 1896. 27 pp.
Humphry Davy, Poet and Philosopher. By T. E. Thorpe, LL.D.,
F.R.S. New York: Macniillan & Co., Ltd. 1896. 240pp. Price, ^1.25.
A Manual' of Quantitative Chemical Analysis for the Use of Students.
By Frederick A. Cairns, A.M. Third Edition. Revised and enlarged
by Elwyn Waller, Ph.D. New York : Henry Holt & Co. 1896. xii, 417
pp. Price, $2.00.
The Chemical Analysis of Iron. A Complete Account of all the Best
Known Methods for the Analysis of Iron, Steel, Pig Iron, Iron Ore,
Limestone, Slag, Clay, Sand, Coal, Coke, and Furnace and Producer
Gases. By Andrew Alexander Blair. Third Edition. Philadelphia :
J. B. Lippincott Co. 1896. 322 pp. Price ;^t.oo.
Bulletin No. 38. Canaigre, the new Tanning Plant. By H. H. Har-
rington and Duncan Adriance. Agricultural and Mechanical College of
I028 BOOKS RECEIVED.
Texas, College Station, Brazos County* Texas. March, 1S96. 11 pp. 7
plates.
Bulletin No. 24. North Dakota Soils. Government Agricultural Ex-
periment Station for North Dakota, Fargo, N. D. June, 1896. 17 pp.
Roentgen Rays and Phenomena of the Anode and Cathode. Princi-
ples, applications and theories. By Edward P. Thompson, M.B., E.E. ;
concluding chapter by Prof. William A. Anthony. 60 diagrams. 45 half-
tones, xiv, 190 pp. N. Y. : D. Van Nostrand Co. Price I1.50.
Foods : Their Composition and Analysis. By Alexander Wynter
Blyth, M.R.C.S., F.I.C., F.C.S., etc. With numerous tables and illus-
trations. Fourth edition, revised and enlarged. 1896. xxxii, 755 pp.
New York : D. Van Nostrand Co. Price $7.50.
Bulletin No. 30. Wheat-cutting at different dates. Agricultural Ex-
periment Station of Nevada State University, Reno, Nevada. December,
1895- 7 pp.
Bulletin No. 32. Commercial Fertilizers and Chemicals. Inspected,
analyzed and admitted for sale in the State of Georgia up to September i,
1896, and other information concerning fertilizers. Under the supervi-
sion of Hon. R. T. Nesbitt, Commissioner of Agriculture of the State of
Georgia, Atlanta, Ga. 132 pp.
Tables for Iron Analysis. By John A. Allen, First Edition, vii +85
pp. New York : John Wiley & Sons.
Geological Survey of Canada. Reports and Maps of Investigation and
Surveys. Annual Report. Vol. VII. 1894. xiv + 124A + 427B -f- 40C+
54F -|- 157J + 149M -|- 68R -|- 187S 4- xvii pp., with maps. Ottawa : Gov-
ernment Printing Bureau.
Vol. XVIII. [December, 1896.] No. 12.
THE JOURNAL
OF THE
AMERICAN CHEMICAL SOCIETY.
[Contribution prom the John Harrison Laboratory of Chemistry.
No. 14.]
METAL SEPARATIONS BY MEANS OP HYDROCHLORIC
ACID QAS/
Bt J. Bird Mover.
RecciTcd September s6, 1896.
INTRODUCTION.
THE action of gaseous haloid acids upon metallic oxides and
their salts, is a field of investigation, which, though not
of recent origin, has been but lately developed. It was Debray*
who first called attention to the volatility of molybdic acid in a
stream of hydrochloric acid gas, with the formation of
MoO(OH),Cl,.
E. Pochard' applied this and showed that molybdic acid was
completely eliminated and separated from tungstic acid, by its
volatility in a current of hydrochloric acid. Since that time
nothing further has been done with single haloid acids, in gas
form, until quite recently. Compounds have been decomposed,
salts volatilized, and separations made, by means of other gases
and mixtures, which may be as effective as hydrochloric acid,
but are not devoid of trouble nor nearly so neat.
Smith and Oberholtzer* repeated and confirmed Pochard's
I Prom author's thesis presented to the Paculty of the University of Pennsylvania
for the degree of Doctor of Philosophy. 1S96. ^
S Compt. rend,, 46 1098, tiud Ann. Chem. (Liebig). 108. 250.
• Compt, rend,, 114. 173.
4 /. Am. Chem. Sac., 15. z.
I030 J. BIRD MOVER. METAI. SEPARATIONS
work in regard to the separation of molj'bdic acid from tungstic
acid, and in addition showed that gaseous hydrobromic, hydri-
odic, and hydrofluoric acids acted similarl}'. Later, Smith and
Maas' made use of the volatilization of molybdic acid for a close
atomic mass determination of molybdenum.
Smith and Hibbs* showed that vanadium behaved like molyb-
denum. Hydrochloric acid gas completely eliminates vanadic
acid from sodium vanadate. A little later they investigated the
action of hydrochloric acid upon the members of Group V of the
periodic system.'
The sodium salts of nitric, pyrophosphoric, pyroarsenic and
pyroantimonic acids were used. They found nitrogen, arsenic,
and antimony to be volatile in gaseous hydrochloric acid, and
made it the basis of a separation of phosphoric acid from nitric
acid. Lead arsenate changed completely to chloride, the arse
nic being volatilized, thus affording a good quick separation.
Smith and Meyer* tried the action of all the haloid acids upon
the elements of Group Vof the periodic system. They worked
with sodium salts and observed : I. That nitrogen was expelled
completely by all the haloid acids. II. That phosphoric acid
was not acted upon. III. That arsenic acid was fully expelled
by hydrochloric, hydrobromic, and hydriodic acids, but only
partially by hydrofluoric acid. IV. That antimony" was com-
pletely volatilized by hydrochloric acid. There was no work
done on bismuth. V. Vanadium went over completely in
hydrochloric acid, but only partially in hydrobromic and hydro-
fluoric acids. VI. Columbium forms volatile products with
hydrochloric and hydrobromic acids. No knowledge of didym-
ium was obtained. VII. Tantalum is onlj'^ slightly volatile
in hydrochloric acid.
P. Jannasch and F. Schmidt'' repeated some of the work of
Smith and Hibbs, in which they confirmed the separation of
arsenic from lead. They anticipated a slight portion of my
work, and in addition separated arsenic acid from iron, tin from
1 Ztsch*-. anoi-g. Chem., 5. 2S0.
ay. Am. Chem. Sot., 16/578.
• Ibid., 17, 682.
4 Ibid., X7, 735.
6 Ztschr. anorg. Chem., 9, 274.
BY MEANS OF HYDROCHLORIC ACID GAS. IO3I
lead, tin from copper, and tin from iron, in a stream of hydro-
chloric acid gas.
The position of bismuth in the periodic system makes it
natural to suppose that it too will be volatile in hydrochloric
acid gas. This I have shown to be true, and was thus enabled
to separate it from lead and copper. The action of hydrobromic
acid on bismuth trioxide was also tried ; it formed the bromide
and then volatilized. It requires a higher temperature and
longer action than with hydrochloric acid. Because of lack of
time, I have been compelled to abandon the experiments in-
stituted with a view of affecting separations, in atmospheres
of hydrobromic acid and hydriodic acid gas and have confined
my labors to hydrochloric acid gas.
METHOD OF WORK.
The hydrochloric acid gas was generated by dropping con-
centrated sulphuric acid from a separatory funnel, upon concen-
trated hydrochloric acid contained in a three liter flask. The
gas evolved at the ordinary temperature was dried by passing it
through two sulphuric acid drying bottles and then through a
calcium chloride tower, when it was considered sufficiently dry
for the purpose. The substance to be acted upon was weighed
out in a porcelain boat and the latter was placed in a combus-
tion tube of hard glass.
The tube had previously been rinsed with alcohol and then
with ether, to remove all moisture. The ether was removed by
drawing a current of drj'- air through the tube. This tube was
connected to a two-necked bulb receiver containing about 300
cc. of distilled water. When working with arsenic ten cc. of
nitric acid were added. The connecting tube from the combus-
tion tube to the bulb receiver was made to enter the receiver and
dip below the surface of the water, thus catching all volatile
products, as well as taking up the hydrochloric acid gas. To
insure safety from the loss of volatile products, a small flask
containing water was attached to the bulb receiver. The appa-
ratus was controlled at both ends by stop-cocks. This is neces-
sary to prevent backward suction on disconnecting the appara-
tus. After the reaction was completed the boat was removed to
I032 J. BIRD MOYBR. MBTAI< SEPARATIONS
a sulphuric acid desiccator from which the air could be
exhausted. In general, the procedure was similar to that
employed by Hibbs.*
I. — BBHAVIOR OP ANTIMONY TRIOXIDE.
Antimony oxide, labelled chemically pure, was dissolved in
hydrochloric acid and precipitated with a large amount of
water. After washing by decantation it was redissolved and
reprecipitated. This procedure was repeated several times,
when it was precipitated by ammonium carbonate, washed, and
ignited. The pure oxide obtained in this manner was sub-
jected to the action of hydrochloric acid gas and it was "found to
volatilize completely. In each trial a one-tenth gram of the oxide
was acted upon. The temperature varied between 150** and 190** C.
It was determined in the following way : The combustion tube
was slipped through two holes made in the sides of a copper
drying oven.
A very slow current of gas was used as the antimony seemed
to volatilize more readily and completelj', if the current was
slow and the heat gentle. This I attribute, on reflection, to the
fact that I ignited the oxide too strongly, (to a red heat) in its
preparation. It dissolved with difficulty in concentrated hydro-
chloric acid. Lack of time prevented the repetition of this
experiment and the separation of antimony from lead and copper.
in which this substance was used. About eight hours was the
time required for the volatilization; very probably a shorter time
w^ould be required if the oxide had been obtained by gentle igni-
tion.
II. — BEHAVIOR OP LEAD OXIDE.
Pure lead oxide was obtained from recrystallized nitrate, by
careful ignition. This oxide changed completely into chloride
at the ordinary temperature and it was only necessary to apply
a gentle heat to complete the change and entirely remove the
water formed. No volatilization was noticed until a tempera-
ture of 225** was reached ; at this point the lead chloride slightly
volatilized.
I think it possible to estimate lead as chloride, if the tempera-
ture is kept under 200^. A weighed amount of lead oxide was
1 Thesis, 1896.
it
BY MBANS OF HYDROCHLORIC ACID GAS. IO33
acted upon by hydrochloric acid gas in the told, for two hours,
and then heated sufficiently to remove all the water formed.
The boat was cooled in the gas, and then placed in a sulphuric
acid desiccator and allowed to stand one-half hour. It was then
weighed.
Experiments.
Lead oxide Lead chlo- Lead chlo-
taken. ride obtained, ride required. Differeuce.
Gram. Gram. Gram. Gram.
Experiment I 0.1017 0.1267 0.1267 0.0000
II 0.1015 0.1258 0.1265 —0.0007
III 0.1 169 0.1454 0.1447 -f-0.0007
The lead chloride dissolved in hot water without residue.
III. — THE SEPARATION OF ANTIMONY EROM LEAD.
The oxides were carefully weighed and thoroughly mixed in
a porcelain boat. Hydrochloric acid gas was passed over them
in the cold, until the lead oxide had been entirely changed to
,the chloride. It was then heated with the smallest flame
obtainable from a fish-tail burner, placed about two inches below
the tube.
Antimony tri- Lead chlo- Lead chlo- Lead chlo-
chloride taken, ride taken, ride obtained, ride required.
Gram. Gram. Gram. Gram.
Ezperiment I • • • • 0.1015 0.1189 0.1470 0.1482
" II>'-> 0.1090 0.1021 0.1266 0.1272
** III... 0.1350 0.0852 0.1057 0.1062
" IV... 0.1250 0.1671 0.2069 0.2083
The time required was seven hours.. The lead chloride was
immediately weighed. It dissolved completely in hot water and
this solution was tested by means of Marsh's apparatus for anti-
mony, without finding the latter present. Experiment II was
slightly varied by first moistening the oxides with a drop of
hydrochloric acid. ^
IV. — BEHAVIOR OF BISMUTH OXIDE.
Bismuth nitrate, as pure as could be obtained, was dissolved
in nitric acid and then thrown down with a large quantity of
water. The precipitate was carefully washed by decantation.
This operation was repeated several times.
It was then dissolved in acidulated water and precipitated
I034 J. BIRD MOVER. METAL SEPARATIONS
with ammonium hydroxide and ammonium carbonate. This,
on ignition, gave pure oxide, which, heated in a stream of
hydrochloric acid gas, completely volatilized as chloride. Here
the same treatment is necessary as obtained for antimony. A
slow current of gas and a low heat were best adapted for the
volatilization (a temperature of 130°, or roughly, the heat
afforded by a fish-tail burner placed two inches below the com-
bustion tube, with a flame an eighth of an inch high). The bis-
muth chloride sublimed nicely, forming awhite crystalline mass
beyond the boat, which could be readily driven along by a gen-
tle heat.
v. — THE SEPARATION OF BISMUTH FROM LEAD.
The same material was used as in the preceding experiments.
The weighed oxides were thoroughly mixed in a porcelain boat.
Usually the gas was allowed to act in the cold for an hour,
which changed the oxides completely to chlorides.
The same conditions prevailed as under bismuth oxide alone.
If an attempt was made to hasten the reaction by heating higher
than iSo"*, a little lead would volatilize. This sublimate, slightly
yellow in color, w^ould appear directly over the boat and could
not be driven along the tube like bismuth, hence it was readily
detected.
The separation of bismuth from lead requires much care, as
it is not as sharp as could be desired. It is also difiicult to tell
exactly when the last traces of bismuth have been driven out of
the boat, as there was no color change to indicate it, both metals
forming white chlorides. The separation is complete in from
six to seven hours. At the end of the separation the position of
the boat was changed and the action continued ; if no further
sublimation occurred it was cooled and removed to a desiccator.
The weight was taken after standing one-half hour over sul-
phuric acid. With care bismuth can be separated from lead in
this manner.
Bismuth
Lead
Lead
Lead oxide
trioxide
chloride
chloride
taken.
taken.
obtained.
required.
Difference.
Gram.
Gram.
Gram.
Gram.
Gram.
Experiment!"" 0.1014
0.2020
O.I 261
0.1264
—0.0003
" II.... 0.1006
0.0642
0.1252
0.1254
— 0.0002
III... 0.1038
0.1003
0.1294
0.1302
—0.0008
IV ... 0.1412
0.1260
0.1759
01 759
4-0.0000
BY MEANS OF HYDROCHLORIC ACID GAS.
1035
The chloride of lead dissolved completely in hot water. It
showed no bismuth. The sublimate contained no lead.
VI. — BEHAVIOR OF CUPRIC OXIDE.
Pure copper nitrate was made by recrystallization. It was
then ignited in a porcelain crucible at a dull red heat, until it
became constant in weight. The pure black oxide was then
subjected to the action of hydrochloric acid gas. In Experi-
ment I, the boat containing the oxide was heated at the outset
to 175**. It was taken out after two hours, placed over sulphuric
acid for half an hour, and weighed. The weight showed that
the copper oxide had hardly been acted upon. It had only been
superficially changed to chloride. It was then moistened with
two or three drops of hydrochloric acid, dried in a rapid current
of the gas, and heated two hours longer. This resulted in the
complete transformation into chloride. The anhydrous chloride
thus obtained, liver brown in color, was placed in a desiccator
from which the air was exhausted. This was done to remove
all the gas that might be retained and prevented a too rapid
absorption of moisture.
Copper chloride absorbs moisture but not so rapidly as to pre-
vent weighing in this form,:
«
Copper
oxide
taken.
Copper
chloride
obtained.
Copper
chloride
required.
Difference.
Gram.
Gram.
Gram.
Gram.
Experiment I . . . .
0 ion
0.1708
O.1713
—0.0005
II....
0.1025
0.1726
0.1736
— O.OOIO
III...
0.1034
0.1756
0.1752
4-0.0004
In Experiment II, the change was completed in the cold by
prolonged action through four hours. It was then heated about
ten minutes at the end to drive out the moisture that had
formed. In all the experiments cited, the copper chloride, after
weighing, was found to dissolve completely in cold water.
VII. — THE SEPARATION OF ANTIMONY FROM COPPER.
The same material was used as in the preceding experiments.
The weighed oxides were thoroughly mixed. The antimony
was completely volatilized, leaving copper chloride which was
1036
J. BIRD MOVER. METAL SEPARATIONS
weighed as such. The volatile antimony chloride was caught
in the bulb receiver at the end of the tube. The bulb and tube
were washed out with acidulated water into a beaker and the
antimony thrown down with hydrogen sulphide. The antimony
sulphide was filtered, thoroughly washed, and while moist dis-
solved in strong hydrochloric acid. The hydrogen sulphide
evolved was conducted into bromine water and oxidized to sul-
phuric acid, which was estimated as usual and the antimony
calculated.
The length of time required was eight hours. On several
occasions the experiment was interrupted at the end of four
hours, but invariably the separation was incomplete and on dis-
solving out the copper chloride formed, black copper oxide and
white antimony oxide were plainly evident. In some cases the
mixture of oxides was moistened with a couple of drops of
hydrochloric acid and then evaporated down in a stream of acid
gas, by heating the tube over a water- bath. This treatment
seemed to facilitate matters but it is not altogether advisable,
because the copper chloride has a tendency to creep over the
sides of the boat. It is quicker in the end to separate them in
the dry condition, allowing plenty of time for the reaction. The
copper chloride obtained was perfectly soluble in cold water and
contained no antimony. It could readily be changed to oxide
and weighed if thought necessary.
Antimony
trioxide
taken.
Copper
oxide
taken.
Copper
chloride
obtained.
Copper
chloride
required
Gram.
Gram.
Gram.
Gram.
Experiment I .. 0.1068
0.1040
0.1750
0.1745
II.. 0.1062
0.1053
0.1774
0.1784
•* III. 0.1022
0. 1020
0.1726
0.1728
IV . 0.1198
0.1020
0.1722
0.1728
Antimonv tri- Antimony tri-
oxide taken, oxide found.
Experiment I
Gram.
0.1068
Gram.
0.1039
Difference.
Gram.
+0.0005
KOOIO
).0002
).O006
Difference.
Gram.
+0.0009
VIII. — THE SEPARATION OF BISMUTH PROM COPPER.
The pure oxides were mixed and treated as directed under
bisiiiuih and lead.
BY MEANS OF HYDROCHLORIC ACID GAS.
1037
oxiae
taken.
Gram.
Experiment I •• 0.1030
'* II.. 0.1004
III. 0.1026
** IV . 0.1019
Bismuth
trichloride
taken.
Grams.
0.1069
0.1077
0.1060
0.1058
Copper
chloride
obtained.
Grams.
0.1738
O.I 701
0.1741
O.1718
Copper
chloride
required.
Grams.
0.1745
O.I713
0.1738
0.1726
Difference.
Grams.
.0007
L00I2
+00003
i.oooS
Bismuth
trioxide
obtained.
Gram.
Bismuth
trioxide
required.
Gram.
Difference
Gram.
Experiment 1 0.1076 0.1069 +0.0007
The time required in each of these trials was seven hours.
It seemed to be advantageous to raise the temperature and heat
sharply for about ten minutes at the end, to insure the complete
removal of the bismuth.
Moistening with acid helped the reaction but subjected it to
the same danger of creeping as noted under antimony and cop-
per.
The bismuth was estimated as follows : It was washed out of
the tube and bulb with acidulated water and then precipitated
as sulphide. The bismuth sulphide was filtered, washed, and
dissolved in nitric acid. It was thrown out of the solution with
ammonium hydroxide and ammonium carbonate, as hydrated
oxide, and then filtered, dried, and ignited. It was weighed as
oxide. The residue of copper chloride in the boat dissolved in
cold water and showed no bismuth.
IX. — ACTION OF GASEOUS HYDROCHLORIC ACID ON SODIUM
PYROARSENATE.
Hibbs' showed that arsenic was completely volatilized from
sodium pyroapsenate, leaving weighable sodium chloride. In
fact, so clean was the elimination of arsenic that he made it the
basis of an arsenic atomic mass determination, with admirable
success.
In working up the separation of arsenic from other metals it
was necessary to start with the pure sodium salt. After purifi-
cation I decided to test it, by weighing the salt produced by the
action of the acid gas upon it. Several determinations gave
close results, proving the salt pure.
^ See next paper, page 1044.
1038 J. BIRD MOVER. METAL SEPARATIONS
Chemically pure arsenate was procured. It was recrystallized
and then ignited (not too strongly) for an hour. Thepyroarse-
nate obtained was used in precipitating the various arsenates
investigated.
Sodium pyroar- Sodium chlo- Sodium ctalo-
senate taken. ride obtained. ride required.
Gram. Gram. Gram.
Experiment 1 0.2021 0.1330 0.1335
" II 0.1039 0.0691 0.0686
X. — THE SEPARATION OF ARSENIC FROM COPPER.
Pure sodium pyroarsenate was used to precipitate the copper
salt.
Copper sulphate was recrystallized five times, a few good
crystals were dissolved and the two solutions mixed. A green
copper arsenate was precipitated. It was washed and dried at
100°. Salkowski* observes that copper arsenate still contains
water above 130°. My salt had the composition Cu,As,0, +
2H,0.
Hydrochloric acid gas completely changes it in the cold to
chloride. A slight heat drives out the arsenic and water and
leaves a brown anhydrous copper chloride, which can be weighed
as such. Care was taken to remove all the acid gas before
weighing.
The arsenic was washed out of the bulb into a beaker, this
was warmed with nitric acid to insure oxidation, and then it
was precipitated from an ammoniacal solution with ** a magne-
sia mixture.'* It was weighed as Mg,As,0,.
Copper arse- Copper chlo- Copper chlo-
nate takeu.
ride obtained.
ride required.
Differem
Gram.
Gram.
Gram.
Gram.
Experiment
; I .... 0.1067
0.0850
0.0851
— O.OOOI
1 1
II.... 0.1240
0.0998
0.0991
-ho. 0007
( (
III.. . 0.1072
0.0860
0.0856
-|-o.ooa4
i t
IV... O.I 155
0.0924
0.0923
+0.0001
( 1
V 0.1042
0.0832
0.0833
— O.OOOI
Experiment I. ASjOj obtained, 0.0498 gram ; As^Oj required, 0.0487 gram.
The residue of copper chloride completely dissolved in water.
It showed no arsenic when tested in a Marsh apparatus.
'^J.prakt. Chem., 104, 129.
BY MEANS OF HYDROCHLORIC ACID GAS. IO39
XI. — THE SEPARATION OP ARSENIC FROM SILVER.
Silver arsenate was made by precipitating silver nitrate with
sodium arsenate. Care was taken to have the nitrate in excess.
The reddish- brown arsenate of silver was washed with boiling
water, until the washings no longer showed silver, when tested
with hydrochloric acid. It was dried at no**.
As was expected, the acid gas attacked it even in the cold.
In fact the action was so vigorous that a couple of analyses were
spoiled by spattering. The trouble arose from the fact that the
arsenate was not finely powdered. Heat was generated in the
reaction sufficiently to send over a portion of the water formed.
Experiment I was run in the cold for one hour and then heated
sharply, for a few minutes, to expel the arsenic and water. The
result was only 0.46 per cent, too high, but indicated that the
salt should be heated longer, and not necessarily as high to
remove all the arsenic.
The succeeding experiments were heated from one to two
hours at 150** with better results :
Silver
arsenate
taken.
Silver
chloride
obtained.
Silver
chloride
required.
Difference.
Gram.
Gram.
Gram.
Gram.
Experiment I
0.2542
0.2381
0.2363
-I-0.0018
II....
0.2325
0.2163
O.2161
-f-0.0002
III...
0.2084
0.1952
0.1938
-fo.0014
IV...
0.2070
0.1927
0.1924
-I-O.OOO3
Experiment i. Ag obtained = 70.45 per cent ; Ag required =69.99 P^r
cent.
The residues in Experiments II, III, and IV were dissolved
and tested for arsenic. None was found.
XII.— THE SEPARATION OF ARSENIC FROM CADMIUM.
Chemically pure cadmium sulphate was precipitated by a
solution of sodium pyroarsenate. Stirring brought out a gelat-
inous arsenate, which changed by additional stirring to a granu-
lar salt. This was thoroughly washed and dried at no®. It
had the composition Cd,As,0^ + 2H,0. Salkowski' observes
that a red heat is necessary to fully dehydrate this salt.
The moisture and arsenic were completely expelled at 150**,
1 Loc. cit.
I040
J. BIRD MOVER. METAI, SEPARATIONS
leaving a uniform mass of cadmium chloride. It was weighed
as such after standing over sulphuric acid for one-half hour.
The arsenic was determined as usual.
cd,A»,o, -h
3H,0
taken.
Cadmium
chloride
obtained.
Cadmium
chloride
required.
Difference.
Gram.
Gram.
Gram.
Gram.
Experiment I . . . • 0.2359
0.1965
0.1977
—0.0012
<i
II ... O.I 166
0.0968
0.0968
—0.0000
<<
III... 0.1030
0.0857
0.0855
+0.0002
<(
IV ... 0.1138
0.0947
0.0946
+0.0001
i(
V .-.. 0.1043
0.0870
0.0867
+0.0003
Cd,Aa,0, +
3H«0 taken.
AS|09
obtained.
Aa^O,
required.
Difference
Gram.
Gram.
Gram..
Gram.
Ezperitneni
t I .... 0.2359
0.0813
0.0822
0.0009
The cadmium chloride dissolved perfectly in water and showed
no arsenic, when tested in a Marsh apparatus.
XIII. — THE ACTION OF HYDROCHLORIC ACID GAS ON FERRIC
OXIDE.
Pure oxide of iron was heated in a stream of acid gas. The
behavior of iron is rather peculiar, as it very readily changes
into chloride, and then only partially volatilizes. On heat-
ing to 200** the greater part is driven over as flaky crystals
of ferric chloride. The remainder consists of a white mass,
which refuses to go over on prolonged action and also on raising
the temperature.
This residue was soluble in water and did not react with
potassium thiocyanate, but immediately gave a blue precipi-
tate with ferricyanide. Reduction was therefore evident ; this
is also noted by Jannasch and Schmidt.* The temperature at
which ferric chloride usually goes into the ferrous condition is
above 1000**.
Care was taken to prepare perfectly pure hydrochloric acid
gas. Chemically pure acids were used to this end. The action
however was the same in all cases.
XIV. — ^THE SEPARATION OF ARSENIC FROM IRON.
Chemically pure ferrous ammonium sulphate was carefully
1 Loc. cit.
BY MEANS OF HYDROCHLORIC ACID GAS. IO41
oxidized with nitric acid, it was taken up in water, filtered and
then crystallized several times. The best crystals were selected
and a solution made to precipitate the arsenate. A white pre-
cipitate tinged with yellow was formed. It was washed by
decantation and then filtered and washed until the washings no
longer gave Prussian blue with ferrocyanide. It was then dried
and gently ignited.
The acid gas acts on it quickly in the cold and it becomes a
light green liquid. In evaporating off the moisture the chloride
of iron was carried over with the arsenic.
In a second trial, .with the temperature lower and occasionally
removing the source of the heat altogether, when ebullition
threatened to cause spattering, ferric chloride was obtained with-
out loss. This was gradually heated a little higher to remove
all the arsenic.
The chloride of iron was dissolved, oxidized, precipitated with
ammonium hydroxide and estimated as usual. The result was
fair and the product tested showed the absence of arsenic, but
all succeeding experiments failed. Either the substance spat-
tered or the iron went along with the arsenic.
Jannasch and Schmidt* separated arsenic from iron by placing
their material in a large hard glass bulb and evaporating down
to dryness with nitric acid, in an air current. This is not appli-
cable when a porcelain boat is employed. They then volatilized
the arsenic in hydrochloric acid gas at 120**.
XV. — SEPARATION OF ARSENIC PROM ZINC.
In some preliminary work zinc oxide was treated with acid
gas at 200**. It completely changed to chloride and was not
volatile. Pure zinc sulphate was used to precipitate the arse-
nate; it was washed, dried and ignited to 150**. The same diffi-
culty appeared as was encountered under iron. Zinc arsenate
melts down to a liquid mass as soon as the acid gas strikes
it, which is extremely hard to evaporate without spattering. A
small glass cover was placed over the boat, which tended to les-
sen the spattering, but did not entirely prevent it.
The zinc was estimated by taking the chloride up in a little
^Loccit.
I042 J. BIRD MOVER. MBTAI. SEPARATIONS
hydrochloric acid and running it down with pure mercuric
oxide. It was then ignited and weighed as zinc oxide. One
good result was obtained, but generally the residues of zinc con-
tained arsenic and the results were far from being concordant.
XVI. — THE SEPARATION OF ARSENIC PROM COBALT AND
NICKEL.
Cobalt and nickel were precipitated as arsenates in the usual
manner, with a solution of pyroarsenate.
Cobalt nitrate, a Merck preparation, was carefully purified;
considerable manganese w^s found and eliminated.
This gave the pink salt Co,As,0^ + 8H,0, which was ignited
to the blue anhydrous compound.
Cobalt arsenate is ver>' readily attacked by the acid gas in the
cold, yielding a pink chloride. A slight heat, not much above
120°, changed it to the blue chloride and drove out the arsenic.
At first it was quickly weighed as chloride, then it was taken up
in a little hydrochloric acid and evaporated down with mercuric
oxide. On ignition, black Co,0^ was obtained and weighed.
The arsenic was estimated as usual.
Experiment I. Experiment II.
Gtum. Gram.
Co„As,0(, taken '•• 0.1509 0.2029
CoCl, obtained 0.1309
CoCl, required o. 1293 ....
CojOi obtained 0.0738 0.0969
CojO, required 0.0731 0.0983
Difference +0.0007 —0.0014
AsjOj obtained 0.0770
AS7O5 required 0.0764
Difference +0.0006
. a • .
...
....
On testing the cobalt residue by the Marsh test, no trace of
arsenic was found. No cobalt was found in the sublimate.
Some of the first experiments gave cobalt too low; it was thought
that they had been heated too high, but testing showed no vola-
tilized cobalt.
A temperature of 125** is sufficient to drive out all of the arse-
nic, and at this temperature there is no danger of volatilizing
the cobalt.
In working with nickel, the green arsenate was simply dried
BY MEANS OF HYDROCHLORIC ACID GAS. IO43
in the first experiment. It 'therefore had the composition
Ni,As,0, + 8H,0.
Hydrochloric acid gas attacked it in the cold. A slight heat
drives out the arsenic and moisture and leaves a salmon-colored
chloride. The nickel chloride was changed to oxide by evapo-
rating it with nitric acid and igniting.
Experiment I.
Gram. ^
Ni,As,Og + 8H,0 taken 0.1502
NiO obtained 0.0554
NiO required 0.0561
Difference — 0.0007
In Experiments II and III the salt was made anhydrous by
ignition.
Experiment II. Experiment III.
Gram. Gram.
NisAs^O^ taken o.i 166 0.1040
NiO obtained 0*0577 0.0523
NiO required 0.0575 0.0513
Difference -I-0.0002 -|-o.ooio
ASfOj obtained 0.0515
AsjOj required . • . . 0.0526
Difference .... — o.ooii
The Marsh test showed no arsenic with the nickel.
XVII. — BEHAVIOR OF MINERALS IN HYDROCHLORIC ACID GAS.
Niccolite. One-half gram of the mineral was finely powdered
and subjected to the action of acid gas for a day, at a tempera-
ture of 200'' C. It was only ver>' slightly affected.
A second portion was dissolved in nitric acid and evaporated
doivn in a porcelain dish. It was then transferred to a boat and
evaporated to dryness. To remove all the acid, it was heated in
an oven to no'' for one-half hour. The dry substance was
acted upon bj' the acid gas in the cold for five hours. It
changed completely to chloride. A temperature of 150" for an
hour removed all the moisture and arsenic.
The nickel chloride was evaporated dowm with nitric acid,
ignited, and weighed as NiO. The arsenic was estimated as
usual.
I044 JOSEPH GILLINGHAM HIBBS. ATOMIC
Per cent
Nickel found 43*79
Nickel calculated 43-6o
Difference o. 19
Arsenic found 56.66
Arsenic calculated 56.40
Difference 0.26
Undoubtedly there is still a wide field open in regard to the
behavior of hydrochloric acid gas upon mineral species. Smith
and Hibbs* showed that mimetite lost its arsenic quantitatively,
when heated in a stream of acid gas. In this laboratory others
are being investigated with favorable indications. The direct
employment of hydrochloric acid gas upon a powdered mineral
would simplify many a tedious gravimetric process, leaving the
separated elements in a desirable condition for further treat-
ment.
In the case of a mineral such as niccolite, where it must first
be decomposed with nitric acid and then transferred to a boat,
the advantage is not so great. This, however, can be modified,
so that the time factor is reduced and the advantage of the
method still retained. Instead of using a boat, which has no
advantage unless the non-volatile chlorides are to be weighed
directly, a hard glass bulb can be substituted. The mineral is
placed in the bulb, dissolved in nitric acid, and evaporated
down by the aid of a current of air drawn through the bulb.
The residual oxides are then separated in a stream of hydro-
chloric acid gas as usual.
[Contribution from thk John Harrison Laboratory of Chbbcistry,
No. 15.]
THE ATOMIC WEIGHTS OF NITROGEN AND ARSENIC
By Joseph Dillingham Hibbs.
Received September a6. i8g6.
THE atomic weight of the metal molybdenum had been
determined by expelling molybdic acid from sodium
molybdate with hydrochloric acid gas, then weighing the resid-
ual sodium chloride.
1 Loc. cit.
2 From author's thesis presented to the Faculty of the UniverBity of PeoDsylvania
for the degree of Doctor of Philosophy, 1896.
WEIGHTS OF NITROGEN AND ARSENIC. IO45
Having found that nitric acid and arsenic acid were driven
from their alkali salts with ease, leaving a chloride that was
absolutely pure, and believing that the atomic masses of nitro-
gen and arsenic determined in this manner would a£Ford a valu-
able contribution to the literature relating to these constants, a
carefully conducted series of experiments was made with two
nitrates and one arsenate. The results are given in detail in the
following lines :
THE ATOMIC WEIGHT OP NITROGEN.
In the past, determinations of the atomic weight of nitrogen
have been made from the density of the gas itself, from the ratio
between ammonium chloride and silver, and from the decompo-
sition of certain nitrates. The first method in particular has
been frequently applied. Thomson, Dulong, Berzelius, and
Lavoisier brought to light many new facts relating to the atomic
weight of nitrogen; unfortunately, however, considerable that
they have presented has been affected by complications that
have introduced inaccuracies.
Dumas and Boussingault* found the mean density of nitrogen
to be 0.972 ; for hydrogen they found a mean density of 0.0693,
which would give nitrogen an atomic weight of 14.026. Reg-
nault obtained a more concordant series of results, the mean
being 0.97137, and a density for hydrogen of 0.0692, which
makes the atomic weight of nitrogen equal to 14.0244.
Clarke gives in detail his computation of the means of the
results obtained by Penny, Stas, and Marignac. Their work on
the determination of the atomic weight of this particular ele-
ment was mainly on the ratio of ammonium chloride and silver,
and the decomposition of certain nitrates. A great degree of
accuracy was maintained throughout the entire investigation ;
but the amount of work required to obtain a single result neces-
sarily lays the method open to a serious error of manipulation.
In this connection a paragraph from Clarke's '* A Recalcula-
tion of the Atomic Weights" may be cited: **The general
method of working upon these ratios is due to Penny. Applied
to the ratio between the chloride and nitrate of potassium, it is
1 Compi. rend.^ 1841—12. 1005.
1046 JOSEPH GILLINGHAM HIBBS. ATOMIC
as follows : A weighed quantity of the chloride is introduced
into a flask which is placed upon its side and connected with a
receiver. An excess of pure nitric acid is added, and the trans-
formation is gradually brought about by the aid of heat, the
nitrate being brought into a weighable form. The liquid in the
receiver is also evaporated, and the trace of solid matter which
has been mechanically carried over, is recovered and also taken
into account.*'
The method indicated in this study, and actually applied with
the results appended, is decidedly less objectionable. In this
method there is no distillation, no precipitate, in fact, nothing
that could involve serious error.
Clarke summarizes the results of Penny, Stas, and Marignac
as follows :
1. From specific gravity of N N = 14.0244
2. ' * ammonium chloride N ^ 14.0336
3. ** ratio number four N =s 14.0330
4. *' silver nitrate N = 13.9840
5. *' potassium nitrate N = 13.9774
6. '* sodium nitrate N = 13.9906
Mean of results for N N = 14.0210
If oxygen is 16, this becomes 14.0291. Stas found the atomic
weight of nitrogen to be 14.044. Dumas found 14 by experi-
ments on the combustion of ammonia and cyanogen (0= 16).
Pelouze found 14.014 by bringing a known weight of silver
nitrate in contact with a known and slightly excessive weight of
ammonium chloride, which excess was titrated. Anderson
found 13.95 by the decomposition of the nitrate of lead, with
just enough heat for decomposition (the same method that was
used by Berzelius). Marignac found 14.02 by dissolving a
known weight of silver in nitric acid and then melting and
weighing the nitrate found.
A. — ATOMIC WEIGHT OF NITROGEN BY ACTION OF HYDROGEN
CHLORIDE UPON POTASSIUM NITRATE.
The purest salt obtainable was dissolved in water, filtered,
and recrystallized six times, a solution of which was tested for
chlorides, sulphates, etc., but no impurity was found. One
more crystallization was made and the best crystals were
WEIGHTS OF NITROGEN AND ARSENIC. IO47
selected. These were washed with distilled water and dried at
210® C. for three hours, powdered, and again dried, and finally
placed in a weighing bottle. This compound was dried before
each experiment. It was also allowed to stand in a balance
case one hour before weighing. The same degree of care was
exercised in the preparation of the boat for weighing.
The weighing bottle was placed on the scale pan and allowed to
stand several minutes in order to regain its normal temperature.
After weighing it was quickly opened and a portion of the salt
removed to* the boat and again closed and allowed to stand in
the balance case for several hours before reweighing. The boat
was then introduced into the combustion tube and the gas
passed over it. The characteristic action took place. The only
difference in the method of procedure adopted here and that
described in the first section of this paper, was a longer time
being given to complete the action, using a lower temperature,
in order to do away with all possibility of fusion of the salt. It
was then carefully removed to a vacuum desiccator and allowed
to stand over night before weighing. It may be said also that
experiments were only conducted on clear days to insure the
non-entrance of moisture.
With potassium nitrate, no great variation of amount was
taken.
Five determinations were made in this case :
«.- - *** •*• sua «*• Oi-z
S« SoS £Si ^lo tt.= t-^lc .S^Sgl 5'=|
0 l« ol- o|« 51-= "S'^l S'S2"S o'S|i:.= 2 --3
Z Zt (SoS u&i: 5s.o u^B u^Sr S^a = 5 <'o5
Gram. Gram. Gram. Gram. Gram. Gram.
1. O.I 1084 0.08173 0.00006 o.cxxxu O.I 1090 0.08177 O.IOII2I 14.01 1
2. 0.14864 0.00960 0.00007 0.00005 0.14871 o.ro965 o. ion 20 14.010
3. 0.21056 0.15525 o.oooii 0.00008 0.21067 0.15533 0.101123 14.013
4. 0.23248 0.17214 0.00012 0.00009 0.23360 0.17223 0.101121 14.011
5. 0.24271 0.17894 0.00013 0.00009 0.24284 0.17903 o. ion 24 14.014
Atomic weight of nitrogen = 14.01 18 ± 0.000472.
The atomic values used in these calculations were taken from
'* Table of Atomic Masses," revised by F. W. Clarke, in Octo-
ber, 1891.
1048 JOSEPH GILLINGHAM HIBBS. ATOMIC
The figures deduced from these values are, of course, subject
to any change made by later revision of atomic weights. It is
not so much the exact figure to which attention is called, as to
the constancy of result brought forward by this method. The
values used were :
Oxygen 16.00
Potassium 39-ii
Chlorine 3S.45
Specific gravity potassium nitrate 2.1
Specific gravity potassium chloride 1.99
B. — ATOMIC WEIGHT OP NITROGEN BY ACTION OF 'HYDROGEN
CHLORIDE UPON SODIUM NITRATE.
The same degree of care and method of procedure were here
observed as in Division A. The results are as follows :
fig «•§ s- s^ s- o'^ ^ ^ tZ
iJS I .2a .2 .2= o «^-3 ^S
•a5 E-g ^6 oS «a wS sss if2
5*^ -SJi ta ts «' ts us; « "s--^ §a
Z ^i: -xc uS uSc uz uSc S^S <o
Gram. Gram. Gram. Gram. Gram. Gram.
1. 0.01550 0.01064 .... .... 0.01550 0.01066 85.061 I4.OII
2. 0.20967 0.14419 0.00009 0.00007 0.20976 0.14426 85.061 14.OII
3. 6.26217 0.18029 0.00012 o.oooc>9 0.26229 0.18038 85.064 14.014
4. 0.66610 0.46805 0.00035 0.00024 0.66645 0.45829 85.064 14.014
5. 0.93676 0.64422 0.00042 0.00034 0.93718 0.64456 85.058 14.008
Atomic weight of nitrogen =3 14.01 16 ± 0.000741.
Atomic values used were
Oxygen 16.00
Sodium 23.05
Chlorine 35.45
Specific gravity sodium chlari(^e 2.16
Specific gravity sodium nitrate 2.26
When these results are compared with those obtained by
Penny and Stas by treatment of potassium chloride with nitric
acid, and the treatment of potassium gitrate with hydrochloric
acid (likewise for sodium), a close comparison can be made.
Penny. Hydrogen chloride method.
For potassium nitrate > * • > 13.9774 For potassium nitrate .... 14.0118
" sodium nitrate 13.9906 " sodium nitrate 14.0116
Sfiowing a difference of
0.0344 for potassium salt,
0.0210 for sodium salt.
WEIGHTS OF NITROGEN AND ARSENIC. IO49
When a mean of the above results is taken, the atomic weight
of nitrogen equals
13.9996 for potassium salt,
14.0011 for sodium salt.
Taking now a mean of these values, the atomic weight of
nitrogen would be 14.0003.
C. — THE ATOMIC WEIGHT OF ARSENIC.
The atomic weight of arsenic has been obtained from the chlo-
ride (AsCl,), the bromide (AsBr,), and the trioxide (As,0,).
Pelouze, in 1845,^ and Dumas, in 1859, determined it by the
titration with known quantities of pure silver in the analysis of
arsenic trichloride. The mean of their results, as computed by
Clarke, giveS the atomic weight of arsenic, 74.829. Wallace*
makes the same titration with silver in the analysis of arsenic
tribromide. His value is 74.046. Kessler made a set of deter-
minations by estimating the amount of potassium bichromate
required to oxidize 100 parts of arsenic trioxide to arsenic pent-
oxide. He obtained a mean value of 75.002.
A mean of these results gives the following :
From AsClj 74 829
** AsBF) 74-046
** ASjO, 75002
General mean # 74-9i8
If oxygen = 16, then the atomic weight of arsenic will equal
75090.
Berzelius, in 1826, heated sulphur and arsenic trioxide
together in such a way that sulphur dioxide alone escaped ; this
method gave 74.840 as the atomic weight of arsenic. But one
experiment was made, so that it does not possess much value.
In the above method there seems to be a wide variation in the
results obtained, the difference between the extreme values is
but little less than one unit.
By the hydrogen chloride method, we have but the weighing
of the material used in the determination — which must neces-
sarily enter every estimation or analysis — and a single weighing
after the action of the acid gas. As in the case of nitrogen, the
method seems to be as short and concise as possible.
1 Compt. rend.^ xo, X047.
sphiLMag.(4), tt, 279.
I050 ATOMIC WEIGHTS OP NITROGEN AND ARSENIC.
The methods and modus operandi were exactly the same as
those used in the determination of the atomic weight of nitrogen.
The sodium chloride obtained was perfectly white in color.
In no instance was it fused. After weighing the salt residue it
showed no traces of arsenic, and was readily soluble in cold
water without residue. The same conditions of atmosphere
were obser\'ed.
As the specific gravity of sodium pyroarsenate could not be
obtained, it was determined by means of the specific gravity bot-
tle, against chloroform, and was found to be 2.205, while the
specific gravity of sodium chloride was taken as 2.16. The
atomic values used were :
Oxygen i6.oo
Sodium 23.Q5
Chlorine 35.45
The results here obtained, besides being to a great degree
constant, compare favorably with those obtained by Pelouze
(74.829) and Kessler (75.002).
A coincidence may here be shown by the fact that the mean
of these values gives 74.9155, while the hydrogen chloride
method gives 74.9158.
In order to give the method a thorough trial, the amounts
taken cover a wide range. The smallest amount used was
0.02176 gram of sodium pyroarsenate, and the largest 3.22485
grams. It will also be noticed that the variation in result is but
0.027 ^or ten determinations.
25 i-c U Ii og ^i i \
0-5 ^.5 =0. c*' 30. aW w^g, vj
-i ^2 -2 ii .2 S V .2 «oo: ^-g
= 5 =•£ weed "5 S «S"S oS Z'^^v JH^
Gram. Gram. Gram. Gram. Gram. Gram.
1. 0.02176 0.01439 o.ooooi 0.00000 0.02177 0.01439 354-oo8 74.904
2. 0.04711 0.03 1 14 0.00002 0.00001 0.04713 0.031 15 354.042 74.921
3. 0.05792 0.03828 0.00003 0.00002 0.05795 0.03830 354.054 74.927
4. 0.40780 0.26970 0.00021 o.oooii 0.40801 0.26981 354.002 74.901
5. 0.50440 0.33028 0.00026 0.00017 0.50466 0.33045 354.033 74.916
6. 0.77497 0.51222 0.00041 0.00027 077538 0.51249 354.034 74.917
7. 0.82853 0.547^ 0.00044 0.00029 0.82897 0.54791 354.034 74.917
8. 1. 19068 0.78690 0.00056 0.00041 1.19K24 0.78731 354.053 74.926
9. 1.67464 1.10681 0.00081 0.00051 1.67545 1.10732 354.057 74.928
10. 3.22485 2.13168 0.00152 0.00099 3-"637 2.13267 354.002 74,901
Atomic weight of arsepic = 74.9158 ± 0.00222.
[Contribution from the John Harrison Laboratory of Chemistry,
No i6.]
THE SEPARATION OF VANADIUM FROM ARSENIC.
Bv Charles Field, 3rd, and Edgar F. Smith.
Received October a. 1896.
AS vanadium and arsenic occur associated in minerals and
likewise in artificial products, their separation becomes a
matter of consequence.
The course usually pursued in carrying out this separation is
that long since recommended for the removal of vanadic acid
from its solutions ; namely, its precipitation as ammonium meta-
vanadate. Other methods have recently appeared in the litera-
ture bearing on analysis. Reference is here made especially to
the publication of Fischer.*
Experiments made in this laboratory on the behavior of vana-
dates' and arsenates' heated in an atmosphere of hydrochloric
acid gas, in which both acids were volatilized, suggested the
thought that if the sulphides of vanadium and arsenic were
exposed to the same vapors perhaps they would show a variation
in deportment. And so it has proved. Perfectly dry arsenic
trisulphide, previously washed with alcohol, carbon disulphide,
and ether, then dried at ioo° C, when exposed in a porcelain
boat, placed in a combustion tube, was almost completely
expelled from the retaining vessel at the ordinary temperature.
The last traces were driven out at a temperature little above
150** C. Brown vanadium sulphide, in a perfectly dry condition,
treated in the same manner, was not altered. It only remained
then to prepare mixtures of known amounts of the two sulphides
and subject them to the action of the acid vapor. To this "end
the following experiments were made :
I. 0.1303 gram of vanadium sulphide,
0.1302 gram of arsenic sulphide.
The arsenic sulphide was volatilized without difficulty and left
0.1297 gi*^™ of vanadium sulphide.
1 Bestimraung von Vanadins&ure : Dissertation, Rostock, 1894.
3/. Am. Chem. Soc., 16, 578.
t/Mf.. 17.6S2.
1 052 SEPARATION OF VANADIUM FROM ARSENIC.
II. 0.1290 gram of vanadium sulphide,
0.2242 gram of arsenic sulphide,
gave after exposure of one hour to hydrochloric acid vapor a
residue of vanadium sulphide, weighing 0.1297 gram.
III. 0.0828 gram of vanadium sulphide,
0.0582 gram of arsenic sulphide,
left 0.0827 gi'sni of vanadium sulphide.
IV. 0.1306 gram of vanadium sulphide,
0.2028 gram of arsenic sulphide,
gave a residue of 0.1308 gram of vanadium sulphide.
V. 0.1403 gram of vanadium sulphide,
0.2409 gram of arsenic sulphide,
left 0.1404 gram of vanadium sulphide.
The temperature in these experiments was not allowed to
exceed 250*^ C, as beyond that point there is danger of affecting
the vanadium and causing its partial volatilization.
The method worked so well and with such evidently favorable
results that the following course was adopted in the analysis of a
specimen of the mineral vanadinite. 0.2500 gram of air-dried
and finely divided material was placed in a porcelain boat : the
latter was then introduced into a combustion tube and gently
heated in a current of dry hydrochloric acid gas. By this treat-
ment vanadic and arsenic oxides were expelled, leaving lead
phosphate and chloride. The receiver containing the vanadium
and arsenic was made alkaline and digested with ammonium
sulphide. From the solution of the sulpho-salts the vanadium
and arsenic sulphides were set free by a dilute acid. After
washing and careful drying these sulphides were separated as
indicated in the preceding lines, then changed to oxides and
determined in the usual manner. The sum of the total con-
stituents determined as lead oxide, phosphoric oxide, vanadic
and arsenic oxides, with some lead chloride, amounted to 0.2501
gram.
The method in addition to being satisfactory in the analytical
way, certainly forms a very excellent means of purifying and
freeing vanadium from arsenic.
[Contribution prom the John Harrison Laboratory of Chem-
istry, No. 17.]
THE SEPARATION OF HANQANESE FROM TUNGSTIC
ACID.
By Walter T. Taggart and Edgar F. Smith.
Received Oc toiler 3, 1896.
THE necessit}' of obtaining pure tungstic acid from time to
time, using wolframite as the starting out material, has
frequently suggested the inquiry as to what course would proba-
bly prove the best in the quantitative separation of this acid
from oxides, such as those of iron and manganese.
In the experiments recorded in this communication only the
results obtained from a study of mixtures of a manganous salt and
a soluble alkali tungstate will be given. The directions taken
in the experimentation were, ist, to effect the separation by the
use of 3'ellow ammonium sulphide in the presence of ammonium
chloride ; 2nd, to eliminate the acid oxide by the use of an
alkaline carbonate.
Following thefirst course, mixturesof definite amounts of ammo-
nium tungstate and manganous chloride were made. To these
was added water and a considerable excess of yellow ammonium
sulphide, together with ammonium chloride. The mixtures
were digested on a water-bath at 70° C, for several hours, and
the vessels containing them were then closed and allowed to
stand during the night. The manganese sulphide was filtered
out, and, after solution, was changed into sulphate and weighed
as such, or it was finally obtained as protosesquioxide in the
customarj' way.
Results,
Manganous oxide
found.
Gram.
0.2I2I
0.2255
O.I 70S
0.1720
0.1760
III every trial tungstic acid adhered to the metallic oxide.
In trying the second suggestion the soluble tungstate and the
Manganous oxide
present.
Gram.
0.1950
0. 1949
0.1290
0.1287
O.1291
I054 SEPARATION OF MANGANESE FROM TUNGSTIC ACID.
soluble manganous salt were digested for some hours in a plati-
num dish, upon a water-bath, with an excess of a ten pe: cent,
potassium carbonate solution, after which the whole was evapo-
rated to dryness, the residue boiled up with water, the mangan-
ous carbonate filtered out, washed, and finally converted into
protosesquioxide.
Results.
Manganous oxide Manganous oxide
present. found.
Gram. Gram.
0.194)9 O.1516
0.1949 0.1534
Several trial were made using a fifty per cent, solution of
potassium carbonate.
Results.
Manganous oxide Manganous oxide
present. found.
Gram. Gram.
O.195I 0.1745
0.1950 0.1528
The experimental evidence given in the preceding paragraphs
leaves no doubt as to the insufficiency of the two methods,
which were tried, in effecting the desired separation. It is
probable that fusion with an alkaline carbonate will alone
answer for this purpose. How complete that course would be
can only be ascertained by careful experimentation.
In the course of analysis molybdenum is quite often obtained
as sulphide. Its conversion into a weighable form is attended
with more or less difficulty. Trials made in connection with its
estimation show that if the sulphide, as generally obtained, be
dried, then intimately mixed with anhydrous oxalic acid, its
careful ignition to trioxide can be made quite rapidly.
Results.
Molybdenum trioxide Molybdenum trioxide
taken. /ound.
Gram. Gram.
0.3000 0.3009
0.3000 0.2990
0.1007 O.IOII
[Contribution prom thb John Harrison Laboratory op Chemistry,
No. i8.]
THE SEPARATION OP BISMUTH PROM LEAD.
Bt Arthur I^ Bbnxbrt akd Bdoar P. Smith.
Received October t. i8q6.
MANY methods have been suggested to effect this separa-
tion. 'In a recent issue of the Zcitschrift fitr angewandte
Chemie (1895, p. 530), Olav Steen reviews thirteen of these
methods and concludes that an early proposal of Rose/ in which
the lead is thrown out as chloride and weighed as sulphate^
another by Lowe,' in which the bismuth is removed as basic
nitrate, and a late suggestion madef by Jannasch,' viz,^ the
expulsion of the bismuth as. bromide from a mixture of lead and
bismuth sulphides by an air current carrying bromine are the
most satisfactory. At least these methods gave Steen the best
results. The separation of bismuth from lead frequently con-
fronts the analyst, and any novelty in this direction cannot be
absolutely devoid of interest, hence the present communication,
which brings data that may perhaps prove of service in the
hands of others who are interested in the solution of this analyt-
ical problem.
It will be recalled that Herzog^ proposed to separate bismuth
from lead by precipitating the former as basic acetate. The
method required considerable time for execution, and in other
hands than those of its author apparently has not yielded entirely
satisfactory results.
An idea closely related to that of Herzog wouM be the sub-
stitution of a formate solution for that of the acetate. This was
done with results that are very interesting.
Solutions of lead nitrate and bismuth nitrate in nitric acid
were made up of such strength that twenty cc. of the first con-
tained 0.2076 gram of lead oxide, and twenty cc. of the second
0.1800 gram of bismuth trioxide. The lead and bismuth were
accurately determined after dilution to a liter. Twenty cc. of
these two nitrate solutions were then introduced into a beaker
1 Ann. ekem, phys. Pi^g.* no, 425.
sy. prakt. Chtm.^ 74, 348.
* Ber. d. ckem, Ges.^ as, 134.
4 Ztsckr. anal. Chem., §7, 650.
1056 SEPARATION OF BISMUTH PROM LEAD.
glass, carefully diluted aud almost neutralized with sodiisn car-
bonate, or until the incipient precipitate dissolved slowly, when
considerable sodium formate solution of sp. gr. 1.084 an^ a few
drops of aqueous formic acid were added. The total dilution of
the liquid was 250 cc. It was gradually heated to boifing and
held at that point for five minutes. The precipitate was then
allowed to subside, but was filtered while yet hot. The basic
formate separates rapidly and is easilj' washed if not boiled too
long. It was washed with hot water, then dissolved in dilute
nitric acid and precipitated with ammonium carbonate. The
'ignited bismuth trioxide weighed too much ; it contained lead.
However, the impure oxide was dissolved in nitric acid, diluted
to 250 cc, and after the addition of sodium carbonate to almost
complete neutralization, sodium formate and free formic acid
were added as before, and the precipitation of basic formate
repeated. This precipitate after solution and the bismuth thrown
out by ammonium carbonate gave 0.1804 gi'am of bismuth
oxide instead of 0.1800 gram as required by theory. Seven
additional separations, in which the quantities of bismuth and
lead were the same as indicated above, gave :
0.1806 gram of Bi^Os.
0.1806 *• "
0.1803 *'
0.1S04 ''
0.1804 "
0.1805 *'
0.1796 *'
The conditions in these determinations were similar to those
previously outlined.
With a solution containing 0.3600 gram of bismuth oxide and
0.2076 gram of lead oxide, operating in an analogous manner,
two results were obtained :
0-3595 gram of Bi,Oj.
0.3605 " •* "
instead of the required 0.3600 gram.
The residual bismuth trioxide was examined for lead, but
none was found.
i( •
c<
(I
<(
(«
[Contributions prom the Chbmicai, Laboratory op ths Univbrsity
OF Cincinnati.]
XLVIII.— ON SOME NEW FORMS OF QAS GENERATORS.*
By Thomas H. Norton.
Received August tj, SS96.
IMPROVEMENTS in the construction of the automatic gener-
ators, for the gases most frequently used in our laboratories,
are always welcome. The following three types, which I devised
some time since, have been subjected to prolonged trial in the lab-
oratory of the University, and have given such satisfactory results ,
that a detailed description would seem worthy of publication.
In Fig. I is represented a gas generator for hydrogen, hydro-
gen sulphide, etc., which differs in several
details from well known types of the same
general outline. It is constructed of glazed
P earthenware, and is easily made in our ordi-
nary potteries. A, the outside container, is
provided with handles on the outside, and is
ordinarily sixty cm. in height. Its chief
peculiarity is the presence on opposite sides of
the inner wall, of the shoulders DDy each
about four cm. wide and slightly concave on
the lower surface. By the gas reservoir, is of
the ordinary bell-jar construction, with orifice
at the top for the introduction of a perforated
stopper and outlet tube. It is provided with
projecting shoulders three cm. wide, corresponding to DD, and
at such a height that they barely slip beneath the latter. At the
bottom are frequent circular perforations, one centimeter in
diameter, to allow of the easy passage of the acid charge. The
recipient C, designed to hold zinc or any solid charge, is pro-
vided with a loose disk perforated with many fine openings and
resting upon the shoulder of the constriction. Beneath the con-
striction are perforations corresponding to those in B. A strong
copper wire or rod, passing through the perforations of both
parts of the apparatus, holds B and C in their mutual position to
each other.
iRead before the American Association for the Advancement of Science at the
Buffalo Meeting.
Fio. I.
I058
THOMAS H. NORTON. SOME NEW
The working of the generator is exceedingly simple. C
receives its charge of zinc, marble or ferrous sulphide, ^is
placed over it. The copper rod is passed through the perfora-
tions at the bottom. B with Cis then introduced into A, and
turned until the shoulders of B are beneath DD. A is then
filled with the acid charge. The buoyancy of B is partly
overcome by the rigid attachment of C, and entirely prevented
by DD, Gas can be drawn off as desired, by opening the tap
at the outlet tube. When, as naturally occurs, the acid in the
lower portion of the generator becomes weak and the evolution
of gas sluggish, the exit tap is closed, B is turned slightly so as
to be free from DD, and is then lifted, by grasping the neck,
along with the holder C, until entirely above the surface of the
acid. Both are then plunged to the bottom of A, and a few
repetitions of this churning movement renders the acid charge
of uniform strength.
This style of generator has rendered excellent ser\nce. For
example, one sixty centimeters in height easily supplies all the
hydrogen sulphide required by a class of thirty in qualitative
analysis. The special advantages of this generator are to be
found in the ease and simplicity with which the buoyancy of the gas
reservoir is overcome and the acid charge is maintained at a
uniform strength until practically exhausted.
In Fig. 2 we have a less compact and less transportable form,
yf but one which maintains the uni-
j][)L form strength of the acid charge
until it is exhausted, without the
need of special manipulation, as
described above. It is particularly
designed for use where small amounts
of hydrogen sulphide are in constant
requisition, as in the laborator)- for
qualitative analysis, and it has the
advantage of being capable of easy
construction from the glassware
found in an}' well equipped labora-
tor}'. /4 is a capacious tubulated
bell-jar inverted and resting upon
Pig. a.
FORMS OP GAS GENERATORS. IO59
either a tripod or the ring of an ordinary support. The perfo-
rated stopper in the neck is traversed by a J tube. One terminal
of this tube is connected with a simple Bunsen valve, B, t\ e,^
a piece of rubber tubing, closed at one end and provided with a
clean cut slit in the rubber some two cm. in length. The other
terminal of the J tube is connected with C in the upper portion
of A, The attachment C is similar to that frequently introduced
between suction pumps and filtering flasks. It is the reverse of
B in its construction, allowing a current of liquid to enter from
the outside through the rubber valve. A serves as a reservoir
for the acid charge. The third external terminal of the \ tube
is connected with the tubulus of the lower portion of an ordinary'
lime drj'ing tower, /?, preferably of the largest size constructed.
Z> serves as the recipient for the ferrous sulphide, etc., which
may be used, and is provided with a perforated disk at E and
the outlet tube F, the latter on a level with the top of A . The
working of the generator is exceedingly simple. A is charged
with acid and D with, say, ferrous sulphide. When /^is opened
the acid flows through C into D, When F is closed the pressure
of the gas evolved forces the acid back into A through B, The
result is that the supply of acid furnished D is alwa3's from the
top of the reservoir -^, and hence stronger than that found in
the lower strata, which are successively of greater specific
gravity, weaker in acid and richer in saline matter, as the bot-
tom is approached. The arrangement permits of a very com-
plete utilization of the acid. When the current of gas is in con-
tinuous demand, and evolution becomes sluggish, it is necessary'
to close the tap at F for a short time until the liquid in D is
driven back into A .
Care must be exercised in constructing the valve at C so that
it will yield to a very slight pressure. To effect this the slit in
the rubber should be at least two cm. in length. When
the apparatus is used exclusively for the evolution of hydrogen
sulphide to be employed" in qualitative analysis, it is desirable to
have beyond F some device which regulates uniformly the
strength of'the current of gas and keeps it within the limits of
easy absorption. In practice this has been accomplished most
simply by introducing into the rubber tube attached to /'a short
io6o
SOME NEW FORMS OP GAS GENERATORS.
piece of glass tubing, one end of which is drawn out so as to
form a very narrow opening.
Essentially the same principle for the control of the strength
of the acid charge is to be found in the generator devised
recently by Professor Harris. In consequence of the costly
character of the latter, due largely to the use of valves of elabo-
rate construction, the form of generator just described may be
welcome to many on account of its simplicity and inexpensive-
ness.
An automatic chlorine generator based upon the use of manga-
nese dioxide, has long been desired. In Fig. 3 is shown such
^"'C^^ a generator which for six years has
rendered satisfactory service, both
on the lecture table and in the
laboratory. The essential parts
only are outlined without the
accompanying supports. ^ is a
copper funnel, provided with a
hollow projection C, on one side,
perfectly similar in make to the
funnels used for hot water filtra-
tion. It can be advantageously re-
placed by the more graceful and
modem type of aluminum funnel,
resting in a ring burner. The res-
ervoir B is of glass, and is an article of current manufacture,
obtainable from all dealers in chemical glassware. The long,
tapering neck is tightly fastened in the neck of the funnel by
means of a section of rubber tubing. A large opening at the
top, closed by a rubber stopper, serves for the admission of
the charge. In a smaller tubulure on the side is a perforated
rubber stopper with outlet tube and tap. The funnel with
its reservoir is held firmly in a support, so that the end of C is
about two cm. above the top of an ordinary burner. A perfo-
rated plate is introduced into j9 so as to prevent solid matter from
falling into the nalrow neck. The latter is connected at Z? with
a large tubulated bottle E^ which serves as a reser\'oir for hydro-
chloric acid, and is attached to a support so that it can be raised
Fio. 3.
MINERAI. CONSTITUBNTS OF THE WATERMELON. IO61
or lowered at will. When in use B is filled to two-thirds of its
capacity with manganese dioxide, large lumps alone being used,
as powdered mineral may easily cause a stoppage of the connec-
tions. E is filled with hydrochloric acid and raised to a level
slightly above the top of B, Water is poured into the funnel A
until it is nearly full, and a lamp is placed under C As soon as
the temperature has reached about 80°, a very small flame suf-
fices to maintain the activity of the generator. When th& exit
from ^ is open, the acid enters and the evolution of chlorine
continues until checked by closing the tap, when the acid is
driven back into E. A slight agitation of the latter before
opening the tap serves to prevent the accumulation of a stratum
of weak acid at the bottom. It is advisable to lower the reser-
voir E when a current is not required, so as to avoid pressure
and any possible escape through minute leaks. In practice it
is also found desirable to connect the opening of ^ by a
flexible tube with a bottle of caustic soda solution, the tube ter-
minating at the surface of the solution. This prevents any
escape into the surrounding air of chlorine, with which the con-
tents of E are soon saturated. When thus arranged a current
of the gas can be taken at will from the generator, the sole con-
dition being the maintenance of a small flame beneath C The
manifold advantages of such a device, especially for the lecture
table, will be appreciated by all who attempt an extended series
of experiments with chlorine. As described above the genera-
tor can be readily constructed from pieces of apparatus ordinarily
found in a well equipped laboratory. I have found a generator
in which the reservoir B contains 1500 cc, a very convenient
size for use in the lecture room.
MINERAL CONSTITUENTS OF THE WATERHELON,
By Gbokob F. Paymb.
Received September a8. iap6.
THE watermelon is not a crop that is widely grown even in
this country with great success. It is this very reason
which makes it a desirable crop to handle in Georgia, as the
watermelons in this state attain finer flavor, crispness, juiciness
and sweetness than anywhere else in the world.
I062 MINER At CONSTITUENTS OP THE WATERMELON.
Upon analysis of two medium-sized watermelons cut up and
mixed together, we found them to contain just one-third per
cent, of pure ash, calculated as free from carbonic acid. The
exact figures were 0.3338, which in our calculations we will
round off into an even one-third, which it practically is.
The composition of watermelon ash is as follows :
Per cent.
Sulphur trioxide 4.41
Calcium oxide 5.54
M&gnesium oxide 6.74
Potassium oxide 61. 18
Sodium oxide 4.31
Silicon dioxide 2.15
Phosphorus pentoxide 10.35
Chlorine 4.94
Iron sesquioxide 0.48
Total 100.00
A good average crop of watermelons is considered to be about
one-half carload to the acre, though much larger crops than this
are sometimes made. Large watermelons are also considered
desirable, hence in considering what is carried off from the land
by the removal of the crop, it is well to consider how much
would be taken off by a large crop, as it is the large crops which
we desire to produce. We have before us a report of a crop of
watermelons upon an acre of land which is an unusually large
one, but which was weighed up in the presence of disinterested
witnesses and sworn to by them as being honestly grown upon an
acre and correctly weighed. This crop weighed 39,766 pounds.
One-third percent, of such a crop would be pure ash, and conse-
quently the mineral plant food taken out of an acre of land b^
such a crop would be as follows :
* Pounds.
Sulphur trioxide 5.85
Calcium oxide 7.34
Magnesium oxide 8.93
Potassium oxide 81.09
Sodium oxide 5.71
Silicon dioxide 2.85
Phosphorus pentoxide 13-59
Chlorine 6.55
Iron sesquioxide 0.64
ToUl 132.55
A MODIFIED FORM OF THB BBULLIOSCOPB. IO63
In the crop mentioned above to replace the phosphoric acid
and potash carried off from one acre by the melons alone, not
taking into account the vines and roots, would require :
Pounds.
Acid phosphate (thirteen per cent. PsO^) 100
Muriate of potash (fifty per cent. K,0) 160
A fair crop of melons upon good land, however, is usually
considered to be about one-third of the above large crop or about
one-half carload. II we estimate then the amounts of phos-
phoric acid and potash required for an average crop of fair char-
acter, such a crop will take from the soil materials to replace
which will require about :
Pounds.
Acid phosphate 33 J
Muriate of potash 53}
This will give about four and one-half pounds of available
phosphoric acid to an acre, and about twenty-seven pounds of
pure potash to an acre. The usual goods on the market guar-
antee about ten per cent, of available phosphoric acid and about
one per cent, of potash. The use of 300 pounds of such goods
upon each acre of watermelons, furnishes thirty pounds of avail-
able phosphoric acid, or about six and one-half times as much
as is needed to replace what is carried off by the watermelons.
It also furnishes about three pounds of potash, which is only
one-ninth of what is carried off by the crop removed. This being
the case it shows with what advantage and economy the water-
melon grower can replace a large proportion of his phosphoric
acid with potash.
[Contribution prom ths Chemical Laboratory op the U. S. Depart-
ment OF Agriculture, No. 22.]
A MODIFIED FORM OF THE EBULLIOSCOPE.
BY H. W. Wiley.
Received September a6, 1896.
THE determination of the alcohol in wines and beers, from
the temperature of the vapors given off on boiling at
atmospheric pressures, has long been practiced. The instru-
ment by means of which this determination is made is known as
the ebuUioscope or ebulliometer. The use of this instrument
I064 H. W. WILEY.
was proposed many years ago by Tabari6, and it has been
improved by Malligand, Salleron and others.
It is evident that if so simple an apparatus could be made to
give accurate data, it would come into general use for ordinary
purposes. The difficulties which have attended the use of the
ebullioscope, however, have been of such a nature as to render
the data given by it somewhat unreliable. Among these difiS-
culties may be mentioned the fact that a wine or beer contains
a considerable quantity of dissolved matters, which serve to
render the temperature of the boiling liquid higher than the
temperature of a mixture of a similar percentage of alcohol with
water. While the temperature of the vapors emitted are, theo-
retically, not influenced in a marked degree by the initial tem-
perature at which they are formed, nevertheless, in practice it
has been shown that the tendency of the higher initial boiling
point is to give a higher reading to the thermometer whose bulb
is sutrounded by the emitted vapors.
Another difficulty attending the use of the ebuUioscope is
found in the fact that the percentage of alcohol in the vapors
emitted is much greater than in the residual liquid. As a result,
it is difficult to establish a balance between the condensed vapors
and the liquid remaining in the flask, in such a manner as to
secure a continuous evolution of a vapor containing a definite
proportion of alcohol.
In the third place, it has been customary to return the con-
densed vapors through the apparatus in such a way that they
come in contact with the uncondensed vapors surrounding the
thermometer. By this means the vapors surrounding the bulb
of the thermometer are subjected to changes of temperature
which render it difficult to get a mean reading of the height of
the mercurial column in the instrument. The variations which
the mercurial column may undergo amount, in some instances,
to two or three-tenths of a degree and as each tenth of a degree
represents approximately a tenth of a per cent, of alcohol, it is
not difficult to see that these variations would tend to lead to
erroneous results.
In the fourth place, barometric changes, which are constantly
taking place in the atmosphere, change the boiling point of the
presented, an effort has been made
A HODIFIBD FORM OF THS BBULLIOSCOPE. lo6s
vapor of water so that it is frequently necessary to clieck the
instrument with pure water, in order to have an initial tempera-
ture for the calculations.
In the apparatus which is
to remedy the difficulties
which hive been mentioned
above. The apparatus con>
siats of the flask F. which
is closed by a rubber stop-
per carrying the large ther-
mometer B and a tube lead-
ing to the condenser D.
The vapors which are given
oS during ebullition are
condensed in D and return
to the flask through the
tube, as indicated in the
figure, entering the flask
below the surface of the
liquid therein.
The flask is heated by a
gas lamp and is placed
upon a circular disk of as-
bestos in such a way as to
entirely cover the hole in
the center of the asbestos
disk , which is a little small-
er than the bottom of the
flask. The whole appara-
tus is protected from exter- \
nal influences of tempera- < s^
ture by the glass cylinder E, which rests upon the asbestos disk
below and is covered with a detachable, stiff rubber cloth disk
above.
The thermometer C indicates the temperature of the ambient
air between FatiA E. The reading of the thermometer ^ should
always be made at a given temperature of the ambient air, as
indicated by C. The tube leading from the top of the conden-
I066 H. W. WILEY.
ser D to the left, is made long and is left open at its lower
extremity, in order to secure atmospheric pressure in /% and at
the same time prevent the diffusion of the alcohol vapors
through D,
The flame of the lamp is so regulated as to bring the tem-
perature of the thermometer C to about ^ in ten minutes
for substances not containing over five per cent, of alcohol.
After boiling for a few minutes, the temperature, as indicated in
the thermometer B, is constant, and the readings of the ther-
mometer should be made at intervals of about half a minute for
two minutes. Some pieces of scrap platinum placed in the flask
will prevent bumping and secure a more uniform evolution of
vapor.
Slight variations, due to the changes in temperature of the
vapor, are thus reduced to a minimum effect upon the final
results.
The apparatus is easily operated, is quickly charged and dis-
charged and with it at least three determinations of alcohol can
be made in an hour.
The thermometer used is the same as is employed for the
determination of freezing and boiling points in the ascertain-
ment of molecular weights. The reading of the thermometer is
arbitrary, but the degrees indicated are centigrade. The ther-
mometer is set in the first place by putting the bulb in water
containing sixteen grams of common salt to loo cc. When the
water is fully boiling, the excess of mercury is removed from
the column in the receptacle at the top and then, on placing in
ordinary boiling water, the column of mercury will be found a
little above the 5° mark. This will allow a variation in all of 5**
in the temperature, and a thermometer thus set can be used for
the estimation of percentages of *alcohol from one to five and a
half, by volume. When the liquor contains a larger percentage
of alcohol than this, it is advisable to dilute it until it reaches
the standard mentioned.
In order to avoid frequent checking of the thermometer, ren-
dered necessary by changes in barometric pressure, I use a sec-
ond apparatus made exactly as the one described, in which
A MODIFIED FORM OF THE BBULLIOSCOPE. IO67
water is kept constantly boiling. It is only necessary in this
case to read the two thermometers at the same instant in order
to make any necessary correction required by changes in baro-
metric pressure.
It is not my purpose here to submit a table showing the per-
centages of alcohol corresponding to any given depression in the
temperature of the boiling vapor. It is only necessary to call
attention to the fact that for the percentages named, the platted
line showing the variation in depression from o** to five per
cent, by volume of alcohol is practically straight and that for
each 0.8° change in the boiling point of the vapor, there is a
change of about one per cent by volume of alcohol. This rule
can be safely applied for practical purposes to all liquors con-
taining not more than five and five- tenths per cent, of alcohol.
For instance, if, in a given case, the temperature of the vapor of
boiling water, as marked by the thermometer, is 5.155'', and the
temperature of the vapor of a sample of beer is ^2.345°, the depres-
sion is equivalent to 2.810°, and the percentage of alcohol by vol-
ume is therefore 2.81 divided by 0.80= 3.51.
The thermometer used is graduated to hundredths of a degree
and is read by means of a cathetometer, which will easily give
readings to five thousandths of a degree.
The reading of the thermometer is facilitated by covering the
bulb with a test-tube containing water. The high specific heat
of the -water distributes evenly any little variations of tempera-
ture which otherwise would cause the mercurial column in ther-
mometer B to oscillate. The water jacket also serves as a pro-
tection against the projection of any particles of the boiling
liquor directly against the bulb of the thermometer.
It is believed that this apparatus is the best form of ebullio-
scope which has yet been offered for practical use to analysts.
VOLUHETRIC DETERHINATION OF ACETONE.'
By Edward R. Squibb.
Received November 9. it90.
IN the Afoniteur Scientijique oi 1893, 41, 4 Serie, Vol. 7, i^'.p.
272-274, MM. J. Robineau and G. Rollin publish a paper
entitled, ** Dosage Volumetrique de L'Acetone," and the fol-
lowing is, first, a free translation and abridgement of this paper;
and second, the detail of an improvement of the process whereby
it is rendered easier, more simple, quicker, and better adapted
to technical uses, whilst still sufficiently accurate for most pur-
poses.
FIRST, FREE TRANSLATION.
The common way of determining the proportion of acetone in
a liquid containing it is to convert the acetone into iodoform by
means of iodine in the presence of soda after eliminating from
the liquid everything that would interfere with the proper reac-
tion.
For this process binormal solutions of iodine and of sodium
hydroxide are used, and the precipitated iodoform is washed,
dried, and weighed, or is dissolved in ether, and the whole or
a fraction of the ethereal solution is dried over sulphuric acid
and weighed.
The appreciable volatility of iodoform at ordinary tempera-
tures introduces a source of error that is objectionable, especially
when dealing with small quantities.
But, aside from this, the time required for this process is rela-
tively so long that we have sought to change it to a volumetric
process that is mor^ rapid.
Our proceeding consists in mixing the acetone with a solution
of potassium iodide and sodium hydroxide, and then transform-
ing it into iodoform with a titrated solution of a hypochlorite.
The end reaction is indicated by the appearance of a blue color,
when a drop of the liquid is touched with a drop of bicarbonated
starch solution.
From the quantity of hypochlorite used the quantity of ace-
tone is deduced.
1 Read before the New York Section of the American Chemical Society, November
6th, 1896.
VOLUMETRIC DETERMINATION OF ACETONE. IO69
For it happens that the presence of even the smallest trace of
an alkaline hypoiodite, in a solution of soda, gives a blue color
with a starch solution which contains an excess of sodium bi-
carbonate.
Again, a liquid containing acetone, an iodide and caustic soda
in excess, and into which a solution of hypochlorite is passed,
gives no reaction with bicarbonated starch until the whole of
the acetone is converted into iodoform.
This proceeding, however, only gives constant results when
certain precautions are taken. Unless the liquid containing the
acetone be sufficiently alkaline, an excess of hypochlorite will
be required to decompose aH the acetone.
The potassium iodide must be in excess.
The dilution must be fairly uniform, and the concentration of
the hypochlorite about the same for the different titrations.
The process should not be used in too strong a light.
It is very important that the liquid should be constantly
stirred during the additions of the hypochlorite.
The strength of the hypochlorite solution is ascertained by
trial against a pure acetone made by the bisulphite process.
PREPARATION OF THE HYPOCHLORITE.
For the titration of liquids containing considerable proportions
of acetone, the hypochlorite solution is prepared as follows :
To 500 cc. of the concentrated solution of sodium hypochlorite
of commerce, which tests from forty-five to fifty-five volumes of
chlorine, an equal measure of water, and ten cc. of solution o*
pure soda of 36° B., are added, and the solution is kept in an
amber colored bottle, well corked.
TITRATION OF THE HYPOCHLORITE SOLUTION.
About two grams of pure acetone from bisulphite is weighed
off and diluted to 500 cc.
Then ten grams of pure potassium iodide is put into a conical
Bohemian beaker and 100 cc. of the diluted acetone and twenty
cc. of solution of caustic soda of 28° B. are successively added,
and the whole is stirred until the iodide is dissolved and the
liquid is homogeneous.
lOyO EDWARD R. SQUIBB.
Into this the hypochlorite solution is passed drop by drop
from a burette, with constant stirring, precipitating the iodoform
in large flakes which easily settle out. When farther additions
of the hypochlorite give but a light cloudiness a drop of the
liquid is transferred to a white porcelain plate by means of a
glass rod and is there brought in contact with a drop of the
bicarbonated starch solution. As soon as the hypochlorite is in
excess the blue color appears very distinctly. The volume of
hypochlorite used is then read off from the burette, and then
for security of result the titration is repeated.
Example, — 2.081 grams pure acetone is weighed off and diluted
to 500 cc ; 100 cc. of this solution requires 22.5 cc. of the hypo-
chlorite. This gives for each cc. of hypochlorite 0.01874 gram
of pure acetone. These results are liable to vary a little if the
conditions of the experiment vary much. The stirring is sup-
posed to be constant, and the hypochlorite solution to be regu-
larly added.
If to 100 cc. of the diluted acetone 100 cc. of water be added
and the same quantities of iodide and soda as above, 22.05 <^-
of hypochlorite is required instead of 22.5 cc. In using forty cc.
of the soda solution instead of twenty cc, twenty-two cc. of the
hypochlorite is required. In using sixty cc. of soda solution
instead of twenty cc. , 21.6 cc. of the hypochlorite is required.
In using ten cc. of soda instead of twenty cc, twenty-three
cc of the hypochlorite is required.
These results show that dilution of the acetone and a small
excess of soda have but little influence, but that a deficiency in
alkalinity has a very considerable effect on the quantity of hypo-
chlorite required. And farther, that the alkalinity indicated by
twenty cc of soda solution of 28** B. appears to be normal.
Under the given conditions of alkalinity and dilution the rela-
tions between acetone and the available chlorine of the hypo-
chlorite is obviously one molecule of acetone to six . atoms of
chlorine.
The solution of hypochlorite used by us was the liquor of
Penot, testing 21.56 volumes.
The titration of the hypochlorite with pure acetone may be
, 39'9S per cent, ace-
tone.
VOLUMETRIC DETERMINATION OP ACETONE. IO7X
omitted, simply determining the available chlorine of the liquor
of Penot instead, but we prefer the titration with pure acetone.
DETERMINATION OF ACETONE IN A COMPLEX LIQUID.
We give as an example of this the titration of a complex
liquid made with precision, which liquid has served us to con-
trol the accuracy of the process.
The complex liquid contained :
I • 5 10 grams water,
1 .677 * * ethyl alcohol,
1.550 ** methyl alcohol, pure
3.149 ** acetone, pure from bisulphite ^
Of this mixture 3.2445 grams was weighed o£f and diluted to
500 cc. Proceeding as before 100 cc. of this dilution, ten grams
of potassium iodide, and twenty cc. of soda solution of 28** B.
required 13.85 cc. of the hypochlorite. This by calculation
gives 39.99 per cent, of acetone, and thus verifies the composi-
tion of the complex liquid ; and it is seen that the presence of
ethyl alcohol is without influence on the result.
The effect of the presence of paraldehyde in the same complex
liquid was tried by a similar titration.
To 100 cc. of the complex solution corresponding to 0.4162
gram of pure acetone, ten cc. of an aqueous solution containing
five per cent, of pure paraldehyde was added (say one-half
gram) or a little more paraldehyde than acetone. This mixture
took 22.4 cc. of the hypochlorite instead of 22.2 cc. as required.
This variation is slight for the relatively large proportion of
paraldehyde, and is greater for larger proportions, but instances
are rare in which paraldehyde is present in such proportions.
In all such instances where the presence of the aldehyde has
been established by the process of Bardy, the acetone should be
purified by this process before titration.
For the determination of acetone in very dilute solutions a
solution of hypochlorite of one-fifth of the above strength is pre-
ferred. That is, a solution containing four or five volumes of
available chlorine, and the degree of alkalinity should be pro-
portionately reduced.
With a little practice it is easy to judge as to how much ace-
tone is present in a liquid to be titrated, and from this to judge
I072 EDWARD R. SQUIBB.
of the corresponding quantity of hypochlorite required, and in
this way keep the conditions of the method nearly uniform, and
the more uniform the conditions the more constant the results.
This process has the great advantage of being rapid, and thus
of permitting a number of titrations being made in a short time
with results sufficiently accurate,
REMARKS.
The reaction used in this titration is very delicate, and where
traces of acetone are concerned it is better seen when there is
excess of iodide and of soda and but little hypochlorite. An
aqueous solution of 0.004 gram of acetone in the liter gives
a heavy cloudiness immediately. The reaction with 0,0012 gram
of acetone in the liter is seen in a few moments. With 0.0008
gram to the liter the reaction is difficult to see. This reaction
should not be made in a bright light. In sunshine or in a very
bright light the traces of iodoform produced disappear vexy
rapidly, the liquid becoming clear, but in a dim light the pre-
cipitate does not disappear.
The titrated solution of hypochlorite should be kept in amber-
colored glass in a cool place and sheltered from bright light.
The titration should be frequently repeated, because it varies
rather rapidly, especially when diluted. We have made a series
of experiments on this point, which strikingly show these varia-
tions under different influences. A solution of hypochlorite
prepared for titrations gave 22.16 volumes of available chlorine;
kept in a cool place, in obscurity for six days, it gave 21.96; kept
in colorless glass, corked, in a bright light, most of the time in
sunlight, for seven days, it gave 12.32. In a water-bath at
100^ C. for a quarter of an hour it gave, when cooled, 19.48.
END OF TRANSLATION.
•
The rapidly increasing uses of acetone in the three years that
have passed since the publication of this important paper of
Robineau and Rollin have given to it so much additional impor-
tance that it seemed well to the present writer — who ejirly
adopted this volumetric method — to attempt to modify the
method in the direction of greater simplicity and rapidity, even
VOLUMETRIC DETERMINASTION OF ACETONE. IO73
if this should be at the cost of a little of its accuracy. As ace-
tone comes more and more to take the place of both ethyl and
methyl alcohol as much the better solvent for most purposes,
and as its manufacture is cheapened, it becomes more and more
desirable to have a rapid and easy way of estimating its propor-
tions in mixtures or under conditions to which specific gravity
is not applicable.
Therefore, taking the above quoted paper as a basis, and giv-
ing full credit to the authors of it for every important principle
and step of the method , the following slight modifications are offered
as the result of about three months' experience with the original
process and over a year's experience with the modifications.
STANDARD SOLUTION OP ACETONE.
A flask of TOO cc. capacity containing about fifty cc. of dis-
tilled water is carefully weighed. To this is added about thir-
teen cc. of pure acetone, made by the bisulphite process. The
weight is then again taken, when it will be found that the ace-
tone added is a fraction more or less than ten grams. The dilu-
tion is then transferred to a measuring flask, the weighing flask
being rinsed in and is farther diluted with distilled water until
each ten cc. of the dilution contains one-tenth gram of acetone.
This is kept in a well stoppered bottle of dark glass, for,
although the writer has no evidence of any change taking place
in acetone, and believes it to be quite as permanent as ethyl
alcohol, still it may be well to keep a dilute standard solution
protected against bright light.
Of this solution or dilution ten cc. equal to one-tenth gram of
acetone, is accurately measured off for each titration of the solu-
tion of hypochlorite.
SOLUTION OP POTASSIUM IODIDE.
Of this salt 250 grams are dissolved in distilled water, and
the solution is made up to one liter, when each ten cc. will con-
tain two and a half grams of the iodide.
SOLUTION OP SODIUM HYDROXIDE.
Of commercial caustic soda, purified by alcohol, 257 grams is
dissolved in distilled water, the solution made up to one liter,
I074 BDWARD R. SQUIBB.
and set aside until it settles quite clear. Then 850 cc. of clear
solution is poured off and added to the solution of potassium
iodide, making 1,850 cc. of total solution.
Of this solution twenty cc. is taken for each titration.
The remainder of the soda solution is again allowed to settle
clear for farther use in the hypochlorite solution.
SOLUTION OF SODIUM HYPOCHLORITE.
The officinal solution of chlorinated soda of the U. S. Pharma-
copoeia (**Liquor Sodae Chloratae," U. S. P.) answers very well
for this process, the officinal strength of two and six-tenths per
cent, of available chlorine being quite convenient.
To a liter of this solution in a bottle of dark glass, twenty-five
cc. of the above described clear soda solution is added and the
mixture well shaken.
If in buying the ** Solution of Chlorinated Soda" of the U. S.
P. for this process it should be found, as is not unfrequently the
case, weaker than is required by the U. S. P., or, if by keep-
ing it becomes weaker, this will be at once discovered on
balancing it against the standard acetone solution, and so long
as the one-tenth gram of acetone does not require more than say
twenty cc. of the more dilute hypochlorite, the formula need
not be modified.
If there be much of this titration to do it is very convenientto
fit this bottle with an automatic zero burette,' as shown in the
following illustration, this form being, so far as is known, origi-
nal with the writer and very convenient for general rapid work-
ing with a burette. The advantage is, beside that of rapid and
easy working, that it does not require a special burette and is
easily fitted up from the resources of any laboratory.
BICARBONATED STARCH SOLUTION.
Starch, 0.125 gram, is mixed with five cc. of cold water, and
then added to twenty cc. of boiling water and boiled. When
cold two grams of sodium acid carbonate is added and stirred
until dissolved. Kept in a colorless bottle this solution does not
sensibly diminish in delicacy or reaction in three months. But
for how much longer it would remain good for this reaction was
not tried.
1 This Journal, i6, 145.
1076 EDWARD R. SQUIBB.
THE TITRATION.
The burette being filled with the solution of sodium hypo-
chlorite, ten cc. of the standard solution of acetone (equal to one-
tenth gram of acetone) is measured into a beaker of about fifty
cc. capacity, and twenty cc. of the mixed solution of iodide and
soda is added and stirred well. Into this the hypochlorite solu-
tion is passed in rapid dropping, with constant stirring, until
eight or ten cc. has been run in. Then the precipitated iodo-
form is allowed to settle out, and a drop or two more hypo-
chlorite is added. Should this produce a dense cloudiness one-
half cc. more hypochlorite is added, and well stirred and again
allowed to settle. Then a drop or two more of hypochlorite is
added. If there should still be a cloudiness, another one-half
cc. of the hypochlorite is added and well stirred, and so on until
the cloudiness is very slight. Then the starch testing begins.
A small drop of the liquid is transferred by a rod to a white
porcelain tile or plate, and a similar small drop of the starch
solution is placed very near it. Then with the first rod the
drops are made to connect by a fine line, so that the whole has
a dumb-bell form. If there be no blue color, one or two-tenths
cc. more of the hypochlorite is added and well stirred, and the
testing is repeated, until finally a blue line will be seen at the
moment of contact of one drop with the other. If the last nega-
tive testing has taken 10.4 cc. from the burette, and this posi-
tive testing, which has given the blue line, required 10.6 cc.,
then the accepted reading would be 10.5 cc, and this would be
the hypochlorite equivalent of one-tenth gram ^f acetone. If
the blue line be very faint, it will be momentary only, and will
indicate that the excess of hypochlorite is very small, and that
10.6 cc. is a closer reading than 10.5, but the process is not
sufficiently accurate to take much account of such differences,
since even with much experience and great care it is hardly
practicable to get any two titrations to agree within one-tenth
cc. of hypochlorite.
Having then 10.5 cc. as the hypochlorite equivalent of one-
tenth gram of acetone at this time, it is easy to estimate any
smaller or larger quantity of acetone that requires a smaller or
VOI,UM£TRIC DETERMINATION OI^ ACETONE. IO77
larger quantity of the hypochlorite by the equation 10.5 : o.i : :
a : X.
But this hypochlorite solution is liable to diminish in strength
by keeping, and therefore must be standardized by this standard
acetone solution as often as the accuracy .of the determinations
may require. At times the change in strength is scarcely per-
ceptible from day to day in several successive day's work, but
in standing for a week or two there will always be a falling off
in strength to the extent of one-tenth to five-tenths cc. in the
h3rpochlorite. The addition of the soda solution appears to ren-
der the h3rpochlorite more permanent, just as the sodium bicar-
bonate renders the starch solution more permanent. But in the
case of the starch the blue reaction does not occur if the bicar-
bonate be not present.
The titration of the acetone present in unknown dilutions re-
quires first that the strength should be estimated by known con-
ditions or by sensible properties, in order to keep the proportions
of the reagents and the dilutions approximately the same, or at
least not differing very widely when close determinations are re-
quired. If then the taste and smell should indicate that the ace-
tone to be tested is below twenty-five per cent., four- tenths cc.
may be taken for the testing. If over twenty-five per cent, and
under fifty per cent., two-tenths cc. may be taken. If over fifty
per cent., one-tenth cc. is sufficient.
For the adjustment of these small quantities with a sufficient
degree of accuracy for rapid technical working, it is convenient
to have a five-tenths cc. pipette divided in o.oi cc. fitted with a
rubber bulb, as shown in the illustration. By screwing the neck
of this bulb up or down upon the glass, with the point in the
liquid, close measurements may be quickly made.
A beaker of fifty cc. capacity containing ten cc. of water is
weighed and the weight noted. The four- tenths, two-tenths, or
one-tenth cc. of the sample to be titrated is delivered in the water
and the weight again taken to give the qyantity of the sample
taken for the titration. Then the twenty cc. of the iodide and
soda solution is added, the whole well stirred, and the hypo-
chlorite dropped in, and the end reaction managed precisely as
described in standardizing the h3rpochlorite, and the quantity of
1078 VOI^UMBTRIC DETERMINATION OP ACETONE.
h3rpochIorite used is noted. Then as 10.5 cc. of the hypochlorite
is to one-tenth gram of acetone, so is the quantity of hypochlorite
now used to the quantity of acetone present in the portion of the
sample taken for titration. Then as the weight of this portion
taken for titration is to the quantity of acetone found in it, so is
100 to the percentage of acetone in the sample.
For example, a sample supposed to be not far from absolute is
to be titrated. A fifty cc. beaker with ten cc. of water weighs
25-283 grams; with one-tenth cc. of the sample added the
weight becomes 25.360 grams, giving 0.077 gram as the weight
taken for the titration. To this is added the twenty cc. of iodide
and soda solution, and the mixture being well stirred, the hypo-
chlorite is dropped into saturation when seven and nine-tenths
cc. is found to have been used. Then as 10.5 is to one-tenth, so
is seven and nine-tenths to 0.0752 gram of acetone in the 0.077
gram of the sample taken. Then as 0.077 gram of the sample
taken is to the 0.0752 of acetone indicated, so is 100 to 97.66 per
cent, of acetone in the sample.
This is the rationale of the operation, but the calculation is
shortened by simply dividing the standard hypochlorite (10.5 cc. )
into the hypochlorite required (seven and nine-tenths cc.)toget
the corresponding acetone (0.0752 gram), and then dividing the
weight of the sample taken (0.077 gram) into the weight of ace-
tone obtained from it (0.0752 gram) to get the percentage pro-
portion of the acetone. (97.66 per cent.).
Of course the method of definite dilution, and the titration of
an aliquot part, as described in the original paper of Robineau
and RoUin (see translation) is available and more accurate than
that here recommended, and takes but little more time.
Where acetone is made, or is much used, and especially in
processes where it is recovered by distillation to be used over
again, there is often much need of testing the strength of very
weak dilutions, and of knowing when acetone is absent. In
many such uses accuracy is not required and rough estimates
are sufficient. For work of this kind, • especially when the
strength is below ten per cent., the weighing of the sample to be
tested may be omitted, because the specific gravity is so nearly
DFTBRMINATION OF SULPHUR IN CAST IRON. IO79
that of water that the measura may be accepted as cubic centi-
meter for gram.
DETERMINATION OP ACETONE IN THE PRESENCE OP ETHYL
ALCOHOL.
The standard dilution of acetone containing ten grams in the
liter was used, and ten cc. of this required 14.3 cc. of the h3rpo-
chlorite solution. On repetition 14.4 cc. was. required.
A dilution of ethyl alcohol was made containing ten grams in
the liter, and ten cc. of this requires one-tenth cc. of the hypo-
chlorite. On repetition 0.125 cc. was required.
To ten cc. of the acetone dilution two-tenths cc. of the alcohol
dilution was added, and this mixture required 14.4 cc. of the
hypochlorite solution. On repetition 14.4 cc. again was required.
To ten cc. of the alcohol dilution two-tenths cc. of the acetone
dilution was added, and this mixture required 0.35 cc. of the
hjrpochlorite. On repetition four-tenths cc. was required.
In each case ten cc. of the iodine and soda solution was used
and all other conditions were kept fairly uniform.
In the case wherein the hypochlorite was added to alcohol
alone no precipitate nor cloudiness was visible, although o.i
to 0.125 cc. was required to obtain the starch reaction. When
acetone had been added to the alcohol one-half this quantity of
the hypochlorite was suflScient to give decided cloudiness.
These results appear to confirm the conclusions of Robineau
and RoUin to the effect that the presence of ethyl alcohol has no
effect upon the titration of acetone by this method, although
ethyl alcohol is an iodoform-yielding substance. The small
quantity of hypochlorite required to obtain the starch reaction
when alcohol alone was titrated was probably in consequence of
traces of impurity in the alcohol.
THE DETERMINATION OF SULPHUR IN CAST IRON.
By Francis C. Phillips.
Received November 10, 18B6.
IN a paper read before the American Chemical Society in
August, 1895,' I have detailed some experiments made in
the determination of sulphur in white cast iron by the evolution
method, and have attempted to show that the loss of sulphur in its
iThU Journal, 17, 891.
I080 FRANCIS C. PHILLIPS.
determination in such iron may be due to the formation of
organic sulphur compounds not oxidizable to sulphuric acid by
the usual means.
By passing the gases evolved during the solution of the iron
in hydrochloric acid through a heated porcelain tube it was found
that the volatile organic sulphur compounds may be decom-
posed and nearly all the sulphur recovered by conversion into
hydrogen sulphide, oxidation and precipitation as barium sul-
phate.
In judging of the correctness of an analytical method it has
been necessary in the case of the majority of the constituents of
iron to depend upon a single criterion ; that method is regarded
as most accurate which, being correct in its details, yields the
highest percentage of the constituent sought to be determined.
For it is hardly possible to add to pure iron a known percentage
of sulphur, phosphorus or carbon, and test the method by a
determination of the added constituent. For the determination
rf sulphur in iron it has been common to regard the method of
oxidation and solution of the iron by nitric acid, followed by
precipitation of the sulphur in form of barium sulphate as the
most accurate, inasmuch that it yields results somewhat higher
than those obtained by other modes of procedure.
It does not seem probable that an appreciable error could
occur in the use of this method unless, in the simultaneous oxi-
dation of the carbon and sulphur of the iron, an organic sulphur
compound should be formed.
It has seemed to be of interest, however, to apply a method
for the determination of sulphur by which all the constituents of
the metal could be completely oxidized in a dry state and at a
high temperature, in order to avoid as eflfectually as possible
the chances of loss due to the conversion of sulphur into a vola-
tile compound not oxidizable by ordinary means to sulphuric
acid.
In searching for a method which should answer these require-
ments, it seemed possible that by heating the iron in the form of
fine powder in presence of a mixture of alkaline carbonate and
nitrate the sulphur might be oxidized directly and completely
to the condition of a sulphate without affording an opportunity
DETERMINATION OF SULPHUR IN CAST IRON. IO81
for the escape of a trace of sulphur in some intermediate volatile
or soluble compound. Accordingly an experiment was tried in
the following way :
An iron containing its carbon in the combined form was
melted in a crucible and poured while fused into water. The
granulated metal was crushed in a steel mortar to an extremely
fine powder. The powder so obtained was sifted through bolt-
ing sheeting.
Two and one-half g^ams of the sifted iron were mixed with
ten grams of a mixture of equal parts of sodium nitrate and car-
bonate in a platinum crucible. The crucible was covered and
heated over a Bunsen burner. At a red heat a sudden and
rather violent reaction occurred, and having been begun, was
easily maintained with very little aid from the burner flame.
The reaction appeared to be complete in a few minutes. After
heating for a half hour the crucible was cooled and its contents
softened in water. A residue of a reddish brown powder, con-
sisting of ferric oxide with a little ferrous oxide, w*as obtained.
This residue was found to contain no sulphuric acid, and on
digesting with hydrochloric acid dissolved without effervescence,
showing that none of the particles of the original iron had
remained unoxidized. Prom the results of this experiment and
others which need not be detailed here, it seemed to be possible
to oxidize finely divided iron so completely by heating with
sodium carbonate and nitrate, that its sulphur might be con-
verted quantitatively into sulphuric acid.
The mixture of sodium carbonate and nitrate although tend-
ing to oxidize finely divided iron, seems to exert a less powerful
acUon upon the carbon contained in the iron, and this carbon
may appear as a black residue after the fused mass has been
softened and extracted by water and the ferric oxide dissolved
in hydrochloric acid. \
It seems to be important for the success of the method that in
the oxidation of the iron the carbon should also be nearly or
completely oxidized, for if the carbon remained unburned a por-
tion of the sulphur might escape oxidation. In general it may
be said that the order of oxidation of these three elements by the
method used is as follows: i, iron; 2, carbon; 3, sulphur ; the
I082 FRANCIS C. PHILLIPS.
iron being the most easily oxidized, and the sulphur the most
difficult to oxidize. This order is not exactly what w^ should
anticipate, but it is to be remembered that unless the iron grains
are fine enough to be penetrated by oxygen, and changed com-
pletely into a soft powder of ferric oxide, the sulphur and car-
bon have no opportunity to oxidize at all. If the iron could be
used as an impalpable powder the order of oxidation would prob-
ably be different. The marked resistance of the carbon to oxi-
dation has been frequently observed, even when using more
sodium nitrate in the fusion than is theoretically enough to com-
pletely oxidize both iron and carbon, supposing that the sodium
nitrate is reduced only to nitrite in the process.
Experiments of a similar kind were tried with ferromanganese.
A metal containing about eighty per cent, of manganese was used.
By crushing in a steel mortar this iron was very easily reduced
to a powder fine enough to pass through bolting sheeting. On
heating the powder with the mixture of sodium nitrate and car-
bonate a most violent reaction occurred, the metal burning with
a long flame, extending several inches above the crucible. In
order to control the reaction it was found necessary to melt one-
half of the fusion mixture to be used in the crucible and then
add slowly the other half, previously mixed with the powdered
metal, while stirring constantly. In this way the reaction could
be easily controlled. On softening the fused mass in water it
was found that the iron had been peroxidized and the manga-
nese changed to binoxide. No trace of sodium manganate was
ever formed, the solution in water being after filtration invaria-
bly colorless. No carbon was found in the residue. The oxi-
dation of the carbon is much more easily effected in the case of
iron containing a high percentage of manganese. In all the
trials made the silicon of the iron was oxidized, but it was found
that when the fused mass is softened in water very little silica
enters into solution as an alkaline silicate, the greater portion
remaining insoluble and in a flocculent form.
Experiments were then tried with a gray iron. This form of
iron could not be crushed to a fine powder, and an experiment
was made in reducing it from small drillings by means of a
DBTBRMINATION OP SULPHUR IN CAST IRON. IO83
chilled iron rubber and plate, such as is ordinarily used for
grinding ores. Several gray irons were tried in this way.
Some could not be powdered by the method just mentioned, the
grains tending to flatten instead of being crushed. Others were
readily reduced, but the powder was not in any case fine enough
for sifting through bolting sheeting. It was found in the case
of a gray iron reduced to powder by the method of grinding,
that on fusion with the mixture of sodium nitrate and carbonate,
used in the preceding experiments, the graphitic carbon of this
iron was more readily burnt than the combined carbon of white
iron.
As it had proved to be a somewhat difficult matter to oxidize
completely the carbon of the iron in the various experiments
made with the fusion method, notably in the case of white iron,
some trials were made in the use of sodium peroxide. This
proved to be a more efficient oxidizing agent for iron and its
contained carbon than sodium nitrate. For these trials a mix-
ture was used consisting of forty-five parts each of sodium per-
oxide and sodium nitrate, together with ten parts of sodium car-
bonate.
White iron was oxidized and its carbon burnt during a fusion
la.sting less than ten minutes.
On heating ferromanganese with this mixture the iron was
found to be completely oxidized. The carbon was burnt and
the manganese was oxidized and converted into sodium manga-
nate, yielding a deep green solution when the fused mass was
digested in water.
An admixture of sodium carbonate to sodium peroxide tends
in all cases to diminish its action upon finely divided iron at a
high temperature and renders the process more easily controlled.
It seemed to be possible to base a method for the quantitative
determination of sulphur in certain kinds of cast iron upon the
reactions described above.
An indispensable condition of success in the use of the method
is found in the extreme fineness of the iron. In the case of
white irons the fineness of the powder has been secured by
I084 FRANCIS C. PHILLIPS.
crushing in a steel mortar until tfae powder passed through a
sieve of bolting sheeting or bolting cloth. ^
Some gray irons cannot be crushed or ground. To these the
method is not applicable. For gray irons, however, the evolu-
tion method answers all requirements.
The following details are given of the method finally employed :
1 . White iron . — About one and one*half grams of the finely pow-
dered and sifted metal was intimately mixed with eight gramsof the
sodium peroxide mixture above mentioned, or with four grams
each of sodium carbonate and nitrate. The somewhat violent
reaction set up on the application of strong heat to the platinum
crucible was completed in a few minutes. The crucible was
heated for about twenty minutes in all. After cooling the con-
tents were softened in water, the solution decanted and the resi-
due ground, while wet, in a mortar. The solution and residue
were then digested in a beaker on the water-bath for one hour
after addition of two cc. of strong bromine water. The liquid
was then filtered, acidulated with hydrochloric acid, evaporated
to dryness to separate the small portion of silica which had
entered in solution and filtered. The sulphuric acid was deter-
mined in the filtrate in the usual manner. The barium sulphate
obtained was always white. If the fusion mixture contains
sodium carbonate and nitrate, but no sodium peroxide, the cru-
cible must be heated for a longer time, but a portion of the car-
bon of the iron may still remain unoxidized.
2. Ferromanganese. — In this case it is better to use a mixture
of equal parts of sodium nitrate and carbonate, omitting the
sodium peroxide.
Ten grams of the mixture were divided into two portions, one
of which was fused in a crucible. The other portion mixed
with two or two and one-half grams of the finely powdered iron
1 Two different materials are sold which are suitable for the siftin^r* One is caUed
t>olting cloth, the other bolting sheeting. The bolting cloth used in these experimenta
contained about eighty-five meshes to the linear inch, while in the bolting sheeting
about one hundred and thirty-five were counted. The muterial having the smaller
number of meshes is made of coarser threads, however, and yields, on account of the
smaller openings, a finer powder. Bolting cloth is, on this account, better suited to the
preparation of a sample of white iron for a determination of sulphur by the method
described.
DETERMINATION OF SULPHUR IN CAST IRON. IO85
was then slowly added. Although too violent combustion of
the iron is to be avoided, it seems to be important, for the suc-
cess of the method, that a reaction of decided intensity should
occur during the fusion.
Sodium nitrate possesses an advantage over sodium peroxide
in its greater purity, the formet compound being readily obtain-
able with practically insignificant traces of sulphur.
Natural gas was the fuel used for the Bunsen burner in heat-
ing the charges. This gas was found by repeated experiments,
not to contain a sufficient quantity of sulphur to affect the purity
of the sodium carbonate when heated in a platinum crucible in
the same manner as in the case of the determinations described.
The usual occurrence of sulphur compounds in coal gas would
preclude its use in the application of the method.
From the experiments, the results of which are stated in the
accompanying table, there seems to be some reason to suppose
that not quite all the sulphur of the iron is converted into barium
sulphate when the metal is oxidized and dissolved by nitric acid.
That it has been completely recovered by the process of fusion
cannot be positively asserted.*
The method I have described is not proposed as a substitute
for any existing method. The purpose of the present work was
merely to ascertain as far as possible whether by a process of direct
oxidation of the iron in a dry state a larger proportion of the sul-
phur could be recovered in weighable form than by the usual
method of oxidation and solution in nitric acid.
My thanks are especially due to Mr. F. B. Smith for great
care and attention to detail in conducting the experiments! have
detailed.
1 The meUiod of preparation of a sample for analysis in the case of the more brittle
forms of iron, by crushing in a steel mortar and sifting, is suggested in Regnault's Ele-
ments of Chemistry, translated from the French by Betton, 1867, a, iia.
io86
DETERMINATION OF SULPHUR IN CAST IRON.
Character of irou used.
White iron A crushed
in mortar and sifted
through bolting
sheeting.
Fusion mixture employed.
Contained equal parts
of sodium carbonate
and nitrate.
5 w o
A« •B.o
O.II2
O.I 12
O.III
0.107
O.I 14
O.I 14
0.106
0.108
0.107
0.103
Means
White iron B crushed
and sifted.
Contained
45 parts NaNOs
45 parts Na^Oj
10 parts Na,COs
Means
Ferromanganese
crushed and sifted.
Contained equal parts
of sodium nitrate
and carbonate.
0.155
0.150
0.130
0.139
0.166
0.156
0.156
0.161
0.151
0.151
0.022
0.027
0.018
0.018
0.018
0.019
0.016
Means 0.020
Gray iron drillings
powdered by rubber
and plate.
Not sifted.
Contained equal parts
of sodium nitrate
and carbonate.
0.034
0.030
0.036
0.034
0.033
0.034
pi4 C.O0 a
O.IOI
0.098
0.096
0.099
O.IOO
0.102
0.102
O.IQ4
0.109 O.IOO
0.143
0.149
0.143
0.147
0.145
0.012
0.013
0.012
O.OIO
0.012
0.027
0.030
0.026
0.028
0.028
0.022
Means
0.033 0.027
CARBON DETBRniNATIONS IN PIQ IRON.
By BERTIUND S. 8UMSCBS.S.
Received October 3, i8|p6.
THOSE chemists who have had occasion to do many carbon
determinations in pig iron, to which was allotted but little
time, have probably felt the need of improvements in some of
our standard methods.
The old oxygen combustion method, although accurate, re-
quires more time than can usually be spared if use is made of a
porcelain or glass tube. However, it has the greatest of all ad-
vantages, that of accuracy. The writer has used for some time
a regular Bunsen furnace with a glass tube, and while the
results were all that could be desired, the time required for a
refractory residue was almost three hours.
A series of experiments was conducted with the ordinary
chromic acid process, but the results were quite unsatisfactory.
Every precaution was taken to insure accuracy, but with high
carbon residue low results were obtained in nearly every case
when checked by the oxygen combustion method. This was
particularly noticeable when a considerable content of graphite
was present. The results checked quite well with each other
and gave satisfactory results when working on steel.
As this state of affairs greatly embarrassed matters in the lab-
oratory, an effort was made to devise some means by which the
carbon could be determined with reasonable speed and accuracy.
Recognizing the advantages of the combustion method, it was
decided to make use of a platinum tube. To avoid delay and
expense the tube was manufactured in the factory. It was made
of 0.200 stock twelve inches long and eleven-sixteenths inch in
diameter. A perfectly tight tube was constructed by using
ordinary gold solder, which may be obtained from any jeweler.
Around each end of the tube copper coolers were brazed, in
order to cool the tube in the neighborhood of the rubber stop-
pers. The inlet of the coolers served the double purpose of
supports and water supplies. In spite of this precaution it was
found that the air circulating through the heated portion of the
tube was hot enough, on reaching the stoppers, to seriously
affect them. In order to prevent this, the scheme shown in Fig. 3
io88
BBRTRAND S. SUMMERS.
was devised. The funnel shape protuberance here seen was
filled with ignited asbestos, and the whole was removed with the
stoppers. This appliance proved an effectual preventive for
further heating of the
r
I
ro5.
Fic.3.
I
i'
Tife^f
F/G.2
Stoppers, as a red heat
could be maintained
two inches from them
and they remain per-
fectly cool.
With this arrange-
ment it was found that
a high carbon residue
could be burned com-
pletely in twenty min-
utes. It became evi-
dent from this that if
the aspirating space
were decreased, good
results could be ob-
tained in a compara-
tively short time.
With this idea in view ,
the train depicted in
the accompanying pic-
ture was designed and
made by our own
glass-blowers. The
train has the further
advantage that rub-
ber connections are
Pig. \—AAy Platinum tube ; BB^ Support and water
outlet ; CC, Coolers ; DD^ Water supplies.
Fig- ^—bb^ Sockets for BB \ dd. Connection for water
supply, DD : E, Main water supply ; F^ waste pipe ;
(7, Gas connection.
Pig. 3'-<^s, Stoppers ; yf j, Glass cup for asbestoses ;
y4^ Outlet.
Pigs. 4 and 5— Showing connections for mercury joint.
avoided, the only rubber tubing in use being at the ends of the
combustion tube.
The purifying train consists of a large ({-tube of one and one-
half inch stock and twelve inches long. The first limb is filled
with broken caustic potash, and the second with fused calcium
chloride. The first limb connects with a Drechsel bottle par-
tially filled with strong sulphuric acid, and the second with the
combustion tube.
CARBON DETERMINATIONS IN PIG IRON.
I090 CARBON DETERMINATIONS IN PIG IRON.
The purifying train on the absorption end is made in one
piece. It consists of a five inch ||-tube of thick walled glass
five-eighths inch in diameter, into the sides of the limbs of which
are fused arms. These arms are made of one-inch stock and
about seven inches long. The first arm is filled with anhydrous
cuprous chloride and anhydrous cupric sulphate. The ||-tube
serves as the receptacle for the sulphuric acid, and the second
arm is filled with calcium chloride previously treated with an
excess of carbon dioxide.
The connection with the Geissler bulbs is established by means
of mercury joints. These serve to facilitate removal of the bulbs
and make a joint which is perfectly secure. The joint can
readily be made by any glass blower, an illustration of which is
seen in Fig. 4. The end of the Geissler bulb is so reamed as to
fit loosely over the tube inside the cup (Fig. 5). A small piece
of rubber tubing (b, Fig. 4) is slipped over the tube and makes
a moderately tight joint with the end of the Geissler bulb.
When the cup is filled with mercury a perfect connection is
obtained. The method of connecting the Geissler bulb with
rubber tubing was both awkward and liable to leakage. These
junctions have been in use for some time in our laboratory and
have given thorough satisfaction.
With this apparatus as described the most refractory residues
are burned in an hour and a half. With residues of less refrac-
tory nature and lower carbon content an estimation may be com-
pleted in less time. The blank on the apparatus never exceeds
three-tenths of a milligram, and is usually one-tenth or nil.
Some results are here appended, thinking they may be of
interest. Those obtained by the chromic acid process were quite
scattering unless great care was exercised and sufficient time was
allowed. The results from this method, given below, are those
where much time was given and great pains taken to insure
complete oxidation. V^ues from the Bunsen furnace are given
to serve for comparison.
Chromic Acid Method. Bunsen Furnace.
Total Carbon. Total Carbon.
323 3-31
3.27 3-33
3.23
%,2S
SOLUBILITY OP BISMUTH SULPHIDE. IO91
Results from the above described process, when compared
with the Bunsen furnace, were very good.
Platinum Furnace. Bunsen Furnace.
Total Carbon. Total Carbon.
303 303
3.03 3.05
3.05
The convenience of this apparatus in expediting work in the
laboratory has led me to write this description, in the hope that
it might be of service to other chemists.
Cbbmicax« I«aboratort» Wbstbrn Slbctrxc Company,
Chicago.
NOTE ON THE SOLUBILITY OF BISMUTH SULPHIDE IN
ALKALINE SULPHIDES.
By Gborob C. Stonb.
Received November 9, 1896.
IN the August number of this Journal there is a note by
Prof. Stillman on this subject ; he shows that if a solution
containing bismuth is made alkaline by sodium hydroxide and
then heated with an excess of an alkaline sulphide a considera-
ble amount of bismuth is held in solution. On repeating his
experiments qualitatively I obtained the same result, but when
the bismuth was first precipitated as sulphide from an acid solu-
tion and then treated with an alkaline sulphide but little if any
was dissolved.
To test the solubility quantitatively I made a solution of about
one and two-tenths grams of bismuth hydroxide in 500 cc. of
very dilute hydrochloric acid ; .in two portions, of fifty cc. each.
I determined the bismuth by precipitation by ammonium car-
bonate, finding 0.0966 and 0.0965 gram.
I next precipitated the bismuth in two more lots of the same
solution by hydrogen sulphide, filtered and heated the precipi-
tate for half an hour with a large excess of potassium sulphide,
filtered, dissolved and reprecipitated by ammonium carbonate,
the bismuth weighed 0.0981 and 0.0970 g^am.
Two more lots treated in the same manser, except that they
^wexe heated with ammonium sulphide, gave 0.0970 and 0.0976
gram of bismuth.
From the above it seem? fair to conclude that bismuth
sulphide precipitated from an acid solution is not dissolved by
subsequent treatment with an alkaline sulphide.
[Contribution from the Laboratory op Agricui^tural Chemistry
OP THB Ohio State UNivBRSiry.]
ON THE BEHAVIOR OF COAL-TAR COLORS TOWARD THE
PROCESS OP DIQESTION.
By H. a. Webbr.
Received October to, x9g6.
IT is very well known that the coal-tar colors have come into
general use for coloring confectionery and other articles of
food and drink. In fact they have almost completely superseded
the vegetable colors, which have been used from time immemo-
rial for a similar purpose. The indiscriminate use of these
colors, some of which are derived from bodies of a decidedly
poisonous nature, has often been regarded with suspicion by
persons who are interested in public health. On account of the
uncertainty existing in regard to these colors from a sanitary
point of view, Austria has prohibited their use tn toto in all arti-
cles of food and drink. Other countries prohibit certain of the
colors, which have been shown to be injurious, and allow all
others to be used.
The experiments made upon the lower animals have, in the
main, revealed negative results. Thus the writer about eight
years ago fed some of the colors most commonly employed by
confectioners to rabbits in order to test this question. One-half
gram of the colors, among which magenta and corallin were
included, was fed to as many rabbits per day for ten days in suc-
cession without any apparent ill effects. The exhaustive treatise
of Dr. Weil, translated by Leffmann, ascribes toxic effects to
only a small number of the many colors employed by him in his
experiments upon domestic animals.
The effect which these colors might exert upon digestive fer-
ments, however, was a subject which had as yet received no
attention, and the following experiments were undertaken in
order to throw some light upon this question. The ferments
employed were Armour's pepsin and pancyeatine, liberal sam-
ples of which were kindly furnished by Armour & Co., of Chi-
cago.
For the purpose of showing the digestive action, blood fibrin
preserved in alcohol was employed. The fiibrin was soaked and
BEHAVIOR OP COAL-TAR COIX>RS. IO93
thoroughly washed with water to remove the alcohol, then
pressed between filter paper, and the amount required for each
experiment weighed off.
In each set of experiments a control experiment was carried
on without the addition of color. The mixture was made as fol-
lows :
Hydrochloric acid solntion (two-tenths per cent.) xoo cc.
Pepsin* - 20 milligrams.
Fibrin i gram.
This mixture placed in a large test-tube was digested in a
water-bath at a temperature of 38^ to 40** C. until the fibrin was
dissolved.
At the same time similar mixtures as above containing in addi-
tion I, 0.5, Q.250, 0.125, And 0.062 gram of the color to be tested
respectively, were digested in the same water-bath for the time
required to dissolve the fibrin in the control experiment. Any
fibrin remaining undissolved in the latter tests, was removed,
thoroughly washed, pressed between filter paper as before and
weighed.
I . PEPSIN AND OROUNB YELLOW.
This color was one of a series employed in the coloring of con-
fectionery, and was found to be what is known in the trade as
Acid Yellow or Fast Yellow, and is a mixture of sodium amido-
azobenzenedisulphonate with sodium amidoazobenzenemono-
sulphonate.
Amouut
Amounfof Amount of Amount of Duration of offibnn
color. fibrin. pepsin. experiment, dlasolved.
Gram Gram. Gram. Hours. Gram.
I 0.0 I 0.020 3 I.O
a 1.0 I 0.020 3 O.I
3 0.5 I 0.020 3 0.12
4 0.25 I 0.020 3 0.22
5 0.125 I 0.020 3 0.35
6 0.062 I 0.020 3 0.73
From this it will be seen that even in test No. 6, where the
color employed amounted to only one part in 1600 parts of the
solution, the presence of the color had still a depressing effect.
For fear that, owing to the nature of this color, the hydrochloric
acid might have been neutralized in part, the experiment was
I094 H. A. WKBER.
repeated with a six-tenths per cent, solution of hydrochloric acid
with similar results.
Of course the determination of the fibrin dissolved is only
approximate, as can readily be inferred from the way it was
done.
In tests Nos. 2, 3 and 4 no change in the amount of fibrin was
apparent to the eye. That a smaU part of the fibrin had gone
into solution was confirmed by the fact that a slight precipitate
of albuminoids was obtained on the addition of a solution of tan-
nin. On the whole it must be conceded that this color has a
marked and injurious effect upon peptic digestion.
2. PEPSIN AND SAFFOLINE.
This is also a candy color and was found to be acridine red.
Amount of
color.
Gram.
Amount of
fibrin.
Gram.
Amount of
pepsin.
Gram.
Duration of
experiment.
Hours.
Amount
of fibrin
dissolved
Gram.
0.0
0.020
3i
I.O
0.020
5
0.5
0.020
S
0.25
0.020
S
0.125
0.020
3i
0.062
0.020
3i
As will be seen from the table above, this color only slightly
retards the digestion of the fibrin in the three stronger solutions,
while in the last two tests there waS no interference with the
process. On the whole it may be said that the effect of this color
on peptic digestion is practically nil.
3. PEPSIN AND MAGENTA.
It is needless to tabulate the results of this experiment. Suf-
fice it to say that the solution of the fibrin in the five tests con-
taining the same proportions of the color as employed above kept
pace throughout the whole duration of the experiment with the
control test, the fibrin in all cases dissolving at the expiration of
three and one-half hours.
This color, therefore, seems not to interfere with peptic diges-
tion.
These four colors were also employed with pancreatin, and
the method was as follows :
BEHAVIOR OF COAVTAR COLORS. IO95
For the control experiment the following mixture was made :
Water 100 cc.
Sodium bicarbonate 1.5 grams.
Pancreatin 0.3 g^am.
Fibrin i.o gram.
This mixture contained in a large test-tube, was digested in a
water-bath until the fibrin was peptonized. To test the effect of
the colors, there was added to similar mixtures as above i, 0.5,
0.25, 0.125 and 0.062 gram of each color respectively.
5. PANCREATIN AND OROLINE YELLOW.
To the great surprise of the writer, this color, which had
proved so effective in stopping and retarding peptic digestion,
was found to exert no action whatever on the pancreatic fer-
ment ; the fibrin in all five of the tests with this color, dissolved
as freely as that of the control test. The solution of the fibrin
in all cases was completed at the expiration of six hours.
PANCREATIN AND SAFFOUNE.
The action of this color was quite different from that of oroline
yellow, as the subjoined table will show :
Amount
Amount of Amount of Amount of Duration of of fibrin
color. fibrin. Pancreatin. experiment, dissolved.
Gram. Gram. Gram. Hours. Gram.
I 0.0 I 0.3 6| 1.0
2 1 .0 I 0.3 6| 0.0
3 0.5 I 0.3 6i 0.0
4 0.25 I 0.3 6J 0.55
5 0.125 I 0.3 6\ 0.65
6 0.062 I 0.3 6J 0.75
These results show, that in the two stronger solutions the
action of the pancreatic ferment was entirely stopped, and that
even in test No. 6, which contained only one part of color to
1600 of the solution the action of the ferment was retarded to a
marked extent.
Tannin precipitates the coloring matter.
7. PANCREATINE AND MAGENTA.
This color was as marked in retarding and stopping the action
of pancreatine as saffoline. The results are given in the table
below :
I 0.0
2 I.O
3 0.5
4 0.25
5 0.125
6 0.062
1096 JEROMB KKLLEY, JR. AND EDGAR F. SMITH.
Amount
Amount of Amount of Amount of Duration of of fiber
color. fiber, pancreatine, experiment, dissolved.
Gram. Qram. Gram. Hour. Gram.
0.3 6i 1.0
0.3 6i 0.0
0.3 6J 0.0
0.3 6J 0.40
0.3 6^ 0.60
0.3 6i 0.73
The solutions of tests 2 and 3 gave no precipitate with tannin.
In all other tests the precipitate was either marked or heavy.
8. PANCREATINE AND METHYL GRANGE.
This color in all of the tests behaved like the last three colors
described, completely stopping the action of the pancreatine in
the two strongest solutions and retarding it to a marked extent
in the weakest. The tabular statement would be similar to the
last.
It seems then, so far as these four colors are concerned, that
none interfere with both peptic and pancreatic digestion, but that
each color interferes seriously with either the one or the other.
What the action of other coal tar colors may be, can, of course,
not be iiiferred from this limited number of experiments, but it
may safely be said that bodies which have such a decided action
in retarding the most important functions of the animal economy,
cannot properly have a place in our daily food and drink.
[CONTRIBtrriUN PROM THE JOHN HARRISON LABORATORY OF CHBMISTRT»
No. 19.]
THE ACTION OF ACID VAPORS ON ilETALLIC SULPHIDES.
* By Jekomb Kbllby, Jr. and Exx»ar P. Smith.
RecclTcd October a, tSgS.
EXPERIMENTS made in this laboratory on the action of
the vapors of hydrochloric acid upon the sulphide of
arsenic proved that the latter is wholly volatilized. The purpose
of the present communication is to record further observations
along analogous lines. Thus, when washed and dried arsenic
trisulphide is exposed to the action of hydrobromic acid gas, it
volatilizes completely. Indeed the action commences in the cold
with the formation of a liquid that passes out of the containing
ACTION OF ACID VAPORS ON METALLIC SULPHIDES. IO97
vessel upon the application of a very gentle heat. In evidence
of this, two quantitative experiments may be given :
Arsenic sulphide taken. Arsenic sulphide expelled.
Gram. Gram.
0.2945 0.2941
0.4632 0.4628
Antimony trisulphide, like that of arsenic, is volatilized by
hydrochloric acid gas. It was quite probable that a like deport-
ment would be observed if hydrobromic acid gas should be sub-
stituted. This was found to be the case. When the gas came
in contact with the sulphide it became liquid and volatilized as
soon as a gentle heat was played upon the boat in which the sul-
phide was contained.
Antimony sulphide taken. Antimony sulphide expelled.
Oram. Gram.
0.1473 0.1469
0.0938 0.0935
Upon substituting stannic sulphide for antimony sulphide, an
experience similar to that observed with antimony and arsenic
sulphides followed. There was a complete volatilization with
but a trifling residue, which proved to be carbon from filter
paper that had adhered to flie metallic sulphide.
stannic sulphide taken. Stannic sulphide expelled.
Gram. Gram.
0.1880 0.1880
0.5527 0.5521
0.4174 0.4169
The oxides of arsenic, antimony and tin (at least in the stan-
nic form) can be volatilized in a current of hydrochloric acid
gas. This is also true of the sulphides of arsenic and antimony,
but how the two sulphides of tin would act under like conditions
was not known.
Experiments recently made demonstrate the perfect volatility
of stannic sulphide in this way. With stannous sulphide it was
found that by the continued action of the gas in the cold there
followed a complete conversion into chloride without any vola-
tilization. That the residue was the chloride was evident from
its action upon a mercuric salt solution. The figures obtained
in the several trials were :
1098 HERBERT A. SCHAFPER AND EDGAR F. SMITH.
Stannous chloride found. Stannous chloride tbcory.
Gram. Gram.
0.3544 0.3523
0.4893 0.4903
Several attempts were made to separate stannous and stannic
sulphides by this procedure. The results were unsatisfactory.
In order to drive out the stannic salt completely it is necessary
to heat the mixture, and this caused a partial volatilization of
the stannous chloride, so that quantitative results could not be
obtained.
Comparatively few metallic sulphides have been studied in
the direction indicated in the preceding lines, so that it is prob-
able a wider application of the method will disclose interesting
behaviors, and that probably new separations can be brought
about in this way. The action of the vapors of haloid acids has
also been tried on natural sulphides with a fair degree of suc-
cess.
[Contribution from the John Harrison Laboratory of Chemistry,
No. 20.]
TUNGSTEN HEXABROMIDE.
By Herbert A. Schapfbr an%Edoar P. Smith.
Received October to, 1896.
THE most recent work upon tungsten bromides is that of
Roscoe,' who endeavored to prepare a hexabromide, but ob-
tained instead a penta derivative from which the dibromide was
subsequently made. By reference to the literature bearing upon
this subject it will be noticed that bromine, diluted with carbon
dioxide, was made to act upon tungsten metal exposed to a
red heat. Experimental evidence is at hand that tungsten at
high temperatures deoxidizes carbon dioxide, thus allowing
ample opportunity for the production of oxybroraides, which, in
spite of the greatest care, are sure to appear in larger or smaller
amount. The thought also suggested itself that possibly the
**red heat" at which the action was allowed to occur might
have been detrimental and have indeed prevented the formation
of the hexabromide.
Hence, we determined to operate in an atmosphere of nitro-
i Ann. Chem, (Liebig), xte, 363.
TUNGSTEN HBXABROMIDB. IO99
gen and to apply a very gentle heat to the vessel containing the
tungsten. In this connection it may be mentioned that the
nitrogen was conducted through a series of vessels charged with
chromous acetate, sulphuric acid, caustic potash, and phos-
phorus pentozide, respectivel3\ It then entered an empty ves-
sel into which dry bromine was dropped from a tap-funnel, and
after passing through a tall tower, filled with calcium chloride,
entered a combustion tube resting in a Bunsen furnace. The
anterior portion of the combustion tube was contracted at inter-
vals, forming a series of bulbs, and at its extremity was con-
nected with an empty Woulff bottle, followed by a calcium chlo-
ride tower, and finally a receiver filled with soda lime and
broken glass. A steady current of nitrogen was conducted
through this system for a period of three days. On the fourth
day bromine was introduced. The tungsten contained in the
combustion tube was heated very gently. In a short time
brown vapors appeared. These condensed to a liquid beyond
the boat and eventually passed into blue-black crystalline masses
that separated from the walls of the tube, when perfectly cold,
with a crackling sound. Very little heat was required to melt
them and they could with care be resublimed in distinct, blue-
black needles. The latter was collected in one of the bulbs (No.
2) previously mentioned. Other products were observed and
isolated. All were analyzed. Bulb No. i— that nearest the
tungsten metal — contained a black, velvety compound, which
upon analysis showed the presence of tungsten dibromide. Bulb
No. 2 contained 0.2103 gram of the blue-black crystals, which
yielded 0.0577 gram of tungsten, or 27.43 per cent., and 0.1543
gram of bromine, or 73.53 per cent. The theoretical require-
ments of tungsten hexabromide are 27.72 percent, tungsten and
72.28 per cent, bromine. The bromine percentage found is
high. This may be due to traces of bromine that had not been
driven out from the crystalline deposit, or to adherent silver
tungstate, as some tungstic acid remained in the solution from
which the silver bromide was precipitated.
A fresh portion of the blue-black crystals was prepared as
before and analyzed. The bromine determination was unfortu-
nately lost. The determination of the tungsten resulted as fol-
IICX) EDMUND H. MILLER.
lows : 0.4351 gram oi material gave 0.1222 gram of tungsten or
28.08 per cent.
A third preparation was made. On subjecting 0.1775 gram
of it to analysis these results were obtained :
0.0496 gram tungsten or 27.94 per cent.
0.1266 gram bromine or 71.32 per cent.
Tabulating the series, we have :
pound.
Mean
Required for
hexabromide
Per cent.
Per cent.
Per cent.
Per cent
Per cent
Tungsten • • •
... 27.4}
28.08
27.94
27.81
27.72
Bromine* •••
••• 73-53
71-62
• • • •
72.33
72.28
These figures give evidence that the body analyzed is tung-
sten hexabromide.
In analyzing the third portion of the blue-black needles the
bromine was determined by placing the material in a small
Erlenmeyer bulb, covering it with nitric acid and then distill-
ing. The liberated bromine was passed into a silver nitrate
solution.
The tungsten hexabromide prepared by us consists, as already
observed, of blue-black needles. Moderately elevated tempera-
tures decompose the compound. It gives off fumes when
brought in contact with the air. Water decomposes it with the
formation of a royal-blue colored oxide. Ammonia water dis-
solves it, the solution remaining colorless. A vapor density
determination resulted negatively,, as decomposition was appar-
ent early in the experiment.
NOTES ON THE FERROCYANIDES OF ZINC AND MAN-
GANESE.
By Edmund H. Millbr.
Received October lo, 1896.
THE composition of the ferrocyanides of zinc and manganese,
formed when salts of these metals are precipitated by
potassium ferrocyanide, is given by Prescott dnd Johnson' as
Zn,Fe(CN), and Mn,Fe(CN)„ while the books on volumetric
analysis, such as Sutton's and Beringer*s, ignore the composi-
tion of this precipitate.
1 QualitAtive Analysis, pa^cs 67 and 57.
FERROCYANIi:>ES OF ZINC AND MANGANESE. HOI
The prevailing idea is that in the titration of zinc by potas-
sium ferrocyanide, a normal zinc ferrocyanide is formed. This
I believe to be incorrect, for if the reaction is
K,Fe(CN). H- 2ZnCl, = Zn,Fe(CN).+ 4KCI,
a solution of potassium ferrocyanide, one cc. of which is equiva-
lent to ten milligrams of zinc, would contain 32.32 grams of
K^Fe(CN),.3H,0 to the liter, not 43.2' to 45* grams, as has been
found by experiment. Using forty-four grams per liter as a
basis for calculation, the reaction becomes
2K,Fe(CN), + 3ZnCl, = Zn.K,(Fe(CN).), + 6KC1.
This reaction is not merely one that may possibly be true, but
according to Wyrouboff,' the precipitate formed by the action of
potassium ferrocyanide on a zinc salt, whichever is in excess, is
3Zn,Fe(CN)..K,F,(CN)..i2H,0, white, while the normal salt,
Zn,Fe(CN),.4H,0, is formed only by the action of hydroferro-
cyanic acid on a zinc salt.
This statement agrees both with the preceding reaction and
with the results obtained in standardizing potassium ferrocya-
nide solution.
The manganese precipitate with potassium ferrocyanide, as
obtained in titration, is given by Stone* as Mn,Fe,(CN),,. This
is a ferri-, not a ferrocyanide, thus making necessary a change
of quanti valence. Mr. Stone also states that an amount of
potassium ferrocyanide which will precipitate four atoms of zinc
will only precipitate three of manganese, thus basing his calcu-
lation on the formation of a normal zinc ferrocyanide.
Wyrouboff* gives the precipitate obtained from potassium fer-
rocyanide and a manganese salt, whichever is in excess, as
5Mn,Fe(CN),.4K,Fe(CN),.4H,0, rose white ;
while the normal salt Mn,Fe(CN)..7H,0, cream, is formed as
in the case of zinc by hydroferrocyanic acid.
The solution used by Mr. Stone had the following strength :
1 Sutton t Volumetric Analysis, p. 3>9 ; Beringer : Assaying, p. 319.
* Purman : Assaying, p. 205.
9 Amh. cAim. pAys., fsj. 8- 485.
^J.Am. Ckem. Soc., 17, 473.
II02 JOHN FIELDS.
One cc. = o.CK)6c>6 gram zinc.
One cc. '-= 0.00384 gram manganese.
If the ratio were exactly four zinc to three manganese, using
the most recent atomic weights, the strength of this solution
against manganese would be one cc. = 0.00382 gram, while,
according to Wyrouboff, loMn = 9K^Fe(CN), and 6Zn =
4K4Fe(CN),, or loMn = 13.5 Zn, or iMn= 1.35 Zn, and the
strength against manganese would be i cc. = 0.003774 gram.
These figures show but little difference between the two ratios
and while Mr. Stone's experimental results are undoubtedly
accurate, this theory based on the formation of Zn,Fe(CN),and
Mn,Fe,(CN)„ is not satisfactorily proved.
This article is only a preliminary note regarding the composi-
tion of the ferrocyanides as they are being investigated in this
laboratory.
In connection with the ferrocyanide of zinc I have found a
very strong solution of hydrochloroplatinic acid, H,PtCl„ acidi-
fied with hydrochloric acid, a most satisfactory indicator for the
titration of zinc by potassium ferrocyanide, when performed in a
hot solution. This indicator is used in the same way as uranium
acetate and is less affected by a varying amount of hydrochloric
acid. The end reaction is a bright emerald green, which takes
a few seconds to develop. It will not work with a cold solution.
ASSAY Laboratory. Columbia Univsrsxty.
A MODIFICATION OF THE GUNNINQ HETHOD FOR
NITRATES,
By John Fields.
Receired October ao, xt9^
THE full text of the official Gunning^ method is as follows :
''In a digestion flask, holding from 250 to 500 cc, place
from seven- tenths to three and five- tenths grams of the substance
to be analyzed, according to the amount of nitrogen pres-
ent. Add thirty to thirty-five cc. of salicylic acid mixture;
namely, thirty cc. sulphuric acid to one gram of salicylic acid,
shake until thoroughly mixed and allow to stand five to ten
1 Ann. chim, phys.^ [5], 8, 474.
s Bulletin 46. U. S. Dept. of A.%r., p. z8.
MODIFICATION OP GUNNING METHOD FOR NITRATES. I IO3
minutes, with frequent shaking ; then add five grams sodium
thiosulphate and ten grams of potassium sulphate. Heat
very gently until frothing ceases, then heat strongly until nearly
colorless. Dilute, neutralize, and distil as in the Gunning
method."
This method has its advantages in that no heavy metals are
added, such as zinc and mercury, which sometimes interfere
with the distillation. It has, however, a few disadvantages
which the following modification partially overcomes. When
working with some materials, there is considerable trouble due
to persistent frothing, and in some cases, it has taken six hours
constant attention to get the digestion safely over this point.
Moreover, unless the contents of the flask are diluted while still
warm, there is a tendency for the sulphates to become hard and
difficult of solution.
In the modification proposed, the following reagents are
necessary :
1. Chemically pure sulphuric acid.
2. Salicylic acid.
3. Potassium sulphide.
The material containing the nitrates is weighed out into a
digestion flask and thirty cc. sulphuric acid containing one
gram salicylic acid are added, and gently heated to facilitate the
solution of nitrates and prevent frothing later. While warm,
six to seven grams of potassium sulphide are added in small
portions, the flask being thoroughly shaken after each addition.
It is then placed over a low flame and the heat rapidly increased
until the acid mixture boils. No further attention is required
and the digestion is usually complete at the end of an hour.
When cold', the liquid is diluted and distilled in the usual man-
ner.
The average difference between the results on sixty samples
of fertilizers containing nitrates by the official method and the
proposed modification was 0.02 per cent., those by the latter
being higher.
The points of difference between the modification and the offi-
cial modified Gunning are the following :
II04
SEPARATION OP AI^KALOIDAL BXTRACTS.
1. The number of reagents used in the digestion is reduced
from four to three.
2. Frothing is obviated and the operation requires no atten-
tion except turning up the lamps until full heat is secured.
3. The time of digestion is shortened.
4. Potassium sulphide is made to do double work by acting as
a reducing agent instead of sodium thiosulphate and then
being converted into potassium hydrogen sulphate serving the
end secured by adding potassium sulphate in the original method.
T
THE SEPARATION OF ALKALOIDAL EXTRACTS.
By Charles Platt.
Received October ao, i8p6.
HE writer has found the accompanying simple device of
great value in the separation of the annoying emulsions
so often met with in alkaloidal anal-
ysis, as, for instance, in the petroleum
ether and benzene extractions of Dra-
gendorff's method. The filtering tube
is nineteen cm. long, the upper 12.5 cm.
having an inside diameter of fourteen mm.,
the lower contracted portion, an inside diam-
eter pf three mm. A stout platinum wire
bent at the upper end is so placed as to
pass through the constricted portion of the
tube to the bottom of the eight-ounce
Erlenmeyer flask. Washed cotton is firmly
packed in the tube to a depth of about
four cm. and the apparatus, connected
with a filter pump, is ready for use. The
filtered liquids may finally be carefully
poured into an ordinary separating funnel
and manipulated as usual. By this method
the most persistent emulsions are separated
into their constituent liquids in as many
minutes as ordinarily are required hours or
days.
Chemical Laboratory. Hahnemann Medical College,
Philadelphia, Pa.
THE PREPARATION OP DIETHYL HALONIC ESTER.
By W. a. Noybs.
ReceiTed October 99, 1896.
HAVING occasion recently to prepare considerable quanti-
ties of malonic ester, it has been found that the process
can be very much shortened by the use of sulphuric -in place of
hydrochloric acid and of acid sodium carbonate in place of potas-
sium carbonate. As the body is the starting point for a great
variety of syntheses the method used may be of interest to
others.
One hundred grams of chloracetic acid are placed in a porce-
lain dish, 21 cm. in diameter, and 200 cc. of wateradded. Thesolu-
tion is warmed and ninety grams of acid sodium carbonate added
in small portions, and the warming continued until a temperature
of 55''-6o** is reached and effervescence nearly ceases. Eighty
grams of coarsely powdered potassium cyanide is then added,
and the whole stirred without further warming, till the some-
what vigorous reaction is complete. The solution is then evap-
orated rapidly on a thin sheet of asbestos paper till the ther-
mometer with which it is vigorously and constantly stirred shows
a temperature of i3o''-;35**. The hand should be protected by a
glove or otherwise, and the glass of the hood in which the
evaporation is conducted should be between the dish and the
lace during this part of the process. The mass should be stirred
occasionally while cooling, and as soon as it solidifies it should
be broken up coarsely and transferred to a liter flask. Add
forty cc. of alcohol and connect with an upright condenser.
Through the latter add, in small portions and with frequent
shaking, a cooled mixture of 160 cc. of alcohol with i6occ. of
concentrated sulphuric acid. The whole may be added within
five or ten minutes (instead of the day and a half required to
saturate with hydrochloric acid by the old method). Toward
the close there is a considerable evolution of hydrochloric acid.
Heat on a water-bath for an hour. Cool quickly under the tap,
with shaking to prevent the formation of a solid mass of crys-
tals. Add 200 cc. of water, filter, wash the undissolved salts
with about fifty cc. of ether, shake up with the filtrate and sepa-
rate. Add a solution of sodium carbonate and shake carefully
II06 NOTB.
with the ethereal solution till alkaline. Separate again, distil
off the ether and dry by heating for fifteen minutes on a water-
bath under diminished pressure, using a capillary tube as for
vacuum distillations. The residue gives, after one distillation,
an almost pure malonic ester.
The sodium carbonate solution appears to contain some of
the acid ester. If this solution is added to the first acid solu-
tion, the ester separates with some ether. The ethereal solu-
tion may be separated, the ether evaporated at a gentle heat,
and the residue added to the contents of the flask in which a
second saponification of the cyanacetate is to be effected. If
this is done, a yield of malonic ester equal to the weight of chlor-
acetic acid used can be obtained. This is ten to fifteen percent,
better than by the old method.
Rose Polttschnic iNSTtruTB, /
Tbr&b Haxttb, Ind., Oct. 37, X896.
NOTE.
Untaxed Alcohol for Use in Manufacturing and in the Arts, —
The Joint Select Committee, createdatthe last session of Congress,
to investigate and report upon the question of the use of alco-
hol free of tax in the manufactures and arts, have prepared
a series of interrogatories, which will be distributed through-
out the country to such parties as are thought to be interested
in the question.
The report of Mr. Henry Dalley, Jr., who was commissioned
to investigate the workings of foreign laws governing the use of
untaxed alcohol in the manufactures and arts has been submit-
ted, and contains very full and extremely valuable data covering
Great Britain, Germany, France, Belgium and Switzerland.
It is the earnest desire of the committee to secure all possible
information bearing upon the subject, and it is hoped that par-
ties interested will submit their views to the committee promptly.
Sets of the circular letter and blank for replies will be supplied
to any applicant by addressing the chairman. Room 21, Senate
Annex, Washington, D. C.
The committee, which is composed of three members of each
House, will probably assemble in Washington soon after the
OBITUARY NOTICE. IIO7
middle of November for the purpose of formulating a report to
Congress accompanied by the draft of a law which will place
domestic industries on as favorable a basis as similar industries
in foreign countries.. During their sessions in Washington
hearings will probably be given in order to supplement the
information obtained through the interrogatories above set
forth. Due notice of the time of such hearings will be given
to tibe public.
OBITUARY NOTICE.
Propbssor ^ugust Kbkiti«£'s part in the advancement of
chemistry has been so important that his death on the 13th of
last July has brought a feeling of sorrow to the hearts of chemists
throughout the world.
Kekul6 was bom at Darmstadt, the birthplace of Liebig, on
the 7th of September, 1829. It was the intention of his parents
that he should become an architect, and he entered the Univer-
sity at Giessen as a student of architecture. He devoted him-
self with application to the studies bearing on his future calling,
but like many another student who came within the range of
I/iebig's influence, he was filled with an enthusiasm for chemis-
try, which changed all his plans for the future, and led him to
devote himself to this science. It is quite possible that his pre-
liminary architectural studies had much to do with turning his
mind toward the ideas of molecular structure or molecular
architecture, which he subsequently developed. Kekul^ also
studied in Paris under Dumas, and in London under William-
son. In 1856 he became privatdocent at the University of Hei-
delberg. He was appointed professor of chemistry at the Uni-
versity of Ghent (Belgium) in 1858 ; and in 1865 was called to
the University of Bonn, where he remained until his death.
Kekul6'sfirstpublished work appeared in hiehig^s Annalaiior
1850. Four years later he published his second paper, in which
he described thiacetic acid and discussed the action of phos-
phorus pentasulphide on oxygen acids.
The period from 1854 to 1874 was one of the greatest activity
with Kekul6. Since 1874 he has made comparatively few con-
II08 OfilTUARY NOTICE.
tributions to chemistry, although occasional papers have
appeared. In spite of the great number of investigations he
has made, chemistry is most indebted to Kekul6 for his great
generalizations and theoretical suggestions.
He extended Gerhardt's t3rpe theory by adding the marsh gas
tjrpe and introducing the idea of mixed t3rpes. These types
made clear 'to him the difference in the power of the elements to
hold other atoms in combination, and he developed the idea of
valence, first put forward by Frankland, so that this new prop-
erty of the elements was at once recognized by chemists, the
conception of atom-linking followed at once, and this made pos-
sible the transition from the type theory to our present concep-
tions in regard to the structure of compounds.
In this paper published in 1858 Kekul6 says: " It is the sub-
stitution and relation of the atoms and not radicals, that we must
look to in order to get a clearer idea of the nature of these com-
pounds.**
He closes this remarkable paper with the following words :
'* In conclusion I believe that I should emphasize that I do not
set much value upon this kind of speculation. But since chem-
istry, in its entire lack of exact scientific principles, must content
itself for the time with the most probable and useful theories ; it
appears proper to present these views, for they, as it seems to
me, give a simple and entirely general expression for the latest
discoveries, and because moreover their application may be
the means of discovering new facts.'*
It is not too much to say that the ideas thus modestly put for-
ward, supported by his subsequent work, were the prime cause
which led to the abandoning of Gerhardt's types for our present
structural formulas.
These ideas had made considerable progress, when in 1865
Kekul6 published his now well known h3rpothesis in regard to
the constitution of benzene. Seldom has a theory in chemistry
been so suggestive or given rise to so much investigation as this
benzene theory. The rich and manifest results accruing from
these investigations testify sufficiently to the utility of the theory.
Many students of chemistry were attracted to Bonn ; these
Kekul6 inspired with a love of investigation that has been
NEW BOOKS. 1 109
exceedingly fruitful for the science. Besides his work as a
lecturer and investigator, he began in i860 and finished in 1861
the first volume of his Lehrbuch der organischen Chemie, a
book that was epoch-making with its new ideas and new methods
of presenting this complex subject. The book was received
with enthusiasm among chemists, and has served as a model for
subsequent works in the same field. Three volumes of this work
were finally published, but the work was never completed. He
was also for many years one of the editors of Liebig's Annalen,
During his last years he suffered much from ill health, having
followed too literally I^iebig's advice: ** If you would become
a chemist, you must ruin your health. He who does not ruin
his health by hard study in these days comes to naught in chem-
istry."
In 1890 the German Chemical Society celebrated the twenty-
fifth anniversary of Kekul^'s benzene theory. The meeting was
largely attended by chemists from all parts of the world.
Addresses were given by A. W. Hofmann, the President of the
Society, Adolph-von Baeyer, Kekulfe's oldest pupil, and by
Kekul6 himself. A full account of the meeting has been pub-
lished.* G. M. Richardson.
Oct. 17, 1896.
NEW BOOK5.
Manual op DBTBRMiNATrvrs Minbralocy with an Introduction on
Blowpipb Analysis. By Geor^ J. Brush. Revised and Enlarged by
Samuel L. Penfield. 14th Edition, pp. iz -f~ 108. John Wiley &
Sons. Price, I3.50.
This revision, with the exception of the tables, is practically a
new book. The author states that **A complete revision of the
tables for the determination of minerals will be made as soon as
possible, and a short chapter on crystallography and the phys-
ical properties of minerals will be prepared, but until this work
can be accomplished, use will be made of the tables and of the
short introduction to them from tb^ last edition of Professor
Brush."
This proposed revision of von Kobell's table is greatly needed.
When it is finished the book bids fair to be as nearly perfect as
text-books can well be. The introductory chapter has been
rewritten with evident care and by a practiced hand, and as it
1 Ber, d, chem. Get.^ S3, 1265.
I no NBW BOOKS.
now stands this edition is a great improvement over preceding
ones.
' ' In preparing the introductory chapters, great pains have been
taken in the selection of the tests for the elements. Many of
them are performed by means of the blowpipe, but chemical tests
in the wet way are recommended when it is believed that they
are more decisive." To this evidence of good common sense it
may be added that in several places. the author shows a desire
and ability to make his knowledge of practical value. This is
shown, for example, under gold, where careful directions are
given for the detection of gold in poor gold ores and the like,
first by the use of mercury and thien without mercury. B. h.
Thb Elbmbnts op Chbmistry. By Paxil C. Prbbr, Ph.D. z+284 ppi
Boston: Allyn & Bacon. XS95. Introductory price, fi.oo.
One feature in particular makes this book especially worth
noticing, and that is its outright recognition of the great import-
ance of quantitative work in an elementary course in chemistry.
The recognition has been a long time on the way, and its absence
has been a great detriment to the chemical instruction in second-
ary schools.
It is also pleasant to find Professor Freer recognizing that cer-
tain so-called physical matters are best reviewed at the outset of
such a course. Indeed it would seem as if some such matters
which are taken up in the present work, rather late in the course,
would better be considered earlier (the laws of Mariotte and
Charles for instance).
The book cannot be used to advantage by an inadequately
trained teacher, but will certainly be found valuable to the
student teacher on account of its excellent collection of experi-
ments which are carefully planned and digested.
Joseph Torrby, Jr.
Tabi«bs and DiRBcnoNS for Quautativb Chbmicai, Analysis. B7
M. M. Pattison Muir.
This little work is evidently intended to increase the possi-
bilities of lecture table instruction in qualitative analysis. It
consists of such brief statements of processes and methods as will
enable the student to attend to what is going on on the lectore
table without running the risk of losing material which ought to
get into his note book. The analytical methods described are,
for the most part, such as have stood the test of time and expe-
rience . Joseph Torrey , Jr .
The Liquefaction of Gases. Papers by Michabl Faraday, F.R.S.
(1833-1845). Alembic Club Reprints No. 12. 79 pp. Bdinbnrgh: Wm.
F. Clay. Price, two shillings.
In this little book of seventy-nine pages there is much matter
CORRBSPONDBNCH. 1 1 1 1
that will be of practical service to every one who teaches ele-
mentary chemistry. Its value to investigators and advanced
students is sufl&ciently obvious. Students ought to be intro-
duced to the classics of chemistry at a comparatively early stage
of their development. They are not- as a rule, at present,
because the original papers are seldom accessible to the teacher.
The publication of Ostwald's ** Klassiker " was the first step in
the right direction, but the fact that they are in German makes
them inaccessible to many who most need them.
Joseph Torrey, Jr.
CORRESPONDENCE.
POLARIZATION BY DOUBLE DILUTION.
United States Department op Agriculture,
Division of Chemistry,
Washington, D. C, Nov. 27, 1896.
Editor Journal of the American Chemical Society ^ Easton, Pa, :
Dear Sir : By accident a portion of the rule for calculating
polarizations by double dilution in our paper published in this
Journal, 1896, Vol. 18, pages 428 to 433, was omitted.
Page 430, beginning at the end of line 9, the rule for the ap-
proximate calculation of results obtained by Scheibler's method
of double dilution should have this addition after the words
'* small flask," ** multiply the difference by two and subtract the
product from the reading in the small flask.*' This is equiva-
lent to multiplying the reading obtained from the solution in the
large flask by four and subtracting the reading obtained from
the solution in the small flask from the product. The re-
sult is the corrected reading and, when a solution of double the
normal strength is polarized in a tube of double the normal
length, must be divided by four to obtain the percentage. In
this case a simpler and equivalent rule for calculation is the fol-
lowing : Subtract one-fourth the reading of the solution in the
small flask from the reading in the large flask and the result will
be the corrected percentage.
Page 430, end of line 17, the word sucrose should be lactose.
Page 432, the figures in the table in the column headed **Vol-
1 1 12 BOOKS RECEIVED.
ume of precipitate/' were calculated before the exact formula on
P^S^^ 43^ ^^s evolved, and are somewhat at variance with the re-
sults objjtained by use of the formula. The formula gives the fol-
lowing numbers : 5.26, 10.71, 4.88, 9.86, 5.05, 5.41, 4.53, 4.12,
3.87, 4.99, 3.33, 4.22, 16.23. The numbers in the column
headed " True volume in 100 cc. flask" must be changed ac-
cordingly.
Respectfully,
H. W. Wiley,
E. E. EWELL.
BOOKS RECEIVED.
Bulletin No. 33. Commercial Fertilizers and Chemicals, and Other In-
formation in Regard to Fertilizers. Under the supervision of Hon. R. T.
Nesbitt, Commissioner of Agriculture of the State of Georgia. Dr. George
P. Payne, State Chemist. Atlanta, Ga. : George W. Harrison, Sttte
Printer.
Manual of Determinative Mineralogy, with an Introduction on Blow-
pipe Analysis. By George J. Brush. Revised and enlarged by Samuel
L. Penfield. Fourteenth Edition. x4- 108 pp. New York : John Wiley
& Sons. Price $3.50.
Jahrbuch der organischen Chemie. Heransgegaben von Gaetano Min-
unni. Palermo. Zweiter Jahrgang. 993 pp. 1894. Leipzig : Johann Am-
brosius Barth. (Arthur Meiner). 1896.
A Brief Introduction to Qualitative Analysis ; for Use in Instruction in
Chemical Laboratories. By Ludwig Medicus. Translated from the
Fourth and Fifth German Editions by John Marshall. Fourth Edition.
Philadelphia : Printed by J. B. Lippincott Co. 1896. 203 pp. Price
I1.50.
Bulletin No. 43. Second Series. Bovine Tuberculosis in North Lou-
isiana. Bulletin of the Louisiana State Experiment Station, Baton
Rouge, La. 1896. 20 pp.
ERRATUM.
On page 994 (November number), seventh line from bottOLi, instead of
'* extra internal pressure'* read '* extra external pressure.'*
Index to Vol. XVIII, 1896.
References to the pafea of the Proceeding are given in Perentbetia.
.CCURACY, limits of in metallurgical analyaia. 35; of chemical analyai8....8oS, (88)
▲csenaphthene, heat of aolntion in methyl alcohol, iss ; in ethyl alcohol, 153 ; in
propyl alcohol, 154; in chloroform, 155; intoluene • 155
▲cetamlde, heat of solution in water, 151 ; in ethyl alcohol 153
▲cctanilid, qualitative examination of, 143 ; heat of solution in methyl alcohol, 15a ;
in ethyl alcohol, 153 ; in chloroform .«•• 155
Acetylene, use in polariscopic work as an llluminant 179, (37)
Acetone, manufacture from acetic acid, 331, (30) ; volumetric determination of 106B
Acid vapors, action of, on metallic sulphides » • 1096
Address, changes of post office .*.
va). (*6), (36), (57)» (65). (71). (M). (97), (99), ("8). (iX9).(ia4)
Addresses wanted, post office (2), (36), (57). (70. (1^4)
Albuminoid nitrogen, source of error in determina tion of 464
Alcohol, determination by means of the ebullioscope, 1063; the tax on 1106
Alknloldal extracts, separation of iiof
Alloys of aluminum, analysis of 77a
Almonds, proteidsof 610
Alumina, determination of, in phosphate rock by the ammonium acetate method,
717: estimation of , in phosphate rock. Tax ; analysisof 779
Aluminum, anal]rsis of, 766 ; determination of, in metallic aluminum, 77a : solders,
analysis of, 777 ; use in cooking vessels, 935 ; in pig iron, (3a): See also erratum (56)
Amandin 611
Amines, occurrence of, in the juice of the sugar cane 743
Ammonia, the separation of trimethylamine from 670
Ammonium phosphomolybdate, gravimetric method of estimating phosphoric acid
^••S3; precipitation of, in steel analysis 170
Amphoteric reaction of milk (33)
AifDnswa, I^AUifCBLOT. On the Reduction of Sulphuric Acid by Copper as a Func-
tion of the Temperature ^i
Ahdkbwb, W. W. Some Sxtensions of the Plaster of Paris Method in Blowpipe
Analysis 849
Anhalonium hydrochlorste, 64a ; see also (83)
Antidiphtheritic serum, method of collecting 930
Anti-friction alloys, determination of bismuth in 683
Antimony cinnabar, formation of g 34a
Antimony, Reinsch's test for, 953 ; trioxide, behavior with hydrochloric acid, 103a ;
separation from lead by means of hydrochloric acid, X033 ; separation from
copper by means of hydrochloric acid 1035
Argon , atomic weight of • ax i
Arsenic, Reinsch's test for, 953 ; separation from copper by means of hydrochloric
acid, XQ38 ; separation from silver by means of hydrochloric acid, X039 ; separa-
tion from cadmium by means of hydrochloric acid, 1039 ; separation from iron
by means of hydrochloric acid, X040 ; separation from sine by means of hydro-
chloric acid, XQ41 : separation from cobalt and nickel by means of hydrochloric
acid, 104a ; atomic weight of, X044 : separation of vana<ttum from lasx
Asplialtum,'technical analysis of 97$
AsMidates elected (i), (a), (a6), (35). (36), (^), (71), (93), (xx9). (xa4)
Atomic masses of silver, mercury and cadmium, determination of, by the electro-
lytic method 990
Atomic weights, report of committee on, X97 ; of nitrogen and arsenic 1044
1 1 14 INDBX.
AVCBT, Obokob. The Prcelpitetioii of Phosphomoiybdftte in Steel Anftlysis, 170 ;
Drown's Method of Detemininff Snlphiir in Tig-iron, 40S: Sonrces of Error in
Volhard't and Similar Methods of Determininir Manganese in Steel, 49^ ; Notes
on the Determination of Phosphoms in Steel and CasUron • 9SS
AUSTBN, Pbtbr TowMSBiiD. A New Specimen Bottle (ttstc) ••••• 4M>
AVBBT, S. See Nicholson, B. H.
IBACTBItlA, study of sas-prodncittff, tS7 : inndtksogar • •..dS7, (73)
Babb, S. H. AiTD A. B. Frescott Dipjrridinc Methylene Iodide and the Non-Foraan*
tion of the Corresponding Monopyridine Frodncts, 9B8 ; see also Presoott, A. B.
Balance, for first years work in general chemistry (note) ••••••••.••. rty
Barium sulphate, the effect of an excess of reagent in the precipitation ci •»•»••*»•• 799
Basxbbviixb, Cbaklbs. Reduction of Concentrated Sulphuric Acid by Copper • • . 94s
Bauxite, analysis of • tAs
Bbadlb C. See Cross, C. P.
Beef Pat, microscopic detection in lard •• •••••••.• 189
Bbbson, J. L. Occurrence of the Amines in the Juice of the Sugar Cane, 743 ; A Sina-
ple and Convenient Bxtraction Apparatus for Pood-stuff Analysis •••• 744
Bbitkbrt, Abthub It. and Smith, BdgarP. The Separation of Bismuth from Vemd iaS9
BsjfNBTT, A. A. and S. B. Pammel. A Study of Some Gus-Produdng Bacteria. • •• • • 157
Bbniibtt, a. a. AMD h. A. Placeway. The QuantltatiTe Determination of the Three
Halogens, Chlorine, Bromine and Iodine, in Mixtures of Their Binary Goos-
pounds.** • • 6M
Bensamidc, heat of solution in ethyl alcohol • • is#
Bensoin, action of acid amides upon, mi ; action of urea upon, 118 ; action of
thiourea upon • • 119
Berthelot's contributions to the history of chemistry (review) 466
Bbyah, B. J. See Cross C. P.
BiGBLow, W. D. Index to the Literature on the Detection and Bstimatlon of Pusel
OilinSpiriU 3Sff
Birch Wood Gum siS
Bismuth, estimation of, in anti-friction allojrs, 6B3 ; oxide, behaTior of, with hydro-
chloric add, X033 ; separation from lead by means of hydrochloric acid, 1034 ;
separation from copper by means of hydrochloric acid, 1036 ; separation front
lead, IOS5 ; sulphide, solubility of, in sodium sulphide, 683 ; sulphide, solubility
of, in alkaline sulphides • •• • • 1091
Blaix, A. A. Method for the Detemlination of Carbon in Steel n$
Blowpipe analysis, some extensions of the plaster of Paris method in..... 849
Boiler scale, the presence of oil in • 741
BOLTOH, H. Cabbimoton. Beitbelot's Contributions to the History of Chemistry
(review) .486. (3^
Book Reviews. The Scientific Foundations pf Analytical Chemistry Treated In an
Blementary Msnner (Ostwald), 98; Practlcsl Proofs of Chemical I«aws (Comlah),
99 ; Organic Chemistry. The Fatty Compounds (Whiteley), 99; Analjrtical Chem^
irtry (N. Menschtttkin), 190 ; On the Densities of Oxygen and Hydrogen and
on the Ratio of their Atomic Weights (B. W. Morley), 19a; Water Supply, Con-
sidered Principally from a Sanitary Stand-point (W. P. Mason), gSa ; Hints on the
Teaching of Blementary Chemistry in Schools and Science Classes (W. A. TO-
den), s^; Chemistry lor Bngineersand Manufacturers (Betram Blount), 745;
Laboratory Bxperiments in General Chemistry (C. R. Sanger), 747; Bxpcrimeata
in General Chemistry and QuaUlatlve Analyiis (C R. Sanger), 747 ; Manual off
Determinative Mineralogy with an Introduction on Blowpipe Analysis (Bmah-
Penfield), 1109; The Blements of Chemistry (P. C Freer), ixio; Tables and I>lree>
tions for Qualitative Analysis (M. M. Pattison Mulr), ixxo ; The Liquefactioii of
Gases (Michael Faraday) txio
Books received 100,196^3x0,4x4,474,964,660,747.848,1007. iiis
INDBX. ZII5
plMsphate, distiiBclion from rock pho^bate..... 491
BoTAcic acid, acidity of milk increased by • • 847
Bottle for tpecimena 4xj
Bimall-attt, protdda of the • 6ai
Bromiae, iodlsie and chlorine, indirect determination of, 1815; qnantitatiTc determina-
tion of, in miztnrea of the binary compoonda of the halogena • ••... 668
BmYAHT, A. P. A Method for BeparaUnir the Iniolnble Phoaphoric Acid in Mixed
FertiUaers Derived from Bone and Other Organic Matter from that Derived from
Sock Phoaphatc 491
Bvas, CBAmLBS S. Petiolettm Prodncta (68)
Bynedeatin • 54a
Bjnin .^.. 55a
Bwtter, vac of calorimeter in detecting adulteratloa of 174
OACTACBAB, the chemistry of the 694, (83)
Cadminm, atomic weight of, aqs; preparation of pure, loai; separation from arsenic
by means of hydrochloric add, 1039 ; bromide, preparation of pnre, loaj ; chlo>
ride, preparation of pure • ion
Caffeine, new method for estimation of, 331 ; perhalides of, 347 ; estimation of 978
Caldnm cartiide, manufacture of , 3x1 : eatimatloa of aulphidea in 740
Caldnm pboaphide, preparation of .^ (s8)
Calorimeter, uae ol, in detecting adulteration of butter and lard 174
CaMPBSix, B. D. A Proposed Schedule of Allowable Difference and of Probable
limita of Accuracy In Quantitative Analyses of Metallurgical Materials 35
CAMraxu., GBonOB P. See Oabome, Thomaa B.
Canned gooda, gaseain ^ 936
Carbon, atomic weight of , sis ; determination of, in steel, 233 ; determination of. in
aluminum, 771 ; dctcrminationa in pig iron, 10B7 : dloodde, determination by ab-
aorption, x ; <ttDKide, produced by growth of bacteria, 157 ; monoidde, cooatittt-
tioaof 386
Caxbonatea, determination of cartMm dioxide in • i
Caatorbean, protdda of the • 6ai
Cerium, atomic wdghtof sio
Cedum fluoride • • 57
Chemical Club in New York (71)
CHBmnrr,-V. K. Pdson ivy as a Skin Irritant (8z)
Chicago Section. See Meetlnga of the Sodcty.
Chloral hydrate, heat of solution In water, 150; in ethyl alcohol, 153 ; in doroform,
135; In toluene... • 156
Chlorine, bromine and iodine. Indirect determination of, iSiK quantitative determi-
nation of « In mixtures of the binary compounds of the halogens 688
Chloroform from acetone made fromacetic add S31
Chromium, volumetric detcrminatloa by means of hydrogen dioxide 9x8
dndnnati Sectioii, See Meetings of the Sodety.
dimabar, electrolytic determination of mercury in 9&
dtrate aolutlon uaed in analysis of fertilisers, method of determining neutrality of 437
CukMMM, P. W. Third Annual 'Report of Committee on Atomic Weights.. ...•• 197
Clasxb, Thomai W. Ace Venable, P. P.
Coal-tar «afors, behavior toward the process of digestion X099
Ooaras, Chablbs B., mud W. &. Dodson. Nitrogen Asdmllatlonln the Cotton Plant 4as
Cobalt, atomic weight of sos
OobaU and nickel, separation from arsenic by meaiu of hydrochloric add • xop
Ooooanut, protddsof the 6az
OoLUBK, Pbtbr. Obitnaiy note • 748
Odor, measurement of, In imtural waters, 364 ; of potable water, valuation of, 484;
photography, Lippmaim's work on 9S9«93S
tll6 INDBX.
COlorlniT BUitter of tMtunl water* < «.•..«••...«• ,4*4A,{'jo)
Columlyiiiiii, reactionsofoaddes with carbon tetrachloride • «•>•• S3>
Colninbiiiiii and tantalom, derivatiTeaof •••-• af
Compreaaed sates, noteaon •••..« •••«....«.••.. (31)
COKB, BvwtN P. The Batimation of Pyrrhotltc in Pyrites Orea « m
Conirlotin • «• 609
Congrreaa of applied chemiatr7,aeoondinteniatioaaU...«« «•••« ,307,660.99
Copper, assay by iodide method, 458 ; accuracy of determinatioa of, 814 ; aa redvcer
of stronir sttlphnric acid, 94a; aeparation from antimony by meana of hydrochloric
acid, 103s ; aeparation from biamnth by meana of hydrochloric acid, 1096 ; aepa>
ration from arsenic by meana of hydrochloric acid—*.... ••.....«..•••.•••• n^
Correspondence ••> ....... 660, 84B,ixn
Corrosion of electric mains « •... (9)
Cofylin • > • icf
Council, minntes of the..... (35)* (S7). (^). (70. (97). ("9). («^)
Caoea, C. P., B. J. Bevan and C. Beadle. The Katural 0<ycellu1oses. ...... ^ 8
Cttpricoacide, behavior of with hydrochloric acid «.«.....«...... »q}
Is CHAIrMOT, G. See Morehead, J. T.
DsFRior, GBoaOB. The Determination of Reducing Sugars in Terma of Cnprlc Ox-
ide, 749 ; aee alao Bolfe, Geo. W.
DBLAFOifTAiKB, M. and C. B. Linebarger. On the Reaction between Carbon Tet-
rachloride and the Ozidea of Niobium and Tantalum.......... 531
Dbnnxs, I.. M. The Separation of Thorium from the Other Rare Bartha by Means
of Potassium Trinitride 9(7
Dbnwts, L. M.'andA. B. Spencer. Zirconium Tetraiodide 673
DsNKia, L. M. and Martha Doan, with cryatailographic notea by A. C Gill. Some
Compounds of Thallium.... 979
Db ScHWBiifiTZ, B. A. and Marion Doraett. Purther Notea upon the Pats con-
tained in the Tuberculosis Bacilli.... • 449
Db Schwbxmits, B. A. and James A. Bmery. The Use of the Calorimeter in Detect-
ing Adulterations of Butter and Lard 171
Deuteroprotcose *• #..... ..••.,.. 557
Dbwbt, Pbbdbbic p. The History of Blectric Heating Applied to Metallurgy (Re-
view), 367, (37) ; The Sulphuric Acid Process of Refining Liadvlaticm Sulphides,
^« (76) ;.The Actual Accuracy of Chemical Analysis «.Ai8, (81)
Diastase, the chemical nature of ••••.. « s3^
Diethyl malonic ester, preparation of ins
Digestion, behaviorof coal-tar colors toward.... 1091
Dipyridine methylene iodide • 9B8
Dipyridine trimethylene dibromide..... • jB
Directora, minutes of the.Board of • (i), (15)
Doan, Martha. See Dennis, T.. M.
Dox>aoN, W. R. See Coates, Charles B.
DoRBMUS, Chablbs A. Notc on the Presence of Oil In Boiler Scalc >...•• • 741
D0R8BTT, Marion. See' DeSchweinits B- A.
Drying oven, steam jacketed •....• , (58)
Dubois, H. W. See Mixer, C. T.
DuDLBT, William L. Nickelo-Nickelic Hydrate...... .......* 901
IBULLIOSCOPB, a modified form of le^
Editor's report « (18)
Blectric furnace, Moissan's • «. 934
Electric heating applied to metallurgy..... 387, (37)
Electroljrtic determination of iron, nickel and sine... fs4
Electrolytic stand,a cheap adjustable » 33$
£lx.m8,J. W. See Richards, Ellen H.
INDBX. 1 1 17
\ jAitBS A. See De Schweinlts, B. A.
Vrrato .•••• • • 414, ma
HtidorplM » (66)
B^TBix, B&viif B. Tbe Chemistry of the Cactaceae •• 634, (83)
BwxLi., B. B. and H. W. Wiley. The Bffect of Acidity on the Development of the
Mitzifyinf Organisms. 47s ; See also Wiley H. W.
Hxcnrslons. to the works of the Orasselll Chemical Co., (24); To works of Otis Steel
Co., COntinenUl Chemical Co., Cleveland Nitrous Oxide Co., (46); To works of
Cleveland Varnish Co., Cleveland Rubber Co., Glidden Varnish Co., and War-
ner and Swasey,(47) ; To petroleum works of Scofield. Shurmers and Teasel,
(51) ; to Crescent Sheet and Tin Plate Co's works, Bmma Blast Pumace, Rolling
Mills 0f Union Rolling Mill Co., Cleveland Rolling Mill Co., (53); To Case School
of Applied Science and Adelbert College,(54); to Lorain Steel Works, (54); R ;cep-
tion by Cleveland Chamber of Commerce (55)
B3Ktracti<m apparatus for food-stuff analysis 744
^•ACTORS, table of 903
pA&mnfOTON, B. H. Acidity of Milk Increased by Boracic Acid 847
Pat, determination of solid fat in artificial mixtures of vegetable and animal fata and
oils, 9S9* (5) ; contained in bacillus tul>erculo sis 449
Pata, see oils.
Perric oxide, action of hydrochloric add gas on 1040
Perrocyanides of sine and manganese iioo
Pcrtilisers. simple method for determining the neutrality of ammonium citrate solu-
tion,457; distinction between bone and rock phosphate > 491
PIber determinations in bagasse, source of ertorin 469
PiXLD, CBAKLBa AND Bdoar P. SMITH. The Separation of Vanadium from Arsenic 1051
PiBi^Dft, JOBir. A Modification of the Gunning Method for Nitrates 1x03
Pllbert, proteids of the 618
PmsMAir, P. A. New Mode of Pormadon of Tertiary and Quaternary Phosphines. • (89)
Pi^RCK, Hmit ANN. The Seps ration of Trimethylamine from Ammonia 670
Plxntx&mann, R. p. and A. B. Prescott Dipyridine TrimethyUne Dibromide.and a
Study of Certain Additive Reactions of Organic Bases a8
Pood-stuff analysis, extraction apparatus for..... : 744
Poods, experlmcntaon calorimetric value of '(63^
POULK, C W. The Bffect of an Bxcess of Reagent in the Precipitation of Barium
Sulphate 793
Pnsel oil in spirita, index to literature on the detection and estimation of 397
-AS pipette for absorption of illuminanta. 67 ; regulator, simple form of. 511 : gen-
erators, some new forms of .-.. 1057
Gases produced by growth of bacteria....* • 157
Gill, Auoustub H. ^u Improved Gas Pipette for the Absorption of Illuminanta,
67 ; see also Dennis, L. M.
Gill, Auoustus H. and H. A. Richardson. Notes upon the Determination of Ni-
trites in Potable Water » • at
Gladding, Tbom as S. A Gravimetric Method of Bstimating Phosphoric Acid as
Ammonium Phosphomolybdate, 23 ; Note on the Microscopic Detection of Beef
Pat in I«ard, 189 ; On the Estimation of Sulphur in Pyrites, 446 ; Determination
of Iron Oxide and Alumina in Phosphate Rock by the Ammonium Acetate
Method, 717; A New Method lor the Bstimation of Iron Oxide and Alumina in
Phosphate Rock • • 7ai
Glasbr, CHARLB8. Estimation of Thorla. Chemical Analysis of Monasite Sand. . 78a
Glncinum , notes on pre pa ration of ( 104)
Glucose and other invert sugars, indirect determination by means of hydrogen di-
oxide * 9«
Glue solntionsi specific gravity of. .,.•. (61)
IIl8 INDBX.
Gold, assay by cyanide process, 309: sccarscy of determiiiatioii of, in copper mate-
rials, 816 : Cassel-Hinman bromine process for extraction of 051, C^)
GoicBBftO, M. On the Action of Wagner's Reagent upon Caffeine and a New Method
for the Bstimation of Caffeine, 331 ; Perhalides of Caffeine. 331 ; New POrm of
Potash Bnlb 941
Gunning method for nitrates, modification of • irot
[AI^IDBS of platinum and potassium 13s
Halogens, quantitative determination of, in mixtures of their binary compounds. . - - 6B8
Hakdt, jAMssOns. Aluminum Analysis •■ 766
Hardin, Willbtt Lbplbt. Determination of the Atomic Masses of Silver, Mer-
cury, and Cadmium by the Electrolytic Method 990
H AftT, Bdward. The Valency of Oxygen and the Structure of Compounds Contain-
ing It (review), 283; Notes on the Preparation of Olucinum (104)
Hasel-nut, proteids of the * 61S
Hacbn, Allbm . The Measurement of the Colors of Natu ral Waters a6«
Hbath, G. h. A Cheap Adjustable Blectrolytic Stand $59
Heats of solution of carbon compounds 14S
Heat of bromination of oils (38)
HuDBHHAiit, H. On the DeterminAtion of Carbon Dioxide by Absorption..... i
Helium, atomic weight of..... sn
Hepthyl thiocyanaie • (7S)
Hbrtt, Chablbs H. Mixed Double Halides of Platinum and Potassium 130
Hbbtt, Cha&lbs H. and J. 6. Smith. Mercuric Chlorothiocyanate 906
Heteroproteose S57
H1BB8, JOBBP^ GiixiNOHAJC The Atomic Weights of Nitrogen and Arsenic... 1044
HiBDS, J. I. D. Photometric Method for the Quantitative Determination of Lime
and Sulphuric Acid • tfi
Honey, estimation of levulose in 81, 189
Hopkins, Ctbil G. A New Safety Distillation Tube for Rapid Work in Nitrogen
Determinations vf
HowB, JAS. Lbwib. Contributions to the Knowledgeof Ruthenocyanides $Bi
HowB, JA8. LBW18 and Paul S. Mertins. Notes on Reinsch's Test for Arsenic and
Antimony i 9S3
Hydrochloric add gas, metal separations by means of, 1099 : action on sodium py-
roarsenate, 1037 ; on ferric oxide, 1040 : behavior of minerals in 1Q13
Hydrocyanic acid, preparation of • • ..••• 1009
Hydrofluoric acid 415
Hydrogen, produced by growth of bacteria, 157 ; density of. 198 ; dioxide, structure
of , a83 ; dioxide, some analytical methods involving the use of 918
Hydrolysis of starch by acids, an analjrtical investigation of 869
XLI/UMINANTS, gas pipette for absorption of 67
Indexing chemical literature, report of committee on 940
Indirect analysis tSt
Inversion of sugar by salts 110
Iodine, bromine, and chlorine, indirect determination of, 185 : quantitative determi-
nation of, in mixtures of the binary compounds of the halogens 688
Iron, electroljrtic determination of, ^ ; separation from arsenic by means of hydro-
chloric add, 1040; oxide, determination of, in phosphate rotk by the ammonium
acetate method, 717 ; oxide, estimation of, in phosphate rock, 721 ; volumetric
determination by means of hydrogen dioxide 9rt
Ironand steel analysis, present status of.. (iB)
JOHNSON, S.W. Composition of Wood Gum U4
\t composition of American 9^9
KbkulA, August. Obituary notice luif
INDBX: 1 1 19
KxixsT.jBftoitx, J&.AiidSiiiitli,BdgarP. The Action of Add Vapors on McUlUc
SulphM^t X096
lKiJOO%, Otis T. 8«e Mabeiy, Charles P.
2C« Across In milk, determination by doable dilation and polarisatiim ....... 438, x iix
Xjunns, Bdwakd K. Indirect Analysis... «• * x8s
X»SLirB,N. J. Determination of Snlpharic Acid... 683
Lard, nse of calorimeter in detectin^f adulteration of, 174 ; microscopic detection of
beef fat in , 189
X«ead, Tolnmetrfe estimation of, 737 ; separation from antimony by means of hydro-
chloric acid, 103^; separation from bismuth by means of hydrochloric acid, 1034 ;
separation of bismuth fiom, xoss; oxide, t>ehaTior of, with hydrochloric acid... 1031
IliCnther, the valueof refuse 565
I,»«Da. AIpSbrt R. Standard Prisms in Water Analysis and the Valuation of Color
in PoUble Waters, 4A4; Bacteria in Milk Sugar 687
Leirvmin of the pea and vetch • 58I3
Lehigh Valley Section. See Meetings of the Society.
tpBirBBR, VicTon. See Rising, W. B.
Lcucoain 547
X«CTulose. estimation in honey, etc • ••*.. 8t, 189
librarian's report • (15)
Ume, quantitatiTe determination of , by photometric method 661
LiXDSXT, J. B. The Value of Leather Refuse • 565
L1VXBAKOB&, C. B. A Rapid Method of Determining the Molecular Masses of
Liquids by Means of their Surface Tensions, 5x4 ; see also Delafontaine, M.
Lnraoir, Laura a. Technical Analysis of Asphaltum. No. 2 37S
Liquids^ some thoughts about 734
Litmus paper, best method of using - (6o|
LoifO, J. R. On the Inversion of Sugar by Salts, xao ; On the Inversion of Sugar by
Salts, No. a, 693 ; On the Ponnation of Antimony Cinnabar • 34s
Lonx>, N. W. A Simple Method for Determining the Neutrality of the Ammonium
Citrate Solution Used in the Analysis of Ptrtilisers • • 457
Low, AiABKT, H. The Copper Assay by the Iodide Method 458
Ll7iiOB,0. On the Bstimation of Sulphur in Pyrites 68s
Lupin, pioteids of • 6ea
ACabSRY, CHARLES P. Lecture on Petroleum, (ao) : See also Robinson. A. B.
MABsnT, Charlbs p. and Otis T. Kloos. Composition of American Kaolins 909
Magenta% effect of, on peptic digestion, X094; on pancreatic digestion « 1095
Malt, the globulin of, 543 ; the proteids of, 541 ; the albumin of, 547 ; the pioteoses of 549
Manganese, volumetric determination of, 338, (30); SftmstrOms method for determin-
ing manganese in iron ores. 385 ; separation from tungstic scid. 1053 ; ferrto-
cyanide; xxoo; in steel, sources of error in Volhard's method for determination
of, 498; in steel, accuracy of determination «• 808
Mannan • * •• 219
Manidte, heat of solution in water • 151
Mabon, W. p. Chemical vs. Bacteriological Examination of Water 166
MARTixf, WixxiAM J., Jr. The Cyanide Method of Extracting Gold from its Ores.
Application to the Assays of Ores ^x>r in Gold and Silver. Preliminary Notice
(note) 309
Mathrws. J. A. Phthalimid, 679; See Miller, Edmund H.
MclLHiUBY, Parkbr C The Cassel-Hinman Gold and Bromine Process .451. (61)
Meetings of the Society, (7). (loi): of the Rhode Island Section, (33), (43). (64}, (68).
(99). (i«». ("5) : of the Cincinnati Section, (5). (33). (40), (60). (68), (7a), (93). (xs6) ;
of the New York Section, (a). (a8), (37), (4a), (61), (69). (7a), (95). (lao), (las); of
the Washington 8ectlon.(a7). (36), (38), (57). (66), (75); of the Lehigh Valley Sec-
II20 INDEX.
tioiif (39) f (45) ; of the Nebruka Section (33), (41). (68). (94) ; of the CldcagD Sec-
tion, (43); of the North Carolina Section (60), (97}
Members elected (x). (25). (a6), (35). (6s), (7x), f93).("9h ("4)
Mercuric, chlorothiocsranate, 906 ; oxide, pre]>a ration of pure, 1004; bromide, prepa-
ration of pure, 1006 ; cyanide, preparation of • iwo
Mercury, electrolytic determination in cinnabar, 96 ; electrolytic determination of,
169; determination of atomic maMof 990
MBarnts, Paul S. See Howe, Jai. I^wii.
Meta-cerium • sit
Metal separationi by mean* of hjrdrochloric acid^t 1009
Metallic sulphides, the action of acid vapors on 1096
Metallurgy, electric heating applied to. 387
Metaphosphinic acids (90}
Methyl orange, effect on pancreatic digestion 1096
Milk, the acidity of, increased by boracic acid, 847 ; amphoteric reaction of, (53); in-
vestigation of (73)
Milk sugar, bacteria in « 6S7
MiLLBR, Bdmttnd H. Notes on the Perrocyanldes of Zinc and Manganese xxoo
MiLLsa, Bdmund H. and J. a. Mathews. Table of Factors ••• goi
Mineral waters, composition of certain northwestemPennsylvania 9^5
MiZBR, C. T. and H. W. DuBois. S&mstr&m's Method of Determining Manganese
in Iron Ores 3^5
Molasses, composition of 937
Molecular masses of liquids, determination by means of surface tension SM
Molybdate solution, a modified 445
Molybdenum, atomic weight of 907
Monasite sand, chemical analjrsis of 781
MoKBHBAi>, J. T. and G. de Chalmot. The Manufacture of Calcium Carbide 3"
MOYBR, J. BniD. Metal Separations by Means of Hydrochloric Acid Gas xm9
Muif BOB, Chablbs B. On the Development of Smokeless Powder (review), 819; (66)
SlfAPHTHALHNBt heat of solution in methyl alcohol, xsa; in ethyl alcohol, 153;
in propyl alcohol, 154 ; in chloroform, 155 : in toluene, 156 ; synthetic prepara-
tion of (3)
Nebraska Section. See Meetings of the Society.
New Books, 98, 190, 569. 745, 1x09. See Book Reviews.
New York Section See Meetings of the Society.
Nickel, electrolytic determination of ^
Nickel and Cobalt separation from arsenic by means of hydrochloric acid i04>
Nickelo-nickelic hydrate 9QX
NxcHOLSON, H. H. and S. Avery. Notes on the Blectroljrtic Determination of Iron.
Nickel and Zinc -. ^
Niobium, see columbium.
Nitrates, modification of Gunning method for xna
Nitric acid, preparation of pure 993
Nitrifying organisms, effect of acidity on the development of « 475
Nitrites in natural water, determination of n
Nitrogen assimilation in the cotton plant, 425 ; determination of, in aluminum, 771 ;
atomic weight of , 1044
Nitrogen determination, safety distillation tube for rapid t*J
North Carolina Section. See Meetings of the Society.
NOBTON, Thomas H. On Some New Forms of Gas Generators ifl57
Notes 189. 307.4x2. 558, 940."^
N0YB8, W. A. The Preparation of Dimethyl Malonic Bster ims
»AT-KBRNBL, proteids of the 6u
INDEX. 1 121
Obituary notice of Peter Collier 748
Oils, determinatioo of heat of brominatioo 378
Oroline yellow, effect of, on peptic digestion, Z093 : on pancreatic digeation 1095
Osborne, T.B. VegeUble Proteids (4)
OSBORMB. Thomas B. and George P. Campbell. The Chemical Nature of DiaaUse,
536; The Proteids of Malt. 54a : The Proteids of the Potato. 575 : Legumin and
Other Proteids of the Pea and the Vetch, 583 ; Conglutin and Vitcllin 609
Oxycelluloses, the natural 8
Oxygen, density and atomic weight, 198 ; valency of and structure of compounds
containing it (review) 383
Ozone, constitution of, a86 ; msnufacture of, use as a disinfectant, for bleaching, etc (46)
Z^AMMBL, B. E. See Bennett, A. A.
Paratoluidine, heat of solution in ethyl alcohol, 154 ; in chloroform, 155 ; in toluene. . 156
Pasteur memorial service 930
Pasteur monument committee « (105)
Patkb, Gborob p. Mineral Constituents of the Watermelon 1061
Pea. the proteids of < 583
Peach kernel, proteids of the 613
pRNNTNOTO!f , Mary Bnolb. Derivatives of Columbium and tantalum 38
Permanganate, probable production by combustion of metallic manganese ....230, (30)
Petroleum, lecture by C. P. Mabery, (ao); Distillation, (51); origin of. (64); petro-
leum products • (68)
Phenanthrene, heat of solution in ethyl alcohol, 153 ; in toluene 136
Phit.i,ips. Francis C. The Determination of Salphur in Cast Iron. 1079
Phosphates, neutrality of citrate solution used in analysing, 457 ; methods of analy-
sis of « 926
Phosphate rock, distinction from bone phosphate 491
Phosphf nes. tertiary and quaternary, mode of formation of (89)
Phosphoric acid, gravimetric estimation as ammonium phosphomolybdate, 33 ; In
fertilisers, various modifications of Pemberton's volumetric method for deter-
mining. 3^; accuracy of determination of ..., 812
Ptaosphorns. precipitation of phosphomolybdate in steel analysis. 170 : modified
molybdate solution, 445 : in pig iron, accuracy of determination. Sri ; in steel and
cast iron, determination of » 9S5
Photometric method for the quantitative determination of lime and sulphuric acid. 661
Phthalimid 679
Pipette, rapid measuring 905
PtACRWAY. L. A. See Bennett, A. A.
Plaster of Paris method in blowpipe analysis, some extensions of the « . . . . 849
Platinum potassium halides 130
PI.ATT. Charlrs. The Qualitative Examination of Acctanilid, T43 ; The Separation
of Alkaloidal Extracts 1104
Poison-ivy as a skin irritant.^ (81)
Polariscopic work, use of acetylene as an illuminant in 179
Polarizing at high and low temperatures, apparaturf'for 83, 85
Popr, Prrd. J. Volumetric Estimation of Lead, 737 : Estimation of Sulphides in Cal-
cium Carbide 740
Porcelain factory at Sevres. Prance, description of 931
Potable water, determination of nitrites in ai
Potash , accuracy of determination 817
Potash bulb, a new form of > 941
Potassium chloride, purificstion of, for atomic weight determinations aoi
Potassium platinum halides ijo
Potansinm and sodium, indirect analysis in a mixture of chlorides of 184
Potassium trinitride, use of, In separating thorium from the other rare earths 947
Potato, proteids of 575
1 122 INDEX.
Potter. Witliam R. Fallacies in Urine AulysU (99)
Pkbscott, Albbrt B. Notes on a Pew Pyridine Alkyl Iodides, 91 ; see also Flinter-
mann, R. P.; see also Baer, S. H.
Prbscott. A. B. and S. H. Baer. Pyridine Alkyl Hjrdrozides - M7
Proteids of malt, 54a : of the potato, 575 ; of the pea and ▼etch,^583 ; vef^eUble.... (4)
Proteoses of malt s$9
Protoproteose 556
PucKif BR, W. A. Notesonthe Estimation of CafTein 97^
Pyridine alkyl hjrdroxides, 247 ; pjrridine propyl hydroxide. 348 ; pyridine isoprapyl
hjrdroxide, 349 ; pyridine alkyl iodides, notes on. 91 ; pyridine ethyl iodide, 91 ;
P3rridine isopropyl iodide, 93 ; pyridine methyl iodide, 91 ; pyridine propyl
iodide 9>
Pyrites» estimation of sulphur in 446* tiiS
Pyrrhotite. estimation in pyrites ores 401
.BPINING liziviation sulphides, the sulphuric acid process 643
Reinsch*s teat for arsenic and antimony • 953
Resorcinol, heat of solution in water, 153 ; in ethyl alcohol tsi
Rhode Island Section. See Meetinips of the Society.
Richards, Bllbn H. and J. W. BUms. The Coloring-Matter of Natural Waters, its
Source, Composition and Quantitative Measurement O
R1CHARD80K, G. M. Obituary notice of August Kekul^ 1107
RiCHARDBON, H. A. See Gill, Augustus H.
Risiifo, W. B. and Victor Lenher. An Electrolytic Method for the Determination of
Mercury in Cinnabar • 9^
Robinson, A. E. and Mabery. Charles P. Composition of Certain Mineral Waters of
Northwestern Pennsylvania 9'5
RoLPB. Gko. W. and George Defren. An Analytical Investigation of the Hjrdrolysis
of Starch by Acids 861
Ross, B. B. Some Analytical Methods involving the Use of Hydrogen Dioxide ..•< 9'^
Rubber manufacture (49)
Rubidium fluoride S7
Ruthenocyanides, contribution to the knowledge of 9B1
fliAARBACH. LUDWIG. A Simple Form of Gas Regulator 5"
Saccharimeter. comparison of scales 933
Saffoline, effect of, on peptic digestion, 1094 ; pancrsatic digestion 1095
Sa'undbrb. W. M. Amphoteric Reaction of Milk (33)
ScHAPPBR. Hrrbrrt A. Bud Edgar P. Smith. Tungsten Hexabromide 1098
School of agriculture at Grignouy Prance 9^
Sbal, Alprbd Nbwlin. Action of Acid Amides upon Bensoin ...• loi
Sewage, disposal of , Paris 93^
Srorby, Edmund C. On Two Sources of Error in Sugar House Analyses 4^
Silicon, determination of, in aluminum 7^
Silver, oxidation of. 254 ; accuracy of determination in cop^r materials 816 ; deter-
mination of atomic mass of, 990; preparation of pure metal, 99a; separation
from arsenic by means of hydrochloric acid, 1039 ; acetate, preparatiottof pare,
998: benzoate. preparation of pure, looi : nitrate, preparation of pure. 995 ; oxide,
preparation of pure, 994; sulphide, refining of 643
Skin irritanU (81)
Slag, barium, in blast furnace (3>)
Smith, Edoar P. See Benkert, Arthur L.; Kelley, Jerome, Jr.; Schaffer, Hert>ert
A.; Taggart, Walter T. and Pield, Charles.
Smith, Edgar P. and Daniel L. Wallace. The Electrolytic Estimation of Mercury 1^9
Smitr, Edward L. Rapid Measuring Pipette 9<9
Smith, J. G. See Herty, Charles H.
Smith, Walter E. The Origin of Petroleum {Hi
Smithsonian Institution, account of (>7)
INDBX. 1 1 23
Smokeless powder, (66) ; the development of • 819
fiodinm, determination of, in aluminum, 770 ; pyroarsenate, action of bjdrochlorlc
acid STMon i<Q7
Sodium and potassium chlorides. Indirect analysis of a mixture of 184
Solution of carbon compounds, heats of 146
Specimen bottle 4^2
Sfshcrr. a. B. See Dennis, I«. M.
Spktkrs, C. L. Heats of Solution of Some Carbon Compounds, 146; Some Thouirbts
about Liquids • 7*4
Squibb, Hdwabd R. The Manufacture of Acetone and of Acetone Chloroform from
Acetic Acid. 331; Volumetric Determination of Acetone 106S
Stabi., Karl P. Hydrofinoric Acid -• 41S
Starch, an analjrtical investiflration of the hjrdrolysis of, by acids 869
Stas memorial « aoi
Steel, carbon determination in, »3 ; present status of iron and steel analysis (^)
Stilucah, Tboicas B. Note on tht Solubility of Bismuth Sulphide in Sodium Sul-
phide with Special Reference to the Bstimation of Small Amounts of Bismuth in
Anti-Priction Alloys ^3
Stoddabd, John Tafpan . A New Balance for Pirst Year's Work in General Chem-
istry (Note) x89
8TOKB8.H. N. MeUphosphinic Acid •-.•• (go)*
Stonb, Gbobgr C. Remarks on Mr. Auchy's Paper on the Volumetric Detennina-
tion of Manganese, 338, (30) ; Probable Production of Permanganate by Direct
Combustion of Metallic Manganese, 230, (30) ; Note on the Solubility of Bismuth
Sulphide in Alkaline Sulphides 109Z
STuifTC. Prof. C. R. Resolutions adopted by Cincinnati Section on death of (34)
Style in writing chemical papers, discussion on • • (77)
Succinimide. heat of solution in water, xsx ; in ethyl alcohol X54
Sucrose, heat of solution in water xsx
Sugar, inversion by salts, 130. 693 ; determiimtlon of reducing, in terms of cuprie
oxide 749
Sugar cane, occurrence of the amines in the juice of 743
Sulphides, estimation of , in calcium carbide. .« 74o
Sulphur in pig-iron, Drown's method of determining, 406 ; estimation in pyrites,
446 ; estimation of. in pyrites. 685 ; determination of, in cast iron 1079
Sulphuric acid, reduction of. by copper, 351 ; quantitative determination of, by pho-
tometric method, 661 ; determination of, 683 ; determination as barium sulphate,
793; reduction of. by copper 942
SUMMRRS, BSRTR AKD S. Carbou Determinations in Pig Iron X087
Sunflower, proteids of the * 6s3
^F AGO ART, Waltbr T. and Smith, Edgar P. The Separation of Manganese fxom
Tungstic Acid 1053
Tantalum, reactions of oxides with carbon tetrachloride SSa
Tantalum and columbium, derivatives of 38
Tellurium, atomic weight of • so6
Tetraphenylasine, study of < ixa
Thallium, some compounds of ^ 970
Thallons trinitride 970 ; thallous thallic trinitride 973 ; thallous tellurate 973 ; thal-
lou^i cyanplatinite > 97^
Thoria, estimation of 79t
Thorium, separation from other rare earths 947
Titanium, occurrence of • 409
Titanium cesium fluoride ...• 60
Titanium rubidium fluoride • S8
Tolnidine. Sec paratoluidine.
Treasurer's report • (14)
1 1 24 INDEX.
Trlmethylamtne. the separatioo of ammonium from 670
TungT'ten hexabromtde T098
TungTfitic acid, separation of raaniranese from • '0S3
XTRKA, heat of nolution in water. 150; in ethyl alcohol iS3
Urethane, heat of solution in water. 150 ; in methyl alcohol. 152 : in ethyl alcohol, iss:
in propyl alcohol. 154 ; in chloroform, 155 ; in toluene ISS
Urine analysis, fallacies in (99)
ID^ANADIUM, separation from arsenic IQSX
Va rnish-making (47)
Veitch, p. p. On the Various Modifications of the Pemberton Volumetric Method for
Determinins: Phosphoric Acid in Commercial Fertilizers 389
Vbnablb. p. p. and Thomas W. Clarke. A Study of the Zirconates 4M
Vetch, the proteidsof sSs
Vitellin 609
Vivisection, objectionable letislation in regard to (87). (94). (95). (97)
Volhard's method for mangranese. sources of error in 498
Volumetric analysis, estimation of lead, 737 ; determination of acetone 1068
'ALLACH, DANIEL L. See Smith. Bdffar P.
^Washington Section. See Meetings of the Society.
Water, constitution of, 286 ; determination in viscous orfranic liquids 937
Water analysis, chemical versus bacteriological. 166; measurement of the colors of
natural waters, 264 ; the valuation of color in, 484 ; recent advances in milk tn-
vestigrations •• (7:^)
Watermelon, mineral constituents of the io6t
Waikwright, J. H. The Determination of the Solid Pat in Artificial Mixtures of
Vegretable and Animal Pats and Oils 9S9
Wait. Charles K. The Oxidation of Silver. 254 ; The Occurrence of Titanium 402
Weber. H. A. On the Behavior of Coal-Tar Colors toward the Process of Diares-
tion lOQ}
Walnut, proteidfl of the 616
Wiley H. W. On the Estimation of Levulose in Honeys and oth<»r Substances. 81.
189 ; Note on the Use of Acetylene Gas as an Illuminant in Polariscopic 'Work,
179 ; Determination of the Heat of Bromination in Oils, 378. (^); Second Interna-
tional Congress of Applied Chemistry, 923 ; A New Pormof Bbullioscope. 1063;
see also Bwell. E. E-
WiLEr, H. W. and E. E. Bwell. Determination of Lactose in Milks by Double Dilu-
tion and Polarization « iiH
WiLTON,A.L. A Modified Molybdate Solution 445
Wood Gum, composition of . 2x4; from birch wood 218
:ylAN * 215
'TTRTUM. atomic weight of 209
SBINC. atomic weight of 203
Zinc, electrolytic determination of 6m
Zinc, separation from arsenic by means of hydfochloric acid 1041
Zinc ferrocyanide • 1100
Zinc oxide, curious forms of (31)
Zirconates. a study of the 434
Zirconium tetraiodide 673
IftSYied witb January Number. 1896.
Proceedings.
BOARD OF DIRECTORS.
The Board of Directors have passed the following resolutions :
** Resolved^ That the Board of Directors hereby approve and
ratify the action of the majority of said Board, as obtained by
their signatures, in granting a charter for a Local Section of the
American Chemical Societ}*^ in North Carolina, and that the
charter date from the time said action was taken, November 8,
1895."
*' Resolved, That the Finance Committee of the American
Chemical Society is hereby authorized to approve, and the treas-
urer to pay to the General Secretary each month during the year
1896 a bill or bills for clerical help, provided, however, that the
total sum called for by said bills does not amount to two hun-
dred and fifty dollars ($250.00).*'
NBW MBMBBRS BLKCTBD XOVBMBBR 31, 1895.
Bailey, Ralph Waldo, Elizabeth, N. J.
Bischoff, Dr. .Ernst, 87-89 Park Place, New York City.
Broadhurst, W. Homer, Polytechnic Inst., Brooklyn, N. Y.
.Doerflinger, Wm. F., Polytechnic Inst., Brooklyn, N. Y.
Uolbrook, Frederick A., 75 Joralemon St., Brooklyn, N. Y.
Jameson, A. H., Cleveland Linseed Oil Co., S. Chicago, 111.
Lc Boutillier, Clement, High Bridge, N. J.
Morgan, J. Livingston Rutgers, New Brunswick, N. J.
Perry, Frank J., B.S., Polytechnic Inst., Brooklyn, N. Y.
Potter, Charles A., 174 Weybosset St., Providence^ R» I.
Shaw, Wm. T., Chem. Lab. Agn Exp. Sta., Bozeman, Mont.
Tucker, S. A., 135 Madison Ave., N. Y. City.
Tyrer, Thomas, Stirling Chem. Works, Stratford, E. England.
ASSOCIATB BI<BCTBD NOVBMBBR 21) 1895.
Tuckerman, Alfred, 342 West 57th St., N. Y. City.
NBW MBMBBRS BLBCTBD DBCBMBBR I3, 1865.
Bellam, Henry Lynch, B.S., Anaconda, Mont.
Cameron, Prof. Frank Kenneth, Catholic Univ. of America,
Washington, D, C.
(2)
Cushman, AUerton S., Washington Univ., St. Louis, Mo.
Cutts, Henry E., care Stillwell & Gladding, 55 Fulton St., N.T
Elliott, E. C, care Univ. of Nebraska, Lincoln, Nebr.
Hobbs, Perry L., Western Reserve Medical College, Clevelanc ,
Ohio.
Meisel, C. F. A., 402 Washington St., New York City.
Moore, Chas. C, Jr., Dept. Agr. Div. Chemistry, Washingto.
D. C.
Schmidt, H. B., 215 E. 4th St., Cincinnati, Ohio.
Stoddard, Dr. H. T., 57 Crescent St., Northampton, Mass.
Thomas, W. S., Belt, Cascade Co., Mont.
ASSOCIATB EI^CTED DBCKMBBR 13, 1895.
Waldman, Louis I., P. O. Box 162, Albany, N. Y.
CHANGES OF ADDRESS.
Appleton, Prof. J. H., 209 AngellSt., Providence, R. I.
Benton, Geo. W., 27 E. St. Joe St., Indianapolis, Ind.
Dalton, Parmly, Swampscott, Mass.
Dunham, E. K., 338 E. 26th St., New York City.
Ehrenfeld, A Clemens, Steele High School, Dayton, O.
Feid, George F., 519 Findlay St., Cincinnati, Ohio.
GriflSth, Dr. S. H., U. S. Naval Museum of Hygiene, Wash-
ington, D. C.
Guiterman, Franklin, care Omaha and Grant Sm. Co., Durango,
Colo.
Hewitt, Edward R., 119 E. i8th St., New York City.
Lammers, Theodore L., Helena, Mont.
Textor, Oscar, 158 Superior St., Cleveland, Ohio.
Trubek, M., Raceland, La.
Volckening, Gustave J., 88 Clinton Ave., Brooklyn, N. Y.
Wood, Edward, Harvard Medical School, Boston, Mass.
ADDRESS WANTED.
Grosvenor, Wm., Jr. Last address. Box 166, Johns Hopkins
Univ., Baltimore, Md.
MEETINGS OF THE SECTIONS.
NEW YORK SECTION.
The regular meeting was called to order December 6th, 1895.
at 8.25, Prof. P. T. Austen in the chair. There were about
sixty members present.
The chairman opened the meeting with the statement that Dr.
Webb, the President of the College of the City of New York,
(3)
and Prof. R. Ogden Doremus, had put the chemical lecture room
of the college at the disposal of the society ; and in his opinion
it was the most satisfactory and most favorably situated of any
that had yet been considered. He then introduced Prof. Dore-
mus, who said that he was as much surprised as any one at the
success of the society's request, as he had been under the im-
pression that there was something in the charter of the college
which prevented such use of the room. He remarked that the
laboratory was now, since the destruction of the University
building, the oldest educational chemical laboratory in the city.
He hoped the society would find it suitable to their purpose
and assured it of the heartiest welcome.
The minutes were then read, and the remarks of Prof. McMur-
trie in regard to Illinois waters, as reported, were corrected, and
the minutes adopted. Prof. McMurtrie moved that the thanks
of the Section be sent to President Webb and Dr. Doremus for
their courtesy in giving the Section the use of the lecture room.
The motion was seconded and carried.
A letter addressed to the chairman from the Secretary of the
English Society of Chemical Industry was then read, thanking
the New York Section and the Lehigh Valley Section of the
American Chemical Society, and the New York Section of the
Society of Chemical Industry for the honor done to the President
of their Society, Mr. Thos. Tyrer, and the Hon. Foreign Secre-
tary, Mr. Ludwig Mond, on the occasion of their recent visit to
New York.
The letter was ordered on file.
Prof. Moale read a paper entitled **A Brief History of Naph-
thalene,*' in which the work of the earliest investigators of this
interesting substance as well as those in recent years, was re-
viewed.
Mr. Neiman was called upon by the chairman and gave his
experiences in attempting to make naphthalene synthetically,
for the purpose of deciding its theoretical constitution.
He stated that the decomposition of certain amido-naphthol-
sulpho-acids having a tendency to show that the position of the
double bonds in the napthalene ring are not symmetrical,
attempts were made to disprove this by the synthetic production
(4)
of naphthalene from ortho-xylene tetrabromide and ethane. By
passing ethane over a heated mixture of granulated pumice
stone and ortho-xylene tetrabromide, a portion of naphthalene
was formed, but circumstances prevented the further investig-a-
tion in this line. This formation would seem to show that the
central bond is a double one, and the formula a symmetrical one
as far as the bonds are concerned.
The. second paper of the evening, on "Vegetable Proteids,"
was read by the author, Dr. T. B. Osborne.
Mr. Hewitt asked if a ten per cent, solution of sodium hy-
droxide would extract all the proteids or only one, or only a few.
Dr. Osborne replied that all the proteids would dissolve.
Mr. Hewitt had extracted the white bean in large quantities,
agitating the bean flour in dilute alkali by machinery, and had
obtained a clear solution which filtered readily.
Mr. Hewett asked if there was any difiference in the product
on repeated precipitations. Dr. Osborne replied, ** No, not if
they are pure. ' *
Prof. Speyers said that the most it\teresting point to him was
the solubility of the glutinoids in a mixture of alcohol and
water, when it appeared that they were insoluble in either water
or alcohol alone.
Dr. Osborne thinks there may be a hydrate formed by takings
up water from the dilute alcohol, and this hydrate then dis-
solves.
Dr. Smith said that no one who had not worked in this diffi-
cult subject could appreciate the value of Dr. Osborne's work,
and especially the classification which had been made of the
compounds.
Mr. Hewitt suggested a method of separating the proteids by
availing of the different behavior of solutions of different osmotic
pressures, and described experiments in which he had used mem-
branes prepared with gelatine treated with formaline, which he
found more satisfactory than potassium bichromate or tannin for
making the gelatine insoluble. He had also found that the re-
sults differed when bichromate or tannin were used.
Prof Austen asked if the vegetable proteids are entirely dif-
(5)
ferent from the animal, and if there is any classification of the
latter.
Dr. Osborne said that superficially they were, quite similar,
but closer study revealed marked difEerences. Nearly all
authors of physiological chemistries give classifications for these
proteids, but that most of these authorities differ to a greater or
less extent from one another. The most comprehensive classi-
fication of the animal proteids that he had seen was that given by
Prof. Chittenden in his Cartwright lectures for 1894.
Mr. J. H. Wainwright read a paper on the ** Determination of
Solid Pats in Artificial Mixtures of Vegetable and Animal
Fats.'' He said that the problem was to make analyses of mix-
tures of solid fats and vegetable oils, as cottonseed-oil, lard, and
oleostearin, which might be classed as compound lards, of
which " cottolene " was an example ; the chief object being to
ascertain the percentage of oleostearin.
In a simple mixture as cottonseed-oil and stearin, the analy-
sis can be readily made by determining the constants of the fat,
iodine number, etc. But in a compound lard containing lard
itself, the determination of constants gives very little satisfaction,
owing to the confusing effect of the lard. Experiments were
made on special mixtures with the result of proving that under
pressure at ordinary temperatures both cottonseed-oil and lard
are removed, leaving the stearin.
At temperatures much above 75** F. or much below 70** F. the
error was considerable, but within these limits he had obtained
results differing not more than a half per cent, from the correct
figure. Until the method was further perfected, he allowed a
plus or minus error of one and a half per cent.
CINCINNATI SECTION.
The regular meeting of this section was held on Tuesday
evening, December 17, 1895, Dr. Alfred Springer presiding.
Prof. T. H. Norton spoke of the loss sustained by the section
in the death of Chauncey R. Stuntz, professor of physics and
chemistry at Woodward High School, and moved that Messrs.
F. Homburg, E. Twitchell, S. P. Kramer, and H. B.Foote, all
former students of the deceased, be appointed a committee to
draft resolutions of respect. Prof. Stuntz was one of the best
(6)
known educators in the Ohio Valley and one of the org^anizers
of the chemical society of Cincinnati and vicinity, which after-
ward became the Cincinnati Section of the American Chemical
Society. He was elected chairman for 1893, and his earnest
work in behalf of the Section was highly appreciated by all the
members.
Prof. J. U. Lloyd read a paper on ** Percolation" and gave a
practical demonstration oi packing the percolator.
The committee appointed to nominate o£Bicers for the Section
for 1896 reported the following ticket :
President, E. Twitchell.
Vice Presidents, Prof. O. W. Martin and Chas. G. Merrill.
Treasurer, H. B. Foote.
Secretary, E. C. Wallace.
Directors, Dr. S. P. Kramer, Dr. S. Waldbott, Dr. John Mc-
Crae,
On motion the secretary was instructed to cast the ballot of
the Section in favor of the above ticket.
IfltYicd with Pcbmary Nvmber, 1896.
Proceedings.
TWELFTH GENERAL MEETING OP THE AMER.
ICAN CHEMICAL SOCIETY.
The twelfth general meeting of the American Chemical
Society was held in Cleveland, Ohio, December 30th and 31st,
X895.
The first session was called to order by the president, Dr. £.
P. Smith, at 9.15 a. m., Monday, December 30th, in the Chemi-
cal Lecture Room of the Western Reserve Medical College.
Mr. M. S. Greenough, President of the Cleveland Gas Light
and Coke Company, was introduced and gave the following
words of welcome :
GentUmen of the American Chemical Society:
It is with great pleasure that I have accepted the invitation of
Prof. Mabery to act as spokesman for the local interests to which
you are allied, and welcome you to the hospitalities of our city.
Cleveland is a very popular city for conventions, and I am in-
formed that no less than 100 have met here during the year now
closing. I venture, however, to assert that no body of men
gathered together in this vicinity or elsewhere could represent a
profession more useful or honorable than your own. What civ-
ilization owes to chemistry is hardly appreciated by the ordinary
citizen. He is so accustomed to enjoy the health, comfort and
prosperity which comes from it, that he looks upon his blessings
as part of the natural order of things, and never stops to consider
to what he is indebted for them. When man was in his primi-
tive state and dressed in skins, lived in a tent on what he could
kill and changed his residence daily, he naturally had not much
use for chemistry, but nowadays without the expert analyst we
should be simply helpless. We depend upon him to know that
our drinking water is safe to use, whether our children's milk is
genuine or diluted, whether our groceries are pure or adulterat-
ed. We invoke his assistance in every department of manufac-
ture. In the steel business for instance, which is the right hand
of this city, the buyer purchases on a guaranteed percentage of
ingredients, and every blow is tested, and where iron ores are
saleable or unsaleable according to their chemical composition,
there the chemist is absolutely indispensable. It might be truly
(8)
said that without the constant, persistent, almost unnoticed work
of the chemist, this city of Cleveland, with its diversified inter-
ests, including every sort of steel work, with its paint works, its
refineries, its chemical works and its great ship yards, would be
a small town, one-tenth its present size, with gardens and or-
chards coming down to the Public Square. Cleveland is built oa
the work of the expert chemist, and yet not one man in a hun-
dred ever stops to realize that fact.
My own business is to furnish illuminating gas to this commu-
nity and, of course, no man here knows so well as I how much
that industry is indebted to chemistry. When I left Harvard
College, twenty-seven years ago, and entered the service of the
Boston Gas Co., gas sold at $2.50 per thousand; now it is sold
there at a dollar, and here this company only nets seventy-five
cents for its product, after paying to the city our franchise tax of
six and one-half per cent. This is not all due directly to chem-
istry, but a great part of it is. An old-fashioned gas manager is
reported to have said **I don*t care a d — n about your hydro-
gens and your oxygens ; you give the coal and I'll cook the gas
out of it." Such a man was once very useful, and may be still,
but if everybody had held his opinions gas would not now be
sold so cheap or pure. There is not a large company in this
country to-day but what either employs a permanent chemist or
has one near by on whom to call. Before the chemist lent his
aid gas companies either ran their tar and ammonia into the
nearest river, or else burned their tar and left their ammonia in
the gas. Without his experiments and analyses we should never
have applied the principles of regenerative gas firing to our re-
tort benches or our gas burners. We should have failed in the
successful enrichment of .decomposed steam by petroleum prod-
ucts, which has been a development of the last twenty years, and
which furnishes the method by which gas can be most cheaply
made in many localities in this country.
Auer Von Welsbach was an Austrian chemist who discovered
the luminous qualities of some rare earths, by heating which a
foot of gas is enabled to give three times as much light as is or-
dinarily obtained by burning it, and by which gas has been fur-
nished with its strongest weapon in the fight for business. Last
of all is this new discovery of calcium carbide with its product of
acetylene, which affords the most beautiful artificial light yet
produced ; and though I am by no means prepared to endorse
the claims of its enthusiastic advocates, yet it must have its effect
upon the lighting interests of the whole country of every
description. *' Every man to his last'' says the shoemaker, and
I speak of these things because they have come under my own
(9)
eyes ; but I have no doubt that every manufacturer in this city
might be heard from in a similar strain as to the cheapening and
improving of his product by the skill of your profession. I know
that I speak for them all when I welcome you to our city, and
dwell upon the respect in which we hold you.
You will find upon the programs a large number of enter-
prises which you are invited to visit. The gas works are not
upon the list, but if any of your body are interested in that di-
rection you will find our works on Willson Avenue a good exam-
ple of modem gas engineering.
I sincerely trust that you will find your stay here both agree-
able and interesting, and that we may have the pleasure of seeing
you again, either individually or collectively.
If there are any eastern members of your body who are con-
sidering the advisability of moving westward, you will, I am
sure, take home with you for reflection the great futiu-e which is
awaiting this city and its environs, and will also realize the oppor-
tunities which are awaiting the man who settles among us
thoroughly equipped with the education of the industrial chem-
ist.
In response. Dr. E. F. Smith, President of the American
Chemical Society, said :
Believe me, sir, that the American Chemical Society fully
appreciates the cordial and • hearty reception that has been
extended to its members, and through me returns to you and
those whom you represent, its sincere thanks.
We are glad to be here, and we are eager to avail ourselves of
the many opportunities which we shall have while in your
midst, of inspecting the many industrial plants within the bor-
ders of this city, and within its immediate neighborhood.
We feel particularly grateful to our Council for having called
us here, where there is such a centralization of enterprises
founded on scientific principles. I can assure you, we will take
advantage of the privileges which you have offered to us.
We feel happy, too, in the thought that in coming here we
have a chance to meet with your local chemists, who are a host
within themselves. They have wrought well, and they have
contributed very largely to placing the name of your city upon a
high pedestal among the cities of this nation which encourage
industries founded upon chemical principles and processes. Two
of them particularly are we proud of : I need not mention the
names of Dr. Morley and Dr. Mabery, the first of whom has
won for himself a reputation by his investigations on certain
constants of nature ; and the second has achieved equal glory by
(lO)
the researches which he has made, and the light which he has
thrown upon thedif&cultiessurroundingthe petroleum problem.
For these reasons, and for the opportunities which we hope to
have while here of inspecting these great industries, and for the
kindly reception given us and the many hospitalities which will
be ours while we are here, we thank you.
I trust that you, and all Cleveland for that matter, if conveni-
ent, will attend our session and join in the discussions of the
papers which are to be presented. (Applause.)
The President then called for the report of the General Secre-
tary, which was read, and by vote of the Society was ordered
placed on file. The Secretary's report is as follows :
To the Members of the American Chemical Society:
Gentlemen : — ^The record of the American Chemical Society
during the past year has been one of enlarged activities, and of
higher attainments and more extended usefulness than ever
before. The membership of the Society has steadily increased ;
three new local sections have been established and many of the
older sections have made commendable progress in numbers and
in the character and influence of their work ; the journal has
been much improved, and the Society to-day exerts a more
potent influence among chemists, both in the old world and the
new, than it did one year ago.
The roll of membership December 26, 1894, was as follows:—
Members, 720 ; associates, 55 ; honorary members, 8 ; total, 783.
On December 26, 1895, there were 884 members, 58 associates,
and 8 honorary members ; total 950. If to this number we
add the names of 54 persons, who have been elected, but have
not yet qualified, (a great majority of them having been elected
since the ist of November, and according to the constitution,
not being required to qualify before January ist), and 31 whose
applications for membership are now under consideration, we
have a grand total of 1035, which n:\ay be considered the
present numerical strength of the Society. The increase in
membership during 1895 has been greater than in any previous
year, except 1894, and there is reason to believe that the momen-
tum which the Society has acquired in this direction during the
past few years will continue for a long time to come.
(II)
The following named members have died since the presenta-
tion of the last annual report of the General Secretary : A. A.
Pesquet, H. B. Nason, J. C. Dittrich, W. H. Whalen, Mark
Powers, Lewis W. HofiFmann, G. E. Moore, W. G. Wallace and
Win. C. Wilson. This list was reported to the Society at the
Springfield meeting last August, and sketches of Prof. Nason,
one of the ex-Presidents of the Society, and of Dr. Moore, one
of the most highly respected members of the New York Section,
have appeared in the Journaf of the Society.
The three local sections established during the past year are
located respectively in Chicago, Nebraska and North CaiDlina.
There are now nine local sections of the Society, viz :
Rhode Island Section : Presiding Officer, Charles A. Catlin,
133 Hope St., Providence, R. I.; Secretary, Walter M. Saun-
ders, Olneyville, R. I.
CincinnaH Section : Presiding Officer, Karl Langenbeck, 27
Orchard St., Zanesville, Ohio; Secretary, E. C. Wallace,
Room 71, Blymeyer Bttilding, Cincinnati, Ohio.
New York Section : Presiding Officer, Peter T. Austen, Poly-
technic Institute, Brooklyn, New York ; Secretary, Durand
Woodman, 127 Pearl St., New York City.
Washington Sectiofi: Presiding Officer, Charles K. Munroe,
Columbian University, Washington, D. C. ; Secretary, A. C.
Peale, 605 12th St., N. W., Washington, D. C.
Lehigh Valley Section : Presiding Officer, Edward Hart, Lafay-
ette College, Easton, Pa, ; Secretary, Albert H. Welles, Lafay-
ette College, Easton, Pa.
New Orleans Section : Presiding Officer, A. L. Metz, Tulane
Medicfil College, New Orleans, La. ; Secretary, Hubert Edson,
Bartels, La.
Chicago Section: Presiding Officer, Prank Julian, South Chicago,
111. ; Secretary, F. B. Dains, 2421 Dearborn St., Chicago, 111.
« Nebraska Section : Presiding Officer, H. H. Nicholson, Uni-
versity of Nebraska, Lincoln, Nebraska ; Secretary, John White,
Box 675, Lincoln, Nebraska.
North Carolina Section .• Officers not yet reported.
The financial outlook of the Society is very encouraging; the
report of the Treasurer shows a good balance after paying all
(12)
indebtedness. A little well directed efifort on the part of the
members to secure advertisiements for the Journal, and increase
the regular and associate membership, would add very mate-
rially to the income of the Society and would enable the Com-
mittee on Papers and Publications to enlarge the scope of the
Journal, and to make it in many ways even superior to what it
is at present.
The membership dues have been collected by the General Sec-
retary during 1895 ^^ 1^ ^^^ previous years. This work has
been looked after very closely, and the results have been of two-
fold advantage to the Society — a considerable sum has been
secured that otherwise would have been lost in unpaid arrears,
and those who have paid their dues, after repeated reminders
from the Secretary, have been saved to the membership of the
Society, and have been more prompt the next time in their
remittances.
During the year 1895 it has been necessary to drop the names
of only twelve persons from the roll of the Society, as required by
the constitution, for non-payment of arrears.
During the year Prof. F. W. Clarke resigned as Chairman of
the Committee, appointed by the Council, for considering the
question of revising the constitution, and Dr. H. W. Wiley was
appointed to fill the vacant, position. This committee has not
yet completed its work. Under the authority and direction of
the Society, the General Secretary secured the passage of a bill
by the New York Legislature, enabling the Society to choose
its directors without regard to their being residents of the State
of New York, or any other State or locality, and also legalizing
whatever action the Society might take at any of its meetings
held outside of New York State.
Prof. Clarke presents his annual report on atomic weights
as a paper to be read at this meeting. The Society is to be con-
gratulated in having among its members a person so able and
at the same time so willing to present fully a regular annual
report upon this subject.
During the year the President, upon the authority of the
Council, appointed Messrs. Hale, Austen and Breneman as a
committee to consider the question of a permanent badge for the
(13)
Society. The committee have met and considered the subject
and requests for suggestions and designs have been sent to
every member of the Society, but no report has yet been pre-
pared.
The Society held its eleventh general meeting in Springfield,
Mass., August 27th and 28th, 1895, just previous to the meeting
of the American Association for the Advancement of Science in
the same city. There was a large attendance and a full pro-
gram of papers. The meeting was one of unusual interest and
inspiration to all who were fortunate enough to attend. A full
account of the proceedings was published in the October number
of the Journal.
Early in the year formal invitations were received from the
officials of the city of Cleveland, the Chamber of Commerce of
Cleveland, the Western Reserve University, the Case School of
Applied Science and the Cleveland Chemical Society, for the
American Chemical Society to hold their annual meeting this
year in Cleveland. These invitations were so hearty, and Cleve-
land is so desirable a city in which to hold a meeting of tiie
Society, that the Council gladly accepted the invitations, with
the result that we are now .the favored guests of these bodies and
enjoying their cordial and unstinted hospitalities.
It is much to be regretted that every member of the Society
could not be present to partake of the rich feast we find pre-
pared for us in this beautiful and enterprising industrial and ed-
ucational centre.
In looking back upon the past, carefully surveying the present
condition and attainments, and anticipating the future, the mem-
bers of the American Chemical Society have every reason for
encouragement and gratification.
If the Society could receive from all its members the loyaltj'
and active support which has always been given by those who
have been most devoted to its interests, the rapid progress of the
past few years would be regarded as little when compared with
what the next decade would witness. May we not hope as we
begin this new year in our history that this active support and
loyalty will be accorded, and that every member will to the
utmost of his ability exert himself to increase the membership.
(14)
the strength and the influence of the Society, both at home and
abroad.
We sometimes feel that we need to establish a league of loyal
Americans in the realm of chemical science ; whatever Ameri-
cans accomplish should go to the credit of America*. Bat this is
not all ; we believe it is a mistake for any chemist under the
existing conditions to think that his best path to recognition by
the scientific wolrld lies through the medium of foreign periodi-
cals. Articles published in our Journal are so fully abstracted
and so often copied entire by foreign scientific periodicals that
it seems that the best means for securing general publication and
wide spread recognition for any deserving paper is through the
columns of our Journal. Thus not only loyalty to the Ameri-
can Chemical Society, but also self interest demands that the
columns of our Journal be kept filled with the records of the
best work done in our own country.
Respectfully submitted,
Albert C. Halb,
Brooklyn, N. Y., Dec. 26, 1895. General Secretary,
Financial Report, 1895.
Received for daes from Dec. i, 1894 to Dec. 14, 1895 % 4365.75
Retained as Commission 436.50
Balance for the A. C. S. Treasurer 39^-35
Paid A. C. S. Treasurer (as per vouchers) 3025.00
Balance not yet forwarded '^'S
Interest ii^S
Balance on Deposit 1 15.73
Albbrt C. Hale,
Dec. 14, 1895. Gen. Sec. A. C. S.
In the absence of the Treasurer his report was read by the
General Secretary, as follows :
New York, December 26, 1895.
TRBASURBR'S REPORT FOR THE YEAR 1895.
Receipts,
Balance on hand Dec. aist, 1894 % 505.95
Net dues and interest received from the Oen'l Secretary 3f940-73
Cash received for subscriptions to Journal 624.93
" " " back numbers 122.83
'' " " advertisements in Journal 5'7'Z^
Interest from Farmers' Loan and Trust Co 9.S0
l5.7«-97
€t
«<
««
(15)
Disbursements .
expenses of Treasurer's office $ 1 1>35
•• " " Gen'lSec'y office 494-03
" •• Editor'soffice 56.40
" Librarian's office 78.18
■ • ** * Springfield meeting 42.17
general expenses • 67.30
salary of editor 350.00
publication of Journal 3,344.15
insurance • • •; 30.00
" rebates to Local Sections, as follows :
New York Local Section 1 195.98
Washington" ** 103.33
Lehip;h Valley •* 30.00
Cincinnati ** *' 60.00
Chicago " " 38.33
Nebraska " *• 21.67
449x3
Balance -on hand Dec. 36th, 1895:
In Farmers Loan and Trust Co $ 443.63
In Bank of Metropolis 356.90
Checks on hand 184.15
Cash on hand 12.00
Postage stamps 2.40
99908
I5.721.97
The following report of the Librarian was read by the General
Secretary :
December 26, 1895.
The library has been in storage during the year and therefore
there is little to report. It is hoped, however, that a suitable
place where the books may be useful to the members will soon
be found. Several places have been suggested but none as yet
that meets the requirements of the case.
There is a growing call for back numbers of the Journal and I
would suggest that the money obtained from their sale be used
to find and care for the library.
The Librarian has received the following exchanges :
UNITED STATES.
American Chemical Journal.
American Joufnal of Pharmacy.
American Manufacturer and Iron World.
American Naturalist.
Annals of the New York Academy of Arts and Sciences.
Anthony's Photographic Bulletin.
(i6)
Bulletin of the American Museum of Natural History.
Deutsch-Amerikanische Apotheker-Zeitung.
Engineering and Mining Journal.
Kphemeris (Squibb).
Engineering Magazine.
Journal of the Franklin Institute.
Journal of the United States Artillery.
New York Medical Journal.
Oil, Paint» and Drug Reporter.
Popular Science Monthly.
Proceedings of the Academy of Natural Sciences (Philadel-
phia).
Proceedings of the American Academ}' of Arts and Sciences
(Boston).
Proceedings of the American Philosophical Society (Philadel-
phia).
School of Mines Quarterly.
Scientific American.
Technology Quarterly.
Textile Colorist.
Textile Manufacturers* Review and Industrial Record.
Transactions of the American Institute of Electrical Engineers.
Transactions of the American Institute of Mining Engineers.
Transactions of the New York Academy of Sciences.
CANADA.
Journal and Proceedings of the Hamilton Association.
Proceedings of the Canadian Institute.
Proceedings and Transactions of the Nova Scotia Institute of
Sciences.
HOLLAND.
Revue Internationale des Falsifications.
ITALY.
Gazzetta Chimica Italiana.
ENGLAND.
Analyst.
Chemical News.
Engineering.
Journal of the Chemical Society.
Journal of the Society of Arts.
Journal of the Society of Chemical Industry.
Jil and Colorman*s Journal.
Pharmaceutical Journal and Transactions.
Sugar Cane.
Transactions of the Institute of Brewing.
(17)
FRANCE.
Annales des Mines.
Bulletin de la Soci^td Chimique de Paris.
Bulletin de la Soci£t6 Industrielle de Rouen.
Bulletin de la Soci£t6 Industrielle de Amiens.
Moniteur de la Teniture.
Moniteur Scientifique de Quesneville.
Repertoire de Pharmacie.
GERMANY.
Archiv der Pharmacie.
Bierbrauer.
Bulletin de la Soci6t£ Industrielle de Mulhouse.
Sitzungsberichte der K. B. Akademie der Wissenschaften zu
Munchen.
AUSTRIA.
AllgemeineOesterreichische Chemiker und Techniker Zeitung.
Oesterreiches Zeitschrift ftir Berg und Htittenwesen.
(Proceedings) Kaiserliche Akademie der Wissenschaften in
Wien.
RUSSIA.
Bulletin de 1* Academic Imperiale des Sciences de St. Peters-
burg.
Memoirs de la Soci^£ des Naturalistes de Kiew.
AUSTRALIA.
Journal and Proceedings of the Royal Society of New South
Wales.
ROUMANIA.
Buletinul Societatii de Sciinte Fizice.
The Librarian wishes to acknowledge the receipt of the fol-
lowing volumes :
Chemical Bulletins U. S. Department of Agriculture.
Reports and Bulletins of the Massachusetts Experiment Sta-
tion.
Reports and Bulletins of the Connecticut Agricultural Exper-
iment Station.
One hundred years of business life, Wm. J. Schie£Felin.
An Introduction to the Study of Rocks. Presented by the
Trustees of the British Museum of Natural History.
Respectfully submitted,
F. E. Dodge,
Librarian.
(i8)
Dr. Hart was then called upon and made a report for the Com-
mittee on Papers and Publications.
He stated that last year 915 pages of the Journal were pub-
lished, this year we published 1092 pages, and we have enottg^h
papers left over to fill the January number and part of the Feb-
ruary number. The committee have been hampered in their
plans by the financial condition of the society. But the treasu-
rer's report is an encouraging one, and we hope next year, if inre
are to go on with the work, to show still better results.
I may say that there are frequent complai nts of non-delivery of tbe
Journal from members of the society. The difficulty in most cases
is not in the sending out, but with the post office authorities* who
are so overwhelmed with second-class matter that they become
careless. The Journal is mailed as carefully as it is possible to
do it, the address printed and kept standing, and there are very-
few mistakes made in the office of distribution. I hope that
members who do not receive the Journal regularly will write to
us, and we will make every effort to get the Journal to them.
Very often when a complaint has been made of non-receipt of
the Journal, another Journal has been sent, and the second one
has not been received. The difficulty seems to be with Uncle
Sam's method of conducting business.
Several plans have been suggested and considered for increas-
ing the efficiency of the Journal, but nothing that has been sug-
gested is yet ready for report.
The question of a good journal is largely a financial question.
If we have money to print and circulate a journal, we can have
a good journal. There is no difficulty about papers. We have
more good papers now than we can manage.
It would perhaps be interesting to the members to know some-
thing about the actual circulation of the Journal, which is con-
siderably in excess of the membership. We sent out for Decem-
ber 11 25 Journals. Of this number less than fifty are exchan-
ges, so our actual paid subscription list is very nearly iioo. The
returns for the next year are beginning to come in, and I am
able to report large accessions to the number of subscribers, es*
pecially foreign subscribers.
(19)
Prof. Sabin reported for the Finance Committee.
Formal reports were then made by members of special com-
mittees as follows :
Committee on Duty- Free Importation, C. £. Munroe ; Com-
mittee on Nomenclature and Spelling of the Journal, Edward
Hart; Committee on Triennial Congre^ of Chemists, F. W.
Clarke.
The Secretary then read a letter from Dr. T. H. Norton, of
Cincinnati, expressing his regret that he was unable to attend
the meeting and sending his best wishes for an enjoyable and
profitable occasion.
The following communication was then read by the Secretary :
Department of the Interior,
United States Geoixxjicai, Survey.
Washington, D. C. November 30, 1895.
To the President of the American Chemical Society :
Sir: In compliance with a request emanating from the
Chemical Division of this Survey, I address you as the head of
the most representative body of American chemists with a view
to securing action on the part of the American Chemical Society
looking toward the general adoption, in this country at least, of
a method for the proximate analysis of coal.
The prevailing method of proximate anal3rsis, though unscien-
tific and far from satisfactory, is still capable of affording infor-
mation which is valuable, as chemists and geologists know,
both as a preliminary to more extended scientific examination
and as to the value of coal for one or the other of the uses to
which it may be put as a fuel. But in practice such wide diver-
sity exists in the details of this method that the analyses of dif-
ferent series of coals, made by different chemists, are seldom of
much value for purposes of comparison, since concordant results
are only to be attained by a rigid adherence to a certain order
of procedure.
This matter is of great importance to geologists and chemists
as well as to those who contemplate investing in coal
properties and to many large consumers of coal. A uniform
method of analysis, which should also cover the determination
of sulphur in coals seems therefore very desirable, and the adop-
tion of such a method can most readily be brought about by the
authoritative sanction of the American Chemical Society.
I would make the suggestion that a committee of chemists
experienced in coal analysis be appointed with instruction to
(20)
gather from all sides the views of those whose opinions are likely
to be of value in connection with their own, and from the data
thus collected to formulate in minute detail a method which may
come to be accepted as the one by which all analyses of coal and
coke infthis country shall be made.
It is not necessary that a nbvel method be devised, but only
that the diversity in detail now practiced be reduced to uniform-
ity by the selection of those features which in the judgment of
the committee will most nearly meet the exigencies of the case.
Yours with respect,
Chas. D. Walcott,
Director.
On motion of Prof. Edward Hart it was resolved that the
President appoint a committee of three to take into consideration
Prof. Walcott's communication and present a report upon the
same at the Summer meeting.
After some announcements by the General and Local Secre-
taries, A. A. Bennett read a paper on *' The Quantitative Deter-
mination of the Halogens in the presence of each other;" and
Wm. McPherson presented a paper on ''Constitution of Oxyazo-
benzene." The latter was discussed by Drs. Prescott, Hart and
Mabery.
In the absence of the author a paper by Willis K. Everetteon
the ''Method of Analysis of Nickel and Cobalt in Ores," was
read by the General Secretary, and was afterwards discussed by
Drs. Mabery and C. B. Dudley.
A. B. Prescott then presented a paper prepared by himself and
S. H. Baer on the "Melting Points of Certain Homologous Pyr-
idine Derivatives,*' and this was followed by another paper enti-
tled * ' Pjrridine Alkyl Hydroxides, * * by the same authors. These
papers were discussed by Drs. Fireman, Smith and Hart. After
some announcements the session adjourned.
In the afternoon visits were made to various works in Cleve-
land, and in the evening the laboratories and lecture rooms of
Adelbert College and the Case School of Applied Science were
inspected, after which the Society held an evening session.
The evening session of the Society was called to order by
President Smith, at 8.15 p. m. in the Chemical Lecture Room of
the Case School of Applied Science. After some announcements
by the General Secretary, Dr. Chas. F. Mabery was introdnced
(21)
and delivered a very valuable and interesting address upon pe-
troleum. Prof. Mabery gave an account of the experimental
methods, products, and results connected with work now in
progress on American petroleums. The different forms of stills
employed in fractional distillation both under atmospheric pres-
sure and in vacuum were shown, together with the apparatus
for distillation under diminished pressure when many operations
are in progress. The determination of sulphur in gases, liquids,
and solids was described and illustrated by the apparatus.
Representative crude oils from the Oil Springs and Petrolia
fields in Canada, from the Lima and Pindlay fields in Ohio, and
the Berea grit sandstone in Ohio were exhibited and their com-
position given as well as the composition of representative oil
rocks, — the Corniferous limestone, the Trenton limestone, and
the Berea Grit sandstone.
A distillation now in operation for the separation of the bu-
tanes and pentanes from a very light gasoline (92^) in which a
distillate was collecting below — 10® was shown in operation,
together with other distillates with low boiling points, and their
halogen derivatives which are now under examination for the
purpose of establishing the identity of the butanes. The puri-
fied octanes and some of their halogen derivatives were also
described.
Prof. Mabery read a letter from Professor Markownikow of
Moscow, which stated that Professor Markownikow had given
no attention to Pennsylvania petroleum. In one of his papers,
the suggestion had been made that the Pennsylvania oil might
prove to contain the naphtenes. This assertion from Professor
Markownikow was obtained to correct the erroneous statements
in German and American works on petroleum that Markowni-
kow had examined Pennsylvania petroleum.
Professor Mabery exhibited many specimens of hydrocarbons
which had been separated from Berea Grit, Ohio, Canada, and
Pennsylvania petroleums for the purpose of ascertaining the
composition of these oils above 150°.
A number of specimens of sulphur compounds, including sul-
phides and unsaturated hydrocarbons were shown that had been
separated from Canadian petroleum.
(22)
After the address several questions were asked of Dr. Mabery
and various points were discussed by Drs. Dudley andPiescott;
Profs. Moulton and Breneman and Mr. Prasch. Upon motion
of Dr. Hale, the Society passed a unanimous vote of thanks to
Dr. Mabery. The evening session then adjourned.
The morning session of Tuesday, December 31st, was called
to order by President Smith at 9. 10 A. m. After some announce-
ments by the General Secretary, the President named the mem-
bers of the Committee on Coal Analysis, in accordance with the
request received by communication from Prof. Walcott. The
committee named were: Drs. W. P» Hillebrand, C. B. Dudley,
and W. A. Noyes.
Mr. James Otis Handy then read a paper on ** Improved
Methods for the Analysis of Aluminum, Alumina and Bauxite;"
this was followed by a paper on "The Cyanide Method of Ex-
tracting Gold from its Ores,*' by Wm. J. Martin, Jr., read by
the General Secretary in the absence of the author.
A paper on * * The Use of the Calorimeter in Detecting Adul-
terations of Butter and Lard," by E. A. de Schweinitz and James
A. Emery, was read by Prof. Sabin, the authors of the paper
being absent. Prof. Sabin also discussed some of the points
contained in this paper.
A paper by H. W. Wiley on ** Determination of the Heat of
Bromination in Oils," was read by Dr. C. B. Dudley, Dr. Wiley
being absent. This paper was discussed by Dr. Dudley and
Prof. McPherson.
After some announcements by Dr. Mabery regarding the after-
noon excursion, a paper on *' Technical Analysis of Asphaltum"
by Miss Laura A. Lynton was read by Dr. Prescott, and was
discussed by Prof. Sabin, Drs. Mabery and Prescott.
A paper on *' The Microscopic Detection of Beef Fat in Lard"
by T. S. Gladding, was read by Dr. Hart, after which Prof. P.
W. Clarke's Annual Report on the Atomic Weights of the Ele-
ments, was read by Prof. Breneman and discussed by Drs. E.P.
Smith, Edward Hart, and C. B. Dudley.
The report of the canvassers for the election of officers for the
year 1896 was presented by the Secretary and the following
(23)
named persons were declared elected: President, Chas. B. Dud-
ley; General Secretary, Albert C. Hale.; Treasurer, Chas. F.
McKenna; Librarian, Prank E. Dodge. Directors to serve two
years: Chas. F. Chandler, Peter T. Austen, Chas. E. Munroe,
Albert B. Prescott. Councilors to serve three years: J. W.
Mallet, Albert B. Prescott, T. H. Norton, G. C. Caldwell.
The retiring President, E. F. Smith, then introduced the
President elect, Chas. B. Dudley, with a few congratulatory
words to the Society in having secured a man so worthy to
occupy the position. After a brief and appropriate respbnse by
Dr. Dudley, he was requested to occupy the chair while the
retiring President presented his address on "A Glance at the
Field' of Electro-Chemistry."
On motion of Prof. Sabin, the Society passed a vote of thanks
to the Mayor and the Cleveland Chamber of Commerce, the
Western Reserve University, Case School of Applied Science
and the Cleveland Chemical Society for their kind invitation to
hold the Twelfth General Meeting of the American Chemical
Society in Cleveland, and for the courtesies extended to the
Society during their meeting. The thanks of the Society were
also voted to the members of the Local Committee on Arrange-
ments, to the proprietors and managers of the various works
visited, to those who received the chemists and conducted them
through the works, and to the persons who conducted the
various excursions and visits.
Upon motion of Dr. Dudley, a vote of thanks was g^ven to
the retiring President, the General Secretary and the Editor for
the highly satisfactory manner in which they had discharged
the duties of their respectives offices and to those who had pre-
pared papers for the meeting.
Dr. Mabery, President of the Cleveland Chemical Society
expressed the great pleasure felt by the people of Cleveland at
the honor the Society had conferred upon them in visiting their
city, and also the appreciation which they felt of the advantages
this visit had conferred upon them.
Dr. A. B. Prescott, one of the Ex-Presidents of the Society
was called upon by President Smith for some remarks, and
spoke briefly of the rapid growth of the Society, not only in
(24)
numbers but also in general tone and character of its work.
The Twelfth General Meeting of the American Chemical Soci-
ety was then adjourned.
Albbrt C. Hale,
General Secretary.
EXCURSION TO THE WORKS OP THE GRASSELLI CHEM. CO.*
This was the only excursion scheduled for Tuesday afternoon »
December 31. It was joined by nearly every visiting and local
chemist and was in charge of Mr. Edwin P. Cone, experimental
and research chemist of the company. Chemists to the number
of seventy-five assembled at a convenient locality and were trans-
ported by electric cars to the plant of the company located in
the southern part of the city. Here they were met by Messrs.
E. R. Grasselli, T. S. Grasselli, J. P. Lihme, gentle-
men of the operating department, and others, and were
escorted through the plant. This company operates ten different
large chemical plants in various parts of the country, one of the
largest being the works visited in Cleveland.
The following were the points of interest that were inspected :
Sulphuric Acid. — Several systems are operated here for burn-
ing lump and fine ore, the latter being especially adapted for
such work. Only pirites is burned obtained from different
parts of this country and abroad. The construction of these plants
was found to be modem and the equipment equal to the best.
In connection with these systems are the concentrating plants
where sulphuric acid in large quantities is concentrated to its
various commercial strengths.
Nitric Acid, — In this plant nitric acid was seen in process
of manufacture from Chile saltpeter on a large scale. In con-
nection with this was a plant for the production of different
grades of acid for the trade.
Hydrochloric Acid, — This plant comprises various modem
devices for the manufacture of numerous qualities of muriatic
acid. Sodium chloride and nitre-cake are used to a large
extent. Salt-cake from these plants is worked up in large
quantities and sold to glass manufacturers.
1 This description, written by B. P. Cone, was received too late for insertion in the
report of the General Secretary.
(25)
Mixed Acids, — In this department sulphuric and nitric acids
of pnq)er strengths are mixed in such proportions as the trade
demands and sold in large quantities to dynamite manufacturers.
Glycerol. — ^This plant is adapted to the manufacture of chem-
ically pure glycerol, which is obtained on the large scale from
crude glycerol by distillation with steam. This department
has achieved considerable reputation for the quality of the prod-
uct, which is equal in every respect to any in the market.
Great care is exercised in its manufacture and many chemical
tests made to insure a high-grade article. A beautiful product
is msrde and each visitor was presented with a small bottle as a
souvenir.
Ammonia. — In this extensive plant large quantities of ammo-
niacal liquor are worked up into all grades of aqua ammonia,
ammonium sulphate and other ammonia products.
Laboratories. — The different laboratories were visited and
chemists were found busy in many operations of interest to the
analytical and research chemist.
The extensive shops of the company as well as the sal-soda
and Glauber's salt plants were also visited.
A pleasant and agreeable surprise awaited the party after the
tour of inspection. In the work's office of the company a spread
was served, in every way adapted to appease the hunger and
quench the thirst caused by the long tour of tlie afternoon.
After the cigars had been passed and a social chat indulged in,
the party were transported back to the city by cars. The excur-
sion was voted by one and all a most delightful and instructive
one.
BOARD OF DIRECTORS.
Resolved, That the Editor be and he is hereby instructed to mail
regularly to the Secretary of each Local Section of the American
Chemical Society a copy of the Journal for the use of the sec-
tion, upon written request of the Chairman and Secretary of the
Section.
NBW MBMBBRS ELECTED DECEMBER 26, 1 895.
Bartlett, Edwin J., Dartmouth College, Hanover, N. H.
Bomberger, F. B., College Park, Md.
(26)
Booty Johannes Cornelius, 24 East 20th St., N. Y. Citj.
Gray, Marietta, care of University of Nebraska, Lincoli, Neb.
Milliard, H. J., 204 Columbia Heights, Brooklyn, N. V.
Hollinger, Myroen John, Sharpsville, Mercer Co., Pa.
Hunicke, H. Aug., 1219 Mississippi Ave., St. Louis, Mo.
Skinner, W. W., College Park, Md.
Summers, Bertrand S., Western Electric Co., Chicago, HI.
Wigfall, Edward Newton, 1822 Arch St., Phila., Pa.
ASSOCIATES KLECTBP DECBMBBR 26, 1 895.
AUison, WilUam O., William St., N. Y. City.
White, Richard A., Grand Central Station, N. Y. City.
NEW MEMBERS ELECTED JANUARY l8, 1 896.
Bartow, Edward, Williamstown, Mass.
. Battle, H. B., Ph.D., Raleigh, N. C.
Poulk, Chas. W., B.A., Ohio State Univ., Columbus, Ohio.
Pox, H., 1224 Rookery Building, Chicago, 111.
Graves, George H., 358 State St., Bridgeport, Conn.
Hall, Clarence, Aetna, Lake Co., Indiana.
Hartwell, Burt L., B.Sc., Kingston, R. I.
Hicks, Edwin P., 52 Beaver St., N. Y. City.
Hopkins, Cyril George, 204 So. 4th St., Champaign, 111.
Magrunder, E. W., Johns Hopkins Univ., Baltimore, Md.
McGeorge, Arthur, 205 West 78th St., N. Y. City.
Pickering, Oscar W,, 2 Milk St., Newburyport, Mass.
Pitman, John R., Prankford Arsenal, Phila., Pa.
' Rhodes, Edward, Highfields, Pordsham, Cheshire, Eng.
Sargent, Chas. S., B.Sc, Peace Dale, R. I.
Seal, Alfred Newlin, 1418 BouvierSt., Phila., Pa.
Warwick, Arthur William, Wickes, Mont.
Williams, Charles B., B.S., Raleigh, N. C.
Woodcock, Reginald C, 636 West 55th St., N. Y. City.
Tennille, Geo. P., Ph.D., 519 West 33rd St.» N. Y. City.
ASSOCIATES ELECTED JANUARY 18, 1896.
Brenke, Wm. Chas., 506 South 5th St., Champaign, 111.
Gazzolo, Frank Henry, 930 West Green St., Urbana, Ohio.
Keeler, Harry, 506 South 5th St., Champaign, 111.
CHANGES OF ADDRESS.
Grosvenor, W. M., Jr., New J. H. Wolfe Hotel, Cripple
Creek, Colo.
Guild, P. N., College of Mont., De^ Lodge, Mont.
(27)
V
Johts, John, care of The Guppinheimer Smelting^ Co., Perth
Amboj, N. J.
Jones, L. J. W., 2126 High St., Denver, Colo.
Maury, Geo. P., Braddock, Pa.
Mtinsell, C. E., 100 Horatio St., N. Y. City.
Pamiiy, Dalton, 9123 Ontario Ave., Chicago, 111.
Prochazka, G. A., 138 W. 13th St., N. Y. City.
Rosel!, C. A. O., 841 Broadway, N. Y. City.
Townsend, Clinton, U. S. Patent Office, Washington, D. C.
Voorhees, S. S., 2101 G St., N. W., Washington, D. C.
MEETINGS OP THE SECTIONS.
WASHINGTON SECTION.
A meeting was held November 14th, 1895, President Mun-
roe in the chair, with thirty-five members present.
Messrs. H. B. Hodges and Allan Wade Dow were elected as
members, and Messrs. W. W. Skinner and J*\ B. Bomberger as
local associates.
Dr. Marcus Benjamin read a paper on *' The Smithsonian In-
stitution's Contributions to Chemisry from 1846 to 1896." He
recalled the fact that Smithson was regarded as one of the most
expert chemists in elegant analysis and thought this fact had
much to do with the provision made for a chemical laboratory
in the original program of the Smithsonian Institution. He
then traced the history of the laboratory of the institution, men-
tioning the many chemists who have occupied it and whose work
has been published by the institution. Among these were J.
Lawrence Smith, Dr. Robert Hare, Edward W. Morley, Genth,
Gibbs, Booth, Carrington Bolton, Clarke, Traphagen, Magee,
and Tuckerman. The paper was concluded with a bibliography
of the chemical papers published by the Smithsonian Institution.
Mr. Cabell Whitehead presented **Some Notes of a Recent
Visit to European Mints." In the discussion of this paper ref-
erence was made to the explosions so common in the lighting of
a Buffalo Dental Company's muffle furnace. Mr. Dewey said
that these explosions can be avoided by raising the whole body
of the furnace by a simple arrangement of movable levers and
then slipping a lighted paper over the burner.
(28)
Under the- title "Calcium Phosphide/* Prof. Chas. E Man-
roe described the process of manufacture which he invented and
carried into operation at the U. S. Naval Torpedo Staion in
1 89 1. Iron crucibles were employed in which quickline was
heated to redness, when white phosphorus in sticks wai added
through an iron tube which passed thtough the cover. The
process was so simple that it was eventually carried on by
unskilled laborers. The phosphide was produced at a cost of
twenty cents per pound, while in the market it was selling for
$2.25 per pound. It was manufactured for use in at±omobile
torpedoes while at practice, and was found so efficient that when
a pound in its container was submerged in eighteen feet of water
it gave a flame on the surface two feet in height, wiich con-
tinned to bum intermittently for three hours.
Discussion was by Messrs. Whitehead, Stokes, Kelly and
Fireman.
NEW YORK SECTION.
The regular monthly meeting of the New York Section was
held at the College of the City of New York, 23d street and Lex-
ington avenue, on Friday evening, January loth. The usual
informal dinner preceded the meeting.
The meeting was called to order at 8:30. Prof. P. T. Austin
in the chair; about seventy members present. After the reading
of the minutes, Mr. Eimer was asked to describe some improved
and novel apparatus which had been placed on exhibition by
Messrs. Eimer & Amend.
Mr. G. C. Henning, M.E., delegate for the American Society
of Mechanical Engineers to the International Conference at
Zurich, 1895, reviewed the ** Present Status of Iron and Steel
Analysis, ' ' calling attention to the discrepancies in some recent
work of different chemists in determining the constituents of
the same quality of steel, with special reference to carbon and
phosphorus, and to the omission of the direct determination of
iron, which he thinks conducive to overlooking such elements
as titanium, tungsten and others, which are more often present
than the usual iron analysis would indicate, as they are bnt
infrequently determined directly.
He reviewed papers by German, French and English authors,
(29) .
giving results of microscopic examination of iron, and methods
of preparing the samples for examination, and described the
group of carbon "compounds'* recognizable under the micro-
scope by suitable methods of surface etching.
He considers rhat the microscope has opened a field which
marks a great advance in methods of determining the condition
and quality of iron and steel, and thinks that chemical methods
need great improvement to distinguish the conditions in which
the carbon exists.
Mr. Rossi in discussing Mr. Henning's paper thought it would '
be very difficult, if not impossible, to recognize the different
combinations of iron and carbon \}y chemical means, at least in
the present state of chemical science, since there is so little out-
side of physical characteristics to distinguish them.
Prof. Breneman asked whether in a *' burned" iron the micro-
scope would show an amount of magnetic oxide proportionate to
the degree of deterioration of the iron. Mr. Henning replied
that this was practically so ; that the oxidation progressed from
the surface inward, and a properly polished and etched specimen
piece would show, when examined by powers over 800 diame-
ters, the grains of oxide interlaced with the iron, in a form
readily distinguishable from the iron.
Dr. McKenna, while admitting the need for chemical methods
of determining the number and kind of compounds, is of the
opinion that physical methods must be employed in conjunction
with chemical methods, and that while chemical methods ma^*^
advance greatly, the physical methods ought never to be
omitted or displaced. Prof. Breneman suggested that the manu-
facturers would contribute greatly to the advancement of the
matter by having the expensive chemical investigations required
conducted in their own laboratories at the iron works, where the
practical side is already highly developed and the material for
research abundantly supplied ; and where the results are most
wanted and can be instantly applied. He also brought out the
looseness of the term "compound" as used by the physicist,
and urged the importance of keeping a clear distinction between
the true chemical compound and the mixtures which were inac-
curately termed compounds. In reply to these remarks, Mr.
(30)
Henaing said that several steel andiron companies in this cosn-
try have already established very complete micrographic labora-
tories, where'in three hours an accurate determination of the
condition of any specimen of the daily output may be secured.
Mr. George C. Stone read a " Note on the Piobable Produc-
tion of Permanganate 1^ Direct Combustion of Manganese."
In discussing this note, Dr. Rosell called attention to the fact
that potassium permanganate, when heated to a red heat, will
decompose, and that the other permanganates behave in the
same way. In fact, the permanganates can only be made in the
wet way. On the other hand, manganates are generally pro-
duced in the dry way, and the^ will stand a very high temper-
ature.
If, therefore, a substance after having been heated to the tem-
perature of the blast furnace, would dissolve in pure water witb
the well-known rich purple color of a permanganate solu-
tion, it seems almost certain that such a substance could not be
a permanganate, but it could be a solution of a ferrate.
It is, of course, also possible that the water used for dissolv-
ing the substance in question was not pure, but accidentally
contained some acid, whereby, on dissolving, the manganate
was converted into permanganate.
A second paper by Aft. Stone was entitled " Remarks on Mr.
Auchy's Paper on the Volumetric Determination of Manganese."
He reviewed the Volhard method and described the conditions
under which he obtained the most satisfactory results. He
found, that, provided all the iron was oxidized, it made no dif-
ference whether nitric, sulphuric, or hydrochloric acid were
used. The only difficulty occurred when the amonnt of manga-
nese was extremely small, in which case it was extremely diffi-
cult to get the precipitate to cohere and give a clear solution in
" ■ ' " " end reaction.
resented a paper on the " Manufacture of
Chloroform from Acetic Acid," in which
y of acetone from its first mention to the
: was quoted as mentioning acetic acid as
one, its vapor being passed through a red-
.mice stone. It was shown that this sub-
(30
stance was well known prior to 1848 and had been made in large
quantity prior to 1882.
Dr. Squibb described his method of .preparing acetone by
destructive distillation of acetic acid, with water vapor in a
rotary still.
In regard to acetone-chloroform he quotes Liebig as giving
the preference to acetone as the most suitable compound for the
preparation of chloroform.
The work of Bottger and Siemerling was described and the
results obtained by them were reviewed. One-third of the ace-
tone used was the largest yield of chloroform obtained by Bott-
ger, its specific gravity was 1. 3 1 and it always contained ace-
tone.
The misleading results of Siemerling's work were accepted so
implicitly and quoted so definitely in standard works of refer-
ence that the further prog^ss of the manufacture of chloroform
from acetone was for many years obstructed, and patents have
been issued in which the claims were based on supposed im-
provements on these erroneous results.
The last paper of the evening, '* Some Notes on Highly Com-
pressed Gases," was read by Mr. J. S. Stillwell. He described
some investigations which had been made of certain explosions
of the containing cylinders.
Some investigators had claimed that the passage through a
minute orifice of light under high pressure, 2,500 pounds to the
square inch, >vould create sufficient friction and consequent
heating to cause explosive union with any oils or fat which
might be present, and which might be volatilized by the men-
tioned source of heat. The author had, in the course of prac-
tical experience, tested this point over a hundred thousand
times, and was satisfied that the heat never rose to the danger
point under normal conditions of working, and that a heat
approaching 400"* P. was necessary before danger of explosion
need be feared. This high temperature of the comjpressed gas
was never reached, except through some careless or accidental
want of properly cooling the compressor cylinder.
The meeting adjourned at 11 : 15.
(32)
LBHIGH VALLEY SSCTION.
The Annual Meeting of the Section was held in the laboratory
of I^afayette College, Thursday, Jan. i6, at 3 p. m. The ballots
for the election were opened and Counted according to the con-
stitution, and the following were found to be elected for the en-
suing year :
Presiding Officer : Albert Ladd Colby.
Secretary and Treasurer ; Albert H. Welles.
Member of Executive Committee ; Edward Hart.
A letter from the General Secretary of the Society of Chemi-
cal Industry was read, thanking the Section for their kindness
to Thomas Tyrer and Ludwig Mond.
The Secretary was instructed to furnish abstracts of the pro-
ceedings, to such journals as might ask for them.
The following papers were presented by Edward Hart : "Note
on Some Curious Specimens of Zinc Oxid" ; '* Note on a Barium
Blast Furnace Slag.'*
He explained that some granulated zinc having been acd-
dently left in an earthenware crucible in a muffle over night, led
to the discovery of a most curious formation of zinc oxide, and
having designedly repeated the experiments, the results weit!
exhibited.
The barium blast furnace slag was from Nova Scotia. The
ore contained 6.30 percent, barium stdphate, and the slag 3.46
per cent, barium oxide, as the chemist of the company reported
it. The question was referred to Prof. Hart how to calculate
the barium in the slag, and from the data which he gave he con-
cluded it was neutral, the barium sulphate being reduced to
barium sulphide, and existing as such in the slag.
Prof. Richards called attention to the notable amount of alu-
minum, w>., sixty-three per cent, in the pig iron produced at
the furnace mentioned. He cited a case of a furnace in the Ju-
niata Valley, which, under abnormal conditions had produced,
as high as one per cent, aluminum, although, as is well known,
the presence of metallic aluminum in pig iron is considered in-
admissible by some authorities.
Mr. Colby suggested that hereafter a topic be chosen for the
(33)
evenings discussion, and a leader be appointed to open the dis-
cussion and it was decided to adopt the plan at the next meeting.
Albbrt H. Welles,
Secretary.
NEBRASKA SECTION.
A meeting of the Nebraska Section was held on Thursday,
Dec. 19, in the Chemical Laboratory of the University of Ne-
braska. The meeting was a pronounced success in every way.
The following papers were read : ( i ) * *The Occurrence of Na-
tive Iron in Nebraska,'* by Prof. H. H. Nicholson.*' (2) "The
Effect of Freezing on the Salts in Solution in Spring and Well
Waters. Preliminary Notice,** by Prof. H. H. Nicholson. (3)
•• The Description of a Shaking Apparatus for Laboratory Use,**
by Mr. R. S. Hiltner.
RHODE ISLAND SECTION.
The December meeting of the Rhode Island section was held
at Providence on Thursday evening, December 12, 1895, Chair-
man, Mr. C. A. Catlin presiding.
Mr. J. C. Hebden read a paper upon *' The Relation of Acid
and Basic Properties of the Artificial Dyes to their Dyeing Pro-
perties.**
The paper was illustrated with diagrams and dyed samples of
wool.
The January meeting was held at Providence, Thursday even-
ing, January 16, 1896, C. A. Catlin in the chair.
A paper upon " Amphoteric Reaction of Milk ** was read by
W. M. Saunders. After mentioning the results obtained by
various investigators upon the subject, the reader described the
experiments performed by himself. The milk of about seventy-
five cows was examined as to the reaction to litmus paper. The
larger number gave a neutral reaction to litmus, the remainder
an acid or alkaline reaction in about equal proportion. Cows
giving milk with an alkaline reaction to litmus on one day gave
the acid reaction a few days later.
CINCINNATI SECTION.
The Section met in regular session Wednesday, January 15,
1896, President Twitchell presiding.
(34)
Mr. P. Homburg, chairman of the committee appointed to
draft resolutions on the death of Prof. C. R. Stuntz, reported the
following :
" Since it has pleased Providence to call from his labors to
rest, Prof. C. R. Stuntz, we, the members of the Cincinnati Sec-
tion of the American Chemical Society, through our committee,
desire to express our deep sorrow at the loss of our esteemed
friend and colleague, and also our sincere sympathy with all who
mourn his death.
*' His genial disposition, his courteous bearing, his devotion
to science and learning in general, and to the success of our or-
ganization in particular, we keenly appreciate.
*' The legacy of his noble example will tend to alleviate the
distress caused by his departure.
**p. homburg,
"Dr. S. p. Kramer,
"E. TWITCHBLL,
**H. B. FooTK,
** Committee."
On motion of Dr. Springer, the resolutions were adopted, and
the committee was instructed to send a copy to the family of
the deceased.
Mr. H. B. Schmidt, of Cincinnati, was elected a member of
the Section.
Papers were read on * 'Mercury: Its Occurrence and Produc-
tion," by Frank I. Shepherd; and "A Few Noteson the Deter-
mination of Ircad,'' by J. Hayes-Campbell.
iMQcd with March Nnmber, 1896.
Proceedings,
COUNCIL.
The following persons have been elected as members of the
standing committees for one year :
Committee on Papers and Publications — ^J. H. Long and
Thomas B. Osborne.
Committee on Nominations to Membership — A. A. Breneman,
P. T. Austen, and C. A. Doremus.
Finance Committee — Durand Woodman, A. P. Hallock, and
A. H. Sabin.
C. F. Mabery has been elected a member of the Council for
1896 in place of Charles B. Dudley, President.
The bills of the Chemical Publishing Co. for $289.24 for the
January number and $272.43 for the February number of the
Journal, have been approved.
NEW MBMBBRS BLBCTBD FEBRUARY I, 1 896.
Bookman, Samuel, 9 East 62nd St., N. Y. City.
FuUam, Frank L., cor. Gold and John Sts., Brooklyn, N. Y.
Hanks, Abbot A., 718 Montgomery St., San Francisco, Cal.
Lihme, I. P., 27 Tift Ave., Cleveland, O.
Lippincott, Warren B., 3179 Ashland Ave., Chicago, 111.
Maywald, F. J., 592 Kosciusko St., Brooklyn, N. Y.
Leret, Fred., Virginia, St. Louis Co., Minn.
Sharpless, Fred. F., 811 Wright Block, Minneapolis, Minn.
Steams, F. C, M.D., 44 Montgomery St., Jersey City, N. J.
ASSOCIATE ELECTED FEBRUARY I, 1 896.
Gordon, Alexander, 44 Montgomery St., Jersey City, N. J.
NEW MEMBERS ELECTED FEBRUARY 24, 1 896.
Baker, Theodore, Box 97, Belford, N. J.
Barrett, Jesse M., Purdue University, Lafayette, Ind.
Borland, Chas. R., E. C. Powder Co., Oakland, Bergen Co., N.J.
Cheney, John P., So. Manchester, Conn.
Christiansen, H. B., Hermitage, Floyd Co., Ga.
Jones, Wm. J., Jr., Purdue University, Lafayette, Ind.
Martin, Alex. M., F.C.S., Douglas Villa, Dunbeth, Road,
Coatbridge, Scotland.
(36)
Myers, H. Ely, Riddlesburg, Bedford Co., Pa.
Slagle, Robert Lincoln, Brookings, S. D.
Smyth, Dr. Geo. A., 900 South Boulevard, Oak Park, III.
Tidball, Walton C, care of E. R. Squibb & Sons, Gold and
John streets, Brooklyn, N. Y.
ASSOCIATES BLBCTBD FEBRUARY 24, 1896.
Pomeroy, Thomas W., Lafayette College, Easton, Pa.
Stover, Edward C, Trenton Potteries Co., Trenton, N. J.
CHANGES OP ADDRESS.
Atkinson, Elizabeth A., Three Tons, Pa.
Baekeland, Leo., care Nepera Chem. Co., Nepera Park, N.Y.
Blalock, Thos. L., 3106 O'Donnell St., Baltimore, Md.
Bromwell, Wm., Ph.D., care Tenn. C. I. and R. Co., 1918-
1920 Morris Ave., Birmingham, Ala.
Campbell, Geo. F., 80 Bristol St., New Haven, Conn.
Chamberlain, G. D., care N. W. Mall Iron Co., Milwaukee,
Wis.
Comelison, R. W., care McKenzie Bros. & Hill, Bloomfield.
N.J.
Doremus, Dr. C. A., 17 Lexington Ave., N. Y. City.
Foote, Henry B., 241 Walnut St., Cleveland, Ohio.
Graves, W. G., 1661 Huron St., Cleveland, Ohio.
Kenan, Wm. R., Jr., care Carbide Mfg. Co., box 45, Niagara
Falls, N. Y.
Kiefer, H. E., 16 W. 4th St., South Bethlehem, Pa.
Morse, Fred. W., Lock Box 30, Durham, N. H.
Spencer, G. L., Centralia, Wood Co., Wis.
Trubek, M., 325 Academy St., Newark, N. J.
Walker, Henry V., 38-40 Clinton St., Brooklyn, N. Y.
ADDRESS WANTED.
Johnson, Jesse, last address Augusta, Ga.
MEETINGS OF THE SECTIONS.
WASHINGTON SECTION.
The regular monthly meeting of the Washington Section was
held December 12, 1895, President Munroe m the chair, with
thirty-six members president. In the absence of the Secretar3',
W. D. Bigelow was elected Secretary, pro tempore. The follow-
ing were elected to membership : W. W. Skinner, F. B. Bone-
berger, and H. Carrington Bolton. A committee was appointed
(37)
to arrange for a social meeting of the Section to report at the
Jafiiiary meeting.
The first paper of the evening was '* Exhibition of Argon and
Helium," by Dr. W. F. Hillebrand. He discussed concisely
the spectra of argon and helium and closed by exhibiting the
spectra to the Society.
The second paper was by Dr. H. W. Wiley, on the ** Use of
Acetylene Illumination in Polariscope Work, with Illustrations."
Dr. Wiley stated that acetylene, while not inferior in point of
accuracy to other forms of illumination, is so intense as to per-
mit accurate polarization with solutions so dark in color that
they cannot be polarized with lights commonly used for this
purpose. He called attention to the ** Schmidt and Haensch
Triple Field Polariscope," which was said to be a great assis-
tance in both rapid and accurate work. The paper was illus-
trated with the acetylene light and the polariscope referred to.
Mr. F. P. Dewey read a paper on ** The Early History of
Electric Heating for Metallurgical Purposes." The paper was
comprehensive, embracing the various patents relating to elec-
tric heating for metallurgical purposes and also many relating to
electric reduction. It was illustrated by photographs and draw-
ings of the various forms of apparatus described.
The last paper of the evening was ** A Tribute to the Memory
of Josiah P. Cooke," by Dr. Marcus Benjamin. An excellent
portrait of Prof. Cooke was exhibited and the sketch of his life
was of special interest from the fact that the statements made
were from a manuscript sent to Dr. Benjamin some years ago by
Prof. Cooke. After discussion by Messrs. Munroe, Tassin, and
Wiley, the Section adjourned.
NEW YORK SECTION.
The regular meeting of the New York Section was held at the
College of the City of New York on Friday evening, Feb. 7, at
8.30 p. M. The following papers were read : ** New Facts about
Calycanthus," by Dr. R. G. Eccles, and ** Items of Interest
from the Cleveland Meeting," by A. A. Breneman.
Dr. Eccles described his work and also that of Dr. H. W.
Wiley on the calycanthus seeds and the alkaloids obtained
(38)
therefrom ; exhibiting the seeds, the principal alkaloid obtained,
its salts, the color reactions of both, and the crystalline forms*of
the salts.
Prof. Breneman described the features of the Cleveland meet-
meeting, which were of particular interest to industrial chemists,
referring especially to the low pressure distillation of light pe-
troleum oils as conducted in Prof. Mabery's specially equipped
laboratory.
Dr. Durand Woodman exhibited a simple lecture table appa-
ratus for experimentally demonstrating the luminosity of the
acetylene flame, generating the gas from calcium carbide.
The meeting was adjourned at 10.45 p. m.
ANNUAL REPORTS OP THE SECTIONS.
The following annual reports from the secretaries of the sec-
tions were received by the General Secretary too late for inser-
tion in their proper place :
WASHINGTON SECTION.
Seven meetings have been held and an abstract appended
gives the list of papers read and topics discussed at these meet*
ings. The following is a list of the present officers :
President — Charles E. Munroe.
Vice Presidents — E. A. de Schweinitz and W. D. Bigelow.
Treasurer— W. P. Cutter.
Secretary — A. C. Peak.
The officers as above with the following constitute the Execu-
tive Committee : H. W. Wiley, F. P. Dewey, F. W. Clarke, and
W. H. Seaman. There are no other standing committees.
The secretary of the local section has no way of determining
the standing of members. According to a statement made by
the General Secretary, December 8, 1894, the membership of
the Washington section was sixty-four. As it now appears to
be seventy -four the gain during the year is ten.
November 8, 1894. — President W. H. Seaman in the chair.
Ten members present. Resignation of Prof. J. C. Gordon read
and accepted. Cooperation of the Society asked by John W.
(39)
Hoyt in the formation of a " National Posi-Graduate Univer*
sity." Prof. H. W. Wiley made a report on the •* First Congress
of Chemists," at the San Francisco exposition. Paper read by
W. D. Biglow on the " Coloring-Matter in California Red
Wines."
December ij, 18^4. — President W. H. Seaman in the chair
Twenty members present. Paper by Oma Carr and J. F. San-
bom on the " Dehydration of Viscous Organic I^iqnids," read
by Mr. Carr. Mr. W. D. Bigelow and E. £. Ewell described a
continuous extractor for large quantities of material.
January 10^ /<^95. — President W. H. Seaman in the chair.
Fourteen members present. The following officers were elected :
President, Charles B. Munroe; Vice Presidents, E. A. de
Schweinitz and W. D. Bigelow; Treasurer, W. P. Cutter;
Secretary, A. C. Peale. Additional members of the Executive
Committee, H. W. Wiley, F. P. Dewey, F. W. Clarke, and W.
H. Seaman. H. C. Sherman, F. P. Veitch, W. G. Brown, and
V, K. Chesnut were elected to membership.
February 14, 18^3, — ^The meeting was devoted to the annual
address of the retiring president, W. H. Seaman, upon '' Chem-
istry in Education." President Charles E. Munroe in the chair,
with members of the Society and invited guests from the Socie-
ties of Washington present.
March 14, J8gs. — President Charles E. Munroe in the chair.
Thirty-five members present. Dr. J. E. Blom€n and G. E. Bar»
ton elected to membership. The following papers were read :
**The Constitution of the Silicates," by F. W. Clarke. ** On
the Chloronitrites of Phosphorus and the Metaphosphinic Acids, * '
by Dr. H. N. Stokes; ** The Manufacture of Soluble Nitrocel-
lulose for Nitrogelatin and Plastic Dynamite," by Dr. J. E.
Blom6n.
April II y i8g5, — President Charles E. Munroe in the chair.
Fifty-three members present. The following papers were read :
** The Determination of Nitrogen in Fertilizers," by H. C. Sher-
man; ** Exhibition of Calcium Carbide," by Charles E. Mun-
roe ; "Precipitation of Small Quantities of Phosphoric Acid by
Ammoniacal Citrate of Magnesia," by E. G. Runyan and H. W.
Wiley. The subject for discussion was * * Can Argon be Accepted
(40)
as a New Element?" Discussion was by Charles K. Munroe,
F. W. Clarke, T. M. Chatard, and H. N. Stokes.
May p, 18^5, — President Charles E. Munroe in the chair.
Forty members present. Messrs. Marion Dorset and S. C. Mil-
ler elected to membership. The following papers were read :
**ANew Meteorite from Forsyth Co., N. C," by E. A. de
Schweinitz ; ** Hydrogen Fluoride Poisoning," by Peter Fire-
man; *' Progress in the Manufacture of Artificial Musk," by
W. H. Seaman. The subject for discussion was. "The Chemi-
cal Action of Micro-organisms." and was participated in by H.
A. de Schweinitz, Surgeon General Sternberg, H. W. Wiley,
Prof. George P. Merrill, and R. B. Warder.
The Society adjourned until November.
CINCINNATI SECTION.
The annual election held December i8th, 1894, resulted as
follows :
President, Karl Langenbeck ; Vice-Presidents, B. D. Westen-
felder and I. J. Smith ; Treasurer, Henry B. Foote ; Secretary,
E. C. Wallace ; Directors, Dr. S. P. Kramer, Prof. O. W. Martin,
H. L. Nickel.
The following were elected chairmen of the standing commit-
tees for the year :
1. Didactic Physical and Inorganic Chemistry, Dr. Alfred
Springer.
2. Organic Chemistry, Prof. T. H. Norton.
3. Analytical Chemistry, Lewis William Hoffmann.
4. Medical, Physiological and Biological Chemistry, Dr. S. P.
Kramer.
5. Technical and Pharmaceutical Chemistry, Prof. J. U.
Lloyd.
The following named persons have been elected members of
this Section since October 31, 1894 : W. G. Wallace, Richard
W. Proctor, Charles E. Jackson and George F. Feid, elected
December 18, 1894; F. Homburg, E. D. Frohman, elected Jan-
uary 15, 1895 ; Harry L. Lowenstein, elected February 15, 1895 ;
Prof. A. F. Linn, and Dr. JohnMcCrae, elected October 15, 1895.
In the death of Lewis William Hoffmann and W. G. Wallace
(41)
the Cincinnati Section sustained a loss of two of its popular
younger members, who were highly esteemed by their associates.
Eight meetings were held during the year, at which the follow-
ing papers were presented. Special meeting held November 7,
1894, addressed by Dr. H. Hensoldt. The subject announced,
* 'Occult Science in the Orient.**
Stated meeting December 18, 1894 : ** Diphtheria Antitoxin,*'
Dr. S. P. Kramer; ** Elective Fermentation in Diabetes,** Dr.
Alfred Springer.
.Stated meeting January 15, 1895: *' Separation of the Solid
and Liquid Fatty Acids,** E. Twitchell ; *' Report of Progress
in Organic Chemistry,** Dr. H. E. Newman.
Stated meeting February 15, 1895 : Papers announced were
postponed on account of sickness of the essayists. '* The Diffi-
culty of Obtaining Distilled Water to Meet Pharmacopeial Re-
quirements,** was discussed by Prof. Lloyd, Dr. Springer and
Prof. Norton.
Stated meeting March 15, 1895: ''Determination of Phos-
phorus in Ferrosilicon,** John H. Westenhoff ; ** The Souring
of Milk,** Robert W. Hochstetter.
Meeting April 16, 1895 : " Recent Important Discoveries in
Chemistry,** Prof. T. H. Norton.
Meeting May 15, 1895: "Adulteration of Powdered Elm
Bark,** Henry B. Foote; "Ammonium Thioacetate,'* Prof. T.
H. Norton.
Stated meeting October 15, 1895: **A Tribute to Pasteur,**
Dr. Alfred Springer ; " Laboratory Uses of Aluminum and Re-
cent Progress in Theoretical Chemistry,*' Prof. T. H. Norton.
A pamphlet issued by the Executive Committee gives names,
occupation and addresses of members of the Section, the names
of the authors and titles of papers read during 1894.
NEBRASKA SECTION.
The Nebraska Section was organized at a meeting held in
Lincoln, June 14, at which meeting officers were selected for the
ensuing year, as follows :
President, H. H. Nicholson ; Secretary and Treasurer, John
(42)
White ; Executive Committee, H. H. Nicholson, John White,
Rosa Bouton, T. L. I^yon, W. S. Robinson.
The first regular meeting of the Section was held in the Chemi-
cal Laboratory of the University of Nebraska on October 30,
with a good attendance of members and a number of invited
guests.
Papers were read as follows :
By Prof. T. L. Lyon : ** The Source of Error in the Estima-
tion of Sugar in Beet Juice by Means of the Sucrose Pipette.'*
By Mr. Samuel Avery : ** Notes on the Electrolytic Determi-
nation of Iron, Nickel and Zinc."
Mr. C. H. Suveau, of the Department of Motive Power of the
Burlington and Missouri River Railroad, was elected a local as-
sociate member.
Other meetings will be held in December, March and Jun^.
Our present membership is thirteen.
CHICAGO SBCTION.
The Chicago Section has held but two meetings, one for
organization, and the other just reported, at which papers were
presented.
The membership is twenty-five.
The officers are as follows :
President, Frank Julian ; Vice-President, J. C. Foye ; Secre-
tary, P. B. Dains ; Treasurer, J. H. Long ; Executive Commit-
tee, Frank Julian, A. L. Smith, F. B. Dains.
NEW YORK SECTION.
Meetings were held and papers read as follows :
November g^ 18^4: **The Rapid and Accurate Analysis of
Bone-black," by William D. Home; "Recent Progress in
Physiological Chemistry,** by Dr. E. E. Smith.
December ij J 1894: The Chemical Nature of Diastase," by
Thomas B. Osborne, of New Haven ; " Glucose from a Sani-
tary Standpoint," by E. H. Bartley, M.D. ; ''Indiscriminate
Taking," by P. T. Austen.
January 10^ ^^95 ' "Improvement in the Manufacture of
Acetone," by Dr. E. R. Squibb ; ** Recent Progress in Photo-
graphic Chemistry," by Dr. J. H. Stebbins.
(43)
February i8y i8g^ : No quorum.
March S, iSpj: ** The Late Prof. Henry B. Nason," by W. P.
Mason; ''Elective Fermentation in Diabetes," by Alfred
Springer ; ** Note on Absorbent Blocks," by W. H. 6n>ad-
hurst ; ** Note on the Precipitation of Iron by Alkali Nitrites,"
by GiUett Wynkoop ; '' Volumetric Determination of Zinc and
Manganese, and a New Indicator for Ferrocyanides," by G. C.
Stone; ** Note on the Reduction of Nitrates by Ferrous
Hydroxid," by P. T. Austen ; " Stability to Light of Haematon-
ylin Blacks on Wool," by P. T. Austen.
May ij, iSpj: ** Recent Progress in Analysis of Soils," byH.
W. Wiley ; ** Tribute to the Memory of Dr. Gideon Moore," by
C. P. McKenna ; " Chemical History of a case of Arsenical and
Antimonial Poisoning," by C. A. Doremus ; "The Estimation of
Acetic Acid in Vinegar," by A. R. Leeds.
/une 14, i8gs '- ** Determination of Nitrogen by the Gunning
Method," by W. D. Field ; "On Asbestos and its Commercial
Application," by G. C. Stone ; ** Examination of Lard for Im-
purities," by David Wesson ; "On Commercial Argol and its
Products," by Wm. McMurtrie ; "A Modem View of Electro-
Chemical Action," by C. L. Speyers ; " On the Relation of the
Chemical Engineer to Factory Management, "by John Enequist.
The informal dinners preceding the meetings have been con-
tinued at a majority of the meetings. The total expenditures of
the section have amounted to I157.98 ; those of the preceding
year were $160.82. The largest item in each case is the con-
tribution to the Treasury of the Scientific Alliance.
The following officers have been elected for the current year ;
Chairman, P. T. Austen; Secretary and Treasurer, Durand
Woodman ; Executive Committee, A. H. Sabin, A. C. Hale,
A. R. Leeds ; Delegates to Council of Scientific Alliance, P. T.
Austen, C. F. McKenna, A. C. Hale.
The list of members is annexed hereto, and shows a total
membership of 234 as compared with 183 last year, or a gain of
fifty-one members.
RHODE ISLAND SBCTION.
The Rhode Island Section of the American Chemical Society
(44)
respectfully transmits the following general report of the busi-
ness of the Section for the year September i, 1894, to Septem-
ber I, 1895.
The work of the Rhode Island Section for the past year may
be described in brief as follows, all the meetings having been
held in Providence :
September ^7, 18^4 : A paper prepared by Prof. E. E. Calder
upon the **Chemistry of Albuminurea," was read by Mr. W. M.
Saunders, the author being unable to be present.
October 18 ^ 18^4 : A paper was read by Mr. W. M. Saunders
upon '* Lantern Slides and their Preparation," illustrated by the
stereopticon.
December ij, 18^4 : A paper was read by Charles A. Catlin,
upon ** Bread and Bread Stuffs."
January 77, i8g§ : A paper was read by Mr. Geo. F.
Andrews upon ** The Accuracy of the fire assay of Silver."
February 2j, 1893 : A paper was read by Prof. J. H. Appleton
upon ** Argon."
March 21, i8gs ' A paper was read by Mr. J. P. Famsworth
upon *' Selection of water for Bleaching and other manufactur-
ing purposes."
Aprit 24, i8g§ : A paper was read by Mr. H. C. Burgess upon
'* A Resum^ of the methods of Bleaching Cotton Piece Goods."
May 2j^ 189s : A paper was read by Mr. E. D. Pearce upon
** The coloring-matter of Pollens," with illustrations under the
microscope."
June i^^ i8gs: The Annual Meeting was held at the Hope
Club House where the members were entertained at dinner as
the guests of the Chairman, Mr. Charles A. Catlin, who pre-
sented a paper upon Chemical-Laboratory Microscopy, illus-
trated by the microscope.
The interest in the local section still continues to be well sus-
tained, and already another new year of its work has begun
with very flattering prospects for the future.
At present date the names of the officers of the Section are :
Chairman, Charles A. Catlin ; Secretary and Treasurer, Wal-
ter M. Saunders ; Executive Committee, Chairman, ex-officio,
Secretary and Treasurer ex-officio, George F. Andrews.
(45)
Number of members belonging to the Rhode Island Section
at the present time, twenty (20). Net increase over last year
two (2).
LEHIGH VALLEY SECTION.
It has been found desirable, as the Section is limited in num-
ber, to hold fewer meetings. Four meetings have been held
during the past year; viz,^ November i, 1894, January 17, May
2, and October 10, 1895. The October meeting was the most
successful in the history of the Section, the Society entertaining
at that time Thomas Tyrer, Esq., President of the Society of
Chemical Industry of England, and invited representatives of
the New York Section of the same Society and the New York
Section of the American Chemical Society. An inspection of
the large government plant of the Bethlehem Iroti Co. was
made, followed by an elegant dinner tendered the visiting chem-
ists, while the stated meeting was held in the afternoon at
Lehigh University.
The following papers have been presented: ** Helmholz's
Contributions to Science," George P. Scholl; '* Castner's Elec-
trolytic Process for Production of Caustic Soda," W. H. Chand-
ler; "A New Ammonia Condenser," Edward Hart; **The
Determination of Graphite in Pig Iron," P. W. Shimer ; ** The
Selection of Samples for Analysis," A. L. Colby ; ** On Stand-
ardization of Iodine Solution," G. H. Meeker; ** A Device for
Sampling Metals," P. W. Shimer ; ** The Rapid Methods Used
in the Bethlehem Iron Co.'s Laboratory," A L. Colby.
Mention should also be made of the interesting paper read by
Dr. William McMurtrie at the October meeting, on ** Chemical
vs. Bacteriological Examination of Water," written by Prof. W.
P. Mason.
We close the year with the same number as we began ; w>.,
21, losses having been made up by new members.
Our annual meeting will be held the third Thursday in Janu-
ary. The ofl&cers of the Section for the year 1895 are as follows :
Presiding OflScer — Edward Hart.
Treasurer — Albert L. Colby.
Secretary— Albert H. Welles,
(46)
Executive Committee — Edward Hart, Albert L. Colby, Albert
H. Welles, and J. W. Richards.
THE CLEVELAND EXCURSIONS.
Owing to delay in the receipt of copy it was impossible to give
a full account of the meeting at Cleveland in last month's issue.
The following additional matter has since been received by the
editor :
One very pleasing feature of the meeting in Cleveland was the
excursions to various works and other places of interest. Both
afternoons were set apart for this purpose, one special part^*^ made
a trip on Tuesday morHiog, and on Monday evening the Case
School of Applied Science and Adelbert College were visited.
Such a large number of excursions were planned, and so many
works were freely opened for inspection, that it was impossible
to visit them all. Routes Nos. i, 6, and 7, as given by the
local comrilittee's program, were omitted, and all the time
available was devoted to the others.
Route No. 2 was led by Mr. D. B. Cleveland, chemist of the
American Wire Works.
The first place visited was the plant of the Otis Steel Co.
Mr. Bartol, the Superintendent, took charge of the visitors and
showed them the plate mill, the basic open hearth furnaces, the
steel foundry, the car axle foundry, the machine shop and the
laboratory.
The Continental Chemical Co; was next visited. They make
red pigments and fuming sulphuric acid from copperas, but had
unfortunately been recently burned out, so that it was impos*
sible to see the works.
The manager, Dr. Ramage, exhibited an apparatus for mak-
ing ozone, which he said brought its cost down to such a point
as to warrant its being used for disinfecting garbage, refuse
from stock-yards, fats, etc. ; for bleaching, for oxidizing sul-
phurous to sulphuric oxide, thus doing away with the lead
chambers in the manufacture of sulphuric acid, and for many
other purposes.
He claimed that treatment with ozone is an almost sure cure
for consumption in the first two stages and for S3rphilitic diseases.
(47)
He stated that with one-fifth to one-seventh of a horse power
he can change one hundred and twenty cubic feet of atmos-
pheric air a minute to a mixture containing fifteen to eighteen
per cent, of ozone, all the oxygen present being changed. He
uses a fifty volt and two to three ampere alternating current,
which he converts to a current of fifty thousands volts.
The Cleveland Nitrous Oxide Co. was next visited, and Mr.
Clark and Mr. Hatch showed the party around.
They sell oxygen and hydrogen, epsom salts, liquid
nitrous oxide and carbonic acid gas. They also make nitrate
of ammonia, as the commercial salt is too impure for their use.
They exhibited some acetylene gas burning from an ordinary
gas jet to show the character and illuminating power of this
much talked-of new illuminant.
By this time it was too late to visit other places of interest,
and the party returned to the hotel.
Route No. 3 was taken on Tuesday morning, the mem*
bers of this party thus missing the regular morning session.
This was done at the suggestion of the Managers of the Varnish
works, as their work of boiling varnish could only be seen in the
morning. The party was guided by Mr. George Marshall, and
included the following places : Cleveland Varnish Co., Cleve-
land Rubber Co., Glidden Varnish Co., and Warner & Swasey,
instrument makers.
A party of six started Tuesday at 9 a.m. from the Hollenden
and proceeded to the Cleveland Varnish Co., where Mr. Stark,
the chemist, conducted them ^rough the works and explained
the different processes. The store-room was first visited, wherein
large boxes of rosin are stored, some from New Zealand and some
from Zanzibar, the first-named place being the chief source. The
gums or rosins used for varnish are amber, fossil and annual ;
amber and fossil are best, as the thousands of years they have
lain in the groCind seems to have cured them. These gums are
assorted according to color, the lightest being the most valuable.
They are found by probing in the sand, in lumps from the size
of a bean to that of a wash tub. The largest piece of Kauri
gum found weighs 250 pounds. This is the chief gum, but Zan-
zibar is also used for fine varnishes. These gums are insoluble
(48)
in common solvents or oil, and must be melted at 560° P. in
order to decompose partially, so that they may unite with the
oil. 'The chemists visited the boilers where the operation of
dissolving the gum was in progress. These boilers are la]:]ge
vessels, in shape somewhat like the farmer's sap or soap
kettles, placed on a small buggy to facilitate removal from the
fire. From twenty to twenty*five per cent, is driven off as water
and non-drying oils on heating. The latter are unsta*
ble, and have not been investigated or utilized, except
in connection with the lampblack industry. The gums are pre-
pared for the boilers by hand, as the best size for melting (about
that of a hen*s egg), is obtained by chopping with a small
hatchet. The machines crush them too fine. Linseed oil does
not dry quickly unless boiled, and dryers are made by adding a
lead or manganese salt to boiled oil. These combine with the
oil, forming a compound which absorbs oxygen quickly and
hardens. The boilers for oil are the same as for melting, gen*
erally larger, with hoods to carry off volatile products. The
gum boilers are fitted with covers to decrease loss from spatter-
ing and to control the irritating jEumes which are carried off by
means of tall chimneys. Different solvents, as turpentine, for
instance, are used to give required consistency to the finished
varnish, and are added to the cooled mixture formed by adding
boiled oil to the melted gum. The varnish is then allowed to
settle in large tanks for from two months to as many years. The
longer the time the finer the varnish made. This is necessary,
as filtering does not remove the sediments. The top is siphoned
off, filtered through filter presses and run into tanks for ageing.
The ageing room is kept at a constant temperature, such that
the varnish is fluid, for from nine to eleven months. The party
visited the cooper shop, storage tanks, shellac mixers, (which
are nothing more than a barrel fastened on a shaft to rotate in
the direction of its circumference) , and a paint mill of the latest
pattern, which does not materially differ from the earliest ones
made. The filters were of the well known Johnson's make, and
the cloths may be used one day, then removed and agitated in
a shellac mixer with turpentine until the gummy sediment is
washed out. Each lot of varnish, japan, or enamel after ageing
(49)
is tried, X. ^., some substance for which it will eventually be
used as a cover, is coated with it and dried or baked.
The most noticeable feature at the Varnish Co., sets aside the
old adage about the shoemaker's wife and blacksmith's colt, for
paint and varnish had been used in a very neat and tasty man-
ner throughout the establishment, and what was particularly
prominent, was the absolute cleanliness that pervaded even the
store-rooms, the settling and ageing rooms, where long lines of
tastefully painted tanks pleased the eye, and the excellent
arrangement of drafts, hoods, covers and stacks to carry off the
offensive odors detrimental to the workman's health.
After visiting the laboratories and drying rooms, the offices
were next in order, where a most pleasant surprise was in store.
At the invitation of the president, Mr. Tyler, the chemists sat
down to a most elaborate luncheon, which was very acceptable.
After a vote of thanks had been given their hospitable host, the
visitors wended their way to the Cleveland Rubber Co.
Notwithstanding the torn up condition of the rubber company
on account of inventory, every courtesy was shown by the fore-
man of each department, who personally explained his part of
the work. The first room visited was the calendering room,
where the crude exudings of the South American rubber trees
are mangled into workable shape. The rubber gum as received
contains fourteen to eighteen per cent, water, and ten to twelve
per cent, extraneous matter, such as stones^ twigs, bark, etc.
Stones are the favorite adulterants, as the crude gum is bought
by weight. The gum is first run through rollers upon which
water plays, to cleanse it. It comes from the rollers looking like
a sheet of thin cork. It is then allowed to cure for three or four
months in a dry room at about 70® F. The South American
natives cure rubber by exposure to air and sun, so that vulcani-
zation is not necessary, and they make very durable shoes from
the product so cured. Modern science has not yet perfected a
system for hastening this curing operation, and it is necessary
to cure at 70** three or four months since higher heat has a
decomposing effect. From the curing room the rubber is passed
through slightly heated rollers again and again until it becomes
a compact, yielding, non-porous mass. A little vaseline added
(so)
in thisjworking serves to make the mass more pliable and softens
it. From the first rollers it passes to others, where different
colored powders are added and worked into the body of the rub-
ber. Pure rubber is black and is useless for many purposes, but
by mixing with various constituents it may be impressed into the
pores of cloth, making a covering impervious to moisture,
rolled into sheets capable of holding gases or liquids, moulded
into any shape, hardened by heat, and welded. The fillers, as
they are called, are zinc oxide, whiting, lampblack, litharge,
sulphide of iron and antimony, and many other substances
known only to the trade. Each filler has a different effect on
the rubber. Sulphide of antimony is used for fine elastic rub-
ber, such as is used in dental operations and for marine valves.
In general, if rubber is to be hardened, as when used for door
mats, or if the surface is made impervious to moisture or air
for gas bags, water bottles, mackintoshes, hose, bicycle tires,
etc., sulphides are used in order that vulcanization may take
place after the article is formed. I/itharge, lampblack and zinc
oxide give color as ' well as body to the rubber. In order to
cover cloth the rubber is wound on rollers and fed through cal-
enders or heated rolls set to such a size that rubber introduced
between the rolls in mass is forced through the cloth and becomes
part of it ; at the same time, by heating the rolls vulcanization
also takes place. Vulcanization consists of forming a compound
of sulphur and rubber in air by heating, and although it takes
much of the elasticity from the rubber, renders it impervious to
liquids or gases. Cloth was shown prepared in this way for
mackintoshes, hose, etc. Cloth so prepared may be sewed
together ; a solution of rubber in any volatile solvent applied to
the stitches, or the seam covered with a strip of rubber wet with
this solution, the whole placed in a steam-heated oven, heated
and when withdrawn it is found the cement has welded the holes
left by stitches, or the strip upon the original pieces, so that it
becomes a compact mass.
The party next visited the molding department. Here the
rubber is prepared as above with a filler of some sulphide and
then pressed like dough into heated molds. It is very plastic,
filling all crevices readily and taking every impression. It does
(5t)
not melt, but the first heat softens it to the consistency of soft t^fi3%
while a greater heat vulcanizes it. In order to keep surfaces in
contact from welding together, a little whiting is sprinkled
between them. Scraps are reworked, and old rubber, such as
boots, is reclaimed and made into coarse articles, such as mats.
The mechanical arrangements were (some of them) wonderful,
but space cannot be given to a detailed description of them all.
As the time for the morning excursion had now been expanded,
the party were obliged to forego the pleasure of visiting the
other places of interest on the list.
It is to be regretted that more did not avail themselves of the
opportunity extended to them to visit these works.
Route No. 4 was for convenience, divided into two excursions,
the Grasselli Chemical Works being visited on Tuesday and the
other places on Monday.
The trip to the Oil works was under the guidance of Mr.
H. L. Payne, chemical engineer, and the visitors were intro-
duced to the practical side of a subject, whose chemical side
was so interestingly presented by Dr. Mabery in his address on
the same evening. Only one refinery was visited.
The one selected is not under the control of the Standard Oil
Co., and works up all of its own product. The visitors were
therefore fortunate in being able to see within the confines of
one muddy hillside all the branches of this vast industry. The
members of this firm, Messrs. Scofield, Shurmer & Teagel, were
all very obliging, and Mr. Daniel Shurmer* and his son person-
ally conducted the party through the extensive works.
The stills are sheet steel tanks set in brick work and have an
open coal fire under them. Some are set on end and others lie
on the side. They are not usually covered in like a boiler, but
exposed to the air on top and sides, and only protected from the
weather by a rough shed. This circumstance would seem to
cause a waste of fuel, but it probably assists in the proper
"cracking** of the oil. The distillate is condensed in a series
of wrought iron pipes, which are kept cool by immersion in a
long wooden trough. The trough is kept filled with cold water
from springs in the side hills. Various methods of procedure
are adopted in the distillation, depending upon the character of
(52)
the product desired, for not all of the various oil products are or
can be made in one distillation. The lighter and more volatile
products are usually collected together and then redistilled with
steam heat in order to separate them into commercial ' * naphtha , ' '
"benzine," ** gasoline," etc. In this distillation the steam is
introduced directly into the oil and the condensed water is drawn
off at the bottom of the still'tank. The very light vapors and
gases which come off first are sucked down by a steam syphon
and burned under the boilers.
The residue left in the crude oil stills may be either a thick
tarry pitch or the distillation can be carried so far that only a
porous coke is left. This coke contains only o.oi to 0.02 per
cent, ash, and is in great demand for the manufacture of elecrtric
light carbons.
The burning oils are all purified by washing in a huge lead'
lined separatory funnel, called an agitator. They are first
washed with concentrated sulphuric acid which unites with and
precipitates the basic matters, such as phenol. The oil after
this washing contains less oxygen than before. The principal
object of this treatment is to remove those bodies which would
cause a coloration of the oil ; a water^white kerosene is sup^
posed to best suit the consumer. The excess of acid is washed
out with water or steam and the oil is completely neutralized by
a littl e caustic soda. This refinery is using some Lima oil, and
they treat it with litharge in the agitator to remove the sulphur.
Other refineries use copper oxide in their stills for the same
purpose.
One of the most interesting products of crude oil is paraffin.
It distills over as a greenish oil, and the visitors were permitted
to examine the crystallizing process where the solid wax is
frozen out and filtered from the more liquid part of the oil. A
second or third treatment of the crude wax with solvent naph-
tha and this freezing process, turns out the pure white chewing
gum. Every paraffin works has its own ammonia freezing plant.
Most of the refineries have no chemist in their employ. They
are mainly concerned with the physical properties of their pro-
ducts, and a boy soon learns to make the test for specific
gravity, flashing point, burning point, freezing point and vis-
cosity.
(53)
The cooperage and shipping departments were large and
interesting, but when the party arrived at that portion of the
works they were ready to return to the hotel.
Tf he other excursion of Route No. 4 was taken by all on Tues-
day morning. The Grasselli Company's works are of such
magnitude that a description is impossible. They make sul-
phuric acid, nitric acid, hydrochloric acid, mixed acid fornitro-
glycerol factories, ammonia, glycerol, and all the various salts
and bye products of such an industry. Mr. E. F. Cone, chief
chemist of the experimental laboratory, was the conductor on
this occasion, and Mr. C. A. Grasselli, president, and his staff
of superintendents were instrumental in showing everything in
the works. None of the chemists will forget the pleasant little
lunch which awaited them in the company's office.
Route No. 5 was of interest to iron works chemists, and com-
prised the Cleveland Rolling Mill and the Blast Furnace depart-
ment and mill of the Union Rolling Mill Co. It was in charge
of Mr. F. E. Hall.
The party left the Square at 1:30 p.m. Monday and proceeded
first to the Crescent Sheet and Tin Plate Co.'s Works on Besse-
mer Avenue, near the N. Y. P. & O. R.R. This company
employs two hundred men and has a capacity of thirty tons per
day of sheet iron and tin plate. The plant is new, having been
in operation about one year, and is fitted up with all the latest
improvements in boilers, engines and all machinery, including
an electric plant for lighting, and operating the electric cranes
for handling rolls and heavy materials.
From here the party proceeded to the Emma Blast Furnace at
the intersection of the N. Y. P. & O. and C. & P. Railroads.
This furnace is operated by the Union Rolling Mill Co., whose
rolling mills were visited later. The furnace department employs
one hundred men and has a capacity of two hundred tons of pig
iron daily. The plant is modern in every respect, has three
blowing engines and three brick hot blast stoves. The company's
chemical laboratory is located at the furnace plant and is in
charge of Mr. Frank E. Hall.
The next place visited was the rolling mill of the same com-
pany, situated some distance farther up the C. & P. R.R. Here
(54)
are employed about 350 men, the daily product of the works
being about 150 tons of merchant iron. No steel is made, the
company making a specialty of high grade wrought iron.
After inspecting this plant the party proceeded to the large
works of the Cleveland Rolling Mill Co. This works is the
largest in the city. The Bessemer Steel plant has a capacity of
1 ,000 tons daily, about seventy-five per cent, of which is made
up into finished products, consisting of rails, shafts and wire,
in the various departments of the company's works. In all about
3.500 men are employed.
One blast furnace is located at this plant. The company's
two larger furnaces are located about three miles farther down
on the N. Y. P. & O. R. R., from which place ** direct metal '*
is run to the converters, the molten metal being carried this dis-
tance over the N. Y. P. & O. R. R.
The chemical laboratories of the company are in charge of
Mr. Chaddock. Ten chemists are employed.
Route No. 8, Adelbert College and Case School of Applied
Science were appointed for Monday evening Dr. Gruener,
instructor of chemistry in Adelbert College, was absent on his
vacation, and Mr. H. L. Paj'ne, a graduate of the first chemis-
try class in Case School, was appointed to head this excursion.
The new physical laboratory of Adelbert College excited the
greatest admiration. The chemical laboratory lacked its most
interesting feature — Dr. E. W. Morley.
At Case School the visitors saw the marks of an active and
well equipped institution for the study of practical applied
science. The entertainment of the evening, of course, was
Dr. Mabery's talk on ** Petroleum.**
Route No. 9 was to the Steel Works at Lorain, O. The trip
was in charge of Mr. Hugo Carlsson, chief chemist of the John-
son Co.
These works occupy about eighty-six acres^of land lying along
the Black river, two miles south of Lorain. The plant was first
put in operation April i, 1895. Their finished products are
billets and special rails for street railways. The plant consi.sts
of the Bessemer department, blooming mill, shape mill, engine
and boiler houses, etc. Plans for the erection of six bla.st fur-
(55)
naces have been completed and work will begin on their erec-
tion soon.
The engine house contains the blowing engine for the Besse*
mer department ; this was made by the Southwark Company »
Philadelphia. It is a horizontal double expansion engine with
blowing cylinder sixty inches diameter and sixty inches stroke.
In the same building are the dynamos and straight line engines
which furnish power for the Johnson Electric Railway between
Lorain and Elyria. There are two boiler houses containing
National Water Tube Boilers with Murphy Automatic Stokers,
the combined capacity of the two batteries being about 6,000
horse power. The feed water is heated and purified before
it enters the boilers. Gas for the heating furnaces is furnished
by a plant of Duff gas producers. Four ten-foot cupolas melt the
pig metal, and there are two eight-foot cupolas for spiegel. The
converting department contains two ten ton vessels. Ingot
molds are arranged, on small cars in pairs. There is no
casting pit. The ingots are transferred from the converter house
to the soaking pits, in which they are kept until ready for roll-
ing. The blooming mill is. drived by a very powerful reversing
engine, built by the Galloways, Manchester, England. It has
double cylinders each fifty-five by sixty inches. The shape mill
is driven by two engines, also of the Galloways' make. The
heating furnaces are provided with two cranes, one for charging
and one for drawing.
An important feature of the works is the special machinery for
straightening rails. The laboratory occupies a two-story brick
building, and contains a 250,000 pound Olsen testing machine.
THE RECEPTION BY THE CHAMBER OF COMMERCE.
The various hosts who had vied with one another in extend-
ing courtesies and hospitalities to the visiting chemists while in
Cleveland, not being satisfied with the royal welcome which
they had already given, tendered their guests a most delightful
reception in the rooms of the Chamber of Commerce, Tuesday
evening, Dec. 31. We quote from a Cleveland paper the follow-
ing description of the elaborate decoration of the rooms :
** The decorations were to a certain extent paradoxical, being
(56)
emblematic of both summer and winter. The walls of the ceil-
ing were draped with holly, heavily laden with red berries. This
drapery came down to within a few feet of the floor, where it
was met by banks and screens of palms and other tropical plants.
This apparent paradox was a pretty tribute to the various sec-
tions of the country, north and south, from which theguestscame.
The floral designs added to the beauty of the scene. One, a
large shield of white, studded with roses, bore the following in-
scription :
* Welcome, 1895 — American Chemical Society.'
In -the center of the assembly room, on a table, stood an im-
mense design which was a tribute to Dr. E. W. Morley and took
the form of a reference to his great genius in determining the
atomic weight of oxygen. It was a huge balance erected on a
base of American beauty roses. From the arms of the balance
hung globes of white flowers. On one in purple was the simple
capital letter *0,' representing oxygen, and on the other the
purple figures * 15.879,' the atomic weight of oxygen."
On entering the Chamber the guests were welcomed by the
Reception Committee, and introduced to the Cleveland gentle-
men who were present. From early in the evening until mid-
night the visiting chemists had the pleasure of meeting in social
intercourse those who had already done everything in their power
to welcome and entertain the American Chemical Society, and
to furnish them opportunities for a successful meeting.
During the evening the Chamber of Commerce Musical Club
and the Schubert Mandolin Club rendered various choice selec-
tions, which were enthusiastically received. The evening was
also enlivened by the humorous recitations and impersonations of
Mr. J. E. V. Cooke.
Refreshments were served during the evening in the commit-
tee room, and it seemed as though nothing was wanting to make
the occasion one long to be remembered. To cap the climax,
however, and to show their appreciation of one of Cleveland's
most distinguished scientists, a message of greeting and compli-
mentary reference to his labors in determining the atomic weight
of oxygen, was sent by cable to Dr. E. W. Morley, who is spend-
ing the winter in Europe.
Some of the chemists were obliged to leave on early trains and
were thus unable to enjoy the whole of the evening. But they,
as well as those who remained, took with them the pleasantest
recollections of their visit to Cleveland, and the Twelfth Gen-
eral Meeting of the American Chemical Society.
Erratum, — Page 32, sixth line from bottom of page y^r sixty-
three per cent, read sixty-three hundredths of one per ceiit.
Iftsned with April Number, 1896.
Proceedings.
COUNCIL.
The Council have approved the nomination of Edward Hart
as Editor for 1896.
CHANGES OP ADDRESS.
Bloomfield, L. M., 1239 Harrison Ave., Cleveland* Ohio.
Furman, H. Van F., Room 118, Boston Building, Denver, Col.
Koebig, Dr. Julius, 306 Market St., San Francisco, Cal.
Penberton, H., Jr., 1008 Clinton St., Philadelphia, Pa.
Phillips, Francis C, P. O. Box 126, Allegheny, Pa.
Sherman, H. C, Columbia University, New .York City.
Spencer, G. L., 134 Rich Ave., Mt. Vernon, N. Y.
ADDRESSES WANTED.
Bachman, Irving A., formerly of Augusta, Ga.
Jones, Dr. Walter, formerly of Lafayette, Ind.
MEETINGS OF THE SECTIONS.
WASHINGTON SECTION.
The annual meeting was held January 9, 1896, and wascalled
to order by the President, Charles E. Munroe, at 8:00 p. m.
The following persons were elected to membership : Messrs.
E. W. Magruder, C. C. Moore, and E. C. Wilson.
The publication of Bulletin No. 9 was announced and arrange-
ments reported by a committee for a social meeting to be heldin
February.
The reports of the Treasurer and Secretary were read and
adopted, after which the election of officers for the ensuing year
was held with the following result :
President — E. A. de Schweinitz.
Vice Presidents — W. D. Bigelow and W. G. Brown.
Treasurer— W. P. Cutler.
Secretary — A. C. Peale.
Additional Members of the Executive Committee — Charles E.
Munroe, V. K. Chestnut, F. P. Dewey, and H. N. Stokes.
(58)
The first paper of the evening was read by H. W. Wiley on a
'* Steam- Jacketed Drying Oven." **In order to surround the
drying space of an oven entirely with steam, the door of inordi-
nary steam-jacketed drying oven is made with double wdls, into
which the steam from the oven is conducted by two metal flexi-
ble tubes inserted at the top and bottom of the door. They are
so arranged as not to interfere with opening the door. By
this method the entire drying space of the apparatus is sur-
rounded with steam, easily securing a constant and even tem-
perature.
The temperature is regulated by a pressure gauge in which
the steam, by acting on a column of mercury, cuts off the gas when
a given pressure is reached. A steam pressure of two inches
will cause a temperature of about 102** in the drying space of the
oven. By setting the gauge at any position desired, the temper-
ature can be regulated, when steam is used, to read from the
boiling point of water up to los"*. For other temperatures other
liquids can be used. For instance, alcohol, or amyl alcohol for
still higher temperatures, and so on. Ether cannot be employed
with safety on account of the danger of explosion in case of
leakage.'*
Dr. Wiley exhibited the drying oven in actual operation.
The second paper, also by Dr. Wiley, was on the **Heat of
Bromination of Oils.'* ** The method of determining the heat
of bromination of oils, as proposed by Hehner and Mitchell, in a
recent number of the Analyst, is very difficult to work from
the meager directions given by the authors. The especial dif-
ficulty in the process is in handling the liquid bromine in quan-
tities of one cc. at a time. I find that the process is made prac-
ticable by dissolving both the oil or fat and the bromine in chlo-
roform, in which condition the bromine solution is easily handled
by means of a special pipette.
In order to make a number of analyses of the same sample,
five grams of the fat may be dissolved in chloroform and the vol-
ume completed to fifty cc. Ten cc. of this solution will contain
one gram of the fat. In like manner five cc. of bromine may be
dissolved in chloroform and the volume completed to fifty cc, or
larger quantities in the same proportion may be used. The
(59)
gradual evolution of hydrobromic acid from a mixture does not
interfere with the analytical process, as the amount of broinine
used is always largely in excess. Ten cc. of the bromine solu*
tion containing one cc. of the liquid bromine are used for each
ten cc. of fat solution.
The pipette for handling the bromine solution is so arranged
as to be filled by the pressure of a rubber bulb, thus avoiding the
danger of sucking the bromine vapor into the mouth. The solu-
tion is poured upon the chloroform solution held in a long nar-
row tube, in which a delicate thermometer, capable of being read
to tenths of a degree, by* means of a magnifying glass, isplaced.
This tube is held in a large cylinder, from which the air can be
removed, thus affording a good insulation in respect to heat.
The determinations should be conducted in a room where the
temperature is as constant as possible and the pieces of the appa-
ratus should be exposed to the open air for at least half an hour
after completing one determination before beginning another, in
order to be restored to the standard room temperature. Dupli-
cates usually agree within one or two-tenths of a degree, though
sometimes the variations are greater.
The ratio of the heat of bromination to the ordinary number
must be established for each system of apparatus employed.
The heat of bromination of various oils was determined by the
method and apparatus described above, and the process seems to
be one of considerable analytical value. For exact scientific
purposes, calorimetric measurements of the degree of heat pro-
duced must be made."
Discussion was by Messrs. Warder, Freeman and Munroe.
Professor Charles E. Munroe then made some remarks upon
the *• Corrosion of Electric Mains." He exhibited sections of
electric light cables in which the lead coating had become so
corroded that in some places the interior conductor was exposed,
while at others the cable was coated with nodular earthy-looking
masses. The cables were parts of and arranged on the three
wire system, which carried a direct current of i lo volts on each
wire, and which had been laid underground in the upper com-
partment of a terra cotta conduit. The corroded main was a
branch in an alley. The principal main in the street was not
(6o)
attacked in the least. Analysis showed the incrustation tc con-
tain nitrate, chloride, carbonate, oxide of lead, water and strace
of organic matter. Surrounding the alley were stables, aid the
author found in the salts in the soil produced by the excieta all
the necessary materials and conditions for effecting chemical
corrosion /^r se.^ without resorting to any electrolytic theory.
Dr. Wiley, in discussing the paper, said he thought there
might have been a denitrifying process.
Professor Munroe said there could have been no constant
moisture present, that is, there was no submergence, but there
must have been water passing through the conduit.
CINCINNATI SECTION.
The Section met in regular session Saturday evening, Feb-
ruary 15, 1896. Vice President Martin presided.
Dr. Alfred Springer read a paper on **The Characteristics of
Illuminates," and exhibited a photograph of the bones of the
hand made by means of the Roentgen X rays. The picture was
kindly loaned for the purpose by Mr. G. W. Zwick, of Coving-
ton, Ky., who had recently brought it from Germany.
** Notes on Helium and Argon " was read by Professor T. H.
Norton.
Dr. S. Waldbott showed how the value of litmus paper as an
indicator could be enhanced. His method was to use a capillary
pipette instead of an ordinary stirring rod, and to hold the point
of the pipette containing a drop of the solution upon the litmus
paper ; a bright red spot would be seen at the point of contact,
even in very dilute acid solutions. The Doctor's paper on "The
Assay of Ipecac," announced for the evening, was postponed
till next meeting.
NORTH CAROLINA SECTION.
On February 22nd about a dozen chemists met in the office of
the Experiment Station in Raleigh to organize the North Caro-
lina Section. The following officers were elected :
President — F. P. Venable, University of North Carolina,
Chapel Hill.
Vice President — Charles K. Brewer, Wake Forest, N. C.
Secretary and Treasurer— W. A. Withers, Raleigh, N. C.
(6i)
The following papers were read :
''Absorptive Power of the Soil for Bases and Its Relation to
FertiUty," by Prof. Withers.
"A Study of the Zirconates," by Dr. Venable and Mr. Clarke.
** Notes on the Reduction of Methylenedi-<?-/-*«-nitraniline,"
by Dr. Baskerville.
NEW YORK SECTION.
The regular meeting of the New York Section was held at the
College of the City of New York, on Friday evening, March 6th,
at 8:30 o'clock. Professor P. T. Austen in the chair.
The following papers were read :
**The Cassel-Hinman Gold and Bromine Process," by P. C.
Mcllhiney."
**The Specific Gravity of Glue Solutions," by E. R. Hewitt.
** Investigations in the Chemistry of Nutrition," by Dr. W. O.
Atwater.
Mr. Mcllhiney enumerated the advantages of bromine over
chlorine in the gold extraction process as (i) greater solubility
of bromine, as three and two-tenths per cent, against 0.76 per
cent.; (2) lesser oxidizing pywer, whereby the iron pyrites is
less acted upon ; (3) greater solvent power for gold.
The bromine is recovered by distillation with live steam in
stone tanks, after addition of sulphuric acid and an oxidizing
agent.
The process is especially adapted to low grade telluride ores,
which have not hitherto been profitably worked.
Mr. Cassel, being present, was asked to what extent the pro-
cess had been worked, and whether ores containing sulphides
could be treated. He replied that fifty tons per diem had been
treated since January ist, and the capacity was to be increased ;
that ores containing small amounts of sulphides had been suc-
cessfully treated, using very weak solution of bromine, and
eighty per cent, of the bromine had been recovered ; but it was
best to roast sulphide ores. The cost, including roasting, was
$1.75 per ton.
Mr. Hewitt, in his work on the ** Specific Gravity of Glue
Solutions," had obtained his results from experiments on all
grades of glue from the best photographic gelatine, to the dark-
est and poorest grades in the market.
(62)
He found the expansion of glue solutions to be the same as
water alone ; that the specific gravity of glue containing water
was less than in the dry state ; that the hydrometer could not
be used in solutions containing over sixty-five per cent., and that
the quality of the glue had no effect on the specific gravity of
the solutions.
He concludes that there is a series of distinct chemical com-
binations of glue with water.
In the discussion of the paper, Dr. Home asked if the specific
gravity of a glue solution could be determined by dropping it
into some solution of known density, not acting on the glue solu-
tion.
Mr. Hewitt replied that this method had been tried, using
xylol, chloroform, and some other liquids, but the results were
not as satisfactory as could be obtained by the hydrometer.
The presence of Dr. C. B. Dudley, President of the Society,
was then announced, and Dr. Dudley addressed the meeting in
part, as follows :
* * Gentlemen of the New York Section : It has been a rare
pleasure to attend this meeting of the New York Section, and I
would like to congratulate yoii on one or two points. First, the
advantage that comes to you from being able to meet together,
read papers, shake hands and dine together. I am so far away
from the chemists that it does me good to meet and shake hands
with a chemist. In the early days of the Pittsburg Society I
tried to meet with them and have been present on many enjoya-
ble occasions, but having joined the Society when there was
only a New York Section, I have felt at home with you and
have wished I could meet with you oftener.
** Another thing on which I wish to congratulate you. Our
General Secretary informs me that we have a good round thou-
sand now in our membership. There are those of you who have
stood by the Society when it was not as prosperous as it is now,
who can appreciate this.
** Now as to what is to be done in the field of our labors. My
daily work, or a great part of it, is with iron and steel, and if I
could, I would give all my time to the study of pig iron.
** There are many problems yet to be solved in regard to it,
(63)
and of which a great deal might be said, but as there are other
papers to come before you this evening, I will not detain you
longer. I am very glad to have been able to meet with you.*'
Dr. W. O. Atwater was then introduced, and after giving a
synopsis of the work which had been done in other countries,
especially in Germany, on the chemistry of food and nutrition,
he described the progress which had been made in this country,
beginning with the early work of Professor Baird, then of the
Smithsonian Institute, who gave the first impulse to this work
by his studies of the food value of a number of varieties of fish.
He then passed to a description of the work recently done under
his direction and that now in progress in determining the heats
of combustion, or fuel values of food. He said that we know the
laws of conservation of energy hold good in the living organism,
but we do not yet know haw they hold good. We must study
these things in the living organism, and for this paper a respir-
atory calorimeter has been constructed at Middletown by which
the experimental determination of heat of radiation, energy of
food consumed, etc., is to be obtained. A man had been kept
in this apparatus for four days, and it was expected to arrange
to extend the experiment to a week or even several weeks.
Eight attendants were require to run these experiments.
Dr. Dudley asked whether Professor Atwater had used a cur-
rent of oxygen instead of potassium chlorate in his experiments
on the heats of combustion of foods, and stated that he had used
the oxygen with very satisfactory results in determinations of
calorific value of coal.
Dr. Dudley also asked whether the quality of the fat of ani-
mals was dependent on the food.
Professor Atwater replied that the fat formation is a function
of both the organism and the food.
On motion of the Secretary, a vote of thanks was passed to
Professor Atwater for his interesting report on the progress of
the chemistry of nutrition.
Professor Breneman moved that a committee be appointed to
make a report at the next meeting on the feasibility of organiz-
ing a chemical club from the members of the New York Section.
Seconded and carried.
(64)
The Chair appointed Messrs. Breneman, McMortrie, and
Hallock.
The Librarian announced the receipt of a bequest from Dr. A.
A. Pesquet, of two microscopes and accessories. The Chair
directed that a suitable recognition of the gift be made.
RHODE ISLAND SECTION.
The regular meeting of the Rhode Island Section was held at
Providence, Thursday evening, Feb. 13, 1896. Mr. Chas. S.
Bush in the chair.
A paper was read by Mr. Charles E. Swett. Subject, "Ultra-
marine."
Th^ reader presented the results of a few experiments he had
performed upon ultramarine, with some of the more common re-
agents.
The March meeting was held on the 19th inst., at Providence.
Chairman C. A. Catlin, presiding.
Mr. Walter E. Smith read a paper upon **The Origin of Pe-
troleum."
In brief, the paper was as follows :
The theories given for the origin of petroleum are in general
divided into three classes :
1. The chemical theories advanced by Berthelot and Mende-
l^efiF, that water on metallic carbides forms acetylene, which is
further changed.
2. The theory that it is indigenous to the rocks in which it is
found.
3. The theory that it is a distillate formed from highly organ-
ized substances.
Issued with May Number, x
Proceedings.
COUNCIL.
The Council has decided to hold the summer meeting at
Buffalo, August 21 and 22.
NEW MEMBERS BISECTED MARCH 26, 1896.
Brown, Thomas, Jr., M.S., Princeton, N. J.
Banner, W'. E., 441 Green St., Philadelphia.
LaWall, Charles H., 305 Cherry St., Philadelphia.
Nagelvoort, J. B., 3237 Michigan Ave., Chicago, 111.
Sprout, Louis P., Scotia, Pa., P. O. Benore.
Stewart, Dr. Andrew, 1420 Q St., N. W., Washington, D. C.
Wagner, John R., Drilton, Pa.
ASSOCIATES EI.ECTED MARCH 26, 1876.
Caldwell, Thomas O., Agr. Exp. Sta., Bozeman, Mont.
Flowers, John, Agr. Exp. Sta., Bozeman, Mont.
Pilgrim, Heber B., Lafayette College, Easton, Pa.
Sieb, Peter, Agr. Exp. Sta., Bozeman, Mont.
Twitchell, Mayville W.. 7098th St., N.E., Washington, D.C.
Walter, Charles Albert, 506 South 5th St., Champaign, 111.
CHANGES OP ADDRESS.
Barton, G. E., care Whitall, Tatum & Co., Flint Glass
Works, Millville, N. J.
Benjamin, Dr. Marcus, Smithsonian Institute, Washington,
D. C.
Berry, W. G., 26 Whitehall St., N. Y. City.
Breyer, Theo., P. O. box 112, Peoria, 111.
Brown, H. F., 113 West Central St., Natick, Mass.
Fields, J. W., Stillwater, Okla.
Johns, John, 306 Toone St., Baltimore, Md.
Kelley, J. H., 26 Snell Hall, Univ. of Chicago, Chicago, 111.
Lloyd, Rachael, care R. L. Lloyd, Lansdowne, Pa.
Low, A. H., P. O. drawer 1537, Denver, Colo.
Maury, George P., care Edgar Thompson Steel Works, Brad-
dock, Pa.
Nickel, Herman L., care N. K. Fairbank Co., St. Louis, Mo.
Pomeroy, Charles T., 190 Mt. Pleasant Ave., Newark, N. J.
Rosengarten, F. H., care Photographic Society, 10 So. i8th
St., Philadelphia, Pa.
Steiger, Geo., 1425 Corcoran St., N.W., Washington, D. C.
(66)
MEETINGS OF THE SECTIONS.
WASHINGTON SECTION.
A regular meeting was held February i3tli, 1896. As the
meeting was devoted mainly to social purposes and the inaugu-
ration of the newly elected president, Dr. E. A. de Schweinitz,
it was held at the rooms of The Washington Down Town Lunch
Club. After the transaction of necessary business a lunch was
served which was enjoyed by thirty-one members. The follow-
ing persons were elected to membership : Clinton P. Townsend,
S. S. Voorhees, and Dr. F. K. Cameron.
The Presidential address before the Washington Section was
delivered by the retiring President, Professor Charles E. Mun-
roe, at a special meeting held Friday, February 21, the subject
being ** The Development of Smokeless Powders." The lecturer
sought to show that the necessity for a high-power, smokeless
propellent had been created by the mechanical perfection to
which ordnance had attained and the precision of the weapons
and the instruments by which they were directed ; that the
possible production of such propellent was dependent on the
discovery of guncotton, nitroglycerol, and certain nitro-substi-
tution compounds, and the improvements in their manufacture ;
that the possibility of producing uniform and reliable propel-
lents was dependent on the invention of pressure gauges and
velocimeters ; and that the possibility of their economical pro-
duction was dependent on the invention of mechanical mixers
and formers applied in other arts. In a historical rdsum6 it was
shown how very recent most prior inventions and discov-
eries were, *and it was pointed out that a very large propor-
tion of the inventions were made by American scientific men.
The many smokeless powders manufactured or prepared were
then described or enumerated and classified into mixtures of
different cellulose nitrates with oxidizing agents ; mixtures of
soluble or insoluble cellulose nitrates with oxidizing agents ;
mixtures of soluble or insoluble cellulose nitrates with nitro-
glycerol ; mixtures of cellulose nitrates with nitro-substitution
compounds ; and pure cellulose nitrate powders ; and the meth-
ods of manufacture were briefly stated.
(6?)
The lecturer then related his own experience in inventing
a smokeless powder. Recognizing at the outset the necessity
for the closest approximation to absolute chemical and physical
tiniformity in a high-powered powder, and being familiar with
the difficulty of securing such constancy in a physical mixture,
he set about producing a powder from carefully purified cellu-
lose nitrate of the highest degree of nitration. This was the first
and only attempt made, 90 far as the lecturer was aware, to pro-
duce a powder which consisted of a single substance in its pure
state.
A factory was erected at the Torpedo Station, prior to his
resignation of his position there, and the powder manufactured
was proved at Indian Head • by Ordnance Officers of the Navy.
Secretary Tracy said of this powder, ** Report of the Secretary of
the Navy, 1892, page 25.'* ** It became apparent to the Depart-
ment early in this administration that unless it was content to
pass behind the standard of military and naval progress abroad
in respect to powder, it must take some steps to develop and to
provide for the manufacture in this country of the new smoke-
less powder, from which extraordinary results had been obtained
in Europe." With this object negotiations were at first attempted
looking to the acquisition of the secret of its composition and
manufacture. Finding itself unable to accomplish this the
Department turned its attention to the development of a similar
product from independent investigation. The history of these
investigations and of the successful work performed in this
direction at the Torpedo Station has been recited in previous
reports. It is a gratifying fact to be able to show that what we
could not obtain through the assistance of others we succeeded
in accomplishing ourselves, and that the results are considera-
bly in advance of those hitherto obtained in foreign countries.''
The conditions that a smokeless powder should fulfill and the
tests prescribed by the lecturer were then set forth, and in
closing he pointed out that the powder was now developed to a
higher degree than the gun and that changes in the latter to
render it more efficient were being considered by ordnance
experts.
(68)
CINCINNATI SECTION.
The Section met in regular session, Tuesday, March 17, 1896.
President Twitchell presided.
The discussion of '*The Scientific Concepts of Etidorhpa"
was announced for the evening. The popularity of the book
was evidenced by the presence of many friends of the author
and of the other members of the Section.
Dr. Alfred Springer read extracts from the book and took
issue with the author on some of the statements. Prof. Lloyd
re-affirmed his belief in the theories advanced and referred the
Doctor to the preface to the author's edition, in which he had
stated he would decline " to make any subsequent comments on
the work." The Professor then read three chapters in the orig-
inal manuscript, which had been omitted from the published
work. He now regrets the omission, as the continuity of the
narrative is somewhat impaired thereby.
RHODE ISLAND SECTION.
The regular meeting of the Rhode Island Section was held at
Providence, Thursday evening, April 16, 1896, Chairman, Charles
A. Catlin, presiding.
Mr. Charles S. Bush read a paper on ** Petroleum Products."
The following is an outline of the paper :
1. Discovery of petroleum.
2. Brief history of the petroleum industry in the United
States.
3. Outline of the distilling and refining process now in general
use in the United States.
4. The importance of petroleum as a means of reducing fric-
tion to a minimum.
5. New methods compared with old ones, especially referring
to ** petroleum products" used for lubricating purposes.
NEBRASKA SECTION.
The regular meeting of the Nebraska Section ^**s held at the
University of Nebraska, on Tuesday evening, March 31, at
eight o'clock.
(69)
The president being absent, Mr. Samuel Avery was elected
chairman /ri9 tern., and called the meeting to order.
The following papers were read :
"Recent Work on the Roentgen Rays," by Prof. D. B.
Brace, of the Department of Physics, University of Nebraska.
** Report on Argon," by Miss Rosa Bouton.
** Calcium Carbide and Acetylene," by Dr. John White.
Prof. Brace exhibited some Crookes' tubes prepared in his
laboratory, made a general statement of the manner in which
these were prepared and used, of the effect of the X or Roent-
gen rays, and exhibited some photogrraphs taken by their use.
Of these one was of special interest ; it represented a shado-
graph of a metal object taken by the cathode and anode rays.
There was no appreciable distinction between them.
Miss Bouton's paper gave a very thorough and clear account
of argon, from the very earliest experiments of Lord Rayleigh
on the density of nitrogen down to and including the present
state of our knowledge of argon, its chemical and physical prop-
erties.
Dr. White exhibited a specimen of calcium carbide, which
had been prepared in the electrical laboratory of the University,
gave a brief historical statement of the carbides in general, and of
their use in the preparation of acetylene. He then prepared
some acetylene by treatment of the carbide with water, and by
burning the gas under proper conditions showed how it may be
used as an illuminant. He followed this by a short lecture, in
which the economic use of acetylene as an illuminant was dealt
with, laying speqial stress upon its advantages and disad-
vantages.
Owing to the lateness of the hour, Dr. White's paper on
** Metallic Suboxides" was postponed.
At the business meeting which followed, Mr. E. C. Ellioet
and Miss Marietta Gray were elected members of the Section.
NEW YORK SECTION.
Minutes of the meeting of April lo.
A report was made by the chairman of the committee appointed
(70)
to consider the organization of a chemical club in New York.
Out of eighty-two replies already received, sixty were uncondi-
tionally in favor of the project.
It was further stated that as there had evidently been some
misunderstanding as to the intended membership » it should be
known that there is no intention of limiting the membership to
any section of the chemical fraternity, but to include chemists
and chemical manufacturers generally.
Dr. Albert R. Leads read a paper on *' Standard Prispis in
Water Analysis, and the Valuation of Color in Potable Waters.*'
In the discussion of Dr. Leed's paper, Prof. Birchmore ex-
plained an arrangement of adjustible colored prisms projecting
inside a glass cylinder, one over the other, by which the Nessler
reagent colors could be matched and recorded. The cylinder is
to be filled with a liquid having the same refractive index as
glass ; oil of juniper was mentioned as suitable ; and the record
is made by readings on the milled heads of the screws by which
the Qverlapping of the prisms is regulated.
Dr. I/ceds moved that a committee be appointed to unify the
methods of color comparison and report upon a standard of
measurement of color in potable waters.
Prof. McMurtrie thought that such committee should be
appointed by the council, and that the secretary should com-
municate the resolution to the President of the Society.
Dr. Leeds' motion, as amended by Prof. McMurtrie, was
seconded and carried.
A paper was read by C. L. Speyers on '* Matter and Energy."
Dr. E. G. Love exhibited some fine photomicrographs of
starches.
Di;. L. Saarbach exhibited and described an improved form of
** Laboratory Temperature Regulator,'* which he had found sen-
sitive, reliable, adjustable, and easily taken apart for cleaning.
Issued with June Number, 1896.
Proceedings.
COUNCIL.
Prof. H. H. •Nicholson, Lincoln, Neb., has been elected a
member of the Council, to take the place left vacant by the elec-
tion of Dr. C. B. Dudley to the presidency of the Society.
The Council has voted to accept the invitation to hold the
-winter meeting at Troy, N. Y., on Tuesday and Wednesday,
December 29 and 30.
The New York Section has asked that a committee be ap-
pointed to unify the methods of color comparison and report on
a standard for measurement of color in potable waters. The
Council has agreed to the formation of such a committee and
named the following persons to act as members : A. R. Leeds,
Wm. P. Mason, Thomas M. Drown.
NEW MEMBERS ELECTED MAY II, 1 896.
Bowman, J. W., Green Island, N. Y.
Hunziger, Dr. Aug., care Weidman Silk Dyeing Co., Pater-
son, N. J.
Yates, J. A., Williamsburg, Ky.
ASSOCIATES ELECTED MAY II, 1 896.
Meade, Richard K., Longdale, Va.
Pilhashy, Benjamin M., 1058 Cutter St., Cincinnati, O.
CHANGES OP ADDRESS.
Dodge, F. E., 316 Bowne Ave, Flushing, N. Y.
Hays, Joseph A., 147 So. i8th St., Pittsburg, Pa.
Hopkins, Cyril G., 409 W. Main St., Urbana, 111.
Lord, N. W., 338 W. Eighth Ave., Columbus, O.
Peale, A. C, box 2043, Station A, Philadelphia, Pa.
Power, Frederick B., 535 Warren St., Hudson, N. Y.
Shepherd, Frank I., Kyle, Ohio.
Stillwell, J. S., box 3015, N. Y. City.
Tonceda, Enrique, care Troy Steel Co., Troy, N. Y.
ADDRESSES WANTED.
Gallaher, Phil. C, formerly of Leadville, Colo.
(72)
MEETINGS OP THE SECTIONS.
CINCINNATI SECTION.
The regular meeting of the Section was held Wednesday
evening, April 15th.
Dr. S. Waldbott presented a paper on ** The Assay of Ipecac,"
in which he outlined the various methods for the alkaloidal assay
of crude drugs and gave some results obtained by applying the
Lloyd method for the assay of fluid extracts, to the determina-
tion of emetine in ipecac root; with some slight modification,
Dr. Waldbott thinks good results may be obtained.
In a paper on ** The iodoso- and iodo-compounds and iodonium
bases, Dr. John McCrae gave an interesting account of some of
the work he had done on these compounds, under the instruc-
tion of Victor Meyer.
NEW YORK SECTION.
The New York Section held its usual monthly meeting in the
chemical lecture room in the College of the City of New York on
Friday evening. May 8, with about fifty members present. Dr.
Peter T. Austen, presiding. In response to inquiries regarding
the progress made by the committee appointed to canvass the
matter of the organization of a chemical club. Prof. Austen
stated that in accordance with the instructious given, it had
increased its numbers to fifteen and had held several meeting^,
to one of which the members of the New York sections of the
American Chemical Society and of the Society of Chemical
Industry, as well as manufacturers and gentlemen interested in
the science and art of chemistry, business men and friends of
chemistry were invited. The meeting was full and enthusiastic.
The committee was instructed to increase its number to fifty or
more and to push the organization of the club as rapidly as pos-
sible. The committee had held another meeting and added a
large number of names of prominent chemists, manufacturers,
and business men to the list. The general opinion seems to be
that the initiation fee should be fixed at $25, and yearly dues at
$25. It is the intention, while in no way hampering or restrict-
ing the evolution of the Chemical Club, which many of the more
enthusiastic supporters of the movement predict, to start the
club in a conservative and economical way, and not to exceed
(73)
the pecuniary limit which shall be decided upon after careful
deliberation. It appears that there is not in existence in this or
any foreign country any real chemical club, as differentiated
from a chemical society. It is believed that the science and art
of chemistry furnish so much that is characteristic that a chem-
ical club may easily be made a unique organization. The mem-
bers of the committee of fifteen are Prof. A. A. Breneman, Dr.
A. P. Hallock, Prof. Peter T. Austen, Dr. W. McMurtrie, Prof.
Morris Loeb, Prof. C. A. Doremus, Dr. E. R. Squibb, Dr. J. H.
Wainwright, Mr. A. H. Mason, Mr. S. W. Fairchild, Mr. W.
H. Nichols, Mr. W. J. Matheson, Mr. T. F. Main, Prof. A. H.
Sabin, and Dr. C. P. Chandler.
Dr. A. R. Leeds, of Stevens Institute, read a paper on the
"Bacteriaof Milk Sugar.'' The author finds that the morphology,
classification, physiology, and botany of bacteria are so rudi-
mentary and unsatisfactory that the most valuable methods of
bacteriological investigation are still of a chemical nature, and
the advances to be made in the near future are to be looked for
mainly on the chemical sides of the subject.
The author was interested to note in the progress of his work
that precipitated zinc hydroxide, which is generally considered
amorphous or gelatinous, is really crystalline.
Dr. H. W. Wiley, of the United States Department of Agri-
culture in Washington, offered a paper entitied ** Recent
Advances in Milk Investigations. ' ' In the absence of the author
the paper was read by Dr. William McMurtrie. It treated of
the bacterial theory of milk decomposition, the composition of
woman's milk as compared with cow's milk, and the relative
value of the two for infant food, and of the commercial standards
which should be fixed for the milks sent to the city markets.
The author reviewed the work of Soldner regarding the pro-
teid content of human milk, and quoted the figures given by
authority for the average composition of human milk, as follows :
Per cent.
Proteids 1.52
Fat 3.28
Sugar 6.50
Ash 0.27
Citric acid ^ 0.05
Undetermined 0.78
Total dry substance 12.40
(74)
The undetermined substances, 0.78 per cent., are mostly
nitrogenous bodies not generally found in cow's milk, and for
this reason cow's milk can never be so diluted or altered as
to properly supply the natural nutriment of the infant.
Soldner follows the method of Munk for determination of pro-
teids, regarding as non-proteid jnatter those nitrogenous bodies
not precipitated by tannin in presence of common salt. In
woman's milk these amount to nine per cent, of the total nitro-
genous constituents, and in cow's milk to about six per cent.
The author then discussed the view of Bechamp that milk de-
rived from healthy animals is capable of spontaneous alteration,
which consists in the development of lactic acid and alcohol and
the development of curds in those milks which contain casein-
ates produced by the precipitating action of the acids formed.
Oxygen and the germs present in the air are held to have noth-
ing to do with this alteration of the properties of milk. The
general conclusion reached is that microqrganisms, such as
vibriones and bacteria, are developed by a natural evolution
from the microzymes, even in milk which has been boiled.
The surprising results of Soldner and Bechamp should lead to
new studies of bacterial action in milk. If it should prove true
that milk contains autogenetic germs for its own change, and that
by the development of these germs into vibriones and bacteria,
the natural souring takes place, it will be necessary to change
completely the common view respecting these processes.
The author further discussed the commercial standards for the
composition of milk, declaring that the value of milk, both for
butter and cheese making, should be gauged by its content of
butter fat, denouncing the claim of dealers that any milk from a
healthy cow should be sold without legal restriction, no differ-
ence what its content of fat may be, and recommending that
the minimum standard for fat content of milk supplied for human
consumption should be placed at three per cent, or higher.
Dr. Leeds considers that in judging of the figures of Soldner
presented it is important to be informed of the conditions under
which the samples for analysis were taken and the quantity used
for analysis, particularly for the determination of such constitu-
ents as citric acid and the undetermined substances. Samples
(75)
of woman's milk usually available are too small for such minute
determinations. Regarding the content of proteids, the figures *
of Soldner do not vary widely from those previously found and
reported. One hundred samples of woman's milk examined in
New York gave an average of less than two per cent., with
variations of 0.75 per cent, to 4.75 per cent. The only explana-
tion of the very low figure of Soldner is that only partial secre-
tion was available. The figure 1.52 given is not surprising.
That the various bodies secreted from the blood should be
present is generally accepted. Variations in the composition of
the milk, due to emotional influences, such as nervousness,
excitement, fatigue, fright, anger, etc.,. are well known.
The fat and total solids given in the analysis are surprisingly
low.
Dr. Bccles questioned the declaration that modified cow's
milk was not a proper food for infants. Constant experience,
forced by necessity, shows that it supplies excellent nutrition for
infants.
Prof. Marston Bogert, of Columbia College, read a paper on
*' Normal Heptyl Thiocyanate."
The steps followed by the author in preparation of heptyl
thiocyanate are as follows : Production of heptyl alcohol from
oenanthol by reduction with zinc dust and acetic acid, conver-
sion of the heptyl alcohol into the bromide, and addition of the
bromide to boiling alcoholic solution of potassium thiocyanate.
The yellow oil finally obtained washed free from potassium^ thi-
ocyanate, dried with calcium chloride and distilled, all passed
over between 230° and 234* C.
Normal heptyl thiocyanate is a colorless, mobile liquid, hav-
ing a slightly alliaceous but rather pleasant odor and a specific
gravity of 0.931 at is"* C.
Dr. Austen exhibited an apparatus for lecture demonstration
of the properties of the heavier gases.
WASHINGTON SECTION.
A regular meeting was held Thursday, March 12th, 1896,
with President Dr. de Schweinitz in the chair. There were
(76)
thirty-five members present, and Dr. Andrew Stewart was
elected to membership.
Mr. F. P. Dewey read a paper on ** The Refining of Lixivat-
ing Sulphides.'' Dr. Dewey's paper reviewed the leaching^
process and the treatment of sulphide precipitates produced. He
described the sulphuric acid process of treating the sulphides, in
which they are treated in strong sulphuric acid to convert the
sulphides into sulphates, after the charge is treated with water,
the silver precipitated by copper and melted, the copper sul-
phate crystallized. In the 1894 run of the Marsac Refinery »
116,519^ pounds of sulphides, carrying 572,544.4 ounces of sil-
ver by the corrected assay were treated, and 574,623.26 ounces
of silver were returned, showing a plus clean up of 2,073.81
ounces, or 0.36 per cent. 96.29 per cent, of the product was in
the form of bars, averaging 999.4 fine in silver, no gold.
Professor H. W, Wiley and E. E. Ewell read a paper* on
"The Determination of Lactose in Milks by Double Dilution
and Polarization."
Professor H. Carrington Bolton read a paper on " Berthelot's
Contributions to the History of Chemistry," reviewing his
** Collection des AlchimistesGrecs," (Paris, 1887 ; 3 Vol. 4to),
and his ** La Chimie an Moyen Age," (Paris, 1893 ; 3 Vol. 4to),
showing their scope, analyzing their contents and indicating the
important changes in (Chemical history resulting from Berthelot's
studies.'
In the discussion of Dr. Bolton*s paper. Dr. Wiley referred to
the fact that the Phoenicians, as early as 1200 years before
Christ, became famous by reason of the remarkable dyes which
they produced, and that they were derived from a colorless sub-
stance found in certain moUusks, which, when exposed on fibers
to the light, turned green, then red and purple. He referred to
the fact that on the continent of Europe many scientific men had
also become famous in politics, • and among them preeminently
Berthelot and Virchow. Berthelot was at least one official
chemist who had attained political distinction, and his career
might be imitated with advantage to the public service by some
1 This Journal, x8, 438.
s This Journal, 18, 466.
(77)
American scientists; and we should not despair of looking for-
ward to the day when chemists should at least be members of
the Cabinet, if not Presidents of the United States. He thought
Berthelot was particularly well suited to write of the alchemists,
because some of his views would do credit to the wildest vagar-
ies of the alchemists, especially his notion that the art of the
chemist in the synthesis of foods, would in the near future ren-
der the practice of agriculture unnecessary. But we should not
criticise a great man because of his vagaries, and after all it
may be true that insanity is the highest type of genius.
The topic of discussion for the evening was * * Style in Chemi-
cal Books and Papers." Dr. Wiley opened the discussion by
saying there are many problems that present themselves to
authors of scientific work. Some of these are of vital import-
ance, while others are mere matters of taste. Not having ex-
pected to discuss the question on this occasion, he would confine
himself to the minor topics. He suggested that there should be
some uniform systsm of abbreviation employed, and for his part
preferred very much small letters without periods. The intro-
duction of capital letters in abbreviations marred the appearance
of a book, and appeared to be entirely unnecessary. He thought
perhaps some abbreviation of common metric terms would prove
advantageous; for instance, the writing of the words cubic cen-
timeters repeatedly not only requires a great deal of space, but
the repetition of the term becomes tiresome. Some short
word might be used to represent this magnitude, as, for instance,
cubics. It would be well for chemists to agree upon some such
system, provided the system were rational and easy of applica-
tion.
Another question which often arises is in regard to the agree-
ment between the noun and the verb, as, for instance, should we
say ICO grams of iron are, or loo grams of iron is ? Another
minor point is in the writing of numerals ; whether they should
be written out or the Arabic numerals used. He has adopted
the plan of writing out in full numbers below loo, and placing
the Arabic numerals for loo and above. This was an arbitrar>'
division, however, which might well be changed if some agree-
ment could be reached in regard to it.
(78)
It appears that most scientific writers are so eager to express
the truth or fact which they wish to convey that they lose sight
altogether of the style in which the expression is made, and, as
a result, their sentences become involved, and their meaning far
from clear.
Another point which merits discussion is in the use of proper
names to indicate any apparatus or process known by the name
of the inventor. He preferred in such cases, where the personal
idea had been lost, to use no capital, but to write the name of
the apparatus or process with a small letter, as, for instance, a
gooch or an erlenmeyer. The same is true of materials or
reagents with geographical adjectives, as for instance, german
silver and canada balsam, both of which should be written with
small letters, just as the French, without disparaging the great
Emperor, write the name of the coin napoleon with a little n or
as we write telford or macadam for the name of a road.
Chemists should be careful about '*take." It is not elegant
to say ''take five grams and place in a dish." " Place five
grams in a dish " is entirely sufficient. In one work on chem-
istry he found the author directing the analyst to *' take twenty-
five grams of Glauber salts " with a big g. *' Weigh out" is
inadmissable. Wedo not weigh out, norin, noron, nor under. We
simply weigh. In measuring it is not necessary to say weigh,
as the chemist knows enough to use the balance without specific
directions. A typically unnecessary form of expression and one
not impossible to find is ''take barium chloride, weigh out five
grams, dissolve in water and filter ofiF the insoluble residue."
Above all, the scientific writer should avoid indulging in fine
writing. Plain, unvarnished statement of fact in a clear, lucid
manner is what we should strive for. An example of how not
to write is the following:
* ' For not only does the soil make possible a very much greater
profusion of land life than could otherwise exist, but it has also
played an extremely important part in that long-continued never-
ending, and sublime process of evolution whereby, as lands have
insensibly changed into sea and seas into land, as mountains
have risen so slowly and silently out of level plains as to spring
their broad arches directly across wide rivers to the height of a
(79)
mile and yet leave their course unaltered, as climates have
changed from cold to warm or from wet to dry, both plants and
animals in this great drama of the world action have been
enabled to change, not simply their costumes, but, if the exigen-
cies of the new scene demanded it, legs for fins or even abandon
them altogether and crawl upon their bellies through the
grass."
Professor Bolton said he thought one*s grammar school edu-
cation must have something to do with style in writing. Great
labor is expended nowadays upon abstracts from foreign publi-
cations. He thought there should be a different method of
treating them. The results might be presented without giving
the steps by which they are reached. He thought that no one
could depend entirely upon the abstracts, but have to refer to
the original papers for details.
Professor Seaman said he was glad the subject was brought
up ; he thought some chemists had an idea that the English
language is sacred, and that no changes should be made in it.
This feeling must be met. He said that most persons read by
words, and not by letters, and if a word has not the usual
appearance to which we are accustomed, our first impression is
that it is wrong, and hence he feared that no changes, however
judicious, would seem agreeable. As to the agreement of col-
lective nouns with verbs, Goold Brown concluded that the only
principle to be followed is euphony. When the best grammar-
ians cannot formulate rules, uniformity can hardly be expected.
As to the use of small letters instead of capitals, the various
changes that are going on in the language generally ought to
be considered. The councils of biological societies have agreed
that small letters should be used. Up to a few years ago specific
names derived from proper names were begun with capitals, but
now the small letters are used. As to the abbreviations used for
weights and measures, he said no system had universal assent.
Physicists and mechanicians have in use a long series of abbre-
viations for linear, areal and cubic measures. In three of the
most important German chemical works, including the ** Be-
richte,'* small letters are used, for the liters (1) ; for the grams
(g) ; and for cubic centimeters (cc), and he would be in favor
(8o)
of adopting these, but unfortunately the pharmacists and physi-
cians who are endeavoring to introduce them into their arts,
have agreed upon the capital G and small r for gram, and capi-
tal C and small c without a point between them for cubic centi-
meter. Remsen in his first edition used cc., g., and 1. Which
are chemists to follow ? The French do not use habitually any
abbreviations. Some chemists, unfortunately, have not adopted
the new spelling.
Professor Clarke said that a friend who wished to become a
journalist, had consulted a newspaper man, and the advice he
received was simple — *'Have something to say and say it."
Sometimes the writer is not sure as to what he wishes to say,
and he tries to say something else, and his writing becomes
involved. Another fault which was observed, especially in those
who have just returned from abroad, was that everything that
has ever been written upon the subject is given in an article,
and the discovery of the authors is either buried in the mass or
occupies a very small place at the end of the article. He thought
a logical order should be followed, and an effort should be made
to state what is said, simply and clearly. He thought Steele's
** Fourteen Weeks in Chemistry'* was a model of bad style.
Professor Munroe said that so far in the discussion there was
apparently very little difference of opinion. He read the fol-
lowing from an article in ** Science.** ** If we hear a baby cry-
ing with two ears, are we to think it is twins? '* as an example
of style in a scientific article. He thought this illustrated
Professor Clarke's remarks about having something to say and
saying it. Professor Munroe thought that the question of style
had to be considered from two standpoints : that of the manual
or text-book, and that of the technical or scientific paper.
Abbreviations that might be properly included in the latter,
should not be introduced in the former until they have long
been used in technical literature. He was especially doubtful
as to the advisibility of changing the adjectives to the substan-
tive as a '*gooch, a bunsen, a ruhmkorff, or a wiley," and the
latter suggests that where one is as fertile as our distinguished
associate, there may be a difficulty in determining which one of
his many devices shall be called a ** wiley."
(8i)
Dr. Fireman said he did not agree with what had been said as
to abstracts. Many papers are not accessible, and possibly only
one journal could be obtained. With a good abstract the
description of a process may be of use. Neither did he agree
with the idea that an historical sketch should be introduced.
He thought a summary was frequently of greater use. They
are generally brief and give valuable references.
Dr. de Schweinitz closed the discussion by saying that he
agreed with Professor Munroe that the style should differ in
text-books and in technical papers. What is proper in one is
not so in the other. He thought that abbreviations should be
dropped as the purpose is to make what is written useful to all,
and he thought the ideas and the statements should be expressed
as simply and clearly as possible.
A regular meeting Was held Thursday, April 9, 1896, with the
the President, Dr. K. A. de Schweinitz in the chair, and thirty
members and ten guests present.
The minutes of the eighty-seventh meeting were read and
approved.
A letter from Dr. Salmon, inclosing a circular letter from the
Director of the Pasteur Institute in Paris was read, asking the
society to appoint a member to represent it upon the committee
to raise funds for the erection of a monument in Paris to Pas-
teur. The President, Dr. de Schweinitz, was unanimously
elected to represent the Chemical Society upon this committee.
There being no further business the reading of papers was
proceeded with.
The first paper of the evening was by Mr, V. K. Chestnut
upon *' Some Vegetable Skin Irritants and their Chemical Com-
position." The paper consisted of a review of the work of Dun-
stan and Miss Boole on Croton Oil, and of Pfaff on Toxicoden-
drol, a new oil-like body from the poison ivy, Rhus radicans;
together with an account of some vesicating plants which have
been but little studied. Specimens of this plant were exhibited
and the effect of an alcoholic solution of lead acetate as an anti-
dote to Rhus poisoning was illustrated by experiments carried
(82)
out by the writer on himself. These experiments also showed
conclusively that toxicodendrol was the vesicating principle of
the poisonous species of Rhus. Discussion was by Messrs.
Tassin, Munroe, Cutter, Stewart, Fireman and de Schweinitz.
Mr. Tassin asked whether it was the lead acetate or the alco-
hol that is the antidote. Mr. Chestnut answered that the alco-
holic solution of lead acetate is the best remedial agent. If the
oil is kept long enough on persons supposed not to be suscepti-
ble, they will be poisoned; the poisoning may take place at the
end of twelve hours, or not for five days. Portions of the skin
that are thick are not so easily affected as are those where it is
thin. Professor Munroe gave his experience as to nitrobenzol,
which he had used in considerable quantity, and to which he
and the workmen were exposed ; it was inhaled as vapor, and
came in contact with the skin, but no one was poisoned. The
vapor is suffocating, but the workmen soon became accustomed
to it. All the books, however, state that it is poisonous. Mr.
Cutter said that he could uphold the books, as he had experi-
enced its poisonous effects ; he had rigor, fever, chills, and pal-
pitation of the heart, and was unconscious afterwards ; the effects
lasted for three days, and the smell even now would affect him.
Dr. Stewart gave his opinion of its poisonous effects upon the
skin ; in his own case it had caused an eruption that lasted three
or four hours. Dr. Fireman thought that different effects might
be produced by vapors and by the liquid; he referred to the effect
of hydrofluoric acid vapors, which are not poisonous in any
degree, although the liquid was well known to be very poison-
ous. Professor Munroe thought there might be differences in
the substance. Dr. de Schweinitz thought that possibly it was
impure in the cases cited by Dr. Cutter and Mr. Stewart.
Mr. Ewell read the second paper of the evening on ** The
Effect of Acidity on the Development of the Nitrifying
Organisms,'* by E. E. Ewell and H. W. Wiley.
*' While it has been known for many years that active nitrifi-
cation occurs only in the presence of some basic substance
capable of neutralizing the free acid as fast as it can be formed,
very little time has been devoted to the study of the exact degree
of acidity that the nitrifying organisms can endure. As
(83)
the authors had some forty samples of soil at their disposal during
the last year for other purposes, it seemed wise to improve the
opportunity to test the influence of acidity on the nitrifying or-
ganism contained in the soils from various parts of the country.
Tests were made with forty-four different soils, from twenty-two
states and territories. The results showed great uniformity in
the relation to acidity of the organisms contained in the various
soils. Excluding five tests in which no nitrification exists, and
m
five tests in which it was excessive because of the calcareous
nature of the soils used for the seeding of the cultures, the
average amount of nitrogen nitrified was twenty parts per mil-
lion ; the minimum result of the thirty-four tests included in
this average was eleven, and the maximum twenty-five parts per
million. The tests are to be repeated with pure cultures of the
nitrifying organisms of the same soils. This series of experi-
ments was made as a study of the nitrous organisms only, but
the results show that the nitric organisms are not more sentitive
to acidity than the nitrous organisms, the final product being
nitrate in nearly every case.
Dr. de Schweinitz, referring to the action of acids on the
growth of bacteria, said they seemed to be able to accommodate
themselves to their environment, especially in the case of the
tuberculous bacillus, and after a time they seemed to grow bet-
ter in an acid medium than in any other, though at first they
needed coaxing.
The third paper of the evening was on ' * The Chemistry of the
Cactacese,'* by E. E. Ewell.
Until very recently other species of cacti than Cereus grandi-
florus and a few related species have generally been regarded as
devoid of constituents of pharmacological value. These and
other species, have been used in medical practice in the coun-
tries in which they grow, but their use has rarely extended to
the more civilized nations. Species of the genus Anhalonium
have long been used for curative and ceremonial purposes by the
Indians of Mexico, and the southwestern parts of our own coun-
try. They found places in the Mexican pharmacopoeia of 1842,
under the name of "pellote," or **Peyotl," but have been
omitted from the later editions. The dried aerial portions of
(84)
species Anhahnium figure in the commerce of our southwestern
border under the name " mescal buttons." The species of this
genus have been the subject of scientific investigation by at
least three groups of persons during recent years : First, a group
of persons at Berlin, where the work was beg^nby Dr. L. Lewin,
the crude material being supplied to him by Messrs. Parke,
Davis & Co., of Detroit; second, a group of persons at the
Pharmacological Institute at Leipsic, where the work has been
conducted by Dr. Arthur Hefifter ; third, a group of persons in
this country, centering in the Bureau of American Ethnology,
and including as associates the Division of Chemistry of the
United States Department of Agriculture for Chemical studies,
Drs. Prentiss and Morgan for a study of physiological proper-
ties, and the Botanical Division of the United States Depart-
ment of Agriculture for the settlement of botanical questions.
Lewin reported the presence of an alkaloid in AnhaUmium
lewinii in 1888. He has given this the name of anhalonin and
made an extended report on its physical, chemical and physio-
logical properties in December, 1894. He has also found evi-
dence of physiologically active substances in the related species.
In August, 1894, HefiFter reported the presence of a poisonous
alkaloid ivLA./issuratum, to which he gave the name anhalin;
he found an extract of A, prismaHcum to be physiologically
active, but did not have sufficient material for a more extended
study ; he separated an alkaloid that he named pellotin from^^.
Tvilliamsi; in A, lewinii h^ found evidence of the presence of
three alkaloids, the description of the first of which accords with
the description of Lewin's anhalonin. He made an extended
study of the chemical, physical and physiological properties of
anhalin and pellotin.
In this country, the separation of the constituents of these
plants, and the study of the action of the substances thus
obtained as well as of the crude materials, upon men and the
lower animals, were begun in the autumn of 1894, but before
receiving the paper of Heffter. A, lewinii^ in the form of
"mescal buttons,'' has served as the material for these studies.
Anhalonin and a second alkaloid have been separated in con-
siderable quantity. These, as well as other constituents of the
(85)
<lrug, including one or more resins, are turned over to Drs.
Prentiss and Morgan for physiological experiments, as rapidly
as they are obtained in an appropriate state of purity* A com-
plete chemical study of the constituents of the plant is in pro-
cess, including those substances of interest to the vegetable
physiologist as well as those of interest to the therapeutist.
The paper was illustrated with specimens of the cactus of dif-
ferent varieties from the Botanical Gardens and the Department
of Agriculture. Mr. Mooney followed with a paper on ^*The
.Mescal Ceremony among the Indians.*'
The mescal plant is a small variety of cactus native to the
lower Rio Grande Region, and about the Pecos River in East-
em New Mexico. The botanical name has finally been fixed
by Professor Coulter as Lophophora ztnUtamst. Mescal is the
name by which it is known to the Indian traders, but it is not to be
confounded with the other mescal (Maguey) of Arizona. The
local Mexican name ispeyote, a corruption of the original Aztec
name, from which it would seem that the plant and ceremony
were known as far south as the valley of Mexico, at a period
antedating the Spanish conquest. Several closely related
species are described by Lumholtz as being used with ceremo-
nial rites among the tribes of the Sierra Madre,
The dry tops, when eaten, produce such marked stimulating
and medicinal results and such wonderiuUy beautiful psycho-
logic effects, without any injurious reaction, that the tribes of
the region regard the plant as the vegetable incarnation of the
deity, and eat it at regular intervals with solemn religious cere-
mony of song, prayer and ritual. The ceremonial and medi-
cinal use of the plant was first brought to public notice by James
Mooney in a lecture delivered before the Anthropological Society
of Washington in 1891, as the result of studies made among the
Kiowas and associated tribes of Western Oklahoma. As the
ceremony is forbidden, and the trade in the plant made contra-
band upon the reservations, the investigation was a matter of
some difficulty. In 1894 Mr. Mooney brought back a large
quantity of the dried mescal, which was turned over to the
chemists of the Agricultural Department for analysis, and to
Drs. W. P. Prentiss and P. P. Morgan, of Washington, for
(86)
medical experimentation. The results thus far would seem to
indicate that the Indians are right in asserting that they have
discovered in the mescal a valuable medicine entirely unknown
to science, and which will probably take its place in our pharm-
acopoeia along with those other Indian remedies, quinine and
coca. The ceremony amd songs are briefly described by Dr.
Mooney, whose full investigation of the subject will ultimately
appear in one of the publications of the Bureau of American
Ethnology.
Dr. Francis P. Morgan followed with a paper on the ** Physi-
ological Action and Medicinal Value of Anhalonium lewinii.
(** Mescal Buttons.") '* Dr. Morgan stated that the investiga-
tion had been intrusted to Dr. D. W. Prentiss, with whom he
was associated. Experiments were tried and observations taken
at regular intervals to determine the action of the entire button
on the system. The most striking result was the production of
visions of the most remarkable kind with e^^es closed, and
especially so in the dark. Changes of color were character-
istic ; tubes of shining light, figures, cubes, balls, faces, land-
scapes, dances and designs of changing colors were among the
most persistent visions. They were hardly seen with the eyes
open ; in full dose no effect on the reason or will is noticed in
most cases. There was direct stimulation of the centers of
vision and dilatation of the pupils. About one-quarter of the
quantity or three buttons, are sufficient to give the visions in the
case of white men. Dr. Morgan detailed the experiences of dif-
ferent persons who had tried the experiments. In some cases
there was slowing of the heart, from seventy-five to forty-five
beats, followed by a risQ to normal ; there is also inability to
sleep, and a loss of the sense of time — hours seem to intervene
between words. The physiological action is not identical with
that of any known drug, it is unlike cannabis indica, cocaine,
etc. The constituents of the mescal buttons are being experi-
mented with, but the investigations are still incomplete.
Anhalonin causes increased reflex irritability and convulsions,
like strychnine. It is evidently not the active principle ;
another constituent has been isolated whose action is widely
different. It does not cause opisthotonos, nor tetanus, and has
(8?)
no action like that of strychnine. A third principle has also
been isolated. The resin is supposed to be the active principle
and will probably be of use in medicine. The experiments are
still being conducted and will be detailed later on.
Dr. de Schweinitz expressed the indebtedness of the Society
to Mr, Mooney and to Dr. Morgan, and said that the further
results would be of interest to the Society.
A regular meeting was held Thursday, May 14, 1896. The
president, Dr. de Schweinitz in the chair, with twenty-three
members present. Mr. Mayville W. Twitchell was elected as
associate member and Mr. Charles N. Forrest as member. The
president presented the following resolutions, endorsed by the
executive committee, and the Society adopted them; the
president and secretary were instructed to sign and transmit
them.
Washington, D. C, May 14, 1896.
To THE Honorable, The President of the United States
Senate.
Dear Sir : — In view of the proposed legislation now before
the Senate in the form of a bill entitled ** An Act for the further
prevention of cruelty to animals in the District of Columbia,**
which, however, is practically an act to limit, and eventually
stop, all experiments upon animals in the District of Columbia,
the Chemical Spciety of Washington, including among its mem-
bers a number of the most prominent chemists in the country,
desires to present to the Senate of the United States a formal
and positive protest against the enactment of any legislation
upon the subject of vivisection.
The laws at present on the Statute books of the District of
Columbia, if properly carried out, will apply to all cases of
cruelty to animals which exist in this District. The proposed
bill is objectionable for very many reasons. The penalties pre-
scribed for the infraction of .the law are preposterous. An
expert who did not happen to possess a permit from the District
Commissioners for the performance of experiments upon animals
might suddenly have placed in his hands material, the danger-
ous character of which could only be determined by an imme-
diate experiment upon an animal. Should such a test be made
without a license, though possibly the lives of hundreds of peo-
(88)
pie were involved, the experimenter would be subject to an
enormous fine and imprisonment, for having in the interests of
humanity inoculated a guinea pig, or a rabbit, or some other
animal, without a formal permit from the District Commission-
ers.
While the majority of* the members of our Society are not
directly engaged in experiments in which animals are used, we
know that in certain lines of work, toxicology, materia medica,
biochemistry, and the like, animal experimentation is absolutely
necessary for the advancement of knowledge.
The agitators of the proposed legislation have not been able
to show a single instance of cruel experiments conducted in the
District of Columbia, either in any of the laboratories, or med-
ical colleges, or public schools, consequently there is no need
for any law on the subject. Furthermore, Washington is
becoming the center of education for the entire United States.
Four large universities are located here ; several more^ are in
prospect, and the proposed legislation would hamper and event-
ually destroy all possibility for advanced postgraduate work in
the biological science, and indirectly in all allied branches.
We therefore, collectively as a Society, and individually as
members, desire to protest strenuously against any legislation on
the subject of vivisection, deeming it to be unwise, unnecessary,
and in direct opposition to the spirit which has for a number of
years actuated the United States government to encourage the
advance of science. We hold further that such legislation would
be a direct contradiction of the well-known practical results that
have already been obtained by scientific investigations con-
ducted under the government, which have made possible the
saving of many thousand dollars worth of property and many
human lives.
Yours very respectfully,
[Signed] E. A. de Schweinitz,
Pres. Wash. Chem. Soc.
A. C. Peale,
Secretary.
The president, representing the Society, as a member of the
Pasteur Committee, reported that the committee had organized
and was ready to receive subscriptions.
There being no further business the reading of papers was
proceeded with, Vice President Bigelow taking the chair.
The first paper was by Mr. Frederick P. Dewey, on ** Practi-
cal Analytical Accuracy."
(89)
The paper did not go into the m^ans of securing accuracy,
but dealt entirely with the results actually obtained when a
number of chemists worked upon the same sample. Not very
much has been published in this line, but sufficient has been
done to show that the ordinary accuracy of analytical work is
not what it ought to be and that there is room for much im-
provement.
The paper gave results from analytical symposiums published
in the Transactions of the American Institute of Mining Engi-
neers and the Proceedings of the Association of Official Agri-
cultural Chemists. It was also somewhat historical in charac*
ter in tracing the development of accuracy in some determina-
tions.
The discussion of Mr. Dewey's paper was by Messrs. Bigelow
and Clarke.
Mr. Bigelow said that Mr. Dewey had selectedthe most accu-
rate of the determinations by the Official Agricultural Chemists,
but Dr. Dewey said he had simply taken those most nearly in
his own line of work. He referred to Campbell's tables in the
Journal and thought it was unfortunate that nothing was said as
to the way they were obtained nor how he was led to adopt the
various figures. He allows usually a small variation, but with
silica he allows a variation of over one-half per cent, when large
quantities are present.
Prof. Clarke thought that a great source of variation between
different observers was due to the fact that too great faith was
placed in the reagents. The work was not done with the same
reagents and reagents are not always the same. Here, there-
fore, is a source of error.
Mr. Bigelow said he thought another source of error was due
to the fact that the work was often done by students or subordi-
nates and these results were published with the others.
Mr. Dewey said his paper was intended to exhibit what was
actually obtained every day. He thought the assistant's work
was not always the poorest. The principal very often was out of
practice.
Dr. P. Fireman read a paper on ** A New Mode of Formation
of Tertiary and Quartemary Phosphines." When phosphoni-
(90)
um iodide is heated with ether in a sealed tube at 160'', for six
hours, both ethyl groups of the ether became available for sub-
stitution, and these form the hydriodic salts of triethj'l- and
tetraethylphosphine according to these equations :
2PH,I + 3(C,H.),0 = 2P(C.H.)..HI + 3H.O.
2PH,I + 4(C.H,),0 = 2P(C,HJ,I + 4H,0.
The author is at present occupied with the preparation of the
homologous phosphines by the action of PH J and homologous
ethers. He is also experimenting with a view of obtaining
amines by the action of ammonium iodide or ammonium bromide
on ethers or alcohols.
In the discussion of Dr. Fireman's paper Dr. Stokes asked if
he had obtained any traces of primary or secondar>' phosphines.
Dr. Fireman answered that primary phosphines are excluded
and as to secondary phosphines he had at one time hoped he
had obtained them, but he could not say with any certainty that
he had. Dr. Stokes thought they might be recognized bj- the
odor. Tertiary phosphines have the odor of hyacinths.
Dr. Stokes then read a paper on ** Metaphosphinic Acids.*'
Dr. H.N. Stokes spoke on his investigation of the metaphos-
phinic acids, a series of acids having the general formula
(PNO,H,)n, i' ^.i metaphosphoric acijds in which one-third of
the oxygien is replaced by NH. They are not, however, stricth'
speaking, derivatives of metaphosphoric acids, for while these
contain a nucleus consisting of phosphorus atoms united by
oxygen, the metaphosphinic acids, as proved by their forma-
tion from the chloronitrides(PNCl,)„, have a nucleus consisting
of alternate phosphorus and nitrogen atoms. Two members of
the series have been studied, viz,, trimetaphosphinic and tetra-
metaphosphinic acids, PjNjOjHo and P^N^O.H^, derived from
PjNjCl^ and P,N,C1,. Trimetaphosphinic acid apparently has
the tautomeric formulas
P(OH), PO.OH
/ ^ / \
N N HN NH
II I and II
(HO),P P(OH), HO.PO PO.OH
\ ^ W /
N NH
(91)
Salts of both forms have been obtained. Under the action of
acids, a successive decomposition is effected into P,N,0,H,,
P.NO.H,, H,P,0„ and H.PO,. The second of these may be
regarded either as PO(OH),.NH.PO(OH), or PO(OH),.0.
NH
PO <Cr)TT'' ^^^ former being supported bj" its derivation from
P,N,OeH„ the latter by its easy conversion into pyrophosphoric
acid. It presents a peculiar case of intra-molecular wandering of the
nitrogen atom, possibly to be explained by a process analogous
to Beckmann's transformation. (Particulars mil appear in the
American Chemical Journal. )
Dr. Fireman said the compounds appeared to him to be of
similar constitution as cyanic acid and its derivatives ; and also
in regard to the tendency to polymerize and to appear in iso-
meric forms, there is a striking resemblance between both classes
of compounds. He thought the results would be of interest in
theoretical chemistry. As to the silver salts he asked Dr.
Stokes if he had tried to prepare the esters.
Dr. Stokes said that a number of lactams are known that are
stable, that open out or have open rings in which the tendency
to break up is not marked. The tri acid is easily broken up but
the tetra acid is not. In regard to the esters, he had tried to
get them from the silver salts, but thej'' are not like the organic
ethers. They are very unpleasant to deal with and are coupled
mixtures with which little can be done. He had thought of the
analogy with cyanic acid and especially with the cyanuric acid
compounds. Another theoretical point is the possibility of
stereo-isomeric forms. When you have an oxime there are two
isomers known. They split up differently — cis and trans bodies.
He had not been able to find triphosphinic acid in anj^ but two
tautomeric forms.
Prof. Munroe said he was glad to see that the methods of
organic chemistry were being applied to inorganic chemistrj^
but he would like to know why the linear form of the salts
was written one way, and read in the reverse way in or-
ganic chemistry. He thought it was very confusing to students.
Dr. Stokes thought it was a matter of custom.
(92)
Dr. Fireman said he thought that the reason for writing the
formula of the organic acid first and then that of the metal was
due to the fact that the formulas of the organic acids were usu-
ally of a complicated nature and therefore it is natural to dis-
pose of them first and that afterwards it is an easy task to fit in
the symbol of the metal.
Prof. Munroe thought this was not the explanation.
« Dr. Stokes said different men developed the two methods
working from two different sides when a series of homologous
compounds is written out. The constants are put down first
and then those that vary. This was why he wrote them this
way.
Prof. Seaman thought this the correct explanation . Ideas have
a different arrangement with different people, normal to each
one. He thought there was more uniformity in this country
than anywhere else.
The Society adjourned until November.
Issued with July Number, 1896.
Proceedings.
NBW MEMBERS ELECTED JUNE 25, 1 896.
Hanna, Prof. Geo. P., Charlotte, N. C.
Harsh, S. A., Revenue Gold Mining & Milling Co., Norris,
Mont.
Lederle, Ernest Joseph, Ph.D., Health Department, N. Y.
City.
Ludwig, H. T. J., Mount Pleasant, N. C.
McFetridge. Joseph, Natrona, Pa.
Melville, W., Woodmere, Mich.
Mewbome, R. G., Raleigh, N. C.
Miller, H. K., Raleigh, N. C.
Parmelee, CuUen W., io8 Tenth St.,Greenpoint, Long Island.
Pegram, W. H., Durham, N. C.
Smalley, Frank W., University of Cincinnati, Cincinnati, O.
Thompson, F., 102 East Seventh St., Covington, Ky.
Uhlig, E. C, care of Whitall, Tatum & Co., 46-48 Barclay
St., N. Y. City.
Wood, Joseph R., 240 Green Ave., Brooklyn, N. Y.
ASSOCIATES ELECTED JUNE 25, 1896.
Howell, John W., Edison I^amp Works, Newark, N. J.
Twining, T. E., Newark, Ohio.
CHANGES OP ADDRESS.
Behr, Amo, P. O. Box I, Jersey City.
Eakins, I^. G., Box 434, Florence, Colo.
Lane, H. M., care of Great Falls Iron Works, Great Falls,
Mont.
Lenher, V., Mechanicsburg, Pa.
Peter, Alfred M., 236 East Maxwell St., Lexington, Ky.
Sargent, Geo. W., Bellwood, Blair Co., Pa.
MEETINGS OF THE SECTIONS.
CINCINNATI SECTION.
The regular meeting of the Section was held Saturday even-
ing, May 1 6th.
Dr. S. P. Kramer presented ** Some New Facts Concerning X
Rays," giving an interesting account of some experiments, and
(94)
exhibiting some negatives made by means of his new five plate
Topler-Holtz machine.
Mr. B. M. Pilhashy, of Cincinnati and Mr. J. N. Hurty, of
Indianapolis, were elected members of the Section.
The meeting adjourned until October 15th.
NEBRASKA SBCTION.
The Nebraska Section held its fourth regular meeting on June
5th, at 8:00 p. M.
The meeting was called to order by the president. In the
absence of the secretary, Mr. J. B. Becher was elected Secretary
pro tern.
The minutes of the last meeting were read and adopted.
The following officers were elected for the ensuing year :
President, H. H. Nicholson; Secretary aud Treasurer, Dr.
John White ; Executive Committee, Samuel Avery, R. S. Hilt-
ner and J. F. Becher.
The Secretary's report was read and approved.
The Treasurer's report having been read, Mr. E. C. Elliott
and Miss Rosa Bouton were appointed an auditing committee.
The committee pronounced the report correct, whereupon it
was approved.
A letter from J. Stanley Brown, Secretary of the Joint Com-
mission of the Scientific Societies of Washington, was then read,
calling attention to the anti-vivisection bill now pending before
Congress.
The President appointed a committee to draft suitable resolu-
tions, which were adopted.
** Whereas, There is now pending before the Congress of
the United States a bill entitled *A bill for the further preven-
tion of cruelty to animals in the District of Columbia ; ' and
Whereas, In our opinion such legislation is opposed to the
proper development of biological and medical science ; and
Whereas, It is feared that such legislation may be further
extended to the several states and territories, thereby very seri-
ously restricting the progress of scientific investigation ; be it
Resolved^ That the Nebraska Section of the American Chemi-
cal Society most earnestly protests against the enactment of such
(95)
legislation as being unnecessary and prejudicial to the best
interests of mankind.
Signed,
H. H. NiCHOMON, President.
Rosa Bouton,
John Whitb,
Edward Elliott,
Committee,
Mr. Benton Dales was elected an associate member.
In the absence of Dr. White, his paper entitled ** Contributions
to the Chemistry of the Suboxides," Iwas read by Mr, E. E.
Nicholson.
NBW YORK SBCTION.
The June meeting of the New York Section was held on Fri-
day evening, June 5th, at the College of the City of New York,
Prof. A. A. Breneman presiding.
After the reading of the minutes the chairman of the commit-
tee on Organization of the Chemical Club reported that at a
recent meeting of the committee, held at the Board of Trade,
much enthusiasm ws shown, and the movement was making
good progress.
A communication from the Joint Commission of the Scientific
Societies of Washington in regard to the Senate bill 1552,
intended to restrict, if not prohibit, vivisection, was taken up
and acted upon.
The sentiment of the meeting was unanimous in the direction
of preventing affirmative action by Congress on the said bill ;
and the following resolutions were unanimously adopted, after a
full discussion, in which Profs. Sabin, Breneman, Doremus,
Hale, and McMurtrie participated.
Resolved, That the New York Section of the American Chem-
cal Society most earnestly opposes the legislation proposed by
Senate bill 1552, entitled **A bill for the further prevention of
cruelty to animals in the District of Columbia."
Resolved, That the proposed legislation is unnecessary and
would seriously interfere with the advancement of biological
science in that district ; that it would be especially harmful in
its restriction of experiments relating to the cause, prevention,
and cure of the infectious diseases of man and of the lower ani-
mals ; that the researches made in this department of biological
(96)
and medical science have been of immense benefit to the human
race ; and that, in general, our knowledge of physiology, of
toxicology, and of pathology, forming the basis of scientific
medicine, has been largely obtained by experiments upon living
animals, and could have been obtained in no other way.
Resolved, That physicians and others who are engaged in
research work having for its object the extension of human
knowledge and the prevention and cure of disease are the best
judges of the character of the experiments* required and of the
necessity of using anesthetics, and that in our judgment they
may be trusted to conduct such experiments in a humane man-
ner, and to give anesthetics when required to prevent pain. To
subject them to penalties and to espionage, as is proposed by
the bill under consideration, would, we think, be an unjust and
unmerited reflection upon a class of men who are entitled to our
highest consideration.
Dx. C. A. Doremus read a ** Note on the Presence of Oil in
Boiler Scale.'*
Mr. J. A. Matthews described ** A New Method of Preparing
Phthalimide.''
The ehair announced this as the last meeting of the season,
and stated that the fall and winter meetings would probably be
held in the same rooms.
iHBued with August Kumber, 1896.
Proceedings.
COUNCIL.
Dr. Drown having resigned from the Committee **to unify the
methods of color comparison and report on a standard for meas-
urement of color in potable waters/* the President of the Amer-
ican Chemical Society has appointed in his place Mr. Allen
Hazen, 85 Water St., Boston, Mass. and Mr. Hazen has accepted
the appointment.
CHANGES OF XdDRKSS.
Bloomfield, L. M., Ohio Experiment Station, Wooster, Ohio.
Booraem, J. V. V., Box 190, Glen Cove, N. Y.
Fuller, Fred. D., Durham, N. H.
Lippincott. Warren B., North Western Iron Co., Mayville,
Wis.
Mar, F. W., 138 First Ave., West Haven, Conn.
Myers, H. Ely, Carnegie Steel Co. Ltd., Lucy Furnace, Pitts-
burg, Pa.
MEETINGS OF THE SECTIONS.
NORTH CAROLINA SECTION.
The summer meeting was called to order at 3.30 p. m., July
7th, in the Chemical Lecture Room of the University of North
Carolina. There were ten members in attendance. The sec-
retary reported ten new applicants for membership, who were
duly elected. There were other applicants who had not yet con-
formed to the condition of becoming members of the American
Chemical Society. The membership roll has doubled in less
than a half-year.
Resolutions were offered and adopted with regard to the vivi-
section bill and the appointment of a director-in-chief of the Sci-
entific Bureaus of the Department of Agriculture. The follow-
ing papers were then read :
^'Crystallized Aluminum," by F. P. Venable; "Detection
and Purification of Saccharin," by B. W. Kilgore : "Reduction
98
of Sulphuric Acid/' by Chas. Baskerville ; * 'Comparison of Di-
gestibility of Raw and Steamed Cotton Seed," by J. A. Bizzell;
**An Attempt to Form some Organic Compounds of Zirconium,"
by ThomasClarke ; * 'Determination of Sulphur in the Presence of
Iron/' by W. A. Withers and R. G. Mewbome ; "Action, of
Phosphorus Trichloride on an Ethereal Solution of Hydrogen
Dioxide," by W. A. Withers and G. S. Fraps ; "Some Diffi-
culties in the Way of the Periodic Law," by F. P. Venable.
The section then adjourned.
iMued with 8e|>teinber Number, 1896.
Proceedings.
CHANGBS OP ADDRESS.
Beeson» J. L., Bethel College, Russellville, Ky.
Best, Dr. Otto, care of Fritzche Bros., Garfield, N. J.
Haines, Reuben, Haines and Chew streets, Germantown, Pa.
Emmens, Stephen H., 179 Washington Building, N. Y. City.
Kelley, J. H., Bentonville, Ark.
Moale, Philip R., 82 Chestnut street, Asheville, N. C.
Mumper, W. N., 823 W. State street. Trenton, N. J.
Nipholsi Wm. H., 32 Liberty street, N. Y. City.
Potter, Wm. R., 100 Broad street, Providence, R. I.
DBCBASED.
Bower, Henry, Gray's Ferry Road, Philadelphia, Pa.
MEETINGS OF THE SECTIONS.
RHODE ISLAND SECTION.
The regular monthly meeting of the Rhode Island Section
was held at Providence, May 21, 1896, Mr. Charles S. Bush in
the chair.
A paper was presented by Mr. William R. Potter, upon
"Fallacies in Urine Analysis due to the Presence of Salicylic
Acid and its Compounds."
After a brief introduction of the value of urine examination
as an aid to the physician in his diagnosis, the reader described
in detail the influence salicylic acid had upon the albumin test
and the glucose test as commonly practiced. The chief source
of error was pointed out to lie in the sparing solubility of sali-
C3^1ic acid in an aqueous solution, and the ease with which its
compounds were decomposed by other acids.
The annual meeting of the Rhode Island Section was held at
Pawtucket, R. I., on Thursday afternoon, June 11, 1896.
Members met upon the invitation of the presiding officer, Mr.
C. A. Catlin, at the Country Club. After dinner the annual
election of officers took place. The following were elected for
the ensuing year:
Presiding Officer, Mr. Edward D. Pearce : Secretary and
(lOo)
Treasurer, Mr. Walter M. Saunders ; Member of the Executive
Committee, Mr. George F. Andrews.
The retiring chairman then presented his annual address,
taking for his topic, the subject of chemically-applied mechanics,
introducing it by brief historical reference to the progress ^f
chemistry, more particularly to the development of apparatus
and improvements along the line of chemical manipulation. It
appears that after all the same forms of retort and crucible that
did service in the time of Zosimus, are still the stereotyped forms
of the chemical supply house.
Great progress in recent years in arts dependent upon chemistry,
has, however forced the development of apparatus, and the
application of mechanical expedients, until there has grown up
what may in all truth be called the science of chemically-applied
mechanics, practically unrecognized as yet by the training schools
of the profession, though covered in a general way by courses
offered in chemical engineering. These courses do not meet
the case. The real demand is, that chemical students shall have
opportunity in training, to pursue the study of practical mechanics
as applied to chemical manipulation, simply a new study added
to the old curriculum. Illustrating something of the scope of this
chemically-applied mechanics, may be cited, hydraulics, for in-
stance, as applied to the handling of liquids, the speaker show-
ing from his own practical experience how the attendant phenom-
ena of the various filtering methods, may, by a general classi-
fication, be brought to useful presentation of the whole subject.
Further may be cited pneumatics as applied to the manipulation
of* air draughts, the charging of liquids with gases, etc., strength
and adaptability of materials to the construction of apparatus,
their acid or alkaline resisting qualities, with effects of saline
solutions upon them ; heat in its varied application ; light in the
practical application of its actinic properties ; and the milling of
materials. Again illustrating particularly, the speaker showed
how the attendant phenomena of the various milling processes
may be brought under general statements for better considera-
tion.
Generally the scope of chemically-applied mechanics may be
stated as the application of mechanical principles to chemical
manipulations. The whole subject. should be presented to the
chemical student in a general way, setting forth at least the
fundamentals along these and related lines, expanding into
particular detail in the more important, thus broadly laying the
foundation for the development and exercise of the inventive
faculty in applying mechanical means to special chemical re-
quirements, whether it be in the factory or the research labora-
tory.
Issued with October Number. 1896.
Proceedings.
THIRTEENTH GENERAL MEETING OF THE
AMERICAN CHEMICAL SOCIETY.
Buffalo, N. Y., August 21, 1896.
President Dr. Charles B. Dudley called the meeting to order.
Dr. Roswell Park, President of the Buffalo Society of Natural
Sciences, welcomed the visiting chemists as follows :
Mr. President and Gentlemen of the Chemical Society : I am very glad
to join wtth my friends in the City of Buffalo in welcoming you h«re. My
idea of what should be said on such an occasion, is that it should be char-
acterized by genuineness rather than eloquence, by brevity rather than
length. I am sure we are very glad to see you here. I know that this
is the first time the Chemical Society ever met in Buffalo, aud we hope
that you will like us so well that you w^ill come again. I have on several
occasions in time past welcomed associations of citizens here. I tell .
them we have pleasant weather here always. I was sure in my own mind
that you would have it. It is a promise we can safely make anytime in
the summer. Buffalo seems to be generally regarded now as the ideal
convention city. We have had a convention here of some kind almost
every week, and this will continue through September. There are meet-
ings here almost all the time. If you study our statistics you will find
us the healthiest city in the country. If you will travel around our
streets you will discover we have the mos^ attractive residential city in
the country. Aud in every way, both from our treatment of you and
what you see for yourselves, we hope you will feel thoroughly welcome,
and thoroughly at home.
It is always proper, I think, on such occasions, to blow our own horn
a little bit. I have found so little appreciation of Buffalo abroad, of what
Buffalo is, that I am going to say a little to you about Buffalo. It is the
sixth commercial city in the world. ' That is not generally appreciated.
A friend of mine went to Boston and while there was talking to a friend
of his in that city about Buffalo. The Boston man said, " Buffalo? Is
that on Lake Erie or Lake Ontario?" At the same time, we have a
much greater tonnage coming into our harbor in one year than comes
into Boston harbor. That he overlooked. About 5,000,000 tons of ton-
nage enter our harbor, aud about the same leave our harbor every year.
There is only one other city can say this, and that is Liverpool. That is
not generally appreciated. Thirteen years ago, when I moved here, the
city had about 125,000 inhabitants; now it has a third of a million, so
(I02)
you can get an idea of how it is growing. We who live here and aeeithe
trend of affairs, look forward to a time when there will be but one city to
Niagara Palls. We are coming nearer and nearer to that all the time.
It is .not far off, I assure you.
Now, with all we have and all we can do for yon, gentlemen, you cer-
tainly are cordially welcome. You will hear more of this, as I expect
you will attend the meetings next week, and perhaps be more formally
welcomed by the city officials on other occasions ; but our homes are
opened to yon, and everything we can do in any way for you, is cordially
placed before you.
To refer just a moment to the scientific aspect of this gathering, I have
never had a chance to talk to professional chemists before, and there is
one appeal I want to make to you as coming from our profession to yours.
Of course we are working in large measure on common ground ; espe-
cially when it comes to physiological chemistry, and in the chemistry of
the fluids, etc., of the body, we are on absolutely common ground; but
there is very much we have to rely upon you for, in order to help our-
selves forward ; and, as one who is eagerly anxious for the discovery of a
particular substance, an ideal in our business, which you only can prob-
ably furnish, I will make this scientific appeal to you. We have been
working for years to find a substance which shall have a germicidal prop-
erty so far as deleterious agents are concerned, and yet which will not be
toxic with the tissues of the human body ; a chemical substance whose
relative and absolute toxicity are far enough apart to make it a safe sub-
stance to use. When we have that, we hope to saturate the human body
with the substance which will be at the same time not toxic with the tis-
sues of the larger organs. I do not know whether that time will ever
Come. It seems to me an ideal substance. I do not know how you, who
are so interested in the affairs of the world at large, as well as humani-
tarians, can make a better discovery than one along the lines I have sug-
gested. It is not for commercial purposes, but purely for the benefit of
humanity. You will pardon this little appeal to your chemical abilities ;
it is the only chance I have ever had to make it.
Permit me only to reiterate what I have said to you about the cordial-
ity of our welcome, our earnest endeavor to extend to you our hospitality,
our earnest hope that your first meeting will not only be so successful
that you will look back to it hereafter, but will be so pleasant to you
that you will want to come here again quite often. (Applause.)
The President.
Dr. Park, The Committee of Arrangements, and Fellow Members of
the American Chemical Society : I am sure I voiee the sentiment of those
who are present when I say that we appreciate this kind welcome, and
we thank you for it. I doubt not there are a good many present who can
well remember when chemical analysis, except for purely scientific pur-
(I03)
poses, was a rarity. In my early student days the chemical analyses
that were made, except as I say, for such purely scientific purposes, were
largely made by the professors in colleges. They were slow. They were
very expensive and any business that wanted a chemical analysis, studied
quite a while before employing a chemist to make it. That state of affairs
is now changed. With the growth of the technical school there has come
forward each year a large crop of young, enthusiastic chemists, and with
this supply, if I may use the word, has come likewise the necessity for
their existence and the work for them. I am not saying anything more
than is known to you all when I say that a very large number of com-
mercial ventures and enterprises to-day cannot live without their chem-
ist. The steel works would not be able to maintain themselves a month
without a chemist. The sugar industry needs the chemist, the brewing
industry, the textile industry, and, indeed, I might go on and enumerate
occupation after occupation which is based largely upon the chemist's
work. The railroads, as you know, are using chemists, and the cities
begin to have their chemists to protect people against fraud and adulter-
ation in products which are for sale. As we all know, agriculture is more
and more every day becoming based on chemistry, and our government
itself supports one of the best chemical establishments in the world.
Now, this increase in chemists, this increase in their work, this demand
for them, has led to another necessity; namely, that the chemists should
occasionally look each other in the face, that they should talk things
over with each other, that they should profit by each other's work, and
that brings us to state what the organization of the Chemical Society is,
an organization with something like i,ooo members, an organization
which supports a Journal that is published every month, and with some
eight or nine local sections located in different parts of the country.
This organization must, as we all know, have a place for meetings. We
are already having two meetings every year and this year we come to
Buffalo, and I may say, that this city is the Mecca to which all scientific
men are travelling this year — this city which may almost be called the
mother of scientific organizations. I believe that the reorganization of
the American Association for the Advancement of Science, one of the
oldest scientific organizations in the country as we all know, took {>lace
here in Buffalo in 1866, after the war. It had previously had existence
but the war injured it, or caused a temporary cessation and the reorgan-
ization took place in Buffalo. Thus much for our reason for existence
and thus much for our coming here. We appreciate very greatly your
kind and gracious welcome. We look forward to an interesting and profit-
able time. We thank you. (Applause.)
The following papers were then read and discussed :
** Mercuric Chlorothiocyanate,'* by Charles H. Herty and J.
G. Smith. Read by Dr. Herty. Discussed by Messrs. Hart,
Prescott and Frankforter.
(i04)
*' The Reduction of Concentrated Sulphuric Acid by Copper,"
by Charles Baskerville. Read by the author.
** Notes on the Preparation of Glucinum,** by Edward Hart.
(An informal description of the progress of work on the prepa-
ration of glucinum and its alloys. A glucina crucible was ex-
hibited and also some nearly pure glucina prepared by the
method already described in the Journal, 17, 604. This glu-
cina apparently contains the same unknown substance already
detected by Kruss, and as 200 pounds of beryl are being opera-
ted on it is hoped that enough may be obtained for its identifi-
cation.) The paper was discussed by Messrs C. B. Dudley and
Hart.
"The Inspection and Sanitary Analysis of Ice,*' by C. L.
Kennicott. Read by the author. Discussed by Messrs. W. P.
Mason, Cochran, McKenna, \V. A. Noyes, Breneman, Miller,
Phillips, Robbins, Frankforter and C. B. Dudley.
•* A New Form of Potash Bulb," by M. Gomberg. Read by
Dr. Prescott. Discussed by Mr. Phillips.
'* Morphine in Puirefactive Tissue," by H. T. Smith. Read
by Dr. Prescott. Discussed by Mr. Miller.
•' Some New Compounds of Thallium," by L. M. Dennis and
Martha Doan, with crystallographic notes by A. C. Gill. Read
by Dr. Dennis. Discussed by Messrs. Prescott, Hart, Frank-
forter and Mason.
The President : It has reached pretty nearly the hour of ad-
journment and I would like to make an announcement or two
as to the work of the Society during the interim. Early in the
spring a letter was received by the Society stating that Canniz-
zaro's seventieth birthday was to occur on the nth of July,
and it was proposed to make a testimonial to him in some way.
This letter asked the cooperation of the American Chemical
Society. After talking tKe matter over it was decided since
Cannizzaro was already an honorary member that we should send
him a testimonial engrossed oq parchment. This was duly pre-
pared and was sent in time to reach Rome some two or three weeks
before his birthday. However, since that time we have received
a second letter stating that owing to the fact that most of the pro-
fessional people who were interested in Cannizzaro were out of
town during the very warm season, it has been decided to post-
pone the public recognition of the occasion until later in the fall,
I think some time in October. So we have not as yet heard
(i05)
from the other side as to what has been done with the testimonial.
I would say likewise that in this letter there was a statement
to the effect that the form, which recognition was taking on
the other side was that of accumulating a fund to be used for
some scientific purpose.
I would also state that at the last meeting of the Society in
Cleveland a committee of three was appointed to take up the
question of coal analysis. That committee consisted of Mr.
Hillebrand of the Coast Survey, Chairman, Prof. W. A. Noyes
and the President of the Society. The committee has been able to
do very little thus far except to get ready. They are not prepared
to make any formal report at this meeting, partly, I think due to
my own fault in the matter. Our progress has not been suffi-
cient to make a formal report. This is simply to let you know
that the subject has not been dropped.
About the beginning of the summer a paper was read in the
New York Section by Prof. Leeds on the color of water, and at
his suggestion a Committee was appointed to report to the
Society, a standard to be used for determining the color of water
and a method. That committee consists of Prof. Leeds, Chair-
man, Prof. Mason and Mr. Allen Hazen, formerly connected
with the State Board of Health of Massachusetts, who has done
a good deal of work on water analysis. We have some regular
or standing committees ; I have not been able to get in communi-
cation with the Chairmen of all of them as yet, and we will try
to-morrow to see whether we can get information from them on
the state of the subjects committed to them. After some an-
nouncements by the general secretary and the local committee
of arrangements, the session adjourned.
Saturday Morning, August 22, 1896.
The President called the Convention to order at 9:40 o'clock.
The President : As we have considerable to get through with
to-day I think we had better start as soon as possible and first
of all I will ask the Society to give two or three minutes to Dr.
de Schweinitz who wants to present the matter of the Pasteur
monument.
Dr. de Schweinitz: Mr. President and gentlemen of the
(io6)
Society : I only desire to detain you for a moment to ask for
subscriptions towards the erection of an international monument
in Paris to Pasteur. The French Government has organized
this movement and requested the cooperation of all scientists,
or I should say, rather, of all members of the different branches
of science in the United States. As Pasteur was a chemist, the
chemists of the United States should be the first to respond to
this request. Printed blanks of a general announcement, giving
the names of the members of the French committee, and also of
the organizing committee of Washington, which has been
started » will be distributed, and in addition to this subscription
blanks, as you see here, upon which you are requested to place
the amount, however small, it does not make any difference,
and however large, the larger the better and the more will the
contribution be appreciated, to be forwarded to Washington.
These blanks with the names and the amounts will be preserved
and will be deposited in Paris in the archives in connection with
this Pasteur monument. I will distribute these blanks and be
greatly obliged to the members of this Society if they will join
in the contribution at as early a date as possible and to the
largest amount that they feel able to give.
The President : I am sure the appeal is one that we are all
interested in, and if chemists can see their way to subscribe for
this purpose, we shall be very glad. We all feel willing un-
doubtedly, but possibly not all of us are able.
Dr, de Schweinitz : Mr. President, I might add that the
subscriptions so far received have varied in amount from twenty-
five cents up, so that no one need have any hesitancy on that
subject.
The President : I presume there is no one can not subscribe
at least the minimum amount.
I wish to say that Dr. Levi has brought up a few samples of
aniline colors made at the aniline works, which there was no op-
portunity to distribute yesterday, and anyone here can avail
himself of the samples if he so desires.
The following papers were then read and discussed :
** Contribution to the Knowledge of Rutheno Cyanides," by
James Lewis Howe. Read by the author.
(xo7)
•' Analytical Methods Involving the Use of Hydrogen Diox-
ide," by B. B. Ross. Read by the author.
Prof, Hart : Mr. Chairman, while we are waiting for Prof.
Ross to place these figures on the blackboard, there is a matter
that has been called to my attention which I would like to pre-
sent to you ; it will only take a half minute ; this is connected
with the subject of advertising for the Journal. By resolution
of the Board of Directors I was appointed a committee of one to
secure advertisements for the Journal. This is an important
source of revenue, and we have derived considerable money to
be applied to the publication of the Journal in this way. It is
believed that with some additional assistance this source of rev-
enue can be still further increased. We have to depend for this
assistance on voluntary aid, and I wish to acknowledge the great
assistance I have already received from Dr. McMurtrie in this
direction. The Society is indebted to him more than is perhaps
generally known. It has been suggested to me that a number of
members of the Society would be willing to assist in the matter
of procuring advertisements, and that it would be well to increase
the committee to ten members. These members would then feel
that it was their duty to assist in securing the advertisements,
and it is believed that this will result in securing considerable
additional patronage. I therefore move that the President have
power to increase the committee to not more than ten members.
Dr. Hale: I second the motion.
Dr, McMurtrie : I think it might be well further to give the
committee power to extend its membership in case that appears
desirable. I would move to amend in that manner.
Prof, Hart : I accept the amendment.
President Dudley put the motion as amended, and it was duly
carried.
The following papers were then read :
*'The Estimation of Thoria ; Chemical Analysis of Monazite
Sand,** by Charles Glaser. Read by Dr. Hart.
'' The Estimation of Thorium and its Separation from Other
Rare Earths," by L. M. Dennis. Read by the author. These
two papers were discussed by F. W. Clarke and L. M. Dennis.
(io8)
** A Complete Analysis of Phytolacca Decandra," by G. B.
Frankforter and Francis Ramaley Read by Mr. Frankforter.
** The Cr>'stallized Salts of Phytolacca Decandra/' by G. B.
Frankforter and Francis Ramaley. Read by Mr. Frankforter.
Discussed by A. B. Prescott.
** The By- Products formed in the Conversion of Narcoline into
Narceine/' by G. B. Frankforter. Read by the author.
** The Composition of American Kaolins," by C. F. Mabery
and Otis T. Klooz. Read by Dr. Hart. Discussed by Messrs.
Dudley, Baskerville, McMurtrie, Noyes, Prochazka, Breneman
and Patrick.
The following papers were read by title :
** Composition of Certain Mineral Waters in Northwestern
Pennsylvania,*' by A. E. Robinson and Charles F. Mabery.
** Zirconium Oxalates," by F. P. Venable and Charles Bas-
kerville.
** Aluminum Analysis," by James Otis Handy.
* * An Analytical Investigation of the Hydrolysis of Starch by
Acids," by George W. Rolfe and George Defren.
* ' The ££fect of an Excess of Reagent in the Precipitation of
Barium Sulphate," by C. W. Foulk. Discussion by T. M.
Gladding.
** Determination of Reducing Sugars in Terms of Cupric Ox-
ide," by George Defren.
** Acidity of Milk Increased by Boracic Acid," by E. H.
Farrington.
*' The Actual Accuracy of Chemical Analysis," by Frederic
P. Dewey.
' * Some Extensions of the Plaster of Paris Method in Blowpipe
Analysis," by W. W. Andrews.
** Device for Rapidly Measuring and Discharging a Definite
Amount of Liquid," by Edward L. Smith.
** Table of Factors," by E. H. Miller.
** A Modified Form of the EbuUioscope," by H. W. Wiley.
'* The Signification of Soil Analysis," by H. W. Wiley.
** Notes on the Determination of Phosphorus in Steel and Cast
Iron," by George Auchy.
•* The Development of Smokeless Powder," by C. E. Munroe.
The President: I would like to announce that the winter meet-
ing will be held in Troy, it having been decided by the Council,
(i09)
on the invitation of our membership in Troy to hold the meeting
at that place. We are hoping to make that meeting one of the
best the Society has ever had and I would like to ask Prof.
Mason to give us a word or two in regard to our meeting next
winter at Troy.
Prof, Mason : Mr. President and fellow members, it has been
very gratifying to me to learn that you have decided to come to
Troy. We are not a large city, but we will do our very best to
make your stay agreeable. There are some things there that
are worth seeing. We will be able to show you the largest gun
plant in the world, much larger than Krupp's. Of course when
you speak about Krupp's plant it means his whole concern,
the gun plant and that for other varieties of iron and steel
manufacture as well, but the gun portion of his plant would go
into a small part of the United States gun plant which you will
see at Troy. As you know, all the artillery now used by the
army is made there, practically ; I believe there are a few un-
finished contracts out, but I am not positive about that. You
will be able to see electric cranes that I think are larger than
you have ever seen elsewhere. You will be able to see guns in
all stages of manufacture. I hope you will be able to see an old-
fashioned smooth bore of fifteen or twenty inches caliber lying
along side of a modern twelve or thirteen. It looks like a soda
water bottle. We have some other institutions there that we are
proud of, for instance the new basic steel plant, which will be in
full operation by the time you get there, the Burden Iron Works
where they make Burden's best iron, which you have often heard
of. The shirt foundries and collar smelting works with their
attendants are well worth seeing. (Laughter.) More particu-
larly the E & W Collar. You have probably heard of them.
They have sent you a special invitation. We have N + 1
breweries in Troy. We can take care of the N and we have as-
signed the I to our President. (Laughter.)
It will give us great pleasure to see you and I am heartily
glad that you are coming and the Mayor of the city sends his
especial invitation.
The President : I am sure we will all look forward to this
(no)
meeting with a great deal of interest, and as I said at the very
outset we hope to make this the most important meeting the
Sochety has ever had. At this point and a propos here I want
to give 3*ou a word of exhortation in regard to the condition of
the society. As everybody knows the most important thing in
the Society is the Journal. The Journal is impossible without
money. Our rates are low, our annual dues being only $5.00.
The Society of Civil Engineers in this country charges $15.00,
the Mechanical Engineers $15.00, the Mining Engineers $10.00,
the Mining Institute of Great Britain two guineas; the German
Mining and Steel Institute charges $10.00. We are trying to
run a Society on $5.00 and the management does not think at
present that it would be advisable to raise that figure. But we
want more money. How can we get more money ? Obviously
by getting more members. If every member of the Society would
get one, think what would happen the doubling of our member-
ship. It is believed there are something like 5,000 chemists in
the United States who are eligible, either as full members or
associates. We have practically now about 1,000. Your
management has in mind plans in regard to the advancement of
the Journal to make it still more representative, having it cover
wider fields, but for this purpose money is necessary, and money
with our present ideas in regard to our present society can only
come to us, at least as far as we can see, through increase in
membership. Will not every member of the societ}- do something
in the next four or five months to increase our membership.
We certainly are well established on a good foundation. It is
an honor to be a member of our society. We give a full requital
for everything we get from our membership, and certainly the
time is fast approaching when any American chemist who ex-
pects to keep up with his profession cannot afford to be outside
of the Society. Let every member bring one member with him
and more if possible, at the Troy meeting or bring them in be-
tween now and then. I will call upon the Secretary for a few
announcements connected with the Society.
The Secretary : Perhaps I might say, Mr. President, that Dr.
Mason with becoming modesty has failed to remind you that the
oldest institution, if I am not mistaken, for the education of
(Ill)
civil engineers, is in Troy, and as a representative of the institu-
tion, he has some modesty in speaking of it. Allow me to call
attention to one point in reference to increase in member-
ship ; there is provided in the constitution a class of mem-
bers who are not necessarily chemists, but who are interested
in chemistry, the associates; and it would seem as though there
might be a large amount of recruiting from this source. Tliere
are very many people who do not feel themselves distinctively
chemists and yet they are interested either through their busi-
ness or by their inclination in the development of chemistry ;
and it would seem possible to have as large a membership of as-
sociates as of active members. We can do a good work in that
way, and the $5.00 of an associate is worth just as much as the
$5.00 of an active member.
In regard to the membership of the society, I would say that
last spring, somewhere about March, I think, for the first time
in the history of the Society, we struck a membership of a full
round 1000 in number. (Applause.)
The President : I am sure those of us who have the pleasure
of being at this meeting can not fail to have recognized that there
Jias been at the helm some guiding hands, and I am going to say
for your information that those guiding hands are not the officers
of the Society but the local committee. I feel that it
would be improper for us to close the meeting without some rec-
ognition of the kindness we have received at the hands of our
members here and also those who have contributed to our hap-
piness during this visit. I will call upon Prof. Mason to propose
due recognition.
Prof, Mason : Mr. President and Gentlemen ; it seems to me
entirely fitting that we should pass a vote of thanks to those who
have so kindly looked after our pleasure and interest, and I will
therefore move you that the thanks of this society are due to the
local committee of arrangements, Drs. H. M. Hill, J. A. Miller,
T. B. Carpenter, L. E. Levi, also to the local committee of the
American Association for the Advancement of Science, especially
Mr. Eben p. Dorr, Secretary, also to the local press and to the
managers and directors of the various works visited; namely, the
Milsom Rendering and Fertilizing Works, Garbage Reduction
(H2)
Works, Lang's Brewery, Buffalo Reduction Company, Calcium
Carbide Works (Niagara Works), Cataract Construction Com-
pany, Clifi Paper Mill, Tonawanda Iron and Steel Company,
Schoellkopf Aniline and Chemical Company, Crystal Water
Company, also Jaeger's Roof Garden and Cai£.
The President put the question on the adoption of the motion,
which was carried unanimously.
The President : Is there any further information desired or any
further question to come up ?
Prof, Mason : May I ask this question : Is it possible to so ar-
range matters as to consolidate the summer meetings of the
Chemical Society and Section C ? I ask it because I personally
can be away but a week. The two meetings occupy more than
a week. I should like to attend the two meetings in full, but I
can not do it. My position is such that I am obliged to return
next Wednesday night. The result is I cut off half nearly of the
American Association meeting. Inasmuch as it is a meeting of
almost the same men under different names, is it not possible to
so arrange matters as to have them all together.
Dr. Norton : I feel very much as Dr. Mason does. In order
to bring this to decisive action I move you that the Council be
authorized to use its discretion in arranging for a joint meeting
of this society and Section C of the American Association next
year. I think this will enable its to give an expression to our
feelings and leave the Council free to take the proper measures.
I know a number of our members are coming on next week.
They do not feel as though they could give nine or ten days to
the meeting of both societies. There are a number present in
the room who will have to leave next Monday or Tuesday. By
a little careful study we can arrange to have the whole chemical
work that would come before the Society and before Section C
of the American Association, carried on in the sessions of the
live days which are given up for that purpose. I think it would
be much more desirable because we do not want our membership
stringing along through some seven days, part of us listening to
papers now, and part at the end of the week. I feel from con-
versation with a number of our members that there is a general
belief that we ought to have some simple arrangement for joint
("3)
meetings, and tliey can be presided over alternately by the Pres-
ident of our Society and the vice-president of Section C.
Mr, Prescott : I second the motion, and I think at the present
time when the meetings of the Association are as the}' are, that
the plan can be carried out much better than it would have been
before the present arrangement had taken place.
Prof. Hart : I second the motion, Mr. President, but I wish to
point out one matter that ought to be thought of, that is, the in-
creasing number of papers. We have ten more papers at this
meeting than we had last year, and most of you have already
received programs of Section C of the American Association and
can see what an enormous program that is. People who take
the trouble and pains to prepare papers for these meetings nat-
urally feel that they would like to have the papers read. That
is a thing to which we should give careful recognition. If any-
thing of the kind is done it is not possible, I think, to secure any
more time in Section C than we have now, and according to the
printed program that time is already' taken up. We have not
read more than one-half the papers.
Prof, Kcnnicoit : It does not seem to me it would be a wise
thing to sink our identity in any other society. Simply to meet
with Section C would seem to me to be loss of identitv.
Dr, Hale : Mr. President, it seems to me the motion that has
been made is eminently a proper one. The various points one
way or the other of difficulty or ease of adjustment would come
properly before the Council for consideration and they would
have plenty of time to confer with one another and consider the
subject. Certain it is that we have a large number of chemists
who are increasingly loyal and devoted both to the American
Chemical Society and Section C, and by bringing the chemists
together at this time we have undoubtedly added to the attend-
ance and the interest and the number of papers of both. It seems
to me that the whole subject is wisely referred to the Council of
the Society, and of course Section C can take whatever similar
action it chooses.
A/r, Breneman : I am quite in accord with the resolution,
but it seems to me it would simplify matters very much if we
should simply decide to abolish the summer meeting and let the
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winter meeting be the only one. Tliat is the annual meeting ; it
is the meeting where the election occurs and the one of greatest
interest. I do not see any reason for a joint meeting. If the
arrangement suggested is made, the winter meeting will be dis-
tinctive and the only annual meeting of the society.
Prof. Kennicott : I see that my predictions are to be verified.
We have already started to sink the identity of the Society. A
great many members would be unable to attend any meeting in
the winter.
Dr, PrescoH : Mr. President, I think the Council would be
very glad if we could have a general expression of opinion like
that of Prof. Kennicott and others very briefly at this time.
Dr, Howe: The suggestion that has been made is one I
remember when the original discussion took place in regard to
the reorganization of the Chemical Society. It was proposed at
that time that the American Chemical Society should have its
winter meeting, but that the summer meeting should not be for
the reading of papers ; that the papers then should be read at
the meeting of the American Association. It certainly is not
desirable to carry on any merging of identity, at the same time
it seems to me that the plan suggested would be a valuable one
to those of us who are present here as chemists, and more valu-
able than the present plan, if we can mass together all the papers
and have all the members present in a four days' session, so that
we could have the fullest and most helpful discussion. Some of
us are unfortunately unable to be present at the winter meeting,
but I think even for us it would be better if all the papers were
presented together in the meeting of the American Association
in the summer. It does not seem to me we want to do anything
to injure the American Association or have things in such a
situation that we feel obliged to come here this week and go ofi
next week and miss everything that goes on in the Association.
I think the Association owes a great deal to the Chemical
Society for what it has done in stirring up an interest again in
Section C. I think there should be some amicable arrangement
of this matter.
Prof. Mason : Just one word I would like to say. We come
here, it is true, to listen to chemical papers, but we also come to
(115)
meet chemists, and if we have an opportunity of meeting all the
members of the American Chemical Society and the members of
Section C as well, we fulfil the second object we came for better
than if we should string the meeting over so many days, and as
a result one man goes before another arrives and perhaps they
want to see each other.
Dr, McMurtrie : Mr. Chairman, there are some difficulties
that occur to me in this connection. The matter has been of
course discussed a good deal during the past three or four or
five years ; it had been when the reorganization of the Chemical
Society occurred, and one of the important difficulties has arisen
to my mind during the last year or so when I have been more or
less active in the work of Section C of the American Association.
In preparing the program of proceedings for last year I was
reminded that it was impossible to have papers presented in the
meetings of Section C by any other than members of the Ameri-
can Association. Now there is a larger portion of the member-
ship of the American Chemical Society who are not members of
Section C. The consolidation of the meetings will necessarily
rule out those men from participation in the meeting. This point
would of course be brought before the Council in a discussion of
the matter, and would, I suppose, have weight. There are a
good many members of the Chemical Society, T know, who feel
that they do not care to have membership in the American Asso-
ciation, and it seems to me that in any action we take in this
regard their wishes should be carefully considered. I think it
might be possible to arrange to have the meetings succeed each
other in the same week, but that arrangement which has been
followed in the past year, has been objected to by the officers of
the American Association, holding that it interfered in a large
measure with the work of the Association. It was in a measure
on this account that the meetings of the Association are fixed
for the week continuously ; that is beginning with Monday. So
that those societies which are called by the officers of the Asso-
ciation, affiliated societies might have their meeting either in
the week preceding or succeeding the meeting of the Associa-
tion. There seems to be a feeling, I think, among a good many
of the officers of the Association that it would be in a measure
(116)
imp^^ible to secure the coalescence of the different societies
with the similar sections. As I say, all these points will be
brought necessarily before the Council in the discussion of the
matter, and it is the only way in which it can be determined
after all. It must, under the constitution, go before the Council
before it is open again to be brought before the Society.
Mr, Cochran : Before the question is put I would like to ask
one question, and that is this : I myself see some objections to it,
but I do want to attain it ; I would like to attend both meet-
ings if I could; I would like to be here when all the chemists are
here. This year particularly, my time is very limited ; I shall
leave Buffalo this evening and be cut out of the meetings next
week entirely. The question I wanted to ask is this : Is it
impossible that both meetings should run on at the same time?
Could we not have a section meeting or the meeting of the
American Chemical Society conducted at the same time
that the meeting of Section C of the American Association is
conducted*? The programs are large. Some of us would desire
to hear papers in one section one week and some in the other,
and in that way we could save our time and get the papers pre-
sented so that we could all hear them. I know there are objec-
tions to it, but at the same time I desire to have the subject con-
sidered.
Dr, McMurtrie : We are not alone in this matter. Nearly all
the other sections of the Association are in about the same posi-
tion, and it is coming to be a serious question as to what shall
be done in this matter, whether the American Association shall
be taken into a confederation of scientific societies, or whether
some such plan as is suggested now shall be carried out. It
seems to me that this might be permitted to grow into a confed-
eration.
The President : I was about to remark on that same subject
that there are othei- affiliated bodies exactly in the same position
as Dr. McMurtrie has said, so that it is obvious this question is
a serious one.
The President put the question and it was adopted.
("7)
Dr. Norton : Mr. President, I would like to say a few words
as to what has been said in regard to the pleasure and profit we
have all had in meeting together as a Society during the past
few days, and I feel that our success, which is actually a marked
one this year in point of attendance and interest, is due not only
to the efforts of our Local Committee, but also to the able prepa-
ration made in advance for the meeting by the officers of the
Society, and I would therefore like to move before we separate
to-day, that the cordial thanks of the Society be expressed to
the President and Secretary for the measures which they have
taken to render this meeting so successful, and I would like to
ask the Nestor of the Society, Dr. Prescott, to put that motion.
Dr, Prescott: I am very glad to place this motion before you
and have an opportunity to vote for it.
Dr. Prescott put the motion which was unanimously carried.
The President : In behalf of the ofiicers, I will only say that
it is a regret on their part that most of us are so busy with our
daily life that we can not give all that is in our hearts and
minds to do for the inteiiests of the Society, and we thank you
for your vote. ( Applause) .
The President : I declare then the meeting adjourned until the
Troy meeting.
ANNOUNCEMENT.
All persons who have papers to offer for the next general meet-
ing, which will be held the latter part of December in Troy,
N. Y., are requested to forward at their earliest opportunity an
abstract, or the full manuscript of their papers together with
titles and names of authors to the General Secretary, Albert C.
Hale, 551 Putnam Ave., Brooklyn, N. Y.^ so that the papers
may all be passed upon by the committee on papers and publica-
tions in time for announcement upon the program which must
be in print before the meeting.
(ii8)
CHANGES OP ADDRBSS.
Burt, M. C, io6 Chestnut St., Springfield, Mass.
Conradson, P. H., Franklin, Pa.
Bakins, L. O., care of Guppenheim Smelting Co., Perth Am-
boy, N. J.
Lane, Henry M., care of Washington Agricultural College,
Pullman, Wash.
Mar, P. W., 32 McDonough St., Brooklyn, N. Y.
McCrae, John, 7 Kirklee Gardens, Kelvinside, Glasgow,
Scotland.
Welles, Albert H., 635 Quincy Ave., Scranton, Pa.
Whitehead, Robt. L., Box 142, Mt. Washington, Md.
iMued with VcnrttobcT Number, .1896.
Proceedings.
COUNCIL.
By direction of the Council a congratulatory address was for-
warded to Stanislas Canizzaro, an honorary member of this
Society, upon his seventieth birthday.
December 29 and 30 has been selected as the date for the
annual meeting at Troy, N. Y.
MEMBERS ELECTED SEPTEMBER 21, 1 896.
Belden, A. W., Chapel Hill, N. C.
Blair, Augustine W., Guilford College, N. C.
Chamot, Emile M., Cornell Univ., Ithaca, N. Y.
Davis, Dr. Floyd, Des Moines, Iowa.
HaUer, H. Loft, F.C.S., 27 Hilda St., Beverly Road, HuU,
England.
Hotopp, C. H., Stroudsburg, Pa.
Kruskal, Dr. Nicholas, 72 Delancy St., N. Y. City.
Marlatt, Miss Abby L., Providence, R. I.
Meade, Richard K., Longdale, Alleghany Co., Va.
Patrick, George E., Dept. of Agr., Washington, D. C.
Slosson, E. E., Laramie, Wyo.
Smith, Prof. E. G., Beloit College, Beloit, Wis.
Stahl, Dr. Karl P., 57th St. and A. V. R. R., Pittsburg, Pa.
Tolman, Prank L., U. S. Naval Lab., Brooklyn, N. Y.
ASSOCIATE ELECTED SEPTEMBER 21, 1896.
Brinton, C. S., West Chester, Pa.
CHANGES OP ADDRESS.
Bachman, Irving A., Allentown, Pa.
Behr, Amo, 17 Lawn Ridge, Orange, N. J.
Doerflinger, Wm. P., 85 Lafayette Ave.. Brooklyn, N. Y.
Boot, J. C, Brooklyn Distilling Co., Kent Ave., Brooklyn,
N. Y.
Dal Molin, A. A., 30 E. i8th St., N. Y. City.
Davidson, Geo. H., 28 Woodbine St., Brooklyn, N. Y.
Fuller, Fred. D.. Agr. Expt. Sta., Geneva, N. Y.
Habirshaw, William M., Glenwood Works, Yonkers, N. Y.
(I20)
Hollick, Herbert, Post OflSce, New York City.
Kutroff, Adolph, 128 Ouane St., New York City.
Loeb, Morris, 118 W. 72nd St., New York City.
Munsell, C. E., no Horatio St., New York City.
Sargent, Geo. W., Univ. of Pa., Dormitories, 37th and Spruce
Sts., Philadelphia, Pa.
Thompson, P., 11 Willmot St., Ann Arbor, Mich.
Tidball, Walton C, 291 Prospect PI., Brooklyn, N. Y.
Volckening, G. J., 65 Van Buren St., Brookl3m, N. Y.
MEETINGS OF THE SECTIONS.
RHODE ISLAND SECTION.
The first meeting for the year 1896-97 was held at Provi-
dence, on Thursday evening, September 24th, Chairman K. D.
Pearce presiding.
Prof. J. H. Appleton read a paper upon the ** Electrolysis of
Salt."
The introduction to this paper was a brief discussion of the
present chemical application of electricity. First in importance
at present is the preparation of metals, copper, gold from cya-
nide solutions, zinc, glucinum, and even some more difficultly
reducible metals or non-metals ; sodium, lithium, cadmium,
cobalt, nickel, and phosphorus. Next, reference was made to
the production of certain compounds in which primarily the
heat of the current is involved : silicon carbide, calcium car-
bide, as well as those metallic carbides, produced by Moissan,
which, with water, yield such varied hydrocarbons (very sug-
gestive in relation to the origin of petroleum).
The electrolysis of salt by several methods, notably Castner's,
was next taken up.
In conclusion, there were presented some comments on the
probable influence of the electrolysis of salt on the alkali in-
dustry.
new york section. — annual meeting.
October 9, 1896.
The meeting was called to order at 8.20 p. m., by Dr. P. T.
Austen, Chairman.
(121)
In the absence of the secretary, Dr. A. C. Hale was appointed
secretary /n? tern.
The minutes of the meeting held June 8th, 1896, were read
and approved.
Reports of officers and committees being in .order, the chair-
man called upon Dr. Hale to report for the delegates to the
Scientific Alliance of New York. Dr. Hale made a brief oral
report, which was accepted.
Dr. P. T. Austen, the retiring chairman of the section,
reported on the work of the year and the general condition and
prospects of the section and the society as well as the outlook
for American chemists generally.
After these remarks by the retiring chairman the election of
officers of the section for the ensuing year was held.
Dr. Durand Woodman was unanimously elected secretary and
treasurer. Other officers were elected unanimously, as follows :
Chairman — Dr. Wm. McMurtrie.
Executive Committee — Dr. Charles A. Doremus, Prof. A. A.
Breneman, Dr. Albert C. Hale.
Delegates to the Scientific Alliance of New York — Dr. Wm.
McMurtrie, Dr. C. F. McKenna, Dr. C. A. Doremus.
Dr. Wm. McMurtrie, chairman-elect, then took the chair, and
upon motion of Dr. Doremus, a vote of thanks to the retiring
chairman was passed unanimously.
Prof. Breneman reported very encouraging progress in refer-
ence to the proposed chemical club.
Papers were read and discussed as follows : ** Some Disputed
Points about the Light of Carbon,** by Woodbridge H. Birch-
more ; discussed by Prof. Speyers, Mr. Birchmore, and Mr. Still-
well. **The Conversion of Cow Milk into a Substitute for
Human Milk," by Henry A. Bunker; discussed by Dr. Eccles,
Dr. Bunker, and Dr. McMurtrie.
Upon motion of Dr. Doremus, seconded by Dr. Squibb, the
following named persons were appointed a committee to cooperate
with other scientific bodies in New York for the purpose of
securing a lecture from Prof. Henri Moissan before his return to
(122)
Prance : C. A. Doremus, A. A. Breneman, M. Loeb, and Wm.
McMurtrie.
Upon motion of Dr. Hale, the chairman of the section was
authorized and requested to appoint a committee, with him-
self as chairman, to arrange the programs for the meetings of
the section during the year.
The meeting then adjourned.
Issued with December Nnmber, 1896.
Proceedings.
COUNCIL.
At the Btt£Falo meeting of the American Chemical Society it
was voted that the Council be requested to take into considera-
tion ways and means for bringing the Summer meeting of the
Society into closer relation with that of Section C of the A. A.
A. S., so that both meetings, if possible, may be held within the
same week, thus affording the opportunity for all chemists to
attend both meetings.
Inasmuch as both these bodies were well* represented at the
meeting referred to, it was suggested that a good deal of time
could be gained by appointing then and there a committee of
conference from each. This was accordingly done, the commit-
tee on the part of the American Chemical Society being Messrs.
W. P. Mason, W. McMurtrie, Edward Hart, T. H. Norton and
A. B. Prescott.
A joint meeting of this Committee was held with a Committee
of Section C, and the following recommendations were agreed
upon :
ist. Section C to have a business meeting for purposes of
organization on Monday of the week of meeting, and the Vice-
President's address to take place late in the afternoon of that
day.
2nd. The American Chemical Society to be given Monday
and Tuesday for their work.
3rd. Section C of the A. A. A. S. to be given the balance of
the week.
4th. The arrangement of the program for the reading of papers
before the two bodies to be left to the discretion of the President
of the American Chemical Society and the Vice-President of
Section C of the A. A. A. S.
These recommendations were approved by Council Oct. 27,
1896.
(124)
In view of the increasing number of papers presented at the
meetings, the Council has decided that the Troy meeting shall
extend over three davs if this shall be found necessarv.
NEW MEMBERS ELECTED XOVEMBEK 5, 1896.
Andrews, Prof. W. W., Sackville, New Brunswick.
Burner, Prof. N. L., Ohio Med. Univ., Columbus, Ohio.
Case, Wm. A., Mt. Washington, Baltimore Co., Md.
Clark, Arthur W., Conshohocken, Pa.
Evans, Wm. Lloyd, Ohio State Univ., Columbus, O.
Fossler, Miss Mary L., 734 N. 9th St., Lincoln, Nebr.
Hochstetter, Robert W., Oak St. and Bellevue Ave., Cincin
nati, O.
Levi, Louis E., Ph.D., 548 Franklin St., Buffalo, N. Y.
Mathews, John Alex., Columbia Univ., N. Y. City.*
Mooers, Chas. A., Agr. Exp. Sta., Knoxville. Tenn.
Schoen, Joseph, 2317 Indiana Ave., Chicago, 111.
Schroeder, J. Henry, Grand and Nassau Sts., Cincinnati, O.
Sturcke, H. E., 284 Pearl St., N. Y. Citv.
Sy, Albert P., Univ. of Buffalo, 24 High St., Buffalo, N. Y.
Wessling, Prof. Hannah L., 147 Milton St., Cincinnati, O.
ASSOCIATES ELECTED NOVEMBER 5, 1 896.
Cooley, Fred. C. 1029 L St., Lincoln, Nebr.
Culver, Frank S., 1610.K St., Lincoln, Nebr.
Dales, Benton, 1242 P St., Lincoln, Nebr.
Himrod, George, 1446 Q St., Lincoln, Nebr.
Hiltner, Martin E., 1301 N St., Lincoln, Nebr.
Lange, Miss Helen P., 346 N. 17th St., Lincoln, Nebr.
O'Sullivan, Miss Eva, 445 N. 13th St.. Lincoln, Nebr.
Pharmelee, Howard C, care of Cooperative Book Co., Lin-
coln, Nebr.
Thatcher, Roscoe W., 540 N. 15th St., Lincoln Nebr.
CHANGES OF ADDRESS.
Allen, Walter S., 34 So. 6th St., New Bedford, Mass.
Cushman, Allerton S., Chemical' Laboratory, Harvard Univ.,
Cambridge, Mass.
Hancock, David, 1720 Fifth Ave., Birmingham, Ala.
Reese, Chas. L., 1801 Linden Ave., Baltimore, Md.
Sturm, Arthur B., Box 92, May wood. 111.
ADDRESS WANTED.
Bradley, Edson, formerly of 35 Broadway, New York City.
(125)
MEETINGS OF THE SECTIONS.
RHODB ISLAND SECTION.
A meeting of the Rhode Island Section was held at Provi-
dence, on Thursday evening, October 29, 1896.
Mr. E. D. Pearce mentioned the results of his experiments in
bleaching brown tower acid. Samples pf acid taken before and
after bleaching were exhibited. Mr. Pearce also stated that
the coloring matter of the anthers of the wild evening prim-
rose was altered by acids and alkalies in the same way as
turmeric.
A paper was read by W. M. Saunders upon ** The Determina-
tion of Sulphur in Iron." The reader described briefly the del-
eterious effect of sulphur in iron. The small amount permitted
in foundry work, and the diflSculty of determining this amount
was mentioned.
Next a description of methods of analysis was given. The
reader considered the evolution methods, although not in every
case giving the full sulphur contents of the iron, to be accurate
enough for practical purposes. The results compare favorably
with the oxidation method.
NEW YORK SECTION.
The November meeting of the New York Section was held on
the 6th, Professor McMurtrie in the chair, and fifty-one mem-
bers present.
The chair announced the acceptance by the executive com-
mittee of an invitation from Drs. Morton and Leeds to hold the
December meeting at the Stevens Institute of Technology.
The death of Mr. Alfred H. Mason was announced and a
sketch of his life was read.
A motion was made and seconded that the executive commit-
tee be recommended to authorize the secretary to employ a
stenographer to report the discussions of papers presented at the
meetings ; such report, when properly edited, to be sent to the
committee on papers, for publication in the Journal.
The following papers were read :
(126)
" The Volumetric Determination of Acetone," by Dr. E. R-
Squibb.
** Notes on a Chemist's Trip Abroad," by C. A. Doremus.
*• A New Form of Pyknometer," by J. C. Boot.
** Improvements in the Colorimetric Tests for Copper," by
Geo. I^. Heath.
*' Note on Solubility of Bismuth Sulphide in Alkaline Sul-
phides," by Geo. C. Stone.
The meeting then adjourned.
CINCINNATI SECTION.
The meeting was held on November 17, in the Woyd Library.
After welcoming the Society^ Prof. J. U. Lloyd read a paper en-
titled "Bibliography of American Pharmacy," giving a concise
history of the different editions of the U.S. Pharmacopeia and
its commentaries, the various dispensatories and formularies.
This paper was rendered doubly interesting by the exhibition of
the rare old editions of these works from the well-filled shelves
of the Lloyd Library. Prof. O. W. Martin read a paper opening
the discussion on the ** Teaching of Elementary Chemistr>-." A
contribution on this subject by Dr. James Lewis Howe was read
by Mr. H. B. Poote. Excerpts from paper which Prof. Paul
Freer presented at the summer meeting of American Association
for the Advancement of Science, elicited considerable discussion
by Dr. Springer, Profs. Norton, Martin and Homburg.
Dr. William H. Crane, of Cincinnati was elected a member of
the Section.