Sir William Crookes.

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traces of aniline were removed. It appeared to be stable
on drying, and its analysis showed the presence of four
molecules of aniline.

I. 0*5382 grm. material gave :—

0*5053 grm. silver chlorides o'X25i grm. chlorines 23*25

per cent chlorine.
o*xo8o grm. zirconium dioxide 00*0798 grm. zirconium

s X4*83 per cent zirconium.

II. 0*4817 grm. material gave :—

0*4538 grm. silver chlorides 0*1x23 grm. chlorines 23*32

per cent chlorine.
0*0982 grm. zirconium dioxide 80*0726 grm. zirconium

sX5*o6 per cent zirconium.

I. 0*5382 grm. material gave : —

0*0600 grm. ammonias 0*0494 grm. nitrogen 39*19 per
cent nitrogen.

II. 0*6x08 grm. material gave : —

0*0678 grm. ammonias 0*0559 S^'"* nitrogens9'i5 per
cent nitrogen.

Calculated for Found.

2rCV4C«H»NH,. I. II.

Chlorine .. •• 23*49 23*25 23*32

Zirconium .. •• 14*98 14*83 15*06

Nitrogen .. .. 9*27 9*19 9*15

Since analysis would show no difference in the com-
position of ZrCl4*4C6HsNHa and a mixture of
ZrCla(C6H5NH)a + 2C6H5NHa*HCI, the following
method was resorted to in order to prove that it was the
first and not the second compound which was formed.
The substance, after having been completely freed from
aniline, was treated with chloroform, in which it proved
to be easily and completely soluble, whereas aniline
hydrochloride is insoluble in the same reagent, and hence
was not present in the compound. Also no substituted
chloraniline, C6H4ClNHai could have been formed, as
this is soluble in ether, and the existence of no such sub-
stance was indicated in the ethereal filtrate. This con-
clusively proves that the compound is purely additive in
nature, and has the formula ZrCl4*4C6H5NHa. This same
proof may be used as an argument for the additive
charaAer of all the zirconium and thorium derivatives
described in this research.

b. Thorium Tetrachloride, ThCl4'4C6H5N Ha.— Aniline
produced a precipitate slightly grey in colour, and soluble
in chloroform. Its analysis indicated a formula in cor-
respondence with that of the zirconium derivative.

0*2536 grm. material gave: —

o*X940 grm. silver chlorides 0*0479 grm. chlorines 18*89

per cent chlorine.
0*0906 grm. thorium dioxide 30*0796 grm. thoriums

31*39 P^c cent thorium.
0*5536 grm. material gave :—
0*0488 grm. ammonias 0*0402 grm. nitrogen 87*41 per

cent nitrogen.

Calculated for
ThCl4-4CeH,NH,. Found.

Chlorine 19*02 18*89

Thorium 31*15 3X*39

Nitrogen 7*6x 7*41

c. Lead Tetrachloride, PbCl4*3C0H5NHa.— Aniline gave
a dark green stable compound with lead tetrachloride in
dilute solution* A more concentrated solution of the lead
salt reads very violentlv with aniline, probably giving rise
to the same chlorinated produ^s as tin tetrachloride, such
as violaniline, mauvaniline, rosaniline, and triphenylen-
diamine blue (Qirard and Pabst, Bull, Soc. Chim., xxxiv.,
33). The dark green compound anal^rsed for three mole-
cules of aniline.

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""'wNSST''} Derivatives of the Tetrachlorides oj Zttconium^ thorium^ &c. 35

0*2x04 grin, material gave : —

0*1950 grm. silver chloride « 0*0483 gnu. chloriaea 22*94

per cent chlorine.
0*2042 grm. material gave :—
0*0963 grm* lead sulphate b 0*0658 grm. lead « 32*22 per

cent lead.
0*40x2 grm. material gave : —
0*1929 grm. platinum « 0*0277 grm. nitrogens 6*90 per

cent nitrogen.

CalculAted tor
PbCVau.H.NH^ Pound.

Chlorine 22*61 2294

Lead 32*96 32*22

Nitrogen 6*69 6*90

F. Toluidim.

a. Zirconium Telrachhridt, ZrCl4*4C6H4CH3NH2.~A8
aniline gave a derivative with zirconium tetrachloride,
tolaidine was also tried with like result. Analysts indi-
cated that this compound contained four molecules of
toluidine, showing it to he analogous to the aniline

0*3772 grm. material gave:—

03240 grm. silver chloride « 0*0802 grm. chlorine b2X '26

per cent chlorine.
0*0694 grm. zirconium dioxide ■> 0*05 12 grm. zirconium

<■ 13*60 per cent zirconium.
0*4296 grm. material gave : —
0*0456 grm. ammonias 0*0376 grm. nitrogen-i8 74 per

cent nitrogen.

Calculated for
ZrCV4CeH4CH,NH,. Found.

Chlorine 21*50 2X-26

Zirconium 13*72 13*60

Nitrogen 8*48 8*74

b. Thorium Tetrachhridt, ThCl4*3C6H4CH3NHa. —
This was a greenish white precipitate and showed a de-
parture from the other derivatives and from its analogous
jtircooium compound in that it only contained three
molecules of the base.

0*50x2 grm. material gave :—

0*4074 grm. silver chloride BO' X008 grm. chlorine « 20*12

per cent chlorine.
o*X940 grm. thorium dioxide* 0*1705 grm. thorium *

34*ox per cent thorium.
0*7500 grm. material gave : —
0*0526 grm. ammonia B 0*0433 grm. nitrogen '5*78 per

cent nitrogen.

Calculated for
ThCI«'3C«H«CH«NH,. Found.

Chlorine 2o*4X 20*12

Thorium .. .. .. .. 33*44 34*ox

Nitrogen 6*04 5*78

c. Lead Titrachloridi, — With toluidine no additive pro-
dad could be obtained even by using quite dilute solutions
of lead tetrachloride, as the amine was decomposed,
giving a deep purple solution. Hence lead tetrachloride
evidently has about the same adion on toluidine as
bleaching lime or tin tetrachloride.

G. Pyridint.
As pyridine and quinoline are strong bases, and as they
may be considered tertiary amines, it was thought prob-
able that these reagents would form derivatives with the
tetrachlorides in a manner similar to aniline and toluidine.
Experiment proved this surmise to be a corred one, as a
compound was formed in both instances. It may be
stated that Classen and Zahorski (Zeit, Anorg, Chim,, iv.,
100) have obtained compounds of lead tetrachloride with
the hydrochlorides of pyridine and quinoline, and they are
described as additive produds. Goebbles {Btr, d, Chtm.
Ois,t xxviii., 792) has also obtained compounds of lead
tetrachloride with the salts of such complex organic bases
at picolinei lutidine, and coUidine.

The compounds of zirconium and thorium tetrachlorides
with pyridine and quinoline are light grey to brown floc-
culent precipitates. Unlike the derivatives with the pre-
ceding amines, they appeared to be rather unstable in
moist air, in consequence of which considerable difficulty
was experienced in obtaining suitable portions for analysis,
as the compounds had to be preserved under anhydrous

a. Zirconium Tttrachloride, ZrCl4'2CsH5N.— The best
analysis that could be obtained for the pyridine derivative
approximated to a formula containing two molecules of
the base.

0*5420 grm. material gave : —

0*7805 grm. silver chloride «o*X932 grm. chlorine* 35*64

per cent chlorine.
0*1758 grm. zirconium dioxide *o*x 299 grm. zirconium

*23'97 per cent zirconium.
o'6ix8 grm. material gave : —
0*0506 grm. ammonia 190*04x7 grm. nitrogen* 6*83 per

cent nitrogen.

Calculated for
ZrCUaC«H«N. Found.

Chlorine 36*35 35*^4

Zirconium 23*19 23*97

Nitrogen 7*18 6*83

b. Thorium Tetrachloride , ThCl4*C5H5N.— 0*5002 grm.
material gave : —

0*6270 grm. silver chloride *o*x 552 grm. chlorine *3X '02

per cent chlorine.
0*2939 grm. thorium dioxide* 0*2583 grm. thorium*

51*64 per cent thorium.
0*4x07 grm. material gave :^

0*0x26 grm. ammonia* 0*0x04 grm. nitrogen *2*53 per
cent nitrogen.

Calculated for
TbCVC«H«N. Found.

Chlorine 3X'3o 31*02

Thorium 51*28 5X*64

Nitrogen .. .. •• .. 3*09 2*53

c. Lead Tetrachloride , PbCl4*2CsHsN.— Pyridine gave
a pale yellow precipitate with lead tetrachloride of much
greater stability than the foregoing compounds.

0*2506 grm. material gave : —

0*2780 grm. silver chloride* 0*0688 grm. chlorine* 27*46

per cent chlorine.
0*3x25 grm. material gave : —
0*1842 grm. lead sulphate *o*X258 grm. lead* 40*26 per

cent lead.
0*3062 grm. material gave : —
o*xxx2 grm. platinum *o*ox6i grm. nitrogen* 5 *2X per

cent nitrogen.

Calculated for
PbCI«*aC«H«N. Found.

Chloiine 28*01 27-46

Lead 4083 40*26

Nitrogen 5*52 5*2X

(To be continued).

Meaara. John J. Griffin and Sons, Ltd., the well-
known makers of scientific instruments, who have removed
from their old premises in Garrick Street to Sardinia
Street, Lincoln's Inn Fields, have sent us their Catalogue
— Part IIL, Magnetism, Ele&ricity, and Galvanism. The
list includes some of the latest pieces of apparatus, as
well as some almost obsolete. We note several forms of
Wimshurst eledrical machines, Kelvin's galvanometers,
Ayrton weather instruments, Rdntgen ray outfits, tele-
phones, arc lamps, and eledric furnaces. The illustrations
are good and numerous, and the catalogue is likely to
prove of great use to any having the responsibility of
schools and technical institutions, especially those in
country places.

Digitized by


i 1


Chemical bfottces from Foreign Sources.

f OBBldCAL NsWt,

I Jan. 20, 1899.


A Manual of Chemical Analysis, Qualilallvt and Quanti-
tativi. By G. S. Newth, F.I.C, F.C.S. London,
New York, and Bombay: Longmans, Green, and Co.
1898. Pp. 462.
Thb volume now before us treats the subje^ of both
qualitative and quantitative analysts in a clear and com-
prehensive manner. Beginning with the simplest readions
m both the wet and dry ways, the student is led on through
simple tests to group analysis, after which the rare earths
and metals are dealt with. When this branch has been
thoroughly mastered, the principles and praAice of quan-
titative analysis are fully explained, both gravimetrically
and volumetrically. A very good plan has been adopted
in first giving an '* epitome of process," and then pro-
ceeding to the more detailed instrudkions for carrying out
whatever analysis or process is being dealt with.

The book is very well adapted for both class and
laboratory work, and should rank among the standard
text- books of science.

Practical Pharmacy : an Account of the Methods of
ManufaAuring and Dispensing Pharmaceutical Prepara-
tions, with a Chapter on the Analysis of Urine. By
£. W. Lucas, F.C.S. With 283 Illustrations. Pp. 528.
London : J. and A. Churchill. 1898.
Although a certain portion of this work is devoted to
manufaauring processes, the bulk of it deals with the
ordinary method and routine of pharmacy and dispensing.
It is essentially a book for students, beginning as it does
with the simplest .chemical instru^ion. There is, how-
ever, too great a tendency in such books now-a-days to
assume that the reader or student knows nothing of the
subjeA he is taking up as a profession ; we very much
doubt if the early chapters are ever read, filled as they
are with descriptions and illustrations of the simplest and
commonest articles used in chemical laboratories. Tables
of weights and measures, and such like information, are
supposed to be learnt at school, and a quarter-page illus-
tration of copper gallon and quart measures surely seems

The book is divided into six parts, comprising general
processes and descriptions of apparatus, pharmacopceial
preparations, dispensing, pharmaceutical tests, volumetric
and gravimetric analysis, tables, and a chapter on the
analysis of urine, in which will be found a number of
excellent enlarged microscopic platet .

After the preliminaries are got over the book will be
found to be sound, and clearly written, and will be of
value to the student. There is a copious index of eleven





To the Editor of the Chemical News,
StR,^In an interesting paper on the above sabjed recently
read before the Royal Society, and published in the
Chemical News (Ixxviii., p. 305)* I^r. M. W. Travers
discusses the source of the gases given off on heating
meteoriteSi The conclusion he arrives at is thus stated
in his own words ;— " It would appear then that the gases
produced by the adion of heat upon meteorites are not
present as such, but are the produds of decomposition of
their non-gaseous constituents. It is therefore impossible
to draw conclusions as to the former history of a meteorite
from the nature of ths gases which it gives on heating.*'

From the tenour of some of the remarks made by Dr
Travers, I judge that he is not aware that the same con-
clusion has t)een reached before. May I therefore draw
attention to a paper in the Philosophical Magauint of
June, 1883, on the " Regenerative Theory of Solar
Adion *' ; where, in discussing the well-known speculation
of the late Sir William Siemens, I have considered the
question as to whether the composition of the gases found
occluded in meteorites supports the view of the existence
of an atmosphere rich, in hydrogen, existing in space.
After quoting the experimental results, and explaining
how the gases can be formed from the substances con-
tained in the meteorites themselves, I conclude "that
they afford us no insight into the composition of the sup-
posed interplanetary atmosphere.*'— I am, &c.,

Ernest H. Cook.

The Clifton Laboratory,
jAooary xo, 1899.


To the Editor of the Chemical News,
Sir,— Inreplytothe second question of your querist **Cox*'
(Chem. News, Ixxix., 12), may I say that the estimation
of lead, outlined in the Appendix of Mr. Brearley*s paper
on the '* Estimation of Molybdenum Compounds,'* could
be readily adapted to the determination of lead in iron
and calcium compounds. As it is very unlikely that
any satisfaAory precipitation of lead molybdate can be
made in the presence of iron, that element would need
to be separated. Either alkaline acetates or soda hydrate
could, I believe, be used to this end.

The very large number of elements in whose presence
molybdenum has been shown to be accurately precipi table
as lead molybdate by a lead salt, at once suggests the
converse operation of estimating lead in their presence.
If in this converse operation there can be added tin,
antimony, and bismuth to those elements Mr. Brearley
has already experimented with, then the method would be
a valuable one for the examination of the numerous com-
mercial lead alloys.

This line of investigation I have been for some time
engaged upon, and hope shortly to publish the results,
amongst others, of special interest to '' Cox."— I am, &c.,

R. Leffler.
The Laboratory,

Thot. Firth aod Sooa, Ltm , Sheffield.


NoTB.— Alldegreaaoftemperatare are Ceaticradenaletiotherwie*

Comptes Rendut Hebdotnadaires des Seances, deVAeadimie
des Sciences, Vol. cxxvii., No. 21, November at, 1898.
Relation between Luminous and Chemical Energy
end DiapUcement of the Halogen Elements by Oxy-
gen. — M» Berthelot.— The author examines -^(x) The
adion of iodine and oxygen, finding that iodic anhydride
and also iodic hydrate are slowly decomposed into their
elements under the influence of solar light at ordinary
temperatures, the effed of the light being the same as that
of heat, if the temperature of the substance is raised in
the absence of light* This adion, however, is not rever«
sible, iodine and oxygen not combining at any known
temperature* This readion proves, what the author has
also studied experimentally, that solar light does not in
any degree change ordinary oxygen into osone. For, this
being the case, iodine must be at once oxidised. The
same experiments were repeated in the presence of water

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Jtn. 30,1899. f

Chemical Notices jrotn Foreign Sources.


with again negative results. (2) The adion of bromine
and oxygen, finding that bromine or chlorine and free
oxygen do not combine. However, chlorine and even
bromine decompose water in the cold, giving off oxygen.
The aaion of bromine on water is almost imperceptible
in darkness, but quite perceptible under the influence of
solar light. Reciprocally bromic acid is decomposed by
oxygen at a high temperature.

Atomicity of Boron.— E. Frankland.— Rcfeiring to M.
Copaux*s paper on the new compound of boron which
indicates its pentatomicity, the author states that in 1876
he obtained with boric methide and boric ethide a number
of compounds, for which were suggested the formulae—
H Me

and —


Me Ammonia boric methide,


Et £t





Diboric altropentethylate,


which confirms the pentatomicity of boron and its power
of uniting with itself in the same manner as carbon.

No. 22, November 28, 1898.
Condensed Oxides of the Rare Earths.- G. Wyrou-
boff and A. Verneuil.— The authors have examined the
oxides of cerium with a view to replacing the confused
notion of basic salts by the exaa theory of successive
condensation of the oxide. It appears much more rational
to consider the combinations as neutral or acid salts of an
oxide, which in condensing necessarily changes its valency.
One of the most charaderistic properties of the rare earths
is their faculty of polymerising, under the influence of the
most varied causes, and also their tendency to form among
themselves very stable compounds of complex oxides,
which properties naturally are expcded from the above

ObservatioDS on the Spedra of Aluminium, Tellu-
rium, and Selenium.— A. de Gramont.— The author
finds that ceitain lines in the spark spedrom of aluminium,
tellurium, and selenium, as measured by Thal^n and by
himself in former papers, are due to impurities. He has
obtained aluminium in a greater state of purity than that
in which it has been obtained before, and from a study of
the spearum attributes Thal^n's lines 637*i3, 634-48, and
505-66, to silicon. In tellurium and selenium the lines
5217, 5X5*3i 5io'5 he attributes 10 copper.

Aromatic Urethanes of Tetrahydroquinoline. —
MM. Cazcneuve and Moreau.— The a^ion of secondary
bases of the aromatic scries on phenolic carbonates gives
rise to urethanes, as shown by the derivatives of pipen-
dine, conicinc. piperazine, before described. The adkion
of tetrahydroquinoline confirmed this readion, which
appears to be general for bodies of this type. An txcess
of base was used. On heating for two hours to the
boiling-point 4 molecules of tetrahydroquinoline with
I molecule of phenol carbonate, the following urethanes
were obtained -.—Phenyl, orthochlorphenyl, guaiacol, and
a- and /B-naphthol. These are all white bodies, very
atable, fusible, and boiling almost without decomposition
at about 300^

Adion of Potash on Oxynitrocellulose. — L€o
ViMon.— Oxycellulose having been nitrated by a mixture
of I part of HaS04and 3 parts o< HNO3, the oxynitro-
cellulose obtained was mixed with KOH, and the temper,
ature raised to 45" for seven minutes. At the same time

the oxynitrocellulose dissolved with a slight evolution of
gas giving a brown liquid. This solution was cooled to
o", and neutralised by acetic acid ; it then became nearly
colourless, and on a current of HaS being passed through
at the ordinary temperature, oxides of nitrogen were
evolved, sulphur deposited, and a brown liquid obtained.
This liquid, to which was added a solution of acetic acid
and phenyl hydrazine, was warmed to 8o^ resulting in
the formation of a crystalline precipitate: 100 grms. of
oxynitrocellulose yielded 8 grms. of this precipitate,
which consists of small yellow crystals. Analysis gave
the following percentages :—C 64*40, N 19*33. H 5-40,
O 11*87. The melting-point, 204, is identical with that
of the osazone of oxy pyruvic acid, and the analysis gives
the same composition. Hence oxypyruvic acid, —

is the result of treating oxynitrocellulose with potash.

journal de Pharmacie et de Chimii, vol. vtii.. No. 4.

Researches on Urinary Phosphorus.- L. Jolly.—
These researches show that the urinary phosphorus which
escapes estimation by the ordinary methods used for
phosphoric acid is not incompletely oxidised phosphorus,
or phosphoglyceric acid, according to one hypothesis
which has been put forward, but simply phosphoric acid
combined with metallic bases, again intimately associated
with nitrog:enous matter, an association which resists the
adion of digestives, and of the intra-organic oxidants.

The Organic Phospboglycerates.— MM. Adrian and
Trillat. — The preparation of the organic phospho-
glyceiates (of cocaine, quinine, phenyl-hydrazine, &c.)
is as follows :— A solution of a neutral glycerophosphate
of lime is treated with dilute sulphuric acid until it is just
acid to heliantine, and is then brought back to neutrality
with a few drops of neutral glycerophosphate ; heat and
filter off the calcic sulphate thus precipitated. After
having added the base until the readion is alkaline, and
then a great excess of alcohol, the whole must be again
heated for a few minutes, and filtered with a filter-pump
to separate the precipitated glycerophosphate of lime ;
the solution must be concentrated at as low a temperature
as possible, and desiccated in vacuo over sulphuric acid ;
the residue is taken up with a little water, and shaken up
several times with ether, to remove all excess of the base ;
the aqueous solution is again evaporated down, and the
residue triturated with strong alcohol. The unprecipitated
phosphogly cerate of lime remains in suspension; the
residue soluble in alcohol is finally dried at 50^ to 60^. The
strong bases only (quinine and cocaine) seem able to
completely displace the lime of the acid phospho*
glycerate according to the equation—

fphO^OH 1* Ca+2C,7HaxN04 -

L \OC3H5(OH)a-»

/OH.Cx7Na,N04 /O^^a

= PhOf.OH.Ci7HaiN04 + PhO^O^^*

\O.C3H5(OH)a XOCaHaCOHja

The less strong bases (aniline, phenyl-hydrazine, pyri-
dine, &c.) precipitate a certain amount of the neutral
phosphoglycerate of lime, but the residue from the filtrate
contains a considerable proportion of a body either in-
soluble or only slightly soluble in alcohol: it has the
formula —

[yOH'Base -la
PhO^C3H5(OH)aJ Ca.

The Decolouration of Wines by means of Salts
of Manganese.— P. Jacob.— Not suitable for abstradion.

The Purification of Potable Waters.— P. Guichard.
—The author points out that the water of the River
Vanne contains 700 microbes per c.c. when it arrives in
Paris, and that this number has increased to 2x2,000 by

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Meetings for the Week.

I ClMMfiAI. MbwAi

I Jan. 90, 1899.

the time it reaches the container. He therefore thinks
that the purification of the water should be undertaken
individually by the use of filters, the merits of some of
which he discusses.

The Coagulation of Albumen.— G. Halphen.— Prom
experiments made, and here described, the author con-
cludes that some ammonium salts, such as the oitrate
and hydrochlorate, favour the separation of albumen ; that
the soda set free at the moment of coagulation displaces
the alkali of the ammonia salt, thus creating a more
favourable medium for coagulation ; that the coagulation
of albumin is complete in the presence of citrate or of
ammoniacal salts ; and that operations carried out for the
purpose of estimating the albumen are much more exaft
and are less troublesome when ammonia salts are used.


Monday, 33rd.— Society of Arts, 8 (Caotor Leauret). " Baaerial

Purification of Sewage," by Dr. Samuel Rideal.

TuiSDAY, 24th.— Royal Inetitntion, 3. ** The Morphology of the Mol-

luica,'* by Prof. B. Ray Lankeiter, M.A., LL.D.

-— Society of Arti, 4.30. **Rhodeiia and i • Mioea ui

X898." by W. Pitcher Wilkioaoo, P.G.S.

Wbdnbbday, asth.— Society of Ana, 8. '* Tuberculoaii in Aninalt,*'

by W. Hunting.
Thursday, 26th.— Royal Inatitntion. 3. ** Tibet and the Tibetana,*'

by A. Henry Savage Landor.
FsiOAY, 27tb.— Royal Inatitution, 9. ** Bpitapha,** by Sir Mount-
Btnart E. Grant Duff, P.RS.
— — Phyaical, 3. ** On the Equivalent ReeiaUnce and

Inductance of a Wire to an O acillatory Discharge,'*
by E. H. Barton, D.Sc. Exhibition of (a) DepbTeg-
mator, (6) A Temperature Tell-Tale, by R. Apple-
yard. ** On the Volume Changes accompanying
Solution," by T. H. Littlewood.
Saturday, aSth.— Royal Insutution. 3. *'Tachaikowtky" fwith
Musical Illustrations), by Sir Alexander C. Mac-
kenzie, Mua. Doc.


Cloth, Gilt- lettered Covers for Binding the Half- yearly
Volumes of the


may now be obtained. Pria is. 6d, sack,

Mr. J. a. LORRAIN, M.I.E.E., M.LM.E, M.S.C.I..

Fellow of the Chartered Institute of Patent Agents^
Norfolk Houas, Noefolk Strbbt, London, W.C.

«« PATENTEE'S HANDBOOK" Poet Frea on a pplication.

Online LibrarySir William CrookesThe Chemical news and journal of industrial science; with which ..., Volume 79 → online text (page 10 of 92)