Sir William Crookes.

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a. Vapours of Aqua R$gia.-^Tht dry vapours of aqua
regia conduded into the solution of sirconium tetra-
chloride gave no readion, the solution only becoming
discoloured by the gases, which were again liberated on
raising the temperature* Portions of the dry sirconium
salt were also placed in a porcelain boat, and heated in a
current of the dry vapours of aqua regia; but the salt
appeared to volatilise unchanged, and no compound was
fbnned. In this behaviour sirconium shows a deviation
from that of titanium, as the tetrachloride of the latter
reads readily with the vapours of aqua regia, giving a
compound corresponding to the formula 3TiCl4*2NOaCl,
Hampe {Ann. Chim.t Litbig, cxxvi., 43). An analogous
compoond with tin tetrachloride has been prepared by the
same Invettigaton Baeyer (Bsr, d. Chun, Q$s. , vii., 1639)
alio records the compotind SnCU'aNOCI.

The solutions of the tetrachlorides of thorium and lead
behaved similarly to that of sirconium, and gave no

b, Nitrogtn Dioxidt. — This gas, obtained by beating
lead nitrate, on being conduded into the solutions of the
tetrachlorides, gave no readion beyond a simple solution
of the gas. The dry salts of sirconium and thorium,
heated in a current of the gas, volatilised unchanged and
gave no compound.

c* Sulphur Monochloridg, — On mixing this substance
with the solutions of the tetrachlorides no readion was

d. Chloridis of Phosphorus.^Tht adion of both the
tri- and pentachlorides of phosphorus was tried on the
solutions of the tetrachlorides, but no combination re-

#. Dicyanoggn.^On conduding this gas into the solu-
tions of the tetrachlorides no readion took place ; nor does
it seem to have formed any compounds with the corres-
ponding salts of titanium or tin.

/. FormonitriU, ^Though both titanium and tin tetra-
chlorides give derivatives with hydrocyanic acid, yet no
produd was obtained by allowing this compound to ad
on the three tetrachlorides here investigated.

g. Cyanogtn Chloridt, — It was prepared by the adion
of chlorine on mercuric cyanide, but it gave no readions
with the solutions of the tetrachlorides.

A. Ac$tonitril4, — The vapours of this nitrile passed into
the solutions of the tetrachlorides yielded no compounds,
although derivatives have been obtained with the titanium
and tin salts.

s. BtnMomtrilt.^-Ukt acetonitrile, this aromatic body
yielded no derivativea with the tetrachlorides.

From these experiments it is to be observed that the
nitriles and the other reagents here used, which for the
most part gave additive compounds with the tetrachlorides
of titanium and tin, are without adion on the corres-
ponding salts of zirconium, thorium, and lead.

(To be costinaed).


Ordinary Mettingt Dtctmbir 15^, 1898.

Professor Dbwar, F.R.8., President, in the Chair.

Cbrtipicatbs were read for the first time in favour of
Messrs* Stuart Blofeld, 4, Camden Gardens, West Ken-
sington Park, W.; Bertram H. Bowles, 53, Dunsmure
Road, Stamford Hill, N.; Thomas John Cheater, 6, Bout-
flower Road, Wandsworth Common, S. W. ; George Ward
Hedley, a. St. Luke's Villas, Cheltenham ; Harold Octavius
Knight, Westfield Villa, Barton-on-H umber ; Dudley
Northall-Laurie,56A,Pall Mall. S.W. ; James McCracken,
j8o, Govan Road, Govan, N.B.; John O'Sullivan, 74a,
Nicola Street, Vancouver City, B.C. ; Arthur Lee White,
29, Huron Road, Upper Tooting, S.W.

Mr. H. P. Bell was formally admitted a Fellow of the

The following papers were read :—

147. <* Th4 Interaction of Bthylic Sodiomalonati and
Mtsityl Oxide.** By Arthur W. Crobslby.

Attempts to prepare dihydrocamphoric acid syntheti-
cally have so far proved unsuccessful (Trans., 1898, Ixxiii.,
33). Isobutylene dibromide does not condense with ethy-
lie sodiomethylmalonate, nor mesityt oxide with ethylic
sodiomalonate, in the expeded manner. The thick, oily
prodttd obtained in the latter case cannot bt distilled in a

Digitized by


uerivaHves of Camphoric Acid.

I Jan. 6. 1899.

vicuum without partial decomposition ; when bydrolysed
with alcoholic potash it yields a dibasic Mid, CX6H24O4,
which crystallises from acetone in colourless, transparent,
lusirous prisms belonging to the monotymmetric system,
and melts at 148—148*5*', the upper part of the capillary
tube becoming covered with a red film. The etkylic salt
separates from light petroleum in thick, transparent, lust-
rous prisms, which usually are twinned, and apparently
belong to the monosymmetric system. It melts at
59*5— 6(^, boils at 252^ in air without decomposition, and,
on bydrolysis, yields the original acid. The iilvtr salt
crystallises from water in feathery needles.

Sodium amalgam is without adion on the acid.
Bromine readily converts it into a <ft6roMo-derivative,
Ci6H2404Brj or Ci6H9a04Bra, which crystallises from
dilute alcohol in colourless, glistening leaflets containing
2HaO, and melts with slight decomposition at X7I^ On
treatment with hydrogen bromide, a dihydrobromitU,
Ci6H2604Br2, is obtained, which crjrstallises in trans-
parent prisms, melts at 169** with decomposition, and is
re-converted into the acidi CX6H24O4, by interaction with
alcoholic potash.

The acid is readily oxidised by alkaline potassium per-
manganate in the cold, and when the produA is treated
with tchroBBic acid an acid melting at 89^ is obtained. It
is hoped that a study of its o»dation prodads will give
some clue to the coostitutioo of the sulntance.

148. ** Thi JnUracliou of Bthylic hialonati and Actty-
Itnt Titrahfomidi in pnsttut of Sodium Eikoxidt." By
Arthur W. Crosslby.

This investigation was undertaken^ in the hope that
ethylic disodiomalooate and acetylene tetrabromide would
interaA according to the equation,—


as the prodttd, on hydrolysis and subieqoent heating,
should yield moconlc acid, COaH*CH:CH*CH:CHCOaH;
from which tetrabromadipic acid could be prepared for
the purpose of investigating its behaviour with weak

The reaAion does not take place as expeded, and is of
a complicated nature, the two main produAs being tri-
bromethylene, CHBnCBra, and tetrethylic acetylene-
tetracarboxylate ; during its progress acetylene is given
off, and tarry prod u As are also formed from which no
definite chemical compound^onld be isolated.

The acetylene tetrabromide used was prepared from
acetylene generated from calcium carbide by the aAion of
water, and porified by Willgerodt's method (Sir., 1895,
xsviii., 2108). It boiled at 151* under 5^ m.m. pressure,
and was a cl^ar, colonrlef s, highly rfefraAlve liqtnd.

0*1548 gave o*3353 AgBr. Br-92*i8.

CaHaBr4 requires Bn- 92-48 per cent.

Acetylene tetrabromide (i mol.) was added to a mixture
of sodium (2 mokt.) dissolved in absolute alcohol and
etbylio malonate (2 molt.), and after the violent reaAion '
had somewhat moderated, the whole was heated on a
water bath for ik hours. Water waa added to the re-
sulting dark, reddish green, feebly*acid produA, and the
whole extraAed with ether. On washing the ethereal
extraA with water, the greater portion of the" red colouring
matter (from which the tarry ptodaAs alhided to #ere
obtained) was removed, and also a small quantity of a
green solid containing sodium and organic matter. When
boiled with acids this green substance partially diiBolved,
forming a red solution, i/^hich'was again turned green by
addition of an alkali $ but the amount was too small for
investigation. On dittiHing tiM rtsidti^ from the dried
ethereal extraA, fraAions were obtained boiling at 65—80°
and at' 225— ^30" under 47 m«m. prettofe^ and not more
than 0*5 cic passed over between these limits.

The fraAkm boiling at 65— 8eP under 47 m.m. pressure
cofAMtted' tribfometM^oe, CHBrtCBfa. This ' clear,
cokmrleaar beavy liqaid) amMMhif^to-63 per cent of the

total ethereal extraA, was repeatedly fraAionated at the
ordinary pressure, and nearly the whole passed over
between 164—166"; the residue, when heated above this
temperature, gave off bromine and hydrogen bromide, and
consisted probably of some unchanged acetylene tetra-
bromide. On analysis the fraAion boiling at 164—166^
gave the following numbers : —

0*3410 gave 0*7251 AgBr. Br«9o*47.

CHBr:Cfira requires BrB9o*56 per cent*

The substance waa further charaAerised by converting
it into pentabromethane by the direA addition of bromine.
The resulting solid crystallised from alcohol in long,
white, glistening needles melting at 55—55*5^.

0*2636 gave 0*5887 AgBr. Br «> 94*31.

CHBra'CBrj requires 3r»94'ii per cent.

The fraAion boiling at 225—230^ under 47 m.m. pres-
sure contained tetrethylic acetylenetetracarboxylate. This
fraAion solidified almost completely. It waa spread on a
porous plate, and then purified by re-crystallisation from
light petroleum boiling at 60—80*, from which it separated
in long, white, silken needles melting at 75 — 76^

0*1518 gave 0*2936 COa and 0*0940 HaO. C •52*76;

(COaBt)aCHCH(COaEt)a requires 0-52*83, H«6*9Z

per cent.

Although the conditions under which the reaAion waa
carried out were varied to some extent, the same resists
were always obtained.

149. •* Dirivaiivis of Camphoric Acid,** Part III. By
F. Stanlby Kipping, D.Sc, F.R.S.

This paper contains an account of the preparatie*^
properties, and transformations of a nvmber ol compeends
which have been obtained from T-bromoeamphorlc acid,
and is a continuation of previous work {Trant., 1896, Mx*,
913; Kipping and Fopt, Trans*, i897,^lxxi., 963).

st0-Dibromocamphoric acid, irts-dibVomocamphoric an-
hydride, and ir-bromocamphanic acid have been already
briefly described {Proc, 1895, x^** ^'O*

wiT'Chlorobromoeamphorie ankydridi, —


is obtained by treating ir-bromocampheric acid with pkos«
phorus pentacbloride, and -then passing chlorine> into the
produA heated at loo*'. It crystaUieea in large, ortho^
rhombic prisms melting at 214 — 215% and resembles the
corresponding dibromo-componad in ordinary propertiea.

wv'Chlorobromocamphoric acid, C8HiaClBr(COaH)i,
can be prepared 1^ heating its anhydride with coneen«
trated nitric add ; it is a coTonrless, crystalline compound
melting at about 197*, and is very like the dibromo^cid in
all respeAs.

When wirchlorobroroocamphorie anhydride is boiled
with dilute acetic acid it is converted into a ir-bronoi'
camphanic acid, identical with the compound melting at
176—177", obtained by the decomposition of vts-dibrotto^
camphoric anhydride.

hictkylic iT'bromocampkanaUf —



is easily obtained from the corresponding acid by the
ordinary methods ; it crystallisei in orthorhdmbic pHsmSi
melts at 87 — 88°, and dissolves freely in most of the
ordinary organic solvents*
it'BromocampkanamidCf —

NHtCOCeHxaBr^^ I ,

is prodtaced when irnr.dlbromoeamphoHc ailhydHde is left
in cebtaAwftfa'aqtieDQi ammonia, and can also be pre*
pared from methync ir:bh>inocAfnpbaAate in a similar

Digitized by


Jan. 6, 1899* I

Commercial Organic Analysis.


manlier ; it cryttalliiei in tranipirent needles melliog at
i6i— i6a'.

The adion of alkalis on irv-dibromocamphoric anhy-
dride results in the formation of hydttxy-cis ir-camphanic
acid (Trails., 1896, lata., 913), but when the anhydride is
heated with an aqueous solution of silver nitrate, it is
partly converted into the 7-ladone of hydroxy camphotri-
carboxylic acid (/oc. cit.); the last-named compound is
also formed when ir-bromocamphanic acid is boiled with
an aqueous solution of silver nitrate.

150. **Synth4sh of mfifi-Trimtthylgluiaric Acid:* By
W. H. Pbrkin, jun., and J. F. Tuorpb.

This acid, which is especially interesting on account of
the fad that Balbiano (B#r., 1895, xsviii., ai6i) obtained
it by simple readions from camphoric acid, may be pre-
pared synthetically in the following way.

Ethylic cyanacetate is digested in alcoholic solution
with sodium ethylate and ethylic dimethylacrylate, and
the produA, which contains the sodium compound of
gthyUc m'CyanO'fifi'dimiihylglHiaraUt''^


is treated with methylic iodide. The resulting ithylie
m-^OHO^aBfi-trimtthylgMarats, —


a colourless oil boiling at iSx" under 25 m.m. pressure,
yields on hydrolysis afifi'trimtikylglutarimidi,

which crystallises in long needles and melts at za6*.
afi$'TrimitkylglHtaric acid, —


is obtained from this imide by heating with hydrochloric
acid at 200* ; it melts at 88% gives an anhydridt melting
at 8a% and an anilic acid melting at 150% and is, in all its
properties, identical with the acid obtained from cam-
phoric acid by Balbiano.

15Z. ** Hydrolysis of Mitkylie and Bthylie y^Cyano'
ocitoacttaitM and tktir Dtrivativa,** Part I. By W.
Tbbvor Lawrbnce.

A preliminary account is given of the resnlts obtained
in an investigation which had, for its primary objed, the
preparation of unsymmetrically disubstituted ethylic
acetonedicarbox^lates, but has led to the discovery of a
new series of acids.

Mitkylie y-eyanodimitkykuitoaeitatsr-*

li the chief produd of the interadion of methylic
y-bromodimethylacetoacetate with potassium cyanide in
ethereal solution. It boils at 126— 128^ under 18 m.m.
pressure. On treatment in ethylic alcohol solution with
dry hydrogen chloride it yields an oil, —


which boils at 146 — 150* under 40 m.m. pressure, and
when hydrolysed with concentrated hydrochloric acid is
converted into aa-dimethyl./3-hydroxyglutaconic acid.
Sodium amalgam does not reduce the nitnle under the
varied conditions employed, bat converts it into dimethyl-
malomc acid*

Methylic v-cyanodimethvlacetoacetate is hydrolysed
rapidly by concentrated hydrochloric acid, and converted
qoantiutively into a substance which is regarded pro*
viaionally as vm^nutkyl'^kydroxyglutasonic acid^^


although several of its readions are difficult to explain if
the formula adopted is corred. Thus» the compound re-
mains unchanged on boiUng with suiphuric and with nitric
acids, is not affsded by potassium permanganate at 6o%
and ^VM no colouration with ferric chloride. The acid
ccystalUsos from water in prisma, melu at 214% and distila
at 245% The kydrogin silver salt, C^HgOsAg, and the

corresponding copptr and zinc salts have been obtained.
The aniltns salt melts at 122°. The ditmikylic salt,
COaMeCH:C^OH)-CMe2'C02Me, crystallises in needles,
melts at 104*, and boils at 285^ The aatyl derivative
melts at 136', and the henuoyl derivative at 2o8^ When
the acid is treated with phosphorus pentabromide and the
produd poured into methylic alcohol, the methylic salt of
a bromo-derivative is obtained which, on hydrolysis with
hydrobromic acid, yields oo-dimethylglutaconic acid.
a»'Dimttkylglutaconic acid, —


is also obtained by the redudion of dimethylhydroxy-
glutaconic acid with hydnodic acid at 130* in sealed
tubes. It crystallises from water in prisms, melts at 148,
and is not reduced by sodium amalgam in the cold.

The following compoundii have also been prepared :—
Btkylic y-bromomitkyUtkylacitoacitatt. —


boiling at i64<> under 75 m.m. pressure; HkyUe
y-cyanomitkyUtkylaectoacitats, —


boiling at 158** under 35 m.m.; aa-mcikylitkyl^kydroxy*
glutacomc acid, COaHCIi:C(OH)*CMe£fCOtH, melting
at 164'' ; itkylic y-bromodictkylacitoacctaU,'^

boiling at z8o" under 100 m.m. pressure ; itkylic y cyano*
diitkylacitoacitati, CN-CHa'CO'CEta'COaEt, boiling at
158° under 75 m.m. pressure; aa-diitkyl-fi-kydroxy'
glutaconic acid, COaH'CH:C(OH)'CEta*COaH, melting
at i59».

Different results are obtained by the hvdrolysis of these
nitriles by means of sulphuric acid and of methyl alcoholic
potash; moreover, the produds of the redudion of the
hydroxyglutaconic acids with hydnodic acid differ with
the conditions. The author is engaged in investigating
these readions, as well as the behaviour of the y-nitriles
of ethylic acetoacetate and its derivatives generally.


Commifcial Organic Analysis. A Treatise on the Proper-
ties. Proximate Analytical Examination, and Modes of
Assaying the various Organic Chemicals and Produds
employed in the Arts, Maaufadures, Medicine, &c.,
with Concise Methods for the Detedion and Deter-
roination of their Impurities, Adulterations, and
Produds of Decomposition. By Alprbd H. Allen,
P.I.C, F.C.S., Past President of the Society of Public
Analysts, Public Analyst for the West Riding of
Yorkshire, the City of Sheffield, &c. Second Edition,
Revised and Enlarged. Vol. IV.— Proteids and Albu-
minous Principles. London : J. and A. Churchill, 7,
Great Marlborough Street.
With this volume Mr. Allen's extensive work is brought
to a conclusion, its produdion having extended over
fourteen years. The work is worthy of the author, and
has already proved of great value to the profession.

In the Preface to this volume Mr. Allen regrets that he
is unable to personally undertake the thorough revision of
the earlier part of the work as he had originally intended,
but proposes to publish an Appendix to each volume
which shall include the more important fads that have
accumulated during recent years. The partial revision of
the earlier volumes ia being undertaken by Dr. Henry
Leffmann, of Philadelphia, and vol. I. is already pub*
lished, while vol. II. will follow skorUy.

Much of the maUer in the preaeot volume Is of speeial
pradieal interest, being the outcome of tbo author's
analytical eitperience. Through the kindness of Dr. T.

Digitized by



Cketnkal Notices from Foreign Sources.

fOiiBiiteAL Mstrv,
1 Jtn. 6, 1899.

B. Thorpe, the Governmeot method for aoalyting milk
hai been included in full detail ; there is also a very com-
plete article on the absorption spedra of haemoglobin and
its allies, followed by a full description of the tpeAro-
•copes and micro-spedroscopes used, with pradical hints
on their manipulation.

At the end of the book will be found Addenda to many
of the articles, giving details of papers by different
authors, bearing on subjeds that have appeared in various
journals up to the present date.

Throughout the work the high standard of excellence
that charaaerised the first volume has been maintained.

MatUr, Emrgy, FofCi, and Work, By Silas W.

Holm AN. London and New York: The Macmillan

This is a well thought out and carefully written treatise
on the fundamental ideas of Physical Science. There is
nothing absolutely novel in the book, yet as a whole it is
a distina advance on any work of its class that we have
come across.

The author takes energy as his starting point, and
shows that force and work, both internal and external,
are fundions of it. Further, starting from the demand of the
kinetic theory of gases for a complex atom, and from the
necessity of the idea of space being filled with something
known as ether, be shows how the vortex-atom, so far as
it has been mathematically investigated, fulfils both de-
mands, and at the same time leaves energy in its position
as the one unchangeable and indestrudible fundion.

We can recommend this work to our readers as being
well worth reading.


Mots.— Alldegrtesofttmptratttrt art CtotlgradeuoleatotberwiM

Compiis Rmdus HAdomadaint det Sianea^ deVAeadimii
\det Seitncis. Vol, cxxvii.. No. 16, Odober 17, 1898.
A New Hydrate of Chromiom.~Q. Bang^.— This
new oxide of chromium is capable of several stages
of hydration, (i), Cr504.HaO, obtained already by
Pcligot. (2), Cr304.3HaO, a brownish yellow hydrate,
which the author prepares very rapidly by closing one of
the ends of the tube containing the brick-red hydrate
mentioned below. The tube is then placed in boiling
water, and the air pumped out until the hydrate loses
some of its water. This substance is comparatively
stable. (3), a brick-red unstable hydrate, of which the
author's analyses have led him to suppose contains four
molecules of water.

Adtion of Soda Ammooium on Arseoic— C. Hugol.
—The author, when aaing upon phosphorus with soda
ammonium, obtained different compounds if the phos-
phorus or the soda ammonium was in excess, but in his
present research with arsenic he can only obtain the one
compound AsNajNHj. To prepare this latter substance
the sodium and arsenic are both very pure. They are
contained in one branch of a double sealed tube, which
also contain liquid ammonia gat. A brick-red body is
formed, which is slightly soluble in liquid ammonia gas,
imparting to it a greenish yellow colour. On evaporating
the ammonia veiy minute crystals are deposited.

Researches on lodated Borates. — H. Allaire.—
Cbloroborate of magnesium, which constitutes natural
boracite, can be considered as the starting point of a
series of compounds of the same crystalline form> in

which tiie chlorine can be replaced by iodine, and the
magnesium by sine, cadmium, manganese, nickel, cobalt,
or iron. These compounds are prepared by ading with
the vapour of the iodide of the metal on the corresponding
borate, at a high temperature and in a current of carbon
dioxide ; on cooling, crystals of the boracite separate
out. The author has prepared the following saJts : —
6Mg0.8BaOsMgIa. 6ZnO.8BaO5.ZnIa. 6Cd0.8BaOsCdIa,
6Mn0.8Ba03MnIa. 6NiO.8BaO3.NiIa, 6CoO.8BaO3.CoIa,
6Fe0 8Ba03.FeTa.

Solubility of Campbor.^C. Israti and A. Zabaria.—
The authors have observed, in the course of synthetic
experiments with camphor, that the latter is soluble in
water and in hydrochloric acid, which probably transforms
it into its derivative-—






^C— C

^C— OH









by dired addition. If to the solution of camphor in con-
centrated hydrochloric acid a little water is added, a slight
precipitate is produced, which dissolves in excess of the
same liquid. This is probably due to separation of the
body into camphor and hydrochloric acid, the camphor
dissolving in excess of water. It is, however, stated by
some that camphor is almost insoluble in water. The
density of an aqueous solution of camphor at 15^ has
been found equal to 1*00071. This solubility has been
confirmed by the polarimeter; an aqueous solution of
camphor saturated in the cold, contained in a tube 22 cm.
long, gave (a)o""0'4^. As regards the combination of
camphor with hydrochloric acid, the body is decomposed
by the least trace of water, but the melting-point (about
243®) is much lower than that of camphor. It was also
observed that camphor was the most soluble in this acid
in the cold.

Researches on Incandescent Bledlric Lamps
charged with a Mixture of Marsh Qas and Air.-^
H. Couriot and J. Meunier. — A description is given of a
method of introducing a mixture of marsh gas and air,
in the most explosive proportions, into eledric lamps
during incandescence. It was found that the incandes-
cence of the filament was at once obscured except at one
point, where, in a minute or so, rupture occurred with a
faint spark. In no case was there an explosion of the
mixture of air and methane ; but combustion had occurred,
as was shown by the produdion of water and carbon di-
oxide, and the disappearance of inflammable gas inside
the lamp. Hence the spark, which passed at the moment
the filament was ruptured, remained without effed. It
has previously been pointed out that incandescent metal-
lic threads are powerless to cause the explosion of the
most explosive mixtures ; the same is the case with the
lamp filaments.

No. 17, Odober 24, 1898.
Properties of Calcium.— Henri Moissan.^The author
further examines the calcium, the preparation of which
was announced in a previous paper. He determines the
fusing-point of the metal, by heating it carefully and
gradually in a vacuum, to be about 760°. On solidifying
the liquid formed, a non-crystalline and soft form of cal*
ciom results. The density of the crystalline form is 1*85,
whilst non-crystalline calcium sinks in propyl iodide of
density 1*78, and floats in allyl iodide of density 1*87.

Digitized by


^"jSSTiS^ } Chemical Notices pnm Foreign Sources.

The non-crystalline form Bcratchet lead, but not chalk.
Calcium crystallises in hexagonal plates or derived

Online LibrarySir William CrookesThe Chemical news and journal of industrial science; with which ..., Volume 79 → online text (page 3 of 92)