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CHEMICAL NEWS,

Schools of Chemistry. Sept. 15, 1876. 3

Analytical and Practical Chemistry.

117

LABORATORY COURSES.

£ s.

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Fees.

Perpe-
Course. tual.
One

2

2

The Chemical Laboratories will be open for Students daily from 9.30 a.m. until 4.30 p.m., except on Saturdays, when they will be closed at 12.30 p.m.

Fees for the Session-For six days per week, £21 ; for four days per week, £17 175.; for three days per week, £13 13s. Students entering the Laboratory Class at or after Christmas will be charged two-thirds of the fees for the whole Session.

Fees for shorter periods--For six months, £17 178.; for five months, £15 155. ; for four months, £ 13 138.; for three months, £10 ios.; for two months, £7.78.; for one month, £4 4s. Students entering under this scale are entitleå to work on every day during the week.

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ROYAL COLLEGE OF SCIENCE FOR IRELAND,

STEPHEN'S GREEN, DUBLIN.
Professor of Practical and Theoretical Chemistry.-R.
Galloway, F.C.S.

Professor of Experimental Physics.-W. F. Barrett,
F.R.S.E., F.C.S.

The Chemical and Metallurgical Laboratories, under the direction of Mr. Galloway, are open every week.day during the Session, except Saturday. Instruction is given in the different branches of Analytical Chemistry, including Assaying, and in the methods for performing Chemical Research. Fee, for the Session of nine months, £12; or for three months, £5; or for one month, £2.

There are four Royal Scholarships of the value of £50 each yearly, with Free Education, including Laboratory Instruction, tenable for two years; two become vacant each year; they are given to Students who have been a year in the College. There are also nine Exhibitions attached to the College, of the yearly value of £50 each, with Free Education, including Laboratory Instruction. tenable for three years ; three become vacant each year.

A Diploma of Associate of the College is granted at
the end of the three years' course.
The Session commences on Monday, October 2nd.
ANDERSONIAN UNIVERSITY, GLASGOW.

CHEMICAL LECTURES AT LONDON HOSPITALS.

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£ s.

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M. Tu. F., II
M. W. F., 10
Da ly, 10

M. Th. S., 9
Mr. Bloxam and M. W. F., 104 5 5

M. W. F., 3
M. F.
Tu. Th. S., 10
Tu. F. S.
M. W. F., 10

to i
Dr. Russell
Mr. Heaton
Dr. Noad
Dr. Debus

Mr. Hartley
6 6 Dr. Wright
8 8 Mr. W. Foster

Dr. Bernays

& Dr. Graham

Dr. A. Dupré
£ S..
5 5 7 7
7 7 10 10

£ s.
M./Tu. W. Th., 7 7 7 7 Dr. Tidy

5
M. W. F., 9
M. W. F., II
Tu. Th. S., II)
M. W. Th., 4
M. W. Fr., 9
Tu. Th, F., 12

W. Th. F., 3
University Coll. & Hosp. Dr. Williamson, F.R.S., Daily (ex. S.)II 7 7 9 9 Dr. Williamson Daily (ex. S.)11 4 4

II
Dr. Debus, F.R.S., and Tu. Th. S., II 5 5
Dr. Russell, F.R.S.
Mr. Heaton
Dr. Noad, F.R.S.

Dr. Stevenson
King's College and Hosp. Mr. Bloxam, F.R.S., Th. S., 10}

and Mr. Hartley
Dr. Wright
Dr. Greenhow
Dr. Tidy

and Dr. Graham Dr. Bernays

Dr. Dupré, F.R.S. St. Bartholomew's Hosp.

and College ..
Charing Cross Hospital

and College ..
St. George's Hospital
Guy's Hospital
London Hospital
St. Mary's Hospital
Middlesex Hospital
St. Thomas's Hospital

and School ..
Westminster Hospital ..

Lecturers on
Chemistry

DEPARTMENT OF SCIENTIFIC CHEMISTRY.

Professor of Chemistry.-W. Dittmar, F.R.S.E., &c.

Young Professor of Technical Chemistry:-Dr. E. J. Mills, F.R.S.

CHEMICAL LECTURES, CLASSES, AND

LABORATORY INSTRUCTION.

Chemical Schools and

Colleges.

BERNERS COLLEGE OF CHEMISTRY AND THE EXPERI-
MENTAL SCIENCES, 44, Berners Street, W.-Prof. E. V.
Gardner, F.A.S., M.S.A. The Laboratory is open morn-
ing and evening throughout the year.

BIRKBECK LITERARY AND SCIENTIFIC INSTITUTION.
Mr. G. Chaloner, F.C.S. Tuesdays, 8.30 to 9.30 p.m.
Manipulation and Analysis, Saturdays, 7 to 10 p.m.
City of LONDON COLLEGE, 52, Leadenhall Sireet, E.C.

SCHOOL OF PHARMACY OF THE PHARMACEUTICAL So-Chemical Lecurer, Thos. Eltoft, F.C.S. Mondays, ciety of Great BRITAIN, 17, Bloomsbury Square.— The 7.30 to 8.30 p.m. Fee 6s. per term, or 155. per session. school opens on Monday, the 2nd of October. Lectures

NORTH LONDON SCHOOL OF CHEMISTRY AND PHAR- on Chemistry and Pharmacy, by Professor Redwood, on MACY, 54, Kentish Town Road, N.W.-Mr. J. C. Braith Monday, Tuesday, and Wednesday mornings, at 9 a.m. waite. The classes meet daily at 8 p.m. Fee ios. 6d. The Laboratories for Practical Instruction in Chemistry per month. The Laboratory is open for Instruction in as applied to Pharmacy, &c., under the direction of Prof. Practical Chemistry.

Attfield, will be open daily at 10 a.m. throughout the ROYAL POLYTECHNIC College.-Chemical Lecturer, / Session. Mr. Thomas Eltoft, F.C.S. The Annual Course consists

South LONDON SCHOOL OF CHEMISTRY, 325, Kenof three terms, each averaging ten Experimental Lectures. nington Road.Dr. John Muter, F.C.S: Daily, at 10 a.m. 7.30 p.m. Fee 6s. per term, Session 155. Practical Che- The Laboratory is open daily for Practical Instruction. mistry, T. Eltoft, F.C.S.; fee, 12s. per term.

BIRMINGHAM.- MIDLAND INSTITUTE.—Mr. C. J. WoodROYAL VETERINARY College, Camden Town.-Pro. ward, B.Sc. Tuesday and Thursday, at 8 p.m.; Friday, fessor of Chemistry, Mr. R. V. Tuson.

at 7; and Saturday, at 3.

118

CHEMICAL NEWS, Development of the Chemical Arts.

Sept. 15, 1876. BIRMINGHAM.- Queen's College.-A. C. Bruce, M.A. | Rhenania, the latter experimentally). According to Tuesday, Thursday, and Friday, at 12.

Deacon's statement more than 1000 kilos. of chloride of LIVERPOOL ROYAL INFIRMARY SCHOOL OF MEDICINE. lime at 35 per cent are obtained from 1500 kilos. of salt, -J. Campbell Brown, D.Sc. Lond.,, F.C.S.

with a consumption of 1000 kilos. small coal. A small School of Technical CHEMISTRY, 7 and 9, Hackin's portion of the hydrochloric acid gas is lost from causes Hey, Liverpool. – Mr. A. Norman Tate.

9.30 a.m.

not as yet fully ascertained, but the portion which passes Evening Laboratory Instruction.

undecomposed through the apparatus is entirely recovered. COLLEGE OF CHEMISTRY, LIVERPOOL - Mr. Martin Besides Deacon's process several other proposals have Murphy, F.C.S. The Laboratories are open from 10 a.m. been made for obtaining chlorine, and in some cases with to 5 p.m. daily.

out the rise of manganese, but they have not been adopted Leeds Mechanics' INSTITUTION.-Mr. G. Ward, F.C.S. in practice.

MANCHESTER Grammar School.-Mr. Francis Jones, Thus Macfarlane* hoped to obtain soda and chlorine F.C.S., F.R.S.E.

simultaneously by passing air over an ignited mixture of MANCHESTER MECHANICS' INSTITUTION.-Mr. M. A. copperas and salt. Sulphate of soda and ferrous chloride Watts, M.A. Friday, 7.15 p.m.

are formed, which latter is converted into iron oxide and QUEENWOOD College, near Stockbridge, Hants.—Mr. chlorine by the oxygen. The mixture of sulphate of soda E. W. Prevost, Ph.D., F.C.S., F.R.S.E.

and oxide of iron on reduction with coal and lixiviation SHEFFIELD BOROUGH Analysts' LABORATORY, 1 and 3, with water yields sodium hydrate (easily convertible into Surrey Street. — Mr. A. H. Allen, F.C.S. Day and soda) and iron sulphide which is reconverted into copperas Evening Classes.

on exposure to the air. Clemmt endeavoured to use SHEFFIELD SCHOOL OF Medicine.—Mr. A. H. Allen, chloride of magnesium for the preparation of chlorine; he F.C.S.

mixed the magnesium chloride with manganese and de

composed it by a current of superheated steam. UNIVERSITY OF ABERDEEN.-- Prof. J. S. Brazier.

Chloride of lime, the only form in which free chlorine ABERDEEN School of Science AND Art Mechanics' is found in the market, has latterly been the subject of a INSTITUTION.—Mr. Thomas Jamieson, F.C.S.

number of published papers, which have not led to any UNIVERSITY OF EDINBURGH.-Prof. A. Crum Brown, material change in the manner of its preparation. The F.R.S.E.

causes of its spontaneous decomposition, sometimes SCHOOL OF Medicine, EDINBURGH.—Dr. Stevenson attended with explosions, and formerly not infrequent, Macadam, F.R.S.E., and Mr. Falconer King.

have been investigated. To avoid such 'misfortunes it is Glasgow UNIVERSITY.-Prof. J. Ferguson.

recommended not to saturate the lime when too hot, and Glasgow MechaNICS' INSTITUTION.—Mr. R. R. Tat- not to carry the process to the uttermost attainable point, lock, F.R.S.E., F.C.S.

and also not to pack it in barrels when still too recent SCHOOL OF CHEMISTRY, 138, Bath Street, Glasgow.- and too moist. The gas which occasions the explosion Dr. Wallace, Mr. Tatlock, and Dr. Clark. Day and of the chloride of lime casks has been found to be oxygen, Evening Classes.

and on such spontaneous decompositions the mass of the Chemical LABORATORY, 144, West Regent Street, compound is converted into a mixture of chloride and Glasgow.—Dr. Milne. Day and Evening Classes. chlorate of calcium. Interesting dissertations of a more

ANALYTICAL LABORATORY, 88, Hope Street, Glasgow. scientific character concerning the nature of chloride of lime —Dr. A. T. Machattie, F.C.S. Day and Evening Classes. I have been published by Kolb, Riche, Bobierre, Scheurer

Kestner, Tschigianjang, Fricke and Reimer, Crace-Calvert, QUEEN'S COLLEGE, Belfast.--Dr. Andrews, F.R.S., &c. brief, as the results of these researches are in part, at

and Göpner, which unfortunately cannot be reported on in Queen's COLLEGE, CORK.—Dr. Maxwell Simpson. Queen's COLLEGE, Galway.--Dr. T. H. Rowney.

least, contradictory. The final solution of the question as ROYAL COLLEGE OF SURGEONS IN IRELAND.- Dr. C. A.

to the constitution of chloride of lime is by no means Cameron.

solved. UNIVERSITY OF DUBLIN.-Dr. J. Emerson Reynolds.

(To be continued). DUBLIN, CARMICHAEL SCHOOL.—Dr. C. R. C. Tichborne.

ON THE ELECTROLYSIS OF THE

DERIVATIVES OF ANILINE, PHENOL, REPORT

NAPHTHYLAMIN, AND ANTHRAQUINON.

By M. F. GOPPELSROEDER. DEVELOPMENT OF THE CHEMICAL ARTS DURING THE LAST TEN YEARS.* I have completed my first experiments on electrolytic

aniline-black, and I am in a condition to give the numerical By Dr. A. W. HOFMANN.

results of my analyses, and the rational formula to which (Continued from p. 87.)

they seem to lead. Quite differently from the salts of

aniline behave the salts of crystallised toluidin and also the Chlorine, Bromine, Iodine, and Fluorine.

salts of pseudotoluidin. The former furnish at the positive By Dr. E. Mylius, of Ludwigshafen.

pole a brown matter, soluble in alcohol and dyeing silk

and wool a yellowish brown. Pseudotoluidin distinguishes When Deacun's process was first made known its in- itself from it very plainly, since on electrolysis we obtain dustrial pra&icability was strongly doubted. The prin at the positive pole a reaction which agrees with that cipal difficulties were considered to depend on the which is obtained by chloride of lime. It forms a violet regulation of the temperature, the enormous volume of colour, which is changed by dilute nitric acid or by the gases to be dealt with, and the considerable consumption solution of permanganate of potash to a red colour. The of fuel. Since, however, the two former obstacles have mixtures of the bases aniline, toluidin, and pseudotoluidin been overcome by the inventor in the manner described, behave differently from the separate bases. Thus an the process seems more and more available. In Great aqueous solution of 1 molecule of hydrochlorate of aniline Britain at least 13 establishments are already working on with 2 molecules of hydrochlorate of toluidin is coloured the new process, and in Germany 2 (Kunheim and the red at the positive pole. Commercial aniline imperfectly • “Berichte über die Entwickelung der Chemischen Industr'e

* Macfarlane, Dingl. Pol. Fourn., clxxiii., p. 129. Während des Letzten Jahrzchends."

+ Clemm, Dingl. Pol. Journ., clxxiii., p. 127.

ON THE

CHEMICAL NEWS,

Certain New Salts of Bismuth. Sept. 15, 1876.

119 saturated with sulphuric acid, in an aqueous solution, mogen or of its electrolytic product. We shall thus with an addition of ammonia, gave, at the dehydro- arrive at substitutions by alcoholic radicals and by the genising pole as a principal product, a red colour, and as phenyl series, just as we succeed by the aid of nitric acid a secondary product a violet" colour. Methylanilin gives or nitrates in producing at the positive pole nitro-derivawhen employed in the form of its salts a violet colour at tives and at the negative pole nitroamido-, amido-, and the positive pole. I have otherwise observed, according even azo-derivatives. The chemistry of colouring-matters to circumstances, other colourations, among them a blue. will find in the researches of which I have spoken, a field Diphenylamin gives, if one of its salts is submitted to so much the more fertile as the oxidations and the deelectrolysis at the positive pole, a blue product soluble in hydrogenisations play the most important part in the proalcohol. Mixtures of diphenylamin and of ditoluylamin duction of colours.-Comptes Rendus. or of diphenylamin, ditoluylamin, and phenyltoluylamin such as are employed to produce the blue colours called diphenylamin blue, or, according to theory, triphenylated ON CERTAIN NEW SALTS OF BISMUTH, rosanilin blue, give, if submitted in the state of salt to a

AND THEIR EMPLOYMENT IN THE galvanic current, this beautiful blue colour soluble in alcohoi. Methyl-diphenylamin which, as Bardy has

DETECTION OF POTASH. shown, yields, with different oxidising agents a blue or

By A. CARNOT. violet colouring matter, undergoes the same transformation in the electrolytic way. Phenol, in an acidulated I HAVE succeeded in preparing certain new salts of bis. aqueous solution or in the form of phenate, gives rise muth, which are distinguished among all the salts of the at the positive pole to a brown body. The salts of same metal with mineral acids, by complete solubility in naphthylanin decomposed by the current, in a neutral or water. These are double hyposulphites of bismuth and acid solution, give rise to naphthylamin violet. Anthra- alkalies. I shall indicate the method of preparation and quinon has attracted my attention. I sought first to trans- the properties of these salts, and shall show that they are form it by electrolysis at a low temperature into alizarin and capable of a very interesting application in analytical the latter into purpurin,, but without success. I com-chemistry. If into a slightly acid solution of chloride of menced then a new series of experiments, operating at a bismuth we pour a concentrated solution of hyposulphite high temperature. Meeting anew with great difficulties, of soda, the liquid immediately takes a yellow colouration; I obtained, however, a result which encourages me to it remains otherwise perfectly clear, and it even resumes a continue my studies. I observed that on operating with complete limpidity if it was at first a little dull for want of caution a part of the anthraquinon is transformed into acid. It may be afterwards mixed with water in any alizarin. This transformation takes place on intro. quantity without there being produced any turbidity, producing into a very concentrated solution of caustic potash vided that we employ a sufficient quantity of hyposulphite anthraquinon reduced to a very fine powder, passing the out 3 grms. to i of bismuth). This liquid, left to itself, galvanic current and heating almost to the melting point changes gradually, and so much the quicker as it is more of potash. The mass is coloured at first red and then concentrated. There is a deposit of sulphide of bismuth violet by the formation of alizarate of potassium. But and a formation of sulphates, a reaction which is easily this colouration is rapidly replaced by a new red coloura- explained by the decomposition of hyposulphite of bistion, which soon changes to a yellowish brown and even muthto a deep brown, and consequently we obtain a violet

Biz,03,3S202+3H0=Bi2S2+3(SO3,HO). product mixed with unchanged anthraquinon and with Heat favours this decomposition and produces a deposit brown electrolytic products. If we continue to heat it the of sulphide in small black crystalline grains, which, under mass becomes more and more clear and finally white. If the microscope, present a cubic form. We may add any at the moment when the last red colouration presents quantity whatsoever of alcohol to the solution which has itself we reverse the current the mass again becomes just been prepared, or pour hyposulphite of soda into an violet, then red and yellowish, because without doubt alcoholic solution of chloride of bismuth without obtaining anthraquinon and even anthracen are formed again. Iany precipitate. But we must remark that, if alone, the may say, moreover, in a general manner that if we do not hyposulphite of soda gives immediately a white precipitate go too far with decompositions, we may by reversing the in alcohol, where it is almost insoluble. The compound poles of the battery regenerate at the new negative pole formed, which is a double hyposulphite of bismuth and of the modified bodies, and reproduce at the new positive soda, is thus distinguished at once both from the ordinary pole the transformations that were previously produced at salts of bismuth by its solubility in water and from hypothe opposite electrode. In the electrolysis described of sulphites by its solubility in alcohol. A small quantity of the derivatives of aniline, phenol, and naphthylamin, the chloride of potassium added to the perfectly clear alcoholic positive pole plays the principal part. In the ele&rolysis liquid, produces immediately an abundant precipitate of a of anthraquinon it is at the negative pole that the violet siskin yellow, which collects easily, especially after some colouration commences and remains most intense during moments agitation. There is not produced, on the conthe whole of the operation. All the experiments of which trary, any precipitate in presence of chlorides of sodium, I have just spoken depend on the decomposition of water lithium, ammonium, calcium, magnesium, aluminium, or an alkaline derivative by the current. It is the elec. iron, manganese, &c.—in a word, all usual metals, which trolytic oxygen which acts in dehydrogenising, or in other are not precipitated by sulphuretted hydrogen. Only the cases it is the oxyhydryl of the potassium or of the sodium chlorides of barium and of strontium give white precipi. which is substituted for the hydrogen of the chromogen. tates in an aqueous or alcoholic solution of hyposulphite.

Up to the present time I have turned my attention The reaction of the salt of potash is therefore quite charac. especially to the principal products, without losing sight teristic. It has seemed to me calculated to furnish a very of the secondary products, the study of which is necessary sensitive and very rapid process for the detection of this to arrive at a clear idea of the metamorphoses which base, a detection which is tedious and delicate by the protake place. It is also necessary to observe the gaseous cesses at present in use. It succeeds not only with a products. The action of the current on mielted organic bodies, solution of chlorides but also with a mixture of chlorides proceeding as we do in mineral chemistry, will present and nitrates, and even with nitrates alone, chlorine playing especially great difficulties, whether because heat alone no part in the formation of the precipitate. It is, on the decomposes them, or because the electric conductibility is contrary, more or less incomplete in the presence of too weak; but the study of these actions ought not to be sulphates, and doubtless cannot be applied directly for the neglected. We ought to try also to arrive at the simul- detection of potash in this class of salts. We know, howtaneous decomposition of other bodies added to the ever, that it is the same with the best processes known up electrolyte, to arrive at substitution products of the chro- to the present time for the separation and the determina

I20
Chemical Constitution of the Alcohols. {

Sept. 15, 1876. tion of this base. All require a previous transformation at the meeting of the British Association in Edinburgh, of sulphates.

some years ago, I drew attention to the existence of two Double Hyposulphite of Bismuth and Potash.-In view closely-related organic family groups, one of them having of an application of the potash compounds in analytical for its parent molecule the ethylic and the other the glychemistry, I have made them the subject of a special colic alcohol. I took also the opportunity of pointing out study. Here are the principal results : The yellow pre- the natural order of succession, in which the basic and cipitate obtained in alcohol is easily soluble in water; its acid members of each group are descended from their solution is greenish; it is, on the contrary, very insoluble respective parent alcohols, and to enlarge on the evident in alcohol. We may then purify it from the salts which parallelism and intimate chemical relations subsisting besaturate it by receiving it at first on a filter, washing with | iween these two series of derivatives. It becomes now alcohol, then dissolving in a little water, and precipitating requisite for me to add thereto a third family group of anew by alcohol in excess. After one or two similar molecules, which have for their common progenitor the operations it may be considered as very pure. It may be glyoxalic alcohol. A simple comparison of these three then dried gently on the filter, and withstands afterwards, systems, as placed side by side in the annexed scheme, without change, a temperature of 100°. It keeps very will, I trust, enable the reader to grasp some of the chewell when dried, but changes rapidly if moist, notably in mical relations just referred to, while it will help to throw contact with the mother liquid, whence it has been pre- a bright and powerful light upon several obscure and discipitated, and which is, moreover, itself readily changeable. puted points, a full elucidation of which cannot fail to In these conditions, it is, at the end of some hours more prove of the highest theoretical value and importance.* or less mixed with sulphide of bismuth, which modifies Taking for granted that, within certain limits, the the colour and composition. The neutral solution of the formulæ embodied in the preceding scheme are well calsalt in water changes likewise and gradually deposits sul- culated to give a correct idea of the internal molecular phide. The salt precipitated by alcohol presents a crys- structure and arrangement of these three sets of deriva. talline aspect the more decided as it is formed more tives, I shall now, on the basis of these formulæ, proceed slowly. I have been able to obtain it distinály crystal to analyse a number of chemical reactions which-from lised on realising by divers methods a gradual mixture of the more or less striking physical and chemical properties the liquids. The difficulty always rests in the want of of the resulting compounds, as well as the deep mystery stability of the liquor, which ought, however, to remain a in which the majority of these reactions continue to be very long time in action for the formation of crystals; thus shrouded-have never ceased to be regarded with special we can scarcely avoid a little sulphide being mixed with attention and interest. In former papers on this subject the crystals of hyposulphite. The process which has (Chem. News, vol. xxviii., pp. 87 and 103) I have already given me the best results consists in making the aqueous had occasion to describe the molecular changes, when the solution of the three substances in the required propor- higher acid heterologues of the second and third family tions (about 1 part of chloride of potassium and 3 parts of groups make their appearance amongst the decomposition hyposulphite of soda in crystals to i part of metallic products of certain bibasic water salts. In particular I bismuth transformed into chloride) precipitating with occupied myself with tracing the various movements of alcohol and filtering to remove the mother-liquor, re-dis- one of the two basic hydrogen nuclei when the tartronatesolving in water, and adding alcohol to the solution, but without producing any turbidity; then we plunge into it a

H2O2. H2O2. H2O2.

F0202,2C203-2C203 dialyser, into which we pour concentrated alcohol so as to raise gradually the alcoholic percentage of the hyposul. is made by heat to split up into carbonic acid and the phite solution. There is formed on the sides of the vessel, glycolate, or when the mesoxalateand principally under the membrane of the dialyser,

H202. H2O2. yellow greenish crystals, very brilliant, presenting the

2C202,2C203–2C203 form of prismatic needles, very fine in general, and from is by the same agent made to resolve itself into carbonic 2 to 3 millimetres in length, but attaining sometimes acid and the glyoxalate ; and from these results I have 10 millimetres in length and 1 millimetre in diameter. been led to conclude that during the conversion of the These crystals keep very well in the air without any mesoxalate into the tartronate by means of nascent hydro. alteration. I have made several analyses of the crystal- gen, that clement must have expended its reducing lised salt or crystalline precipitate. They have always given energies upon the carbonous acid adjunct in preference to me results which correspond rigorously to the formula

the more highly oxidised oxalic acid principal, a mode of Bi203,3 S202+3(KO,S202)+2HO.

viewing which is strongly supported by the fact that both or in hundredths

the oxalate and the glyoxalate can be speedily transformed Hyposulphurous acid ..

42'25

into the glycolate by means of this powerful reducing Bismuth oxide

34'33

agent. It is, noteworthy, however, that on treating the Potassa ..

20*78

latter compound with oxidising agents the resulting proWater

2.64

duct is not, as might be expected, the glyoxalate, but the

so-called glyoxylate, clearly showing that the two moleIt remains for me to indicate in what manner the acid adjunct with elimination of two water molecules,

cules of oxygen, instead of regenerating the carbonous formation of this salt may be practically utilised for the prefer to combine direAly with the formic acid principal. separation and the determination of potash.

İf now we bring a second pair of oxygen molecules to act upon the latter compound, the resulting product is un.

doubtedly the oxalate, clearly showing that it is the car. The CHEMICAL CONSTITUTION OF THE HIGHER ACID HETEROLOGUES

* The chemical formulæ employed are generally the double of the ordinary formulæ. The notation is simplified by means of symbols

representing hydrogen or bicarbon nuclei variously modified by their ETHYLIC, GLYCOLIC, AND GLYOXALIC

chemical union with different hydrocarbon and halogen adjuncts. ALCOHOLS,

Strokes placed above these symbols indicate the number of substi

tuted bromine molecules in the associated hydrocarbons. The fol.

STANDPOINT lowing is a list of the symbols embodied in the formulæ of the OF THE “ TYPO-NUCLEUS" THEORY.

text :-(1.) Formyl in the two isomeric modifications, F0=2C2; H,

and 2Fo=2H ; 2C, (bromformyl, 2Fo=2Br; 2C2). (2.) Methyl, By OTTO RICHTER, Ph.D.

Mez=2H,C,; Hz. (3.) Ethyl, Etq=2H.C.; Hz. (4.) Acetyl 'in

two isomeric modifications, Ácy=2H,C.; H, and 2Ac=2H,C,; 2C, În a paper on the chemical constitution of glycolic alcohol (bromacetyl, zāc=2H,C,Br; 2C, ; dibromacetyl

, ZAC=2HC,Brą; 2C, and its heterologues, which I had the honour of reading i tribromacetyl, 2Ac=2C,Brg; 2C2). H =2; C =12; 0,=16.

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100'00

OF THE

AS VIEWED AND INTERPRETED FROM THE

CHEMICAL News,
,
Chemical Constitution of the Alcohols.

121 SYNOPTICAL ARRANGEMent of Chemical FORMULÆ EXPRESSING THE CHEMICAL CONSTITUTION OF THREE

CLOSELY-RELATED ORGANIC FAMILY GROUPS.
First Group
Second Group

Third Group.
H2O2.
H2O2. H202.

H2O2.
Ethylic alcohol, Et202
Glycolic alcohol, F0202,Me202

Glyoxalic alcohol, 2C202, Mezo
H202.
H2O2. H202.

H202. De-ethylic alcohol, Ac202 De-glycolic alcohol, F0202, F0202

De-glyoxalic alcohol, 2C202, F020, (acetylic). H202. H2O2. H202.

H202. Acetite,

2AcO
Glycolite,
F0202, 2F00
Glyoxalite,

2C202, 2Foo (acetaldehyd). (oxyacetaldehyd).

(glyoxal).
H2O2.
H2O2. H2O2.

H2O2. Acetate,

2ACO3
Glycolate,
F0202, 2F003 Glyoxalate,

2C202, 2F003
H202
H2O2, H2O2.

H2O2. Acetoate,

2 AcOg
Glycoloate, F0202, 2F005

Glyoxaloate, 2C202, 2F00s (oxyacetate). (glyoxylate).

(oxalate). bonous acid adjunct which has been regenerated with while the third derivative, although endowed with the elimination of two water molecules. In connection with attribute of stability, is, under certain conditions, prone the term "glyoxylate" the reader will not fail to recall to pass into the ß variety – to mind a very keen and spirited controversy, regarding

H202. the true formula of that water-salt, which was inaugurated

=2C2Br2,2F00g. last year at one of the meetings of the London Chemical Society, where Messrs. Perkin and Debus took a very As regards the molecular changes attending these me. prominent part. Having carefully pondered this inte tamorphoses they are believed to consist, with reference resting problem from the novel and more elevated stand to the first two derivatives, in the splitting up of the point of my " Typo-nucleus ” theory, I feel confident that brom- or dibrommethyl adjunct into formyl-bromide, which a condensed report of the results of my speculative labours instantly re-unites as adjunct with the residual formic or will be welcomed by many as a pleasant and profitable bromo-formic acid principal ; but with reference to the interlude, while fresh data are being gathered on the rich third derivative the molecular changes are held to consist and productive soil of experimental research. I have in the splitting up of the tribrommethyl adjunct into therefore bethought myself of embodying an epitome of bromo-carbonous acid, 2C2Br2, which, by its transition my researches in the present communication, and shall at from the hydrocarbon type into the acid nucleus type, be. once proceed to state the leading topics of my programme, comes now qualified to re-enter into chemical union with which I have found it advisable to divide into two parts. the residual bromo-formic acid principal. I have not as In the first part I shall expound the molecular changes yet succeeded in gathering reliable data for studying the accompanying the substitutional action of bromine and action of bromine on the glycolate and glyoxalate which, perbromide of phosphorus on the water-salts of acetic, in theory, ought to give rise to the bromo-glycolate and glycolic, glyoxylic, glyoxalic, and oxalic acids. In the bromo-glyoxalate. The first of these derivatives may, second part I shall expound the molecular changes which however, be got in another way,-namely, by treating ensue when the dry or dissolved combinations of the the glyoxylate with perbromide of phosphorus, and bromacetic, dibromacetic, and bromoglycolic acids with decomposing the resulting bromoxyglycolyl-bromide, the alkalies, oxide of silver, and oxide of ammonium are F02Br2,2F004Br, with water, where it is plain that the subjected to the decomposing influence of temperature. molecular changes must consist in the replacement by Let us then, in the first place, inquire into the contents hydroxyl of that particular bromine molecule which forms of the first part of my programme.

a constituent element of the dioxyformyl-broniide prin

cipal; while the second may be got as an ether salt by PART 1.

treating the oxalate of ethyl and potassium,On the Principal Molecular Changes accompanying the

Et202.K202. Substitutional Action of Bromine and Perbromide of

2C202,2C204, Phosphorus on the Water-Salts of Acetic, Glycolic, (the ordinary oxalovinate of potash), with oxybromide of Glyoxylic, Glyozalic, and Oxalic Acids.

phosphorus, where the previously-formed glyoxalic ether Commencing with the acetate, its brominated deriva. | bromide, tives—whether obtained by the action of bromine on that

Et202. compound or by the more expeditious method of employing

2C202,2C2O3Br, acetic anhydride instead-are the following three :

may be supposed to pass more or less readily into the H2O2.

isomeric bromo-glyoxylate of ethyl, -
(1) The a bromacetate, 2ĀCO3,

Et202.
H202.

2C202,2F003.
(2) The a dibromacetate, 2ACO3,

Reverting again to the above-mentioned bromoxyH202.

glycolyl-bromide, the reader will bear in mind that its

formation depends upon the successive action of two And (3) The a tribromacetate, 2ACO3,

molecules of perbromide of phosphorus on the glyoxalate, bu: the first two derivatives are believed to be so entirely and, being impressed with the theoretical importance of destitute of the character of stability that they are immé- the fact that a third molecule of perbromide is yet capable diately made to merge into the isomeric modifications of acting substitutionally upon this derivative with proof the

duction of a body which is found to be identical in all H2O2.

respects with the dibromoxyacetyl-bromide as obtained B bromacetate = F02Br2,2F003,

by the action of the perbromide on the dibromacetate, I

have deemed it desirable of submitting to him a full H202.

analysis of the molecular changes which mark the various and the ß dibromacetate Fo2Br2, 2003,

stages of the process. In taking for my guide the analo.

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