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Abstracts of the Proceedings of the Chemical Society, Vol. 3, No. 36 |
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Proceedings of the Chemical Society, London,
Volume 3,
Issue 36,
1887,
Page 47-56
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 36. Session 1887-88. March 30th, 1887. Annual General Meeting. Dr. Hugo Miiller, F.R.S., President, in the Chair. The President delivered an address, of which the following is an abstract :-The number of Fellows of the Society is 1508, of whom 30 are honorary foreign membsrs. One foreign member, Professor A. Butlerow, has died during the year; and the Society has lost 12 Fellows by death :-Robert Alexander ; Dr. James Apjohn, F.R.S. ; Prof. F. S. Barff; Richard Cowper; M. G. Crossman; H. Sugden Evans; Rev. W. Flett; George Hirst; Dr. A. P. Price; J. A. Phillips, F.R.S. ; E. R. Southby ; and H. H. Watson. 20 Fellows have withdrawn:-W. E. Benton; T. P. Best ; L. M. Deane ; A. F. Dimmock : H.W. Field ; W. J. Puller ; A. E. Garrod ; Norman Graham ; Thos. Harrison ; Thos. Jamieson ; Herbert Jones ; Paul Mathews; P. B. Mills; J. D. McCarthy; Dr. A. P. Page; Dr. Robert Smith ; G. Tunbridge ; James Steel; A. H. Scott White; Philip Wright ; and Wm. Cort Wright. 28 Fellows have been removed on account of arrears:-F. H. T. Allan; P. S. Brown; Robert Blair; Henry Child; G. Crampton; John Dale; Dr. Arthur Gamgee ; A. M. Graham; G. Jarmain; R. H. Jude; F. Jordan; Wm. Marriott; J. E. Mayall; J. D. Mucklow; Dr. C. S.Marsden ; John McCarthy ; A. A, Nesbit ; F. J. O’Farrell ; Alfred Payne; A. W. Postans; J. E. H. Richardson; F. I. Scard; J. Steiner ; I<. Takemura; G. Valentine ; Stcphen Williams; and James Wilson. 110 new Fellows have been elected during the year.The number of Papers communicated to the Society since the last, anniversary meeting is the largest on record, being 118,or 5 in excess of the number read in 1880-11, and 14 in excew of the number read 48 -----.--last year. The President expresses the opinion that the Society has every reason to be satisfied with the share which it has contributed to the general progress of chemical science, adding that as we contem- plate the ceaseless activity in chemical research now manifested a11 over the world, and which from year to year is continually on the increase, we are, nevertheless, bound to recognise the fact that vast as the work thus accumulated may appear, there remains still much to be accomplished.The more the field is worked the richer will be the harvest. The number of Abstracts and Papers published in the Journal during the past five years are given in the following table :-1882. 1883. 1884. 1885. 1886. -__ --General and Physical Chemistry.. 219 205 237 331 235 Iiiorganic Chemistry. ........... 188 189 189 191 223 Mineralogical Chemistry ........ 135 204 192 201 223 Organic Chemistry ............. 837 739 939 1047 1056 Physiological Chemistry ........ 112 73 118 142 100 Chemistry of Vegetable Physio-logy and Agriculture ......... 2'70 163 324 218 160 Analytical Chemistry .......... 284 195 356 337 289 Technical Chemistry.. .......... 228 212 286 280 66 Total ........................ 2273 I 1980 2541 2747 2352 -Papers in Trmsactions.......... 65. 63. 57. 85. 85. After dwelling on the importance of the determination of physical properties, the President gave a brief review of the more noternorthy chemical investiga,tions of the year ; and reference was then made to the work of the City and Guilds of London Iiistitute for the advnnce- ment of technical education, with which the President of the Chemi- cal Society is ea oficio associated. Dr. Muller concluded his address with the following statement :-The mistaken notion is still too prevalent that technical education has to confine itself to t,he theoretical considerations of known technical processes, and that a more extended acquisition of scientific knowledge is not required. It is obvious that a pupil educated on these lines may find by the time he is able to enter on his practical career that the processes with which he has been made acquainted have in the meanwhile become obsolete, and unless his education has been sufficiently comprehensive to enable him to strike out new lines for himself, he will be ill fitt'ed to compete with those who have been educated on a wider basis.' Essential its it is to impart scientific knowledge to t'he future 49 manager, it is above all necessary to train him by practical work and research in the laboratory how to investigate a subject which may present itself in his daily occupation, whether it be some unexpected development in a new direction, or whether it be some new difficulty which confronts him in carrying out the processes under his direction.It is self-evident that such knowledge and such practical experience in carrying out investigations is not to be attained by merely attending one or two courses in the lecture room or in the laboratory. Those who mean to effectually qualify themselves for such functions can only accomplish this object by devoting years of patient and intelligent work under the guidance of the professor in properly appointed laboratories. Prof. Odling proposed that the thanks of the meeting be given to the President for his address, and that he be requested to allow it to be printed. This motion was seconded by Dr. Gladstone, and accepted with acclamation by the Fellows present ; the President acknowledged the compliment. Professor Ramsay moved that thanks for their important services be given to the Editor, Sub-editor, Abstractors, and Librarian ; the motion was supported by Mr.Dunstan. Mr. Groves replied. Dr. A. K. Miller and Dr. Rideal were then appointed scrutators, and a ballot having been taken, the following were declared elected as Officers and Council for the ensuing year :-Presidesd : W. Crookes, F.R.S. Vice-Presidents who laavefilled the ofice of President : Sir F. A. Abel, C.B., D.C.L., F.R.S.; Warren De La Rue, D.C.L.,F.R.S.; E. Frank- land, D.C.L., F.R.S.; J. H. Gilbert, Ph.D., F.R.S.; J.H. Gladstone, Ph.D., F.R.S.; A. W. Hofmann, D.C.L., F.R.S.; H. Miiller, Ph.D., F.R.S.; W. Odling, M.B., F.R.S.; W.H. Perkin, Ph.D., F.R.S.; Sir Lyon Playfair, Ph.D., K.C.B., F.R.S. ; Sir H. E. Roscoe, LL.D., F.R.S.; A. W. Williamson, LL.D., F.R.S. Vice-Presidents LI J. Dewar, M.A., F.R.S. ; David Howard ; H. McLeod, F.R.S.; Ludwig Hond; C. Schorlemmer, Ph.D., F.R.S. ; W. A. Tilden, D.Sc., F.R.S. Secretaries; H. E. Armstrong, Ph.D., F.R.S. ; J. Millar Thornson, F.R.S.E. Foreign Secretary : B’. R. Japp, M.A., Ph.D., F.R.S. Treasurer : W. J. Russell, Ph.D., F.R.S. Ordilzary Members of Council: Messrs. T. Carnelley, D.Sc. ; M. Car-teighe ; A. H. Church ; Frank Clomes, D,Sc. ; P. F. Frankland, Ph.D. ; R. 5.Friswell; E. Kinch ; R. Messel, Ph.D. ; H. F. Morley, M.A. ; J A. R. Newlands ; W. Rarnsay, Ph.D. ; Thomas Stevenson, M.D. The Treasurer, Dr.Russell, gave an account of the Society’s finan- cial condition. The receipts by admission fees and subscriptions had 50 been $2999 2s.; by sale of Joui-nd, $369 19s. 2d. ; by dividends on invested capital, $305 0s. 9d. The expenses on account of the Journal had been $2026 16s. 9d.; on account of the Abstracts of Proceedings, $163 4s. lld. : on account of the Library, S32.3 11s. 1Od. ; on account of the Catalogue, $249; the total expenses being $3416 14s. 2d.; $500 had been invested in Netropolitan Board of Works 3+ per cent. stock, and there was a balance in hand of $1301 10s. 3d. Mr. David Howard moved that the thanks of the Society be ten- dered to the Treasurer for his services during the past year; Mr. Friswell seconded the motion.The Treasurer in the course of his reply took occasion to point out that the expenses connected with the issue of the circular relating to the Imperial Institute and the collcc- tion of contributions thereto would not be borne by the Society, and that his connexion with the fund was a purely private one. Mr. J. Spiller proposed a vote of thanks to the Auditors, which was seconded by Dr. H. I?. Morley, and acknowledged by Mr. Wyndham Dunstan. A vote of thanks to the Officers, Council, and Committee, was pro-posed by &. Warington, seconded by Mr. Davies, and acknowledged by Dr. Armstrong. April 7th, 1887. Mr. William Crookes, F.R.S., President, in the Chair. Mr. A. H, F. Ruppel was admitted a Fellow of the Society. @ert,ificates were read for the first time in favour of Messrs.L. C. Daniell, The Brewery, West Bergholt, near Colchester ; Frederick William Freeman, Melbourne House, St. Albans ; Herbert James Gover, 28, Broad St,reet, Hanley, Staffordshire ; Edward Day Gravill, 106, Loughboro’ Park, Brixton, S.W.; Richard Nelson Jones, L.R.C.P., Swansea Hospital, Swansea ; Leonard James Reade, 12, Larches Lane, Wolverhampt,on; Frank Traphagen, Ph.D., Staunton, Va. The following Papers were read :-33. ‘‘ Researches on the Constitution of Azo- and Diazo-derivatires. 11. Diazoamido-compounds (continued) .” By R. Meldola, F.R.S., and F. W. Streatfeild. The authors describe the results of their experiments on the decom- posibion of the dinitrodiazoamido-compounds and their ethyl-deriva- 51 tives by cold chlorhydric acid.By a method described in the paper the products can be isolated and identified without the application of heat at any stage. The results show that the decomposition by cold acid takes place in the same manner as with hot acid, the most note- worthy instance being that of the unsymmetrical compound of m. p. 211"and its ethyl-derivative of m. p. 148",both of which yield the same mixed products as when hot acid is employed. Thus the former compound yields m-and p-nitrodiazobenzene chlorides and m-and p-nitraniline, and the latter yields the same diazobenzene chlorides, together with the two corresponding ethylnitranilines. The two ethyl- derivatives prepared respectively by the action of diazotised p-nitr- aniline upon ethyl-m-nitraniline (m.p. 187") and of diazotised m-nitraniline upon ethyl-p-nitraniline (m. p. 174-175") behave in an analogous manner when decomposed by cold acid, the first giving p-nitrodiazobenzene chloride and ethyl-m-nitraniline and the second m-nitrodiazobenzene chloride and ethyl-p-nitraniline. The mode of decomposition of the 187" m. p. ethyl-derivative and the facility with which it breaks up thus negatives the idea which had at first been formed as to this derivative being an amidoazo-compound. A more thorough examination of the substance has shown that it possesses all the characters of a true diazoamido-compound. It gives on complete reduction a mixture of ethyl-m-phenylenediamine and p-phenylene- diamine.A number of the salts of the dinitrodiazoamido-compounds are described in the paper, the chief result to which their examination has led being that only one atom of displaceable hydrogen is present in these compounds. It is pointed out in conclusion that the existence of three isomeric ethyl-derivatives containing p -and m-nitraniline residues is inexplicable by the generally received formula which admitls only of the two modifications :-This fact, combined with the difficulty which has hitherto been experienced in accounting for the identity of mixed diazoamido-com- pounds, has led Professor Meldola to propose a revision of the commonly accepted formulae of these compounds. DISCUSSION. Mp.GROVESasked Professor Meldola whether the mixed diazo-mmpound yielded practically the para- and meba-nitranilines in the Same proportions when it was acted on by cold and by hot hydro- chloric acid ; also whether different preparations of the compound yield the same results-that is, whether the substance is really hqmo-geneous.52 Mr. A. G. GREENasked Professor Meldola whether the individuality (3) (1) (4)of the compound C6H,(N0,)*N2H*C6Hp(NO2)and its ethjl-derivative of m. p. 147"was determined with certainty. Considering the ten- dency which certain nitro-compounds (e.g., m-and p-nitraniline) have of forming tolerably stable molecular compounds with each other with fixed melting point lower than those of either constituent, it seemed possible that this diazoamido-compound (and its ethyl-derivative) might ,be such (3) (1) (4) a molecular compound of the two isomers C,H,(NOz) *N*NH*C,H,(NO,) (3) (1) (4)and C,H4(NOz)*NH*N2*C6H4(N02).This would explain the decompo- sition by acids into m-and p-diazonitrobenzene and m-and p-diazo-nitrobenzene and m-and p-nitraniline (or their ethyl-derivatives).The ethyl-derivative of m. p. 147"would then be a compound of the ethyl-derivatives of m. p. 175" and 187". He suggested that the transference of .the N,-group from one amine to the other (especially in strongly acid solution as given in Professor Meldola's previous paper) might be explained by assuming that an inverse change to diazotisa- tion can occur in a solution of a diazo-compound, resulting in the partial reproduction of the amine and nitrous acid, which latter would then diazotise the second amine.Professor M&DOLA,in reply to Mr. Groves, stated that there was no doubt that the so-called unsymmetrical compound vdas a definite chemical substance and not a molecular combination of the dipara- and dimeta-compounds. This point had been fully considered in the paper, and the experiments which had led to this conclusion were described therein. With reference to the question whether the same quantities of decomposition products were obtained .from all the dinitrodiazoamido-compounds when decomposed by acid under similar conditions, he stated that quantitative experiments had not yet been made, but that it was proposed to extend the work in this direction.As far as could be estimated, however, by the appearance of the pre- cipitates (nitrobenzeneazonaphthols) and the nitranilines, it seemed that the compounds all gave about the same results. The question raised by Mr. Green as to the possibility of the unsymmetrical corn- pound being a molecular combination of the other two dinityo-compounds, was substantially the same as that pat by Mr. Groves, and did not therefore call for any further reply. With reference to Mr. Green's other suggestion, that diazobenzene salts might by a reverse action be transformed into aniline and nitrous acid, Professor Meld&, said that so far as he was aware there was at present no evidence in favour of such a view, and that even if this assumption were granted it would not help to explain any of the di6culties connected with the diazoamido-compounds. 53 34.“ Conjugated Siilphates and Isornoi-phous Mixtures of the Copper-magnrsium-gronp.” By P. C. Roy, l3.S~. Miss Aston and S.U. Pickering having recently called in question the accuracy of Volil’s conclusions, which are supported by Ram- melsberg’s investigation of 1854, the author has analysed the follow- ing salts, prepared according to Vohl’s directions :-(1.) Nickel-Cobalt-Potassium Sulphate. (2.) Zinc-Manganese-Ammonium Sulphate. (3.) Copper-Iron-Ammonium Sulphate. (4.) Copper-Cobalt-Potassium Sulphate. (5.) Copper-Magnesium-Potassium Sulphate. From the result it would appear (1) that whenever two sulphates of the copper-magnesium group are dissolved together in equal mole- cnlar proportions, with the requisite quantity of an alkaline sulphate, and the solution is left to evaporate spontaneously salts of the type le(M”S0, + M’&304+ 6H,Oj + y(M”S0, + M‘2S04+ 6H20)are always formed, x and y being small integers.Thus in (1)x :y = 2 :1, in (2) the ratio is as 9 : 2, and so on. The first crop of crystals as a rule does not conform to Vohl’s formula, in fact, in no single instance is there the ra:io of equality between x and y. This is strictly in accordance with the behaviour of isomorphous mixtures, for the first crop is always rich in the least soluble component. The author’s conclusions tally with hhose of Rammelsberg ; it is true that his analyses show that in many instances the component sulphates do not occur in exact molecular proportions, but this Rammelsberg justly attributes to the fact that it is often difficult to discriminate between any two successive crops.DISCUSSION. *Mr. PICKERINGsaid that Mr. Roy’s experimental results entirely confirmed those obtained by Miss Aston and himself, although the conclusions which he deduced from them were very different. It seemed inconceivable that mrlien solutions of the snlphates were mixed in the molecular proportions of 1: 1 the crystals obtained should consist of the salts in different but still definite proportions, whereas if they were not mixed in this simple proportion the crystals were indefinite in composition.Mr. Roy’s own experiments disproved such a view, for after the first few cryst’als had been deposited the solution would no longer contain the sulphates in the original propor- tion or 1:1,and yet Mi-. Roy contended that this solution continued to yield crystals of definite composition. The whole question 54 depended on whether an analysis of salts containing only 1.3 to 12 per cent. of the metals was sufficiently accurate to determine whether the salt was definite or not. Mr. Pickering considered that it was not so. By taking x and y in the above formulze to be small integers (not greater than 10) as Mr. Roy does, a formula could be obtained which would represent any indefinite mixture of the sulphates within the limits Gf analytical error.In the same way the crystals which Mr. Roy obtained from solutions of the copper and nickel salts mixed in indefinite proportions, and to which he says it would be absurd to assign any formula, would correspond exactly with the formula if11CuSO~,2NiS0~,13K2S04,78H,0, there were an error of only 0.25 per cent. in the determination of the copper or 0.44 in that of the nickel ; errors much smaller than some of those observed in duplicate analysis. The analysis of these salts, therefore, is quite incompetent to deterinine whether they are definite or not, it is only by performing whole series of experiments that conclusions of any value can be drawn, and these series, as 1\IIiss Aston and Mr. Pickering hare shown, prove clearly that the composition of the crystals varies continuously with variations in the circumstances under which they are produced.35. “ Suboxide of Silver, Ag4O.” By G. H. Bailey and G. J. Fowler. The authors have repeated the experiments of Wohler, and find no evidence of the formation of an argentous citrate when argentic citrate is heated to 100” in a current of hydrogen. The change is a progressive one, the citrate undergoing reduction with the formation of CO, and HzO. In an experiment in which argentic citrate had been exposed to hydrogen at 100” for 36 hours the residue after extraction with ether contained 85.8 per cent. of silver, and by carrying the reduction still further there would in all probability be a complete transformation into metallic silver, water, and carbon dioxide, along with itaconic or the kindred acids.The oxide precipitated from the aqueous extract by means of potash contains metallic silver, and is only obtained in quantities too minute to admit of a determination of the relation of silver to oxygen of sufficiently decisive character. Faraday’s suboxide of silver is also described, and found to be a modified form of ordinary oxide of silver. DISCUSSION. Dr. ARMSTRONGpointed out that at the recent Naturforscher-versammlung at Berlin, von der Pfordten of Munich had adduced evidence in favour of the conclusion that an argentous oxide may be obtained. 55 36. '' Action of Trimethylenebromide on the Sodium Compounds of Ethylic Acetoacetate, Benzoylacetate, Paranitrobenzoylacetnte, and Ace tonedicarboxylate." By W.H. Perkin (junr.), Ph.D. The sodium compound of ethylic acetoacetate, when treated with triniethylenebromidc, is converted into ethylic methyldehydrohexone- carboxylate, CH3-C-0'\ II ,a colourless oil boilingat 225". C00C2HbC CHZ4CH2*CH2 This ethereal salt 011 hydrolysis yields the corresponding acid, C7H,,03(m. p. 118O). When treated with hydrobromic acid in the cold, the ethylic salt is converted into alcohol, carbonic anhydride, and the bromide of acetobutyl alcohol, thus :-C,H,,O, + H20 + HBr = C02 + CZ&OH + CH3-CO*CHz*CHz* CH2* CHS*Br. The free acid, C7Hl0O3,on boiling with water, is converted quanbi- tntively into carbonic anhydride and acetobutyl alcohol, thus :-C~H~OO~+ HzO = C02 + CH,.CO.CH,.CH,.CH2*CH~*OH.Similar results were also obtained with the sodium compound of ethylic benzoylacetate ; the principal product of the reaction being an C,H,-C-O\ ethereal salt of the formula II \ (crystallineC0OC2H5*C*CH2*CH2*CH2 solid, m. p. 60'). c6&-C-o\ The corresponding acid, II \ (m. p. 150'))C00H*C*CHZ*CHz*CHz when treated with hydrobromic acid, yields the bromide of benzoyl-butyl alcohol, C6H5*C0,CH2.CH2'CH~*CHr*Er,and when boiled with water is decomposed into carbonic anhydride and benzoylbutyl alcohol, C'sHS*C0.CH2*CH2.CH2.0H. Similar derivatives were obtained from ethylic paranitrobenzoyl- acetate. The disodium compound of ethylic acetonedicarboxylate, when treated with trimethylenebromide, is resolved into ethylic methyl- CO0CzH5.CH2-C II -"\(colour-dehydrohexonedicarboxylate, C00CZH5*C CH*CHz*CH2 less oil, b.p. 238-240°, 150 mm.). On hydrolysis this substance is first converted into its acid ethylic salt, CloH,,O,(crystalline, ni. p. =114"), and then into the dicarboxylic acid, C8HlJ&(m. p. 160"). The acid ethylic salt on distillation splits up quantitatively into 56 ethylic methyldehydrohexonecarboxylate and carbonic anhydride, The acid, CSH1005,when boiled with water, is decomposed into 2 mols. of carbonic anhydride and acetobutyl alcohol, thus :-CsHloOj + HZO = 2C02 + CH,*CO*CH2*CH2*CH2*CH,*OH. ADDITIONS TO THE LIBRARY. Doiaations. Proceedings of the Literary and Philosophical Society of Liverpool : vol.xxxix, 1884-85 : vol. xl : First Report on the Fauna of Liverpool Bay, 1885-86 : from the Society. Journal of Analytical Chemistry: edited by W. Hart: vol. i, Plate 1: Eaton, Pa., U.S.A. : Les Soies des Vers Sauvages de 1’Inde et leur Emploi dans ]’In- dustrie, par T. Wardle : Paris, 1887: EssaJ sur les PropribtBs Physiques de la Soie : par N. Roudlot: Paris, 1887 : from T. Wardle. Bulletin of the United States Geological Survey: Nos. 30, 31, 32, 33. Record of Work done in the Chemical Department of the Owens College, 1857-1887 : by Sir H. E. Roscoe : London, 1887: from the Author. Thomas Young: A Discourse by Professor Tyndall, delivered at the Royal Institution, January 22, 1887: from the Institution. Yorkshire Philosophical Society : Annual Report, 1857: York, 1887: from the Society. Bulletin de la Soci6tb des M6decian et Naturalistes de Jassy. lare AnnAe: No. 1and 2: from the Society. At the next Meeting, on April 21st, there will be a ballot for the election of Fellows, and the following papers will be read :-“ The Atomic Weight of Gold.” By Professor T. E. Thorpe, F.R.S., and A. P. Laurie, B.Sc., F.R.S. ‘‘ The Atomic Weight of Silicon.” By Professor Thorpe and J.W. Young, B.A. “Note on Substitution in the Benzene Series.” By Dr. H. F. Modey. “ A Contribution to the Study of Well Waters.” By R. Warington, F.R.S.
ISSN:0369-8718
DOI:10.1039/PL8870300047
出版商:RSC
年代:1887
数据来源: RSC
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