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Abstracts of the Proceedings of the Chemical Society, Vol. 2, No. 28 |
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Proceedings of the Chemical Society, London,
Volume 2,
Issue 28,
1886,
Page 245-252
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 28. Session 1885-86. November 18th, 1886. W. Crookes, Esq., F.R.S., Vice-president, in the Chair. Mr. 9.Wentworth Jones was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. Horace Edward Brothers, Zaffre Cottage, Solden Hill, Stoke- on- Trent ; Francis James Henderson Coutts, 61, East View, Turton Road, near Bolton ; Tamemasa Haga, 1,Sadowara-machi, ItchomQ, Tokyo, Japan ; Michitnda Kawakita, Engineering College, Tokyo, Japan ; Stephen James Pentecost, Nottingham Road, New Basford, Nottingham ; Henry Joshua Phillips, G.W .R. Laboratory, Swindon ; P. Yeshwant Sheshadri, Jalua, Bombay, India ; Tetsukichi Shimidzu, Noshomusho, Tokyo, Japan ; William Phillips Thompson, 95, Shrewsbnry Rod, Birkenhead ; Hikorokura Yoshida, Science College, Imperial Univer- sity, Tokyo, Japan.The following were elected Fellows of the Society :-Messrs. B. F. Davenport, M.A., M.D. ; W. Ralph Dodd ; Laurence Hislop ; A. B. Lyons, A.M., M.D. ; James B. Readman ; Alfred RQe ; V. Phelps Richard; F. T. Shutt, B.A.; Edgar F. Smith, Ph.D. The following papers were read :-98. “Researches on the Relation between the Molecular Sti-ucture of Carbon Compounds and their Absorption Spectra. Part VIII. A Study of Coloured Substames and Dyes.” By W. N. Hartley, F.R.S., Royal College of Science, Dublin. The author refers to a paper by Dr. Otto N. Witt, published in 1876, in which it is stated that the tinctorial characters of benzenoid 246 compounds is conditional upon the simultaneous presence in the molecule of a colour-producing group and a salt-forming group of atoms: a group of atoms of the former kind being designated a ckronzogen, and of the latter a chronzophor.He has studied the relation of the hydrocarbons to the more complex compounds which are colouring matters dei-ived therefrom. It is shown that benzene and the derived hydrocarbons have the property of selecting and absorbing certain rays of the spectrum, and may thus be regarded as coloured bodies, the colours of which are too subtle for the eye to perceive them. By certain reactions, two or more benzenes may be linked in such a way that the rate of vibration of the new molecule is reduced so that it absorbs rays within the region of visibility. That which has been called a chromogen is an invisibly coloured substance, and that which is termed a chromophor is an atom or group of atoms capable of so reacting as to reduce the rate of vibrat’ion of the molecule, with the result that it absorbs rays of no higher refrangi- bility than the violet. Under certain conditions oxygen and nitrogen are chromophors, hence also hydroxyl and nitroxyl.The spectrum measurements of a number of nearly related dyes and colouring matters are given, together with diagrams indicating their molecular vibrations. The modification seen in the curve of benzene when an alkyl radicle displaces hydrogen consists in three out of the four absorption-bands being merged in one, and the rate of vibration of the absorbed rays is less.When a body like triphenylmethane is examined, the absorption curve has much of the general character of that of benzene, but the modifications which it has undergone are much like what one might expect from its constitution. First, there is one broad band of absorption with just an indication of a second being merged in this. Secondly, a great increase in the amplitude of the vibrations. Thirdly, the rate of vibration of the absorbed rays is greatly reduced. When magenta, Hofmann’s violet, and iodine-green are examined it is seen that the curves are modifications of that of triphenylmethane ; they follow each other closely, but ihe molecule of greatest mass transmits least light, and the light is composed of rays vibrating with least rapidity, thus indicating a greater amplitude and less rapidity of vibration of the molecule.Azobenzene and a number of its deri-i-atives of very varied constitu- tion exhibit curves remarkably similar. It is remarked that when absorption takes place in the visible region the ultra-violet rays are generally completely absorbed. 99. " Spectroscopic Notes on the Carbohydrates and Albumenoids from Grain.'' By W. N. Hartley, F.R.S., Royal College of Science, Dublin. According to C. v. Nnegeli (" Theorie der Gahrung '7 fermentation is a process which may be described as the transference to fermentable matter of the molecular or rather intra-molecular vibrations of the different constituent substances entering into the composition of living protoplasm (which remains itself unchanged in composit,ion), and hence the equilibrium of the molecules of the fermentable matter becomes so disturbed as to cause their resolution into simpler molecules.The author has had recourse to spectrum observations, in order to obtain, if possible, some information as to the mode and rate of vibration of the molecules of the bodies which initiate and participate in fermentative changes. It is pointed out that animal albumens of various kinds examined by M. L. Soret are distinguished by absorption-bands produced by small thicknesses of dilute solutions, while the albumenoids inv ertase and diastase, and the water in which yeast has been washed, afford solutions which are very diactinic, and as far as could be ascertained do not exhibit absorption-bands.Moreover, gelatine is very diactinic when quite pure, and so also are the carbohydrates starch, cane-sugar, and glucose. It does not therefore appear that there is anything in the mode and rate of vibrations of invertase which is incompatible with a transference of its viErations to glucose, nor of the vibrations of diastase to starch ; hence it is possible that some material within the yeast cell may communicate its motion to the sugar outside of it, and so resolve the complex molecule into simpler molecules. Putting the theory of fermentation on one side, it is of interesi; to know that the facility with which the ultra-violet rays traverse solutions of the carbohydrates is quite in accord with what we know of their constitution, notwithstanding the complexity of their molecules.It is further no less interesting to know that the alhumenoids associated with the carbohydrates are evidently of very different constitution from those found in the animal organism. It is pointed out that gelatine dry plates very rarely receive impressions of rays of higher refrangibility than 2146, and this is due to some slight impurity ill the gelatine, since some specimens of gelatine transmit the line of zinc 2024. DISCUSSION. Mr. SPILLER,referring to the differences in sensibility of gelatino plates to the most refrangible rays commented on by Professor Hartley, said that owing to the difficulty experienced in getting silver bromide emulsion to set and dry sufficiently rapidly in summer time, it 248 had sometimes been the practice of makers to add a minute proportion of chrome-alum: this might account for some of the differences observed.Professor HARTLEYsaid that he had long thought that the soluble bromides had not been completely washed out, but as plates prepared with special care for him by Messrs. Mawson and Swan had also manifested the differences described, he now thought that thsy were probably due to actual diff erences-some minute impurity-in the gelatine used at different times in preparing the plates. 100. "Preliminary Note on the Electrolysis of Ammonic Sulphate." By Herbert McLeod, F.R.S. When a neutral solution of ammonic sulphate is electrolysed in aU -tube provided with platinum plates as electrodes, nearly pure oxygen is evolved at the positive pole and hydrogen at the negative.For one volume of gas from the positive pole, a quantity varying between 4.7 and 5.4 volnmes is evolved from the negative pole. A small amount of ozone is produced. On mixing together the elec- trolysed liquid at the poles a strongly alkaline liquid is obtained, containing a, considerable quantity of " active '' oxygen. When the liquid is first neutralised with sulphuric acid, then treated with excess of baric chloride, and the baric sulphate filtered off, the liquid deposits bnric sulphate on boiling, an indication of the presence of persulphnric acid in the solution.When sulphuric acid that has been electrolysed is exactly neu- tralised with baric hydrate, the precipitate filtered off and the liquid boiled, baric sdphate is precipitated; at the same time the liquid becomes acid and a further quantity of baric sulphate is thrown down on the addition of baric chloride. DISCUSSION. In reply to a question by the President, Professor MCLEODsaid that Faraday in the experiments which gave results differing from those now described, had used an alkaline solution of ammonium sulphate in ammonia. Dr. MESSELasked if the deficiency in oxygen might not be due to the formation of hydrogen peroxide. In experiments on the electro- lysis of sulphuric acid solution (with a current of 60 amper&), he had at all events observed the characteristic colour on application of the chromic acid and ether test.Professor MCLEODsaid that he had always failed to detect hydrogen peroxide. 249 101. “The Preparation and Hydrolysis of Hydrocyanides of the Diketones.” By Francis R. Japp, F.R.S., and N. H. J. Miller, Ph.D. The authors have attempted to hydrolyse Zinin’s benzil-dihydro- cyanide, ClaHlo(OH),(CN),, by means of concentrated chlorhydric acid, but without success. However, by dissolving bend in alcohol, adding an excess of hydrogen cyanide, saturating the liquid with hydrogen chloride, and allowing the whole to stand for some weeks, a compound of the formula C16HlZ’NzO was obtained, a reducing action having taken place.The compound crystallises from benzene in lustrous yellow flat needles or lamina+ melting at 196-197’. It is feebly basic, yielding a colourless hydrochloride which is decom-posed by water. At the same time an acid of the formula C16H,,NOa was obtained. By the action of a strong aqueous solution of hydrogen cyanide upon phenanthraquinone, a dihydrocyanide, CldHS( OH)z(CN),, corre-ponding with the bend-derivative prepared by Zinin, was obtained. It crystallised in tufts of very slender needles, which when heated decomposed with evolution of hydrogen cyanide. Treated with fuming chlorhydric acid in the cold, this compound slowly evolves carbonic anhydride, and yields a mixture of two compounds, C,,H,NO (needles melting at 241”) and C15HllN02(needles melting at 183”).The compound C15H,N0 appears to be a lactam or lactim. It unites directly with metallic hydroxides to form salts, without elimi- nation of water, and from the solutions of these salts mineral acids precipita6e the original substance. It decomposes carbonates. The compound C15H11N02is an acid ; its salts appear to be isomeric with those of the compound C15H9N0,but are so unstable that satisfactory analytical figures could not be obtained. In a preliminary note on the above subject (Rer., 16, 2418) the authors erroneously ascribed the formuh C,,Hl,NO and C16H13NOzto those two compounds. The difference in percentage composition between the C15 and C,, formulae is very slight, affecting chiefly the hydrogen, which was found too high in the earlier analyses.102. “ The Action of Salicylic Aldehyde on Sodium Succinate in presence of Acetic Anhydride.” By Gibson Ilyson, Demonstrator of Chemistry, Normal School of Science, South Kensington. By heating a mixture of 10 grams sodium succinate, 15 grams salicylic aldehyde, and 13 grams acetic anhydride, in a sealed tube for 40 hours, at a temperature of 140” C., the author obtained a substance having the composition ClsHloOa, to which he has given the name “ Uicounzarine.” It is an extremely stable body, insoluble in water, ether, alcohol, benzene, and chloroform, but soluble to a slight extent 250 in hot glacial acetic acid, from which it separates on cooling in xcicular crystals.It dissolves in a hot solution of sodium hydrate, but is reprecipitated unchanged on addition of an acid. By acting on its alkaline solution with sodium amalgam, hydro- dicoumaric acid, CI8Hl4O5,is formed. This acid, when heated at 130"C., gives off a molecule of water, yielding an anhydride (hydro- dicoumarine) CleH1404 (m. p. 256" C.) ; hydrodicoumaric acid also combines with bromine to form addition products. By further reduc- tion of hydrodicoumaric acid, an acid having the composition C,,Hl8OSis obtained. This dil~ydrocounzaricacid yields an anhydride, C18H1404,melting at 222-224'' C. Zwenger (Annulen, Sup. 8, 321, by reducing a saturated alcoholic solution of coumarine with sodium amalgam, obtained hydrocournaric acid, C18H1806,which yields an anhydride, C18H1404, melting at 222"C.The constitution assigned by Zwenger to his acid is the same as that given by the author to dihydrocoumaric acid ; the two acids are, how- ever, not identical. Both acids yield an anhydride C18K1404,melting at 222" C. It is probable that we have here another case of isomerism similar to that observed by Perkin to exist betwen a-and p-coumaric acid. 103. "The Reduction of Nitrites to Hydroxylamine by Hydrogen Sulphide." By B.Divers, F.R.S., and T. Haga. On decomposing silver nitrite with hydrogen sulphide, hydroxyl- amine is formed as chief product. Mercurous nitrite, supposed hitherto not to exist, has been prepared by the authors, and will be described in a future communication; it also yields hydroxyl- atmine on treatment with hydrogen sulphide. In a preliminary note (ante, p.95) reference was made to the production of yellow crystals of unknown nature, together with metallic mercury and hydroxylnmine, on treating mercurous nitrate with nitric oxide : having sirice prepared mercurous nitrite, the autliors have now learned that these yellow crystals were this salt ; and having ascer-tained that hydrogen sulphide converts it partly into hydroxylamine, they further rccognised that tmhe appareiit iormation of this base from mercurous nitrate aad nitric oxide had really been its formation from mercurous nityite and the hydrogen sulphide used to remove the mercury from the solution, as mercurous nitrite is soluble in nitric acid with but partial decomposition.The green solution prepared by mixing alka,li nitrite with copper sulphate also yields hy droxylamine when treated with hydrogen sulphide. Alkali nitrites alone treated ait,h hydrogen sulphide and then acidified, yield no hydroxylnmine. The formation, here described, of hydroxylamine from the nitrites of 251 the silver-mercury group of metals, is the only indisputable evidence there yet is of the conversion of an inorganic nitrite into hgdroxyl- amine. 104. “Note on Some Double Thiosulphates.” By J. B. Cohen, Ph.D., Assistant Lecturer on Chemistry, Owens College. Rammelsberg found that by the action of copper sulphate upon R solution of potassium thiosnlphate a cuprous potassium thiosulphate was formed of the composition K,S20,.Cu,S20j.2H20.By increasing the proportions of potassium thiosulphnte, a hydrated and anhydrous salt of the composition Cu2S20,*2K2S20,.3H,0and Cu2S2032*K2S203, may be obtained, both of which give the same cuprous barium thiosulphate on addition of BaC1,. An anhydrous silver potassium thiosulphate of the composition K2S,0,-2A’192S203 has also been prepared. 105. “ Preliminary Note on the Action of Triphenylmethyl Bromide on Ethyl Sodio-malonate.” By George 0. Henderson, M.A., B.Sc., Assistant to the Professor of Chemistry, University of Glasgow. When triphenylmethyl bromide, dissolved in absolute ether, is treated for some time with an equivalent quantity of ethylic sodio- malonate, a reaction gradually takes place ; ethylic triphertylmethyl-nzalonate [CH.C:(C,H,),*(COOC2H,),] being formed.This substance crystallises from alcohol in colouriess shining prismatic cryetals which melt at 133.5”. When hydrolysed with alcoholic potash, it is partially decomposed, arbon dioxide being split off, and the sodium salt of 6-triphenyl-propionic acid is formed. The acid itself [C(C,B 5)3*CH,*COOH] crystallises from alcohol in small colourless prisms which melt at 177”. The sodium salt (C2,HI70,Na.H2O)crystallises from water, in which it is very soluble, in long silky needles. The barium salt [(C21H,~02)2Ba.H2B],is difficultly soluble in water, but readily soluble in alcohol, from which it separates in white crystals.The silver salt [C,,H1,O2Ag] is obtained as a white micro-crystalline precipitate, almost insoluble in water and alcohol. 106. (‘Action of Silicon Tetrachloride on Aromatic Amido-coni- pounds.” By Arthur Harden, B.Sc., Dalton Scholar in the Owens College. The author finds that primary amines react with silicon tetra-chloride, forming diamines of the formula SiCl,(NHR’),. He has 252 prepared sach compounds from aniline, orthotoluidine, isoxylidiiic, and betanaphthylamine. Pyridine and quinoline form the additive compounds, 2C5H5NvSiClI,. 2C,H,N*SiC 14. RESEARCH FUND. A meeting of the Research Fund Committee will be held in December. Fellows desiring grants are requested to make appli- cation before December 11th.Titles of Papers of interest to Chemists recently read before Societies in the United Kingdom :-“ On the Action of Hydrocliloric Acid Gas upon certain Mekals;” and “On the Capillary Constants of Benzene and its Homologues occurring in Coal Tar.” By T. B. Cohen. Manchester Literary and Philosophical Society, Nov. 2nd. “ On the Specific Heats of Minerals.” By J. Jolg. “ On the Method of Condensation in Calorimetry.” By J. Joly. “ A Theory of Voltaic Action.” By J. Brown. Rloyal Society of London, November 18th. At the next meeting, on December 2nd, there will be a ballot for the election of Fellows, and the following Papers will be read :-“ Bismuthates.” By M. M. P. Muir. “ The Action of Inorganic Compounds on Living Matter.” By James Blake, M.D. “Morindin and Morindon.” By T. E. Thorpe, F.R.S., and A. T. Grcenall. HARRISON AND SONS, PlCINTEltS IN OBDINARY TO HER MAJESTY, ST. MAaTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8860200245
出版商:RSC
年代:1886
数据来源: RSC
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