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Proceedings of the Chemical Society, Vol. 20, No. 287 |
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Proceedings of the Chemical Society, London,
Volume 20,
Issue 287,
1904,
Page 247-254
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摘要:
Issued 3I 112/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 20. No. 3B7. D.Mc.,Wednesday, December 14th, 1904. Professor W. A. TILDEN, P.R.S., President, in the Chair. Messrs. J. C. Gain and W. H. Willcox were formally admitted Fellows of the Society. Gertificates were read for the first time in favour of Messrs : James Hector Barnes, B.Sc., The Briars, King’s Norton, Birmingham. Bernard Mount Jones, B.A, ‘‘ Alcala,” Hermitage Road, Upper Norwood, S.E. Herbert Louis Leech, 3, London Road, Blackburn. Alfred Courtenay Luck, The Naval Arsenal, Zarate, Argentina. Andrew Norman Meldrum, D.Sc., 16, Mooroaks Road, Sheffield, Charles Watson Moore, B.Sc., 38, Demesne Road, Whalley Range, Manchester. Ernest Quant, 2, Park Crescent, Torquay. Gustav Arthur Troye, P.O.Box 2706, Johannesburg. William Phillip Want, 11, Pearfield Road, Forest Hill, S.E. John Wells Wilkinson, M.A., 2S, Egerton Terrace, Bexley Road, Belvedere. Alan Herbert Williams, 127, Roseneath Road, Urmston, near Manchester, 248 The following Certificate was authorised by Council under Bye-law I(3): H. Chandra Chatterjee, Citwnpore, India, Of the following papers, those marked * were read : “209. ‘‘Hydrolysis of ammonium salts.” By Victor Herbert Veley. When aqueous solutions of ammonium salts are heated to their boil- ing points, the evolution of ammonia and the concomitant acidity of the solutions result not from a direct dissociation, but from hydrolysis, Three cases are presented : (i) the hydrolysis is Id or inappreciable, (ii) it is dependent on the dilution, and (iii) it is independent of dilution when beyond a certain limiting value.The persistence or avidity with which the several acids retain the ammonia in combination is analogous to their activity or avidity in the cases of hydrolysis of methyl acetate and the inversion of cane sugar, the relative, but not the absolute, ordor of magnitude being the same in all these three chemical changes. DISCUSSION. Professor CROSSLEYsaid that this behaviour of ammonium salts on distillation was capable of being of great service in the separation of organic acids, and instanced the case (Trans.,le98, 73, 13) where it had been found possible to separate isopropylsuccinic acid from a com-plicated mixture of fatty acids by distilling in steam a solution of the mixed acids in ammonium hydroxide, when ammonium isopropyI-succiaate was left in the residue.*210,“The viscosity of liquid mixtures. Part 11.” By Albert Ernest Dunstan. The author’s conclusions in a previous paper (Trccrts.,1904,85, 817) are confirmed by the present series of results, and by means of a slightly modified apparatus the viscosity-concentration curves for the following mixtures have been investigated. 1. Ally1 alcohol and water :-Maximum point at 51-52 per cent. allyl alcohol, corresponding with 1 allyl alcohol, 3 water, and a discon-tinuity with 40 per cent. ally1 alcohol corresponding with 1 allyl alcohol, 5 water. 2. Propyl alcohol and water :-Maximum point at 61-62 per cent.propyl alcohol, corresponding with 1 propyl alcohol, 2 water. 3. Glycol and water :-Sagged curve approximating to the normal, Maximum divergence from the straight line at the point 1 glycol, 2 water. 4. Lactic acid and water :-Sagged curve as for glycol and water. Maximum divergence at the point 1 lactic acid, 2 water. 5. Benzene and acetic acid :-Minimum point at 89 per cent. benzene, corresponding with 5 benzene, 1 acetic acid. 6. Benzene and propyl alcohol :-Minimum point at 95 per cent. benzene, corresponding with 12 benzene, 1 pi opyl alcohol. Although it might be expected that such very viscous substances as glycol and lactic acid, which at the same time are associative, would give maximum points in a similar way to other hydroxylated liquids, yet this is not the case, because further association or the formation of higher complexes with water is impossible; a breaking down into simpler groups takes place, although it is quite likely that aggregates are formed as in other cases.The minima obtained with benzene solutions are regarded as being due to the formation of definite aggregates less complex than those of the original hydroxylated substances. 6‘“211. The diazo-reaction in the diphenyl series. Part 11, Ethoxybenzidine.” By John Cannell Cain. The author has examined the action of heat on the solution of the diazonium salt prepared from ethoxybenzidine and has shown that one diazonium group is normally substituted by hydroxyl whilst the other remains intact.It seems certain from the fact that dianisidine is much more stable than benzidine in this connection that the diazonium group which is adjacent to the ethoxy-group is the one which remains unchanged. The diazonium sulphate has the formula OH*C,H,*C,H,(OEt)*N( iN)*HSO,, and can be recrystallised from boiling dilute sulphuric acid ;it forms long, acicular, brown crystals easily soluble in water. The free diazonium hydroxide is precipitated by sodium carbonate as a lilac mass which dissolves in acids forming the corresponding salts. 4’-Hydroxy-3-ethoxydiphen yl-4-d iazonium sulphat e and the corre- sponding chloride, bromide, iodide, nitrate, and platinichloride have been prepared. “212.(( The sulphate and the phosphate of the dimercurammonium series,” By Prafulla Chandra R$y.It has already been shown that when dimercurammonium nitrite, NHg,NO,, is treated with a halogen acid the molecular structure of the compound is destroyed, and a double salt of t,ha type 2HgX,,NH4X is formed, where X represents n halogen atom (Trrcns., 1902, 81, 644). If, however, an oxy-acid is substituted for the halogen acid, the dimei.cura?,2??tonizcnzcomplex remains in tact, and the NO,-group is simply replaced by the corresponding acid ion. In this way, the author has lately succeeded in preparing the sulphate, (NHg,),SO,,H,O, and the phosphate, NHgH,PO,, of the seriey, “213. “A method for the direct production of certain aminoazo-compounds.” By Raphael Meldola and Lewis Eynon.The authors have found that most diazotised amines when treated in aqueous solution with a strong solution of sodium dichromate give crystalline precipitates of diazonium chromates which can be isolated and used in the solid condition. It is pointed out that this method is at present the only practical process for isolating diazonium salts with inorganic acid radicles from aqueous solutions. In the case of diamines, a means for the direct production of aminoazo-compounds has thus been found. Diazotised p-phenylenediamine gives a chromate having the formula NH,*C,H,*N,*HCrO,, which combines at once with phenols and amines to form aminoazo-com pounds. p-Aminoben zeneazo-F-naph thol (Tra*ns., 1885,47,663) has been prepared by this method and character- ised by its acetjyl derivative, which crystalliees in red needles melting at 259-260’. p-Aminophenol forms a normal diazonium dichromate, [HO*C,H4*N,],Cr,07.These solid chromates are all more or less explosive when dry, and it is suggested that some of them might find technical application as high explosives. DISCUSSION. Dr. HEWITTsaid that the much greater stability of p-aminophenpl-diazmium salts as compared with salts not containing an amino-group may perhaps be accounted for by assuming that the former compounds have a quinonoid constitution. ProfeFsor Meldola’s chromate would then have the formula NH:C,H,: N,H*HCYr04, whilst the stable diazonium sulphate just described by Dr. Gain would have a siinilar formula, 0:C,H,: C,H,( OEt):N,H*HSO,.Dr. CAINinquired whether the diazonium chromate of p-nitroaniline had been prepared. It would be interesting to know whether this salt gave the ordinary “p-nitraniline red ” on cloth padded with P-naphthol or whether the chromic acid had any effect on the COlOllr produced on the fibre. Prof. MELDOLA,in reply to Dr. Cain, said that he had prepared di- azonium chromates of the nitroanilines, but these substances were highly explosive when dry, and dangerous to make in yaantity. In the moist st'ate, they might perhaps be used for the purpose indicated. With reference to a question by Dr. Morgan, he had not been able to isolate cbromates of the tetrazo-derivatives of simple diamines.With the heteronucleal diamines of the diphenyl series, it might be possible to obtain such tetrszonium chromates, but the experiments had not been carried very far in this direction at present. He agreed with Dr. Hewitt as to the remarkable stability of some of these diazonium chromates, bnt as to the inference that these salts might have a quinonoid structure on account of their colour, the fact that the acicl radicle was.itself coloured interfered with this interpretation, a1 though t,here was no valid objection against such a view of their constitution. *214. '(The combination of mercaptans with olefinic ketonic com-pounds. " By Siegfried Ruhemann. According to Posner's researches (Be?.., 1901, 34, 1395 ; 1902, 35, 799 ; 1904, 37,502), mercaptans generally interact with mono-olefinic ketones in the presence of hydrogen chloride, both by addition at the ethylene linking and by condensation with the ketonic group, to yield tri thio-compounds.The author showed that, on using piperidine or sodium ethoxide as catalytic agents, instead of hydrogen chloride, only additive products I!of mercaptans with the olefinic ketonic compounds -C:CCO-are formed, and several substances of this type have been obtained from benzylideneacetone, ethyl benzylideneacetoacetate, benzylideneacetyl-acetone, and ben zy lidene benzoy lacet one. Moreover, in the presence of piperidine, dibenzylideneacetone, a It Ii diolefinic ketone containing the residue C:C*CO*C:C, unites either 1 I with 1 or 2 molecular proportions of a mercaptan, whilst Posner, by means of hydrogen chloride, has only been able to obtain additive products with 2 mols.of mercaptans. On the other hand, cinnamyl- II I I idenencetophenone, a ketone with the grouping U:C*C:C*CO-, takes I up only one molecule of either isoamyl mercaptan or phenyl mercaptan ; whilst according to Posner, this ketone, under the influence of hydrogen chloride, unites with 2 mols. of mercaptans. The author has, however, obtained from this ketone and pbenyl mercaptan a compound identical with the substance described by Posner, but which has the formula CHPh:CH*CH(SPh)'CH,'COPh, and not CHPh(SPh)*CH,*CH(SPh)*CH20COPh,as stated by this investigator, 252 215. “Studies in optical superposition. Part I.” By Thomas Stewart Patterson and Francis Taylor.Nenthy1 acetate, I-rnenthy1 d-tartrate, and Z-menthy 1 diacety 1-d-tartrate have been prepared and their rotations examined between 0“ and loo0 and compared with each other and with that of menthol between the same temperatures. Menthyl diacetyltartrate is dimor- phous, one modification melti.ng at 84.5“and the other at 108O. It is shown that for menthol there is a temperature (58-59O) of minimum rotation (maximum negative rotation), but no such temperature has been observed for its derivatives. It is shown to be possible by analogy to trace the separate effects of the different active groups composing menthyl tartrate and its diacetyl derivative. ADDITIONS TO ’I‘HE LIBRARY.Bolton, Henry Carrington. A select bibliography of chemistry, 1492-1902. 2nd supplement. Smith. Mis. Coll. Vol. XLIV. Washington 1904. From the Smithsonian Institution. Dobbin, Leonard, and Marshall, :Hugh. Salts and their reactions. With a pmfnce by A. Crum Grown. pp. 198. Edinburgh 1904. From the Authors. Gordon Memorial College, Khartoum. First report of the Wellcome Research Laboratories. By the director, Andrew Balfour. pp. 84 + ... 111. ill. Khartoum 1904. From the Director. Haldane, J. S., and Wade, John, Reports to the Local Government Board on the destruction of rats and disinfection on shipboard. pp. 28. ill. London 1904. From the Local Government Board. Lewkowitsch, J. Cantor lectures on oils and faks : their uses and applications.pp. 52. ill. Tondon 1904. From the Author. Lewkowitsch, J. Chemical technology and analysis of oils, fats, and waxes. Third edition. pp. 1152. ill. 2 vols. London 1904. From the Author. Lodge, Richard W. Notes on assaying, and metallurgical labora- tory experiments. pp. viii + 387. ill. New York 1904. From the Publishers. Rostoski, 0. Manual of serum diagnosis. Authorised translation by Charles Bolduan. pp. 86. ill, New York 1904. From the Publishers. 253 Thornson, J. J. Elektrizitat und Materie. Autorisierte Ubersetzung von G. Siebert. pp. 100. Braunschweig 1904. From the Publishers. 11. By Purchase. (31he misch- technische Un tersuchungsmet hoden. Herausgegeben von Georg Lunge. Funfte Auflage. Biinde 1 und 2.pp. xxvi+953+ xlix, xix +842 + viii. ill. Berlin 1904. De la Coux, H. L’ozone et ses applications industrielles. Pro-pri6ti.s physiques-Physiologie-Production-Actions chimique et rnicrobiologique-Applications-Analyse. pp. 557. ill. Paris 1904. Hager, Hermann. Das Mikroskop und seine Anmendung. Hand-buch der praktischen Mikroskopie und Anleitung zu mikroskopischen Untersuchungen. Nach dessen Tode vollstandig umgearbeitet und in Gemeinschaft mit 0.Appel, G. Brandes, P. Stolper, neu herausgegeben von Carl Dlez. Neunte Auflage. pp. xii + 392. ill. Berlin 1904. Hantzsch, A. Grundriss der Stereochemie. Zweite Auflage. pp. viii + 188. Leipzig 1904. Kobert, Rudolf. Lehrbuch der Intoxikationen. I1 Eand, 1 Halfte. Zmeite Autiage. pp. 400.ill. Stuttgart 1904. Schelenz, Hermann. Geschichte der Pharmazie. pp. xi + 935. Berlin 1904. 111. Fccnhplblets. Borm, H. Die Elektrochemie im Jahre 1903. (From Die CImnische lizduslrie, 27, 1904.) Chace, Ed. Mackay, Tolman, L. M., and Munson, L. 8. Chemical composition of some tropical fruits and their products. I. A study of Cuban fruits. 11. The composition of fresh and canned pine-apples. (U.S. Dept. of Agric. Bureau of Chemistry, Bulletin No. 87.) Dymond, T. S., and Bull, B. W. Variation in the milk of a dairy herd during the summer months. pp. 15. Chelmsford 1904. -Variation in the milk of a dairy herd during the winter months. pp. 19. Chelmsford 1903. Dymond, T. S., and Hughes, F, Notes on agricultural analyses, made in the County Technical Laboratories, Chelmsford, during 1901-1903.pp. 50. Chelmsford 1904. Grindley, H. S. The nitrogenous constituents of flesh. (From J. Amer. Chem. Soc., 26, 1904.) Haywood, J. K., and Warner, H. J. Srsenic in papers and fabrics. (US. Dept. of Agric. Bureau of Chemistry, Bulletin No. 86.) Howard, Albert. Hop experiments, 1904. pp. 29. ill. Kent 1904. 264 Richardson, Clifford. The constitution of Portland cement from a physico-chemical standpoint. pp. 20. New York 1904. Storer, F. H. A supplement to the article (No. 3) on the occurrence of mannan in trees, roots, and fruit. (From the Bulletin ofthe Bussey Institution, 3,1904.) Tolman, I,.M., and Munson, L. S. Olive oil and its substitutes. (U.S. Dept. of Agric. Bureau of Chemistry Bulletin, No.77.) Travers, Morris W. Researches on the attainment of very low temperatures. (From the Snzithsonian Miscellmeous Collections, 46, 1904.) Wiley, Harvey W. The influence of environment upon the com- position of the sugar beet, 1902, including a study of irrigated sections. (U.S. Dept. of Agric. Bureau of Chemistry, Bulletin No. 78.) WISLICENUS MEMORIAL LECTURE. The Wislicenus Memorial Lecture will be delivered by Professor W. H. Yerkin, F.E.S.,on Wednesday, January 25th) 1905, at 8.30p.m. At the next ‘Meeting, on Wednesday, January 18th, 1905, at 5.30 p.m., the following papers will be communicated :-‘‘ Nitrogen ha logen derivatives of the sulphonamides. Part 1. Sulphondichloroamides and sulphonalkplcbloroamides.” By F. D. Chattaway.‘(Nitrogen halogen derivatives of the sulphonamides. Part 11. Sulphondibromoamides and sulphonalkylbromoamides.” By F. I). Chattaway. ‘‘Electrolytic oxidation of aliphatic aldehydes.” By H. D. Law. “The diazo-derivatives of the ber,zenesulphonylphenylenediamines.” By G. T. Morgan and F. If, G. Micklethwait. R. CLAY AND SONS, LTD., BHEAD ST. WILL, E.C., AND UUNGAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9042000247
出版商:RSC
年代:1904
数据来源: RSC
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