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Proceedings of the Chemical Society, Vol. 30, No. 430 |
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Proceedings of the Chemical Society, London,
Volume 30,
Issue 430,
1914,
Page 155-164
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摘要:
[Issued 30/5/14 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 30 No. 430. Thursday, May 21st, 1914, at 8.30 p.m., Professor W. H. PEICKIN, LL.D., F.R.S., President, in t.he Chair. The PRESIDENTannounced that in connection with the Van’t Hoff Memorial a Fund has been established for the endowment of research in the field of Pure and Applied Chemistry. The amount available during 1915 for purposes of research is about 367. A Committee consisting of Professor A. F. Holleman (President), Professor S. Hoogewerff, Professor A. Smitx, and Professor F. M. Jaeger (Secretary), has been appointed to award grants. Applica-tions for grants should be sent before November lst, 1914, by registered post to “Het Bestuur der Koninkklyke Akademie van Wetenschappen ;bestemd voor de Commissie van het ‘Vaii’t Hoff-fonds ’ Trippenhuis, Kloveniersburgwal, te Amsterdam,’ ’ and applicants are requested to submit a detailed account of the manner in which they propose to spend the grant.Papers embodying the results of the Rwearch may be published in any Journal, but acknowledgment must be made of the source of the grant. Copies of the papers embodying the results of the Research must be forwarded to the Committee. Messrs. L. J. Hudle‘stone, A. U. Newton, B. N. Ghosh, T. E. Hodges, G. P. Furneaux, A. Coulthard, A. Baxter, R. 0. Bishop, and S. M. Bosworth, were formally admitted Fellows of the ChemicaI Society . 156 Certificates were read for the first time in favour of Messrs: Frederick George Henderson, 44, Dene View, Wallsend-on-Tyne.Victor Henri, 8, Rue du Puits de l’Ermite, Paris Robert Ernest Machin, B.Sc., 5, Redcliffe Road, South Ken-sington, S.W. Thomas William Thompson, M.A., Queen Elizabeth’s Grammar School, Gainsborough. A Certificate has been authoricjed by the Council for presentation to ballot under Bye-Law I. (3) in favour of Mr. Probodha Chundra Chattopadhyay, M.A., 90, Maiiiktala Main Road, Harrison Road P.O., Calcutta. Of the following papers, those marked *were read: “141. 6rIonisation and the law of mass action. Part 111. Utilisation of the osmotic data and a new dilution law.” By William Robert Bousfield, K.C. Excellent freezing-point and vapour-pressure data for concen-trated solutions of lithium chloride exist, and less complete data for sodium and potassium chlorides, the vapour-pressure data ranging from 40° to looo.An empirical vapour-pressure formula of the form h6p/p=2-Gh-H+ Ak-1-Bh-? is found, which gives expression to the data obtained by extra-polation to lao. A new dilution law is proposed of the form a2---K(h-12)’.1 -a By using this in conjunction with the o.smotic relations it is possible to evaluate both a and n. The values of a and 12 independently obtained from the freezing-. point and vapour-pressure data are found to be in good accord, and give values for n at infinite dilution which are in fair accord with those derived from conductivities. With the more complete series of data for lithium chloride, it is found that a relation exists between a and ?a which is independent of temperature in the range considered, namely, oa =38a -14.This enables the conditions of a saturated solution of lithium chloride at 18O to be examined, which shows that the ionisation reaction may be taken to be’ 2LiClAq +Aq, S 2LiAq + 2ClAq. This gives, according to the law of mass action, the relation where B is the weight fraction of the free water, h-92, which exists in the form Aq,, or dihydrol. This is identical with the assumed dilution law, if It is shown by reference to the figures for a, 12, and B that the relatIon holds, and that K’ has the same value both at infinite dilution and in saturated solutions of lithium chloride. Alternatively, the reaction might be taken to be 2LiClAq +Aq3+ Aq 2LiAq + 2ClAq 4-Aq,, which leads also to the form of the dilution law.“142. ‘‘ The alkaloids of ipecacnanha.” By Francis Howard Cam and Frank Lee Pyman. A detailed description was given of an investigation of which a part has previously been reported in a preliminary note (P., 1913, 29, 226). The salts of emetine, cephaeline, and psychotrine have been fully characterised. Emetine sulphate, C29H41304N2 ,H2SO4,7H20, m. p. 205-245O (corr.) ;cephaeline hydrobromide, C28H3804N2t HBr,7H20, in. p. 266-293O (corr.) ;psychotriize nitrate, C,sH3f504N, 9 2HN03,H20, in. p. 184-187O (corr.); psychotrine sdphate, C28H,j04N2,H2S04,3H20, m. p. 214-217O (corr.) ;and psychotrine hydriodide, C2,H,04N,,2 I1I, in.p. 222O (corr.), are new crystalline salts. In correction of the previous statement it was shown that emetine and cephaeline are secondary-tertiary bases. Emetine yields a crystalline N-ben :oyl derivative, C2,K3,04N,*COPh, m. p. 185-186O (corr.), which is a monacidic tertiary base. Emetine is the 0-iiietliyl ether of cephaeline. It gives N-metJzyZenzetilie, an amor-plious base yielding crystalline salts, on methylation. Cepliaeliiie 158 yields on methylation a mixture of emetine, M-met~~yleephaeki.1ze, m. p. 194-195O (corr.), and 2V-methylemetine. Psychotrine ha3 the formula C28H&0,N2,4H,0,and yields on reduction it mixture of cephaeline and isocephaeli7te (m. p. 159-160° [corr.]). The relation between these alkaloids can be expressed as follows: Psychotrine, C2,H2, /\x P’ N-Methglemetine, C25H27NMeCM”” The hydrochlorides obtained by the oxidation of cephaeline with ferric chloride were shown to have the formulze C,8€I,803NC1,~Cl and C,H270,NC1,,HCI respectively. 143.The viscosity of sugar solutions.” By Heber Green. In a recent paper Powell (T., 1914, 105, 1) claims that. the relation between the viscosity and concentration of sugar solutions can be expressd by the equation q.=qoAS, where x is the ratio of solute to solvent, and in his discussion of previous work quotes the present author (Green, T., 1908, 93, 2027) as having concluded that I‘ the connexion between viscosity and concentration is not accurately expressed, even within the limits of experimental error, by any of the various formulze that have been suggested.” This is, however, an incomplete quotation, the continuation of the same sentence being to the effect that the best concordance is 159 obtained by the use of an expression of the forin =I~~A~/~~,where ZI and w are the volumes of the solute and solvent respectively.It was shown that the form of this expression supported by Powell merely neglects any possible contraction which may occur when the sucrose dissolves in water and is not that which gives the nearest approach toaccuracy. The discrepancies between the calculated and observed viscosities are, In any case, far beyond the experimental error of the memure- ments made by the present author more than five years ago, and he sees no reason to alter the conclusion arrived at then.144. Compounds of phenaothraquinone with metallic salts.” By Joseph Knox and Helen Reid Innes. The following additive compounds of phenanthraquinone and metallic salts have been prepared and analysed : C14H802,ZnBr2, (c14H802)2,zn12, C,,H80,,Cda2, C1,H802,CdBr2, C14H802,Cd12, (C14H802)2,HgBr2*The relative stability of the zinc and cadmium compounds has been determined by finding the concentration of metallic haloid in aqueous solution with which mixtures of phenanthraquinone and the various double compounds are in equilibrium. This equilibrium concentration is a measure of the relative stability. The lower the equilibrium concentration, the greater is the stability of the com- pound.It has been found that with a given metal the iodide corn- pound is more stable than the bromide, and the bromide than the chloride, whilst the cadmium compounds are more stable than the corresponding zinc compounds. The stability of the compounds, therefore, increases with diminishing electro-affinity of both the metal and the halogen. The mercuric compounds are more stable than either the zinc or the cadmium compounds, as is shown by their behaviour towards water, and mercury is the metal of weakest electro-affinity of the sub-group. The greater complexity of the mercuric compounds compared with the zinc and cadmium mni-pounds, and of the zinc iodide compound compared with the zinc chloride and bromide compounds, also illustrates the increasing tendency to complex-formation with diminishing electro-affinity.145. Quinone-ammonium derivatives. Part 111. Dihaloid, monoazo-, bisazo-, nitrotriazo-, and bistriazo-compounds: attempts to prepare derivatives containing an asymmetric, quinquevalent nitrogen atom.” By Raphael Meldola and William Francis Hollely. Taking advantage of the partial and complete reducibility of the nitro-groups in 2 :6-dinitro-4-trirnethylammonium-1-benzoquinone 160 (T., 1912, 101, 912; 1913, 103, 177), the authors have prepared a number of new quinone-ammonium derivatives containing naphtho’lazo- and triazo-groups in place of one or both of the original nitro-groups. The constitution of the 2 : 6-dibronio-derivative (T., 1913, 103, 185) has been proved directly by synthesis from 2 : 6-dibromo-p-aminop henol.Syst’ematic attempts to obtain a quinone-ammonium compound of the type (I) with t,hree dissilmilar radicles attached to the nitrogen atom have led 0 0.c. NO,/jNO, \d \/N.a.b.c. N.#.b, (1.1 (11.) to the discovery that this nitrogen atom appears to be incapable of carrying t,hree different’ radicles when the weight or size of the latter exceeds some limit, at present undetermined. If t-his limit is exceeded, the alkylation apparently takes a normal course, in spite of steric hindrance, and the isomeric phenolic ether (11) is obtained. 146. ‘‘ The estimation of carbon monoxide.” By Joseph Ivon Graham and Thomas Field Winmill. As is well known, carbon monoxide is oxidised to carbon dioxide by iodine pentoxide, and various methods of estimating carbon monoxide have been described, based on this reaction.The authors have studied the temperature at which the reaction takes place, and the influence of other gases on its course. A modified form of Haldane’s gas-analysis apparatus was described, in which the oxida- tion may be carried out rapidly, and carbon monoxide estimated with an accuracy of 0.02 per cent. 147. ‘‘ Alcoholometry and rational fractionation.” By Hendrik Pieter Barendrecht. A new distilling apparatus, made from copper, was described, which allows the estimation of alcohol in a fermented liquid, con- taining between 2 and 3 per cent. of alcohol, by conceiitratiiig automatically and in one operation all the alcohol in one-twentieth of the original volume.By this arrangement accuracy is easily obtained, even in using an alcoholometer. From very weak soln-tions, for example, 0.01 per cent., all the alcohol may be distilled off at once in the liundredth-part of a sample of 3 litres. 161 The construction of this apparatus, as well as of another one (also described), made out of ordinary laboratory glassware, is based on the following principle. The rectifier, surrounded on the top by an open water-reservoir as a dephlegmator, should have a large volume, filled with a porous substance, to store up and concentrate the volatile liquid, until all of the latter has been boiled out of the sample, and has thereby heated the dephlegmator so far that the liquid can pass to the condenser.148. “The resolution of 5-nitrohydrindene-2-carboxylicacid.” By William Hobson Mills, Horace Victor Parker, and Robert William Prowse. With the object of obtaining an optically active benzene deriva- tive’ in which it should be necessary to take into consideration the relative distribution in space of the substituent groups to account for the optical activity, the authors have prepared 5-nitrohydrindene-2- carboxylic acid, N02*C6H3<ggi> CH*CO,H, and have shown that it can be resolved by means of its quinine salt into two aiitinieric components. Unless the configuration of the nitrophenyleiie radicle is taken into’ account, the reason for the molecular asymmetry of this compound does not appear.It is evidently due to the asymmetrical disposition of the nitro-group with respect to t’he two methylene groups, it being in the meta-position to one and in the para-position to the other. 149. ‘*Researches on pseudo-bases. Part I. Some condensation reactions of cotarnine, hydrastinine, and isoquinoline methyl hydroxide.” By Gertrude Maud Robinson and Robert Robinson. Cotarnine condenses with 6-iiitrohomoveratrole, nitrohomo-piperonyl alcohol, or nitropiperonal to yield nitrohomopiperonyl-, nitropiperonylidene-, or nitropiperonoyl-hydrocotarnine respectively. The condensation of isoquinoline methyl hydroxide with 6-nitro-liomoveratrole, and of hydrastinine with itself, was also described.150. ‘‘Molecular conductivities of iodoanilinesulphonic acids.” By Mary Bogle. The f ollowiiig iiioiioiodoaiiiliiiesulphonic acids have been pre-pared and the conductivities of their aqueous solutions at 25’ determined : 2-, 3-, and 4-iodoaniline-6-sulphon~cacids, 2-, 3-, and 4-iodoaniline-5-sulphonic acids, and 2-and 3-iodoaniline4-sulphonic acids. In all cases where iodine is introduced into an ortho-position to the amino-group, a very considerable increase in molecular conductivity occurs ;the increase is much less marked in the case of. 912-and piodo-substituted acids. 151. LL The action of steam on sodium chloride.’’ (Preliminary note.) By Solomon English and William Ernest Stephen Turner. Some years ago Einich (Ber., 1907, 40, 1482) described an ex-periment in which the production of hydrogen chloride from salt and water was demonstrated by dropping water on sodium chloride heated in a platinum crucible.Another and simpler way of demonstrating the reaction is to drop a solution of salt on the surface of a platinum basin at bright-red heat, when not only hydrogen chloride can be detected in the issuing vapour but the residue is distinctly alkaline. The authors have attempted to determine the extent to which this hydrolytic decomposition occurs by passing steam over sodium chloride in a platinum boat heated to varying temperatures. There is no appreciable action at and below 500°, but it becomes recog- nisable at 700°, and increases steadily with rise of temperature, measurements having been made up to 1000°.Sodium chloride possesses an appreciable vapour pressure below its melting point (BOOo), and the reaction appears to take place mainly between the salt vapour and steam. In porcelain tubes, however, the amount of hydrogen chloride found exceeds the alkali left as residue, and so far the authors have been unable to trace the reason for the discrepancy. They hope to repeat the determinations in a platinum tube. 152. ‘‘Experiments on the synthesis of the benzoterpenes. Part I. Derivatives of benzonor-p-menthane.” By Francis William Kay and Allan Morton. An account was given of the synthesis of some representatives of a new class of terpenes, described as the benzoterpenes, which have been obtained from the various derivatives of a-naphthoic acid with the aid of Grignard’s reagent.163 ADDITIONS TO THE LIBRARY. I. Donutions. Brame, John Sumuel Straford. Fuel. Solid, liquid and gaseous. London 1914. pp. xv+ 372. ill. 12s. 6d. net. (Recd. 20/4/14.) From the Author. Bucherer, Hun8 Theodor. Lehrbuch der Farbenchemie, einsch-liesslich der Gewinnung und Verarbeitung des Teem, sowie der Methoden zur Darstellurig der Vor-und Zwischenprodukte. Leipzig 1914. pp. xii + 557. M.22.-. (IZecd. 21/4/14.) From the Publisher : Otto Spamer. The Chemical News and Journal of.Physica1 Science. A journal of practical chemistry in all its applications to pharmacy, arts, and manu- factures. Vols. 56 and 57. London 1887-1888.(To comnplete circu- Zating set.) From Sir William Crookes, O.M., F.R.S. Weimarn, P.P.von. Zur Lehre von den Zustanden der Materie. Dresden 1914. 2 vols. pp. 190 and Atlas of 52 plates. M.7.-. From the Publisher : Theodor Steinkopff. 11. By Purchase. Allen, H. Stanhy. Photo-electricity. The liberation of electrons by light. With chapters on fluorescence and phosphorescence, and photochemical actions and photography. London 1913. pp. ix + 22 1. ill. 7s. 6d. net. (Recd. 13/5/14.) Barcroft, Joseph. The respiratory function of the blood. Cam-bridge 1914. pp. x+320. ill. 18s. net. (Recd. 13/5/14.) Dony-HQnault,O., Gall, Henyi, and Guye, Philipplz Augwte. Principes et applications de 1’6lectrochimie. Paris 1914. pp. xiv + 686.ill. 30 fr. (Recd. 13/5/14.) Mathet, L. Trait& de chimie photographique. 3rd edition. Paris [1914]. 2 vols. pp. viii +309, viii + 477. 20 fr. (Recd. 21/5/14.) Simmersbach, Oskar. Grundlagen der Koks-Chemie. 2nd edition. Berlin 1914. pp. viii+ 314.. ill. M.10.--. (Recd. 13/5/14.) Tammann, Gustav. Lehrbuch der Metallographie. Chemie und Physik der Metalle und ihrer Legieruugen. Leipzig 1914. pp. xviii + 390. M.19.-. (Recd. 13/3/14.). Wallach, Otto. Terpene und Campher. Zusammenfassung eigoner Untersuchungen auf dem Gebiet der alicyclischen Kohlenstoff verbind- ungen, 2nd edition. Leipzig 1914. pp. xxvi +580. M.24.-. (Recd. 13/5/14.) 164 111. Pamphlets. Auerb ch, Friedrich, and Pick, Hans. Das Verhalten von B1 1-carbonat, basischem Bleicarbonat und Bleisul fat in w asserigen Losungen kohleosaurer Alkalien.(From the Arb. K. Gesund., 1913, 45.) --Das Verbalten von Bleichromat urid basischem Blei-chromat in wasserigen Losungen kohleasaurer Al kalien. (From the Arb. K. Gasund., 1913, 45.) Die Bleiahgabe schwerloslicher B1t.i~ lze an Natrium-hydrocarbonat enthalterlde Lo3ungen. (From the Arb. K. Gesund., 1913, 45.) Baker, R. T.,and Smith, H. G. A research on the eucalypts of Tasmania and their essential oils. Tasmania 1912. pp. 71. ill. Batschinski, A. Utitersuchungen uber die innere Reibung der Flussigkeiten. I. (From the Ann. Xci. d’Emour. Sci.Exp., Suppl. 3, 1913.) Beam, William. The determination of humus in heavy clay soils. (From The Cairo Sci. J., 1913, 7.) The next Ordinary Scientific Meeting will be held on Thursday, June 4th, 1914, at 8.30 p.m., when the following papers will be communicated : “ Studies in the succinic acid series.Part I. The chlorides of succinic and methylsuccinic acids and their constitution.” By G. F. Morrell. “ The dilut’ion limits of inflammability of gaseous mixtures. Part I. The1 determination of dilution limits. Part 11. The lower limits in air of hydrogen, methane, and carbon monoxide.” By H. F. Coward and F. Brinsley. “A comparative study of the absorption spectra of some com- powids of phosphorus, arsenic, antimony, and bismuth.” (Preli-minary note.) By C. R. Crymble. “ The reactions of /3-liydroxy-a-alnino-compounds as cyclic struc- tures.” By J. C. Irvine and A. W. Fyfe. R. CLAY AND SONS, LTD., BRCSSWICK ST., STiUFOltD ST., S.E., ASD BUXQIP, SGFFOLB.
ISSN:0369-8718
DOI:10.1039/PL9143000155
出版商:RSC
年代:1914
数据来源: RSC
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