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Proceedings of the Chemical Society, Vol. 19, No. 260 |
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Proceedings of the Chemical Society, London,
Volume 19,
Issue 260,
1903,
Page 37-42
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摘要:
Zssuccl 11/2/03 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 19. No. 260. Thursday, Febi,uary Sth, 1903. Dr. E. DIVERS,F.R.S., Viee-President, in the Chair. Mr. W. Carter White was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. : Arthur William Eastwood, B. A., Newton College, S. Devon. John Percy Edgerton, 39, White Hart Lane, Barnes, S.W. George Howsam, School of Science, Peterborough. Alfred Owen Jones, 18,Queen’s Gardens, Tetherdown, Musmell Hill. James Stewart Kerr, The Grove, Lzdywood Road, Birmingham. George Siddle, il!!tidclleton-One-Rot, R.S.O. William Francis John Wood, B.Sc., Doncaster Road, Barnsley. Edward Chancey Worden, Millburn, New Jersey, U.S.A. Of the following papers, those marked * were read : *18.L6 The solubilities and transition points of lithium nitrate and its hydrates.” By F. G. Donnan and B. C. Burt. Lithium nitrate was found to yield two hydrates, LiNO,,SH,O and LiNO,,~-H,O. Of these, the former has been obtained previously by bott, who showed it to be the trihydrate and not LiKO,,B$H,O as stated by Kremers and by Troost. Determinations of the solubility of these hydrates and also of the anhydrous salt were carried out, and in this way the various quadruple points of the system located, the position OF these points being also confirmed by thermometric and dilatometric measurements. The trihydrate is of special interest as it possesses a stable melting point, The equilibrium curve in the neigh- bourhood of this point was fully investigated.The following is a list of the melting points and quadruple points of the system : Cryohydrate point of LiN0,,3H20, -17.8'. Melting point of LiN0,,3H20, 29.88'. Transition point, trihydrate + semihydrate zzsaturated solution, 29.6'. Transition point, semihydrate anhydrous salt + saturated solu- tion, 61.1'. "19. The synthesis of aa-diglutaric acid." By 0. Silberrad and T,H. Easterfield. The action of iodine on the sodium derivativs of ethyl a carboxy-glutarate does not lead to the formation of the hexa-ethyl ester, C0,E t *CH,*CH,*C(CO,Et),*G( CO,E t), CH,*CH,*CO,Eh, f porn which aa-diglutaric acid could be obtained by successive hydrolysis and loss of carbon dioxide, but gives rise to the hitherto unknown etl$ a-iodo-a-ccci.box~glutc6rate(ethy2 a-iodobutane-eary-tr icarboxybate), the reaction taking place in accordance with the following equation : CO,Et*CH,*CH,*CNa(CO,Et),+ I, = C0,Et *CH,*C'H,*CI(C0,E t), + NnI.Bromine behaves similarly, yielding ethgl a-bromo-a-ccwboxygltarate (etJuJ a-bromobutune-aay-tricccrboccyZate)(sp. gr. 1.325 at 15'/4O). Again, on heating the sodium derivative with these halogenated esters, no condensation occurred, but instead a mixture of alkyl carboxyglutarate and a new ethyl carboxyglutaconate (b. p. 173-176' under 15 mm. pressure) was produced, the latter differing from its isomeride (ethyl isoaconitate) in that it does not contain a mobile hydrogen atom and can therefore neither assume the enolic form nor yield a sodium derivative.As the preceding method failed to give rise to the desired ester, its synthesis was next tried by one of the authors (0. S.) in the manner represented by the following equation : 39 C0,Et*CH,*CH21: + NaF(C0,Et)2 = 2NaI + CO,Et*C,K,*~(CO, Et), C0,Et *CH,*CH,I NaC(C0,E t), CO,Et* C,H,*C(CO,Et),. This process proved successful and yielded ethyl aa.di-a-carboxy- glutarate (isolated as aa-diglutaric acid) together with ethyl A"F-a-di-hydromuconate (I),ethylbutane-ayy88-pentacarboxylate(b. p. 2 15-2 18" under 17 mm. pressure), which, on saponification, yielded butane-ay8- tricarboxylic acid (m.p. 122O), and ethyl ethylenetetracarboxylate. A fractionator was described for distilling under greatly diminished pressure; this apparatus was designed in order to overcome the difficulty due to the variation of pressure caused by throttling, which is experienced under these conditions when the ordinary columns are employed. "20.Distillation of chlorine water." By A.Richardson. Pickering (Tmns., 1870, 37,139) has shown that, when aqueous solutions of chlorine are heated in an open vessel, a residue containing hydrochloric acid remains behind after all the active chlorine has been expelled, and the present work was undertaken in order to find out whetherthe escaping chlorine was present wholly in a free state or mixed with one of its oxy-acids. When chlorine water was heated in a retort, the distillate, which was obtained below looo, contained free chlorine, the gas being readily displaced by a current of air; the solution in the retort, however, still contained active chlorine, for it liberated iodine from potassium iodide, bleached indigo solution immediately, and gave, on shaking with mercury, a brownish -yellow deposit resembling that obtained with hypochlorous acid.This result- proved to be independent of the action of light, and was not influenced by further purification of the chlorine, Quantitative estimations of the chlorine in the aspirated distillate gave, for the active chlorine estimated iodometrically, values double those obtained for the total chlorine found with silver nitrate after treatment with sulphur dioxide, These results show that the active chlorine is present as hypochloraus acid.Distillation of chlorine water in a current of chlorine gas showed that the hydrochloric acid formed in the residual solution was equiva- lent to the hypochlorous acid found in the distillate, indicating that a portion of the chlorine reacts with the water according to the equation CI, +H,O =HC1+ HClO. Again, when aliquot parts of the distillate and residue obtained on distilling chlorine water were mixed, a solution having all the proper -ties of the original chlorine water was reproduced. It would appear, therefore, that hydrochloric and hypochlorous acids are separated duiing distillation as the products of the partial change of chlorine water. When chlorine water was heated in a flask provided with a reflux condenser, so that the distillate returned to the original solution, the ratio of active to total chlorine found was that required for a solution of free chlorine, showing that the solution is stable when the separation of the two acids is prevented.A further study of the change showed that the amount of hypo-chlorous acid pAssing over decreased with the increase in strength of the hydrochloric acid formed in the solution. With very dilute solutions of chlorine water, the whole of the free halogen employed entered into reaction with the solvent, the oxy-acid only having been found in the distillate. Finally, distillation of very dilute chlorine water in a vacuum at the ordinary temperature gave a distillate containing the oxy-acid, showing that the reaction occurs at the ordinary temperature as well as at the boiling point. 21.“A new vapour density apparatus.” By John S.Lumsden. This apparatus is based on the principle that the molecular weights of all substances in the state of gas, when occupying the same volume and at the same temperature, exert the same pressure. The pressure produced at a given temperature by the molecular weight in milligrams is either found experimentally by vaporising a substance of known molecular weight or calculated from the dimensions of the apparatus ; then, from the pressure produced by vaporising a weighed quantity of the substance the molecular weight of which is required, the weight in milligrams which would produce thu milligram molecular pressure is found. This is taken as the molecular weight.No barometric reading is necessary, and when the constant of the apparatus has been found and the substance weighed, the experiment is completed in two minutes, and the calculation of the result may be made in another two minutes. By slightly modifying the arrangement of the apparatus, the substance may be vaporised under diminished pressure or in an inert gas, and the experiment may be performed at any temperature. The instrument, which is quite as accurate as the Victor Meyer apparatus, is, owing to its simplicity, well adapted for general laboratory work. 41 22. A new form of pyrometer.” By John S. Lwmsden. A constant volume instrument was described in which a weighed quantity of a substance is vaporised and the pressure measiired by ft mercury gauge.The pressures produced by equal weights of substance are pro-portional to the absolute temperatures ; therefore, if at two tempera- tures the pressures produced by equal weights are measured and one temperature is known, the other can be calculated. The instrument may be made of glass, porcelain or metd, and high temperatures may be measured within a few degrees. 23. Tertiary butylphenol.” By E. W. Lewis. The author draws attention to the non-formation of phenyl-ter.- butyl ether on digesting phenol in alcoholic solution with ter.-butyl- chloride and excess of alkali, and to the production in these circurn- stances of the isomeric ter.-butylphenol.Other instances of the difficulty attending the preparation of phenol ethers containing n tertiary radicle in place of the hydrogen of the phenolic hydroxyl group are cited in the paper. ADDITIONS TO THE LIBRARY. Danger, Ferdinand Philippe. The art of glass-blowing, or plain instructions for making the chemical and philosophical instruments which are formed of glass. ill. London 1831. Baumd, Antoine. MBmoire sur la meilleure manihre de construire les alambics et fourneaux propres A la distillation des vins pour en tirer les eaux-de-vie. ill. Paris 1778. Klaproth, Martin Henry. Analytical essays towards promoting the chemical knowledge of mineral substances. Translated from the German. London 1801.Rideal, Samuel. Glue and glue testing. London 1900. From the Author 42 Bigelom, W. D. Foods and food control. Parts I-V. (being U.S. Dept. of Agriculture, Bureau of Chemistry, Bulletin No, 69.): Washington 1902. 11. By Purchase. Boyle, Robert,. De ipsn natura, sive libera in receptam naturz notionem disquisitio ad amicum. London 1657. RAy, Praphulla Chandra. A history of Hindu chemistry from the earliest times to the middle of the sixteenth century A.D. with Sanskrit texts, variants, translation, and illustrations, Vol. I. London 1902. LBvy, Lucien. Les mouts et les vins en distillerie. Paris 1903. Whetham, William Cecil Dampier. A treatise on the theory of solution, including the phenomena of electrolysis. Cambridge 1902.ANNIVERSARY DINNER. It has been decided by the Council to arrange for zt Dinner of the Fellows of the Society and their friends on Wednesday, March 25th, 1903, this being the day fixed for the Annual General Meeting. Further particulars will be announced shortly. At the next meeting, on Wednesday, February ISth, at 5.30 p.m., there will be a ballot for the election OF Fellows, and the following papers will be communicated : (‘The molecular rearrangement of N-substituted imino-ethers.” By G. D. Lander. ‘‘The nature and probable mechanism of metal replacement in tauto-meric compounds.” By G. D. Lander. u The chlorine derivatives of pyridine. Part ‘VIII. The interaction of 2 :3 :4 :5-tetrachloropyridine with ethyl sodiomalonate.” By W. J. Sell and P.W. Dootson. ‘‘The biological method for resolving inactive acids into their optically active components.” By A. McKenzie and A. Harden. RICHARD CLAY AND SONS, LIMITEL), LOXDON AND BUNGAY.
ISSN:0369-8718
DOI:10.1039/PL9031900037
出版商:RSC
年代:1903
数据来源: RSC
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