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Proceedings of the Chemical Society, Vol. 10, No. 133 |
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Proceedings of the Chemical Society, London,
Volume 10,
Issue 133,
1894,
Page 29-34
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摘要:
Issued lOj2/ 1894 PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 133. Session 1893-94. February lst, 1894. Dr. Armstrong, President, in the Chair. Certificates were read for the first time in favour of Mess1.s. I?. E. Allhusen, Jesus College, Cambridge ; Charles Henry Ashdown, Belmont, St. Albans, Herts; Harry Bowes, 9, Union Terrace, Cliatham Hill ; Thomas Chambers, Dudley House, Coatbridge, N.B. ; Edwin Terry, 41, Nightingale Lane, Balham, S.W. ; Arthur Robert Golden, B.A.,17, Trinity Street, Norwich ; William Albert Knight, Sexey's Trade School, Bruton, Somerset ; James Mansell, B.A., L9, Upper Tichborne Street ; Charles McMullan, Holywood, co. Down, Ireland ; Frederick Wallace Stoddart, Grafton Lodge, Sneyd Park,Bristol ; Henry L. Wheeler, 1812, Prairie, Chicago, U.S.A.Of the following papers those marked Q were read :-"108. "Note on the liberation of chlorine during the heating of a mixture of potassic chlorate and manganic peroxide." By Herkert McLeod, F.R.S. In 1889 the author suggested an explanation of the catalytic action which takes place when an " oxygen mixture '' is heated, an essential feature in the explanation being the evolution of a small quantity of chlorine ; a few months later 0. Brunck published in the Berichte ft statement that the gas evolred together with oxygen is not chlorine but ozone. The author has made several experiments to endeavour to solve the question. A mixture of potassic chloratc and manganic peroxide was heated in a test tube by means of the vnpour of boiling mercury, and the evolved gas was passed through a U-tube filled with small glass beads to re move-any potassic chloride carried over mechanically, and 30 then through another U-tube containing an ammoniacal solution of argentic nitrate.On subsequently acidifying the solution with nitric acid, argentic chloride was precipitated. The quantity of chlorine calculated from the amount of the precipitate was not dissimilar from the quantity given in the previous paper. On extracting the residue with water, filtering and adding litmus soluiion, the liquid was found to be slightly alkaline. The alkalinity was determined by means of a centinormal solution of oxalic acid, and was found to correspond fairly well with the quantity of chlorine in the argentic chloride.One test only was made for the presence of ozone in the gas. The beads in the first U-tube were moistened with a strong solution of potassic iodide, the mixture was heated as before in mercury vapour and no coloration was seen on acidifying the potassic iodide solution, indicating that under the conditions of the experiment, ozone was not produced. DISCUSSIOX.. Professor DUNSTANrernmked that the odour of the gas evolved from the mixture was more like an oxide of chlorine than chlorine itself. He enquired whether Professor McLeod had ascertained whether a, mixture of potassium chloride and manganic oxide furnished chlorine when heated in mercury vapour. If so, then not only the production of chlorine, but also of permanganate and alkali, from the chlorate was susceptible of another explanation.Professor MCLEODstated that he had not hitherto closely investi- gated this question. 109. “The examination of some recent freezing point determinations.” By S. U. Pickering, F.R.S. Mi.. Harry Jones has recently made a number of freezing point cleterminatioris with weak solutions for which a very high degree of accuracy is claimed, and which have led him to the unexpected con- clusion that non-electrolytes exhibit abnormally large depressions of a character similar to those exhibitcd by electrolytes. This must necessarily invalidate all the conclusions drawn from the abnormal depressions given by the latter. On esarriiiiing his results, it was found that they all formed figures of a curvilinear character, even in cases where the author’s previous determinations showed comparn- tive regularity and constancy. It was considered probable that this peculiarity of Mr.Jones’s results might be due to some error in the calibration of his instrument, and this was borne out by the fact that the differences between his and tbe ail thor’s determinations were in every case-there being eight cases available for the cornparifinn-of 31 t!he same sign at the s,ame temperatures, these differences forming, when plotted, a wavy curve. As the author used two different thermo- meters in his determinations, the error can scarcely be attributed to his instruments. A further comparison with one series of results by Raonlt and six series by Loomis gave confirmatory evidence of the existence of an error of this wavy character in Mr.Jones's results ; so also did a comparison of his values with those calculated from Kohlrausch's conductivity determination. The total error in Mr. Jones's results amounts to at least 0*01",and is quite sufficient to account for the abnormal results which he has obtained with non-electrolytes, and for the wavy character of his results generally. His results give clear indications of the existence of changes of curvature in many cases, which would not appear to be negatived by the error of his measurements. In the case of sulphuric acid the peculiar character of the figure which his results form confirms in a striking manner the author's previous results (Trans., 1890, 357), since they shorn breaks at the same points as the author's did, and the two figures are practically identical when Mr.Jones's results are corrected according to a mean deduced from the comparison with thc various authorities mentioned. 110. "Salts of dehydracetic acid." BYJ. Norman Collie, Ph.D., and H. R. Le Sueur, B.Sc. The reason for preparing these salts was, if possible, to obtain additional evidence bearing on the constitution of dehydracetic acid. During many years this substance was considered to be a true acid, that is to say, it was supposed to contain a carboxyl group. Owing, however, to one fact first noticed by Ostwald, namely, the extremely low dis-sociation constant, this idea was abandoned, and Feist first suggested that the substance was a lactone.Naturally, therefore, if dehydracetic acid were a lactone of the formula C8H804, its salts should possess the general formula C,H,O,M; and the examination of these compounds ought to at once decide the question. The salts prepared are the following:- Sodium salt, C8H9O5Na*H20. Potassium salt, C,H,O,K*H,O. Mag-nesium salt, (C8Hg0,),Mg-&Hz0. Calcium salt, (C,H,O,)Ca*H,O. Barium salt, (C6H905)2Ba. Zinc salt, (C8H,05)2Zn. Cadmium salt, (C,Hg05)>Cd. Cobalt salt, (C8Hg05),Cd-$H,O. Manganese salt, (C6Hg05)2Mn. Copper salt, (C8H704)2C~. Silver salt, C8H,0,Ag. Lead salt, (C,H,O,),Pb. Ethylic salt, C8H,04CzH,. Nearly all of these were perfectly stable at loo", but all of them (with the exception of the copper salt and the ethylic salt!, which did not lose water) when heated to as high as 145”,gave off water and left, without exception, salts of the formula C,H,O,M.The examination of the salts, therefore, has not enabled the authors to decide the question ; for, although all the salts lose water when heated, leaving compounds which are derivatives of the substance C8H804,still owing to the high temperature necessary in some cases to effect this change, the water may be other than that of crj-stallisation. 111. “A new method of producing carbon tetrabromide.” ByJ. Norman Collie, Ph.D. Whilst working with a yellow uaphthalene compound which he had obtained from dehydracetic acid (Trans., 1893, 329), the author noticed that when it was heated with a strong solution of sodium hypobromite, it yielded a volatile, solid compound.This substance was found to be tetrabromide of carbon and was formed to the extent of about 2-3 grams from 10 grams of the naphthalene derivative. On experimenting with other compounds, the author finds that this interaction is very general and that widely diverse carbon derivatives all yield tetrabromide of carbon when warmed with strong solution of sodium hypobromite. Amongst others may be mentioned alcohol, glycol, glycerol, mannitol, malic acid, citric acid, maleic and fumaric acids, sugars, starches, celluloses, &c. Amongst benzene derivatives, the phenols, especially carbolic acid, orcinol, resorcinol, a-and &naphthol, alizarin, &c.;oxypyridine derivatives give it easily, also a large number of the alkaloids. It is evidently a very general interaction and depends to a large extent on the powerful oxidising or breaking down power of the alkaline solution of sodium hypobromite. Bromoform is prob-ably formed prior to the final stage which the author is inclined to believe involves the conversion of bromoform into carbon tetra- bromide. 112. ‘‘Metallic derivatives of acetylene. Mercuric acetylide.” ByM.Travers, B.Sc., and R. T. Plimpton, Ph.D. Berthelot (Ann. Chim. Phys., [4], 9, 386), by passing acetylene through a solution of mercuric iodide in potassium iodide made alkaline with ammonia, obtained an explosive mercury acetylide, of which, however, he seems to have made no analysis.The authors have prepared this substance in various ways and studied its compo- sition and properties. They have prepared it by the action of acetylene, 1, on freshly precipitated mercuric oxide; 2, on solu-tions of mercuric cyanide mixed with ammonia, or, better, with 33 ammonia and cupric sulphate OF zinc cliloride; 3, 011 solutions of mercuric acetate or sulphate with ammonia, when a part only of the mercury is precipitated ; 4, on mercuric oxide dissolved by the aid of ammonia and ammonic carbonate. The latt,er method is the most convenient. The heavy, white powder which separates is well washed and dried at 100”. Analysis gave as the mean of four deter- minations : mercury, 87.1 ; carbon, 10.1 and 10.3. Calculated for 3CzHgHz0: mercurF,87 ;carbon, 10.4 per cent.The substance could not be obtained free from water even aEter long drying at 100”. Mercuric acetylide belongs to the same class of bodies as the silver and copper acetylides; it is explosive, yields part of its carbon as acetylene when warmed with chlorhydric acid and part as aldehyde, and yields the compound C,I, and eventually C,I, when acted on by iodine dissolved in potassium iodide. It differs altogether from the sub-stance obtained from solutions of mercuric acetate described in a pre-vious note (Proc., 1892, log), and which is non-explosive and in othcr respects resembles the allyene derivatives obtained by Katscheroff from solutions of mercuric chloride and acetate (Ber., 17, 13). &I--curic acetylide detonates violently when suddenly heated or struck sharply ; it can, however, be handled with safety even when dry.Dr. E. H. Keiser, who had apparently overlooked Bertbelot’s dc-scription of the substance and the note published in the Proceedings by one of the authors, has recently (Amer. Chern. J., November, 1893) obtained the same substance, and attributes to it the formula C,Hg: the authors have not been able to obtain either this or the silver compound free from water. 113. (‘Synthesis of indene, hydrindene and some of their derivatives.” By W. H. Perkin, junr., F.R.S., and E. RBvay, Ph.D. It is shown that when the barium salt of the hydrindenecarboxylic acid prepared by v.Baeyer and W. H. Perkin, junr., is heated, either aloiie or with sodium methoxide, it yields indene and not hydrindene. Thc indene thus obtained has a somewhat lower density but some-what higher refractive and magnetic rotatory power than the inderie separated from coal tar, although they are not chemically distinguish- able. The authors incline to the view t,hat the two products are isomeric, and that they perhaps correspond to the two formulre The action of bromine on hydrindenecarboxylic acid, and a numher of ketones and their derivatives prepared from this acid, are described. 34 ADDITIONS TO THE LIBRARY. I. Donations. Quantitative Chemical Analysis, by F. Clowes and J. B.Coleman. 2nd edit. London 1894. From the Authors. Californian State Mining Bureau. Eleventh Report of the State Mineralogist ; two years ending September 15th, 1892. Sacramento 1893. From the Bureau. 11. By Parchase. A Manual of Dyeing, by E. Knecht, C. Rawson and R. Lowenthal. London 1893. A Text-Book of the Physiological Chemistry of the Animal Body, by A. Ganyer. London 1&9$. A Treatise on Hygiene and Public Health, by T. Stevenson and S. F. Murphy. Vols. I and II. London 1893. On the Chemistry of the Blood and other Scientific Papers, by the late L. C. Wooldridge, M.D.,arranged by V. Horsley and E. Starling. London 1893. At the nest meeting, on February 15th, there will be a ballot for the election of Fellows, and the following papers will be read :-“ The analytical determination of available ‘ mineral ’ plant food in soils. (Illustrated by examination of the permanent barley soils of Hoos Field, Rothamsted.)” By Bernard Dyer, D.Sc. “ The asrial oxidation of turpentine and essential oils.” By C. T. Kingzett. TIASKISON AND SONS, PRIBTEXS IN ORDINARY TO HER MAJESTY, ST. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8941000029
出版商:RSC
年代:1894
数据来源: RSC
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