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Proceedings of the Chemical Society, Vol. 30, No. 425 |
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Proceedings of the Chemical Society, London,
Volume 30,
Issue 425,
1914,
Page 53-62
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摘要:
[Issued 27/2/14 PROCEEDINGS OF THE CHEXIICAL SOCIETY. ~~ Vol. 30 No.425 Thursday, February 19th, 1914, at 5.30 p.m., Professor W. H PERKIN,LL.D., F.R.S., President, in the Chair. The PRESIDENTreferred to the loss sustained by the Society through the death of: Elected. Died. Gustavus Anthony Abrines (Gibraltar).. ...... Dec. 4th, 1890 June 22nd, 1913 Charles Cunningham Connor (Belfast) ......... Feb. 18th, 1875 Feb. loth, 1914 Arthur Ellson navies (Edinburgh) ......... . Feb. Ist, 1866 Feb. 9th, 1914 Certificates were read for the first time in favour of Messrs. : Arthur Baxter, B.Sc., 360, York Road, Camden Road, N. Albert Coulthard, B.Sc., Ph.D., 9, Portland Avenue, Stamford Hill, N. Robinson Percy Foulds, M.Sc., Stanley Villa, Colne.Arthur Bertram Hobson, M.Sc., 13, Westy Lane, Latchford, Warrington. James Riddick Partington, B.Sc., The University, Manchester. Walter Ryley Pratt, B.Sc., 17, Bloomsbury Square, W.C. Walter William Reeve, B.Sc., 4,Gowlett Road, E. Dulwich, S.E. Herbert Corner Reynard, B.Sc., West Ewell, Epsom. Certificates have been authorised by the Council for presentation to ballot under Byelaw 1(3) in favour of Messrs.: Clifford Girdlestone Gill, Cawnpore Sugar Works, Ltd., Cawn- pore, India. Yusuf Ismail Mulla, Alembic Laboratory, Club Road, Mandalav Shore, Burma. announced that the following changes in the The PRESIDENT Officers and Council were proposed by the Council: Vice-Presideiits to relzre.-Dr. G 2’. Beilby and Prof.W. Jack-son Pope. Ordii~ary illembers of Coui2cil to retire.-Sir Boverton Redwood, Bart., Mr. W. R. Bousfield, Prof H. &larsliall (Deceased), Prof F. G. Donnan. As President.-Prof. W. H. Perkin. As Vice-Presidents who have filled the ofice of President.-Prof H. E. Armstrong, Prof. A. Crum Brown, Sir William Crookes, Sir Jarnes Dewar, Prof. H. B. Dixon, Prof. Percy F. Frankland, Dr A. G. Vernon Harcourt, Prof. R. Meldola, Dr. H. Muller, Prof iV. Odling, Sir William Ramsay, Prof. J. Emerson Reynolds, The Right Hon. Sir Henry E. Roscoe, Sir Edward Thorpe, and Sir William A. Tilden. As Treasurer.-Dr. ‘Alexander Scott. As Hotz. Secretaries.-Dr. Samuel Smiles and Prof. J. C. Philip. As ForeigTz Secretary.-Prof Arthur W. Crossley. As I’ice-Presideiats.-Prof. H.Brereton Baker, Prof. P. P. Bedson, Dr. Horace T. Brown, Mr. C. T. Heycock, Prof. E. J. Mills, and Prof. G. T. Morgan. As New Ordinary Members of Council.-The Earl of Berkeley, Dr. R. H. A. Plimmer, Dr. G. Senter, Prof. J. M. Thomson. Dr. Samuel Rideal, Prof. J. J. Dobbie, and Sir Alexander Pedler were elected Auditors to audit the Society’s Accounts. Ethelbert William Blair, B.Sc. Albert Frederick (lalvert. Sydney George Clifford. Lionel Cohen. Behari LB1 DBs. Sydney Edward Davenport. Thomas Alexander Davidson. Thomas Eynon Davies, B.Sc. Richard Charles Denington. Charles George Fernie, E. Sc. George Ingle Finch. Reginald Fnmess, M.Sc. John Garth. Ivan Richard Gibbs, B. A. James Stanley Hale.Theophilus Harper. Eric Russell Harrap. Oswald Ryle Horwood, M.A., M.R. C.S. L.R. C.P. Manappadam Ramaswami Viswanatha Iyer. Dan Ivor James, M.A., B.Sc. Gopal Balkrishn Kolhatker, M.A. Alfred John Leigh, B.Sc. Frederic Williarn Leighton. Alexander Williamson McLaren. Archibald Macpherson. Fredk. Arthur Makin. Thomas Morris. Raymond William Nichols. William Julian Odlum, B.A. Rowlaiid Ernest Oldroyd. Fredexick Alfred Pickworth. William Henry Pick, B.Sc. 55 Cody Hunter Riley. Horace Gilbert Stone, €3. Sc. William Pawson Robson, B.A., Ph.D. Harold Edwin Temple. Chandra Bhusan Roy, M.A. Eustace Ebenezer Turner, €3. Sc. Joseph de Carle Smith (jnninr), B.Sc. Robert James Wriglit, M.A. Charles Alfred Stamp. “48.“The production of high vacua by means of finely divided copper.” By Thomas Ralph Merton. It has been found that the vapour pressures of gases absorbed by finely divided copper are so low that the absorption of gases by this substance may be used for the production of high vacua. DIScusSION. Prof. H. B. BAKERwas able to confirm Mr. Merton’s results, as, in some work he had done with Prof. Strutt, a tube of copper gauze which had been left with a pressure of 1-2 mm. of nitrogen over- night was found next morning to resist the passage of a very powerful electric discharge. He thought that the method would be of great importance in dealing with small traces of gases. Dr. LOWRYsuggested that the power of absorbing gases was perhaps a function of the amorphous, as contrasted with the crystal- line, form of copper.This was in agreement with the fact that this power was lost on heating to 250°, a temperature that was practic- ally identical with the annealing-temperature of hard-drawn copper wire ; further, that repeated heating at lower temperatures pro-duced the same effect. *49. Hydroaromatic ketones. Part 111. l-isoPropylcycZohexan-3-one.” By Arthur William Crossley and Walter Ryley Pratt. l-isoProyyZcyclohexan-3-o~ze(11) has been prepared from l-iso-propyldihydroresorcin (I) by a series of reactions indicated by H,C/\CH2 -3 ClC‘ Ico\/CH Tt boils at 208O, gives a semirnrhnzone melting at 187O, and a liqnid oxitne, the bruzoyl derivative of whicli melts at 91---92O.l-isoP~o~~yZcyclohercall-3-oZ(TIT) is a viscid liquid, boiling at 1140/ 28 mm., and possessing a characteristic pungent odour. The o-nitrobenzoyl derivative crystallises in small, white prisms, melting at 47-48O. Both the alcohol and the ketone give 8-isopropyladipic acid on oxidation with potassium permanganate. It is intended to make the ketone the starting-point in the synthesis of certain meta-terpene derivatives, as it has been found possible by varying the original conditions (T.,1902, 81, 676) to improve the yield of isopropyldihydroresorcin so that it may now be obtained in about 70 per cent. of tlie theoretical amount. *50. (‘The spitting of silver.” By Herbert Brereton Baker. The amount of oxygen absorbed by melted silver is so large that it seems difficult to explain on the hypothesis of a mere solution of such a gas in such a liquid.It seemed conceivable that there might be formed an oxide of silver which was stable at high temperatures, but decomposed on allowing the temperature to fall; a case analogous to the well-known behaviour of silicon trichloride. An attempt has been made to apply a test for the presence in the molten metal of an oxide of silver. It is found that if silver oxide is dropped into melted boron trioxide silver borate is formed, although the temperature is much above the decomposition point of the silver oxide. Accordingly, some highly purified silver was melted in a stream of oxygen, a part only of the surface of the metal being covered with boron trioxide.This procedure was rendered easy by the convexity of the surface of the liquid meta!, a ring of the trioxide surrounding tlie exposed surface. In these circumstances silver borate is formed in large quantity. If, how-ever, the metal is covered entirely, even by a thin film of the trioxide, no silver borate is produced. It cannot be claimed that an absolute proof of the existence of an oxide of silver has been obtained, because there is the possibility of the reaction of three substances together, no two of which will otherwise unite. It seemed worth while, however, to put the experiments on record. “51. “The rate of transformation of ammonium cyanate in absolute alcohol.” By John David MoBeath Ross. The experiments of Walker and Kay (T.,1897, 71, 489) on the velocity of the transformation of ammonium cyanate into carbamide 57 in aqueous alcohol have been extended to solutions containing more than 90 per cent. of alcohol.On the assumption that the action primarily takes place between the ammonium ions and the cyanate ions, it is found that the acceleration previously observed continues up to alcohol of 99.94 per cent. by volume, the increase in the speed of the transformation being most noticeable in solutions containing a large percentage of alcohol. The same conclusions hold good when the action is considered to be primarily due to thO non-ionised ammonium cyanate, although in this case the change in the velocity-coefficient is smaller than on the other assumption.DISCUSSION. Dr. SENTEE,referred to the contention of E. E. Walker (Proc. Idoy. SOC.,1912, A, 07, 539) that in determining the influence of alcohol on the rate of decomposition of carbaniide in aqueous solu- tion, the solutions should not be made up to a definite volume, but the ratio of carbamide to water should be kept constant and vary- ing proportions of alcohol added. Apart from the objections urged by the author of the present paper, the latter method of making up solutions was open to criticism on kinetic grounds. Comparing two solutions in which the ratio carbamide: water was the same, but one of which contained alcohol in addition, the total volume of the latter was considerably greater, and therefore the number of collisions between the reacting molecules or ions, and consequently the rate of reaction differed in the two cases on spacial grounds, apart.altogether from other effects. For this reason the usual method of making up to a constant volume, although not free from objection, would appear to afford a much truer representation of the effect of alcohol on the reaction than the method advocated by E. E. Walker. 52. ‘‘ Condensations of cyanohydrins. Part 11. The condensation of chloralcyanohydrin with chloral hydrate and with bromal hydrate.” By Horace Leslie Crowther, Hamilton McCombie, and Thomas Harold Beade. The compound described by Wnllach (AnnaEen, 1874, 173,297) and Cech (Ber., 1876, 9, 1020) as being formed by the action of potassium cyanide on excess of chloral hydrate has been shown by the authors to have the constitution (I).In this reaction it is produced by the condensation of normal chloralcyanohydrin (which is first formed) with two molecules of chloral hydrate. This con- densation has been shown to take place in the presence of potassium hydroxide. Further, using the same condensing medium, the 58 authors have been able to condense chloralcyanohydrin with bromal hydrate with the production of compound 11: CH(CCI,)* CO*TH CH(CCl,)*CO-rH o<CH(CCI,)-O--C H*CCI, o<cH(csr,)-o-c K.CB$ (1.1 (11.1 It has been decided to call the parent seven-membered ring (111) 1 : 3 :5-dioxazseytcoa, so that (I) is called 6-keto-2 :4 :G-tri(triclr/oro-methyl)-l :3 :5-tliozazseptcitt.The dioxazseptan derivatives give rise to inoiioacyl derivatives, in which the acyl group is attached to the nitrogen atom. The benzoyl derivatives when treated with hydrochloric acid, in glacial acetic acid, are decomposed, one chloral (or bromal) residue is eliminated from the molecule, and there results, in the case of the benzoyl derivative of (I), P-t,.ic?~loro-a-(8‘-tricT~Toro-af-~~~dro~~-ethozy)-poyionobe11 zu ?tLide (IV): ,CH,*CH,* NH CH (CCla)*CO*NHBzo<l ;\CH,--U-CH, 0<~~(~~~,)*~~G3 (III.) (IV. 1 This compound, on treatment with sodium carbonate, or hydr-oxide, yields 4 :4-dichloro-3:5-o~iino-5-trich7oro??7 eethyl-2-l~~~rolidoi~ (V), a compound which is readily soluble in alkalis, but is precipitated unchanged on the addition of acids.An analogous compound can be prepared from the berizoyl derivative of 11. Another interesting change which is undergone by the benzoyl derivatives is brought about by the action of dilute potassium hydroxide. In this case one molecule of hydrogen chloride is eliminated, and the resulting compound has the constitution VI or VII: ,CH--CO CH*CO-NBz o,,//E---CO--N Bz /Io<’ dc1, I ,\I\I \I \\“C(CCI,)*NH ‘C(CC1,) O*CH*CCJa ‘CH(CC1,) *O*C*CCI, (V.) w.1 (VII.) 53. The system : ethyl et her-water-potassium iodide-mercuric iodide. Part 11. Solutions saturated with respect to solid phases in the four-component system. ” By Alfred Charles Dunningham. The equilibria are reyreseiitecl by means of a tetrahedroii, of which a diagrammatic projection was shown.Saturation surfaces exist for the solid phases : potassium iodide, potassium mercuri- 59 iodide, potassium mercuri-iodide hydrate (KHgI,,H,O), and mercuric iodide. The surfaces are divided by binodal curves into homogeneous and heterogeneous areas, on which liquid mixtures, in equilibrium with the solid phase, exist as one or two layers respectively. In the case of potassium iodide and potassium mercuri-iodide, the liomogeneous portions of the saturation surfaces are entirely separated by a heterogeneous area. This corresponds with the fact that in contact with either of these phases, water and ether are only miscible to a very limited extent. In the case of potassium mercuri-iodide hydrate and mercuric iodide, the saturation surf aces are divided into homogeneous and heterogeneous portions by critical curves.The homogeneous portions thus formed extend almost across the tetrahedron, corre- sponding with the fact that in contact with these phases water and ether can become miscible in almost all proportions. 54. Lc The connexion between the dielectric constant and the solvent power of a liquid.” By William Ernest Stephen Turner and Crellyn Colgrave Bissett. In a series of investigations on the factors affecting the solu- bility of electrolytes, Walden (ZeitscIL. physikal. Chem., 1906, 55, 683) drew the conclusion that a parallelism exists between dielectric constant and solvent power, and later (ibicl., 1908, 61, 633) formu-lated an expression, c,’vp =constant, applicable to tetraethyl-arizmociuiii and tetrapropylammonium iodides dissolved in n number of solvents, E representing the dielectric constant of tlie solvent, and p the molecular percentage solubility of the solute.It was now shown that this expression is not generally valid, and does not apply to the solubility data of Peddle and Turner (T., 1913, 103, 1202) or of Turner and Bissett (T., 1913, 103, 1904), and on investigation with additional solvents it does not apply, as Walden considered it did, to tetrapropylammonium iodide. An attempt to find another equation wits unsuccessful, and it was pointed out that the order of solvent action is in many cases not the order in which the dielectric constants run.Solvent action depends both on the nature of the solute and on that of the solvent. It was further shown that the solvent action of a number of liquids on pnitrobenzyl chloride and trimethylamine, as measured by Halban (Zeitsclr. yltysikcrt. C~CM.,1913, 84, 129), and on carbon dioxide and nitrogen (Just, Zaitsrh. pltysikal. Cliem., 1901, 37,342), is not connected with their dielectric coiistants. 55. (‘The viscosities of some binary liquid mixtures containing formamide.” By Ernest Wy ndham Merry and William Ernest Stephen Turner. The viscosities of mixtures of formamide with water, methyl and ethyl alcohols, formic, acetic, propionic, and ?~-butyric acids have been determined at temperatures of 25O and 40°.From the results of the investigation it was concluded that: (1) Formamide and the lower alcohols give viscosity curves differing little from the straight line, but as the series is ascended, the calculated and observed viscosities differ by a value which is at first negative and later becomes positive, until, with isoamyl alcohol, a curve is obtained which contains a maximum point. The experimental values in the last case were drawn from thwe of Drucker and Kassel (Zeitsch. physikal. Chem., 1911, 76,367). (2) Formamide and the aliphatic acids give viscosity curves resembling in general character those obtained with aqueous solutions of these acids, there being no maximum point with formic acid, although the calculated values are less than the observed.In the other cases, maximum points were obtained on the curve. (3) Maximum points on viscosity curves are not always due to the formation of compounds, and that, in consequence, viscosity measurements do not form a trustworthy method of testing for tlie formation of compounds in solution. (4) With a series of associated, similarly constituted liquids, each inixed with a common, associated liquid, the observed viscosity departs inore and more from the calculated value as the moleciilar weight increases in the series. 56. ‘4The conversion of d-glucoaamine into cl-mannose.” By James Colquhoun Irvine and Alexander Hynd. A detailed account of an investigation, the results of which have already been communicated in the form of a preliminary note (P., 1913, 29, 306) 57.‘‘ The catalytic activity of acids in ethyl-alcoholic solution.” By Harry Xedforth Dawson and Frank Powis. Measurements of the rate of isomeric change of acetone under the catalytic influence of acids have been made in ethyl-alcoholic solution. From similar experinieiits in aqueous solution (T.,1913, 103,2135) it was previously found that the catalytic effect of the acid can be represented as the sum of effects produced by the iouisecl and non-ionised acids. The dat.a for alcoholic solutions also indicate that the “hydrogen ion” is not the only active component, but that the non-ionised acid is also possessed of considerable catalytic power. It was shown that the observations in aqueous solution afford no information as to the real nature of the ionic catalyst, but.that some light is thrown on this question by a comparison of the phenomena of catalysis in water and alcohol. If a comparison is made between aqueous and alcoholic solutions of acids according to their electrical conductivity, in which the acids are ionised to about the same extent, it is found that the speed of the catalysed reaction in alcohol is many hundred times greater than in water. This is explained by the assumption that the active ionic catalyst is the free hydrogen ion which is present in very small concentration in aqueous solutions of acids, but in relatively much greater concen- tration in alcoholic solution. The retarding influence of small quantities of water on the velocity of this and other reactions in alcoholic solution is in agreement with this hypothesis. 58.“Heats of evaporation; association in liquids and mixtures of liquids.” By James Rihdick Partington. The equation of Bakker for the latent heat of evaporation of a liquid, which is deduced from the characteristic equation of van der Waals, gives results in poor agreement with experiment. It was shown that the characteristic equation of D. Berthelot leads to an equation giving results in much closer agreement with the experimental numbers. The equation is : where A is the molecular heat of evaporation at the temperature TI;v1 is the molecular volume of the liquid; pk, Y‘k are the critical pressure and temperature, and R is the gas-constant.Some thermal properties of liquid mixtures were considered from the point of view of thermodynamics. ANNUAL GENERAL MEETING. The Annual General Meeting will be held on Thursday, March 26th, 1914, at 4.30 p.m., when the President will deliver his address, entitled ‘I Recent R.esearches on Tautomerism.” The next Ordinary Scientific Meeting will be held on Thnreday, March 5th 1914, at8.30 p.m., when the following papers will be communicated : ‘‘A redetermination of the atomic weight of vanadium.” By H. V. A. Briscoe and H. F. V. Little. “The isomerism of the oximes. Part 111. The hydroxy-benzaldoximes.” By 0. L. Brady and F. P. Dunn. “ The constituents of the leaves and stems of Daviesia Zntifolin.” By F.B. Power and A. H. Salway. “ The composition of some mediaeval wax seals.” By J. J. Dobbie and J. J. Fox. “Experiments on the rate of nitrification.” By R. M. Beesley. ‘I Studies on the constitution of soap solution. The alkalinity and degree of hydrolysis of soap solutions.” By J. W. McBain and H. E. Martin. (‘The influence of configuration on the condensation reactions of polyhydroxy-compounds. Part I. The constitution of mannitol triacetone.” By J. C. Irvine and B. M. Paterson. “The formation of ethers from maniiitol. An example of steric liindrance.” By J. C. Irvine arid B. M. Paterson. “ The relative strengths of ammonium and the substituted ammonium hydroxides, as measured by their action on a pseudo- base. Part I.” By C. K. Tinkler. The interaction between nitric acid and brucine in the presence sf inetallic nitrates.” By E. H. Rennie and A. E. Dawkins. R. CWY AND SONS, LTD., BBUNSWICB ST., STAUFORD 61.. S.E.. 4ND BUNGAT, BUTPOLK
ISSN:0369-8718
DOI:10.1039/PL9143000053
出版商:RSC
年代:1914
数据来源: RSC
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