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Proceedings of the Chemical Society, Vol. 13, No. 176 |
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Proceedings of the Chemical Society, London,
Volume 13,
Issue 176,
1897,
Page 57-68
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摘要:
Issued 17/3/1097. PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES, --~ ~-_____ ~ - No. 176. Session 1896-7. Narch 4th, 1897. Mr. A. G. Vernon Harcourt, President, in the C hair. Certificates were read for the first time in favour of 3Jessrs. Alaric Vincent Colpoys Fenby, B.Sc., Hutton Grammar School, Preston ; R. Glode Guyer, 20 Queen’s Road, St. John’s Wood, N.W.; Tom Mitchell, Cemetery House, Shaw, near Oldham ; Robert Howson Pickard, B.Sc., Southfield, Priory Road, Edgbaston, Birmingham. MR.CASSALasked whether the officers had withdrawn the Certificate of a Candidate from the list to be balloted for that evening. THOMSONPROFESSOR stated that the Certificate of one of the Candi- dates had been postponed pending further information.DR. ARMSTRONGremarked that such action had been taken by the officers on former occasions, and was within their discretion. The following were duly elected Fellows of the Society :-Mesers. John Owen Alexander ;Thomas Hannibal Aquino ;William Arbuckle ; John €3. Ashworth; John Barclay, B.Sc.; Frank Bastow; Jyoti Bhushan Bhaduri, M.A. ; James Herbert Brown ; F. Hewlett Burton- Brown, M.A. ; Alfred Cartmell ; Masumi Chikashigk, B.Sc. ; Alfred Foster Cholerton ;Clarence Hamilton Creasey ;James Crowther, €3.8~.; William Slfred Davis ; William Diamond ; John Wallis Dodgson, B.Sc. ;Lawrence Dufty ;William Buckland Edwards ; Joseph Lake Gibbons ; Alexander W. Gilbody, M.Sc., Ph.D. ; Harold Walter Gough, B.A. ; Ernest Goulding ; Edward Graham Guest, M.A ; Vaughan Harley, M.D.; Ernald G. Justinian Hartley, B.A. ; Thos. Hartley ; Charles Heppenstall ; John Holmes ; Fred Ibbotson, B.Sc. ; William Rose Innes, B.Sc., Ph.D. ; David Smiles Jerdan, M.A., B.Sc. ; Harold Johnson ; Otis C. Johnson ; Herbert King ; William Robert Lang, B.Sc. ; Theophilus Henry Lee ; Charles Henry Martin ; Barker North ; Charles Henry Parker ; Samuel Pollitt, B.Sc. ; Herbert Spindler Pullar ; William Ralston, 16.S~. ; John Stewart Remington ; Edward Rosling ; Alfred Rutter ; Frank Southerden ; William James Stainer, B.A. ; Henry Potter Stevens, R.A. ; Leonard Sumner, B.Sc. ; Ha rry Thompson ; Andrew Turnbull, Ph. D. ; Basil William Turner ; Rustomji Navroji Unwalla ; Samuel Matthew Walford ; J.Wallace Walker, M.A., Ph.D. ; and Meyer Wilderman, Ph.D. In accordance with the bye-law, the lists of the names of the Fellows recommended for election as official and ordinary Members of Council were read from the Chair. Of the following Papers, those marked * were read. "34, '$ Some hydrocarbons from American petroleum. I. Normal and Iso-pentane." By Sydney Young, D.Sc., F.R.S.,and G. L. Thomas, B.Sc. The two pentanes were separated by fractional distillation from the "pentane " supplied by Merck of Darmstadt. This substance, which is obtained by the distillation of American petroleum, is a complex mixture of butanes, pentanes, and liexanes, with some benzene and a little hexanaphthene. A combination of a dephlegmator with a constant (or rather 'regulated ') temperature still-head was employed ; the apparatus is fully described in the paper.Some of the constants of isopentane were determined so as to compare them with those of the two specimens prepared synthetically: the agreement was found to be very satisfactory. The boiling points under normal pressure are :-isopentnne 27.95"; normal pentane 36.3." The specific gravities at 0" are :-isopentane 0.63930, normal pentane 0*64539. *35. '' The vapour pressures, specific volumes and critical constants of normal pentane; with a note on the critical point." By Sydney Young, D.Sc., F.R.S. The critical temperature of normal pentane is 197*2",the critical pressure is 25,100 mm. and the critical volume of a gram 4.303 C.C.The vapour pressures and specific volumes were determined from low temperatures to the critical point, and the observations were taken as near to the critical point as pdssible (197.15"),in order to obtain more complete experimental evidence regarding the condition of a Substance at and very near that point. The ratios of the absolute temperatnres (boiling points) and volumes to the critical constants, also the ratio of the actual to the theoretical density at the critical point (3*765),lead to the conclusion that, at the critical temperature and in the liquid state, the molecules are simple, like those of the gas. DISCUSSION. The PRESIDENTsaid that for many years he had been interested in the isopentane derived from American petroleum, having proposed that its flame should be used, under specified conditions, as a standard of light.He had purified it by shaking with sulphuric acid, and after- wards with soda, He had no doubt it was an improvement to use nitric acid, as Dr. Young had done. He had used a dephlegmator very similar to that described, but had never succeeded by fractional distilla- tion in obtaining a substance of such a constant boiling point as that obtained by Dr. Young. He was much interested to hear this proof by Dr. Young of the identity of isopentane with that which is obtained from amyl iodide, as experiments on the illuminating power did not quite settle this question. DR.ARMSTRONGthought that it was not quite certain that the iso-pentane used by Dr.Young was a single thing, and it was probably very difficult to obtain satisfactory proof of purity. In the case of the specimen derived from amyl alcohol, he considered it likely that this was a mixture of two hydrocarbons, as it did not appetw that the amyl alcohol of fusel oil had first been separated into its two con-stituents. DR.CRAWsaid that Dr. Young seemed to have shown that the critical temperature could be determined accurately for the class of compounds on which he had worked ;but he asked whether the critical temperature is capable of being determined with the same accuracy for all classes of compounds, MR.GROVESagreed with Dr. Armstrong as to the necessity of taking special precautions in purifying materials and of not trusting to those supplied by manufacturers.DR.THORPEsaid he had had some experience in the preparation of isopentane. He had obtained it from amyl alcohols of very different origin. The question was whether the isopentane derived from fusel oils of very different origin would give the same hydrocarbon. He had found that all the specimens of isopentane gave practically the same boiling-point and density numbers as those obtained by Dr. Young. Nevertheless, Mr. Rodger and he had found that the viscosities of iso-pentane derived from different sources varied considerably, and it was significant that their specific volumes and specific gravities agreed closely with those recorded by Dr. Young. In the case of other liquids differently prepared and purified, the same viscosity numbers G 0 were obtained ; for example, Professor Dunstan had pi-ovided him with n sample of pure ether and Dr.Perkin also provided him with a sample, and the viscosities of the two were in perfect agreement. Similarly, he had compared two samples of benzene of different origin, and here also the two samples gave the same viscosity number. Cln this account he was inclined to question the homogeneity of isopentane prepared from amyl alcohol. DR.YOUNG,in reply, said he had spent many months in purifying the materials and was satisfied that they were pure. He was, indeed, surprised that doubt should be cast upon the matter. In the fractionation of the pentane and isopentane, he started with considerable quantities of materials, about 1,500 grams, and he obtained about 110 grams of pure substance.The liquid was fractionated about 20 times, and the loss was nearly 20 grams in each fractionation. There were only, as far as he knew, three isomeric pentanes, and as they had distinctly different boiling points, he did not see that there could be any mistake as to their identity. The critical temperatures and pressures are very delicate tests of the purity of the substance. With slightly impure ether, the difference in critical pressure is very considerable. With regard to the fractionation of pentane and isopentane, the ordinary methods of fractional distillation would not answer. With the ordinary still-head, the loss by evaporation was greater than the gain by distillation, but the regulated still-head he had used gave most satisfactory results.He had no hesitation in saying that, with all substances which do not undergo decomposition when heated, the critical point can be determined within one-tenth of a degree. "36. '' On the freezing-point curves of alloys containing zinc." ByC. T. Heycock, F.R.S,, and F. H. Neville. The paper is divided into two sections, the first dealing with cases where the freezing point of zinc is depressed by the addition of another metal, the second with the cases where it is raised by such an addition. In section I, complete binary alloys of the following pairs of metals, zinc-cadmium, zinc-aluminium, zinc- tin and zinc-bismuth, are given.In the first three cases the metals appear to be miscible with each other in all proportions, but for zinc-bismuth the freezing-point curve shows the horizontal line of identical freezing points characteristic of the state when the alloy has separated into two conjugate liquids. Taking the freezing point of zinc as 419O, the authors find for the temperatures of freezing and the composition of the eutectic mixtures the following 61 Alloy. F.P. Atomic percentage of Zinc. Zn-Cd. 264.5 74 Zn-Al. 28: 11 Zn-Sn. 198 84 Zn -Bi. 254.5 91% They do not consider that there is any indication of these metals combining chemically to form definite compounds when they are melted together. Dilute solutions of the following metals in zinc were :tlso examined : lead, thallium, antimony, magnesium.The authors find that, with the exception of aluminium and Cadmium, all the above-mentioned metals, when added in small quantities to molten zinc, cause the same atomic fall : that is, an alloy containing 1 atomic weight in solution in 99 atomic weights of zinc has a freezing point lower by 5.1' than that of pure zinc. Cadmium causes a somewhat smaller and aluminium a decidedly smaller depression. The atomic depression of 5*1°,when used with Van 't Hoff'sequation for the latent heat, gives 28.3 calories for the latent heat of fusion of zinc, instead of Person's value of 28.13. In section 11, dilute solutions of copper and of gold in zinc are con- sidered, and also a complete freezing point curve for all alloys of zinc and silver. When small quantities of any one of these three metals are added to molten zinc the effect is the same: the freezing point is raised, arid the whole mass of metal appears to solidify at a temperature above the freezing point of pure zinc.The rise in the freezing point, more- over, is proportional to the amount of the second metal present. But when as much as 2 atomic per cents. of silver or of copper or 3.3 of gold have been added the phenomenon alters, apparently abruptly. There are now two freezing points, a higher one which is very fugitive, and which is followed by the precipitation of much solid, and a lower one which is very constant, and which is independent of the amount of the added metal so long as the above-mentioned minimum is present. In the zinc-silver curve singularities are also found near 70 and 60 atomic per cents.of zinc, indicating the existence of more or less stable compounds, but the formula of these compounds is uncertain. Kear 37.5 atomic per cents. of zinc there is another well-marked angle and a series of eutectic second freezing points, the phenomenon being possibly due to the separations of the alloy into conjugate liquids. The authors also describe briefly some of the physical properties of the zinc-silver alloys, which appear to change in character at the angles of the curve. The composition of the silver zinc alloys at each freezing point was 62 determined by extracting a portion in the liquid state, and estimating the percentage of silver by a volumetric analysis.DISCUSSION. Mr. NEWLANDSasked whether the formulae of the compounds which were supposed to exist at certain points, viz., AgZn, AgZn,, and AgZn,, represented atoms of the metals, or only that the metals were present in that proportion. Mr. GROVESasked whether there was any connection between the colour of the silver-zinc alloy and any of the points on the curve. Mr. JENKINSasked whether the colour of the alloy was in any way due to the effect of mechanical stress during sudden cooling. DR. CRAWasked whether the atoms in the alloy were in the mon- atomic state, and whether the alloy might be compared with a solution.Mr. NEVILLE,in reply, said the formulie were only empirical. They were disposed to think that the dissolved metal was in a monatomic state. The colour of the alloy did not seem to have any connection with the points on the curve, and although great mechanical stress occurred in its production, this did not seem to afford an explanation of the colour. “37. “The oxides of cobalt and the cobaltites.” By Arthur H. McConnell and Edgar S. Hanes. The authors describe a method for the preparation of alkali cobaltites, and show that cobalt forms an oxide, COO,, and an acid, H,CoO,, which have hitherto been looked upon as hypothetical, and a series of alkali salts on the type of potassium cobaltite, K,OCoO,. The conclusions the authors arrive at are as follows.(1) That Durrant (Proc., 1896, 12, 96, 244) has not produced sufficient evidence for the existence of either cobaltic acid or cobalt percarbon ate. (2) That cobaltous acid corresponds with cobalt dioxide, and forms alkali salts fairly stable in solution, which solutions have an unmis- takable green colour. (3) That cobalt forms a series of compounds with other metals in which the cobalt is part of the acid radicle. (4)That cobalt40us acid and cobaltites are strictly analogous to man- ganous acid and manganites, thus showing that the properties of cobalt are closely allied to those of the other elements associated with it in the periodic classification. Manganese is readily oxidised to the peroxide MnO,, but cobalt much less readily yields the corresponding peroxide coo,.(5) In view of the fact that cobalt dioxide does undoubtedly exist in a number of compounds, the authors suggest that the oxides of cobalt should be renamed, to bring them into line with the corresponding oxides of manganese. (6) It is highly improbable that the formation of this green solution will prove to be of any use for the separation of cobalt from nickel, either quantitatively or qualitatively. *38. A new synthesis in the sugar group.” By Henry J. Horstman Fenton, M.A. In previous communications, it has been shown that the acid (dihydroxyndeic acid) obtained by oxidation of tartaric acid in presence of iron decomposes, on heating with water, almost quantita- tively into glycollic aldehyde and carbon dioxide.Also, that this aldehyde, when heated in a vacuum, undergoes condensation, yielding a sweet-tasting, solid gum which has the formula C6H1206. The present paper describes an investigation which bas been made upon the properties of this condensation product. It is easily soluble in water, and its solution quickly reduces Fehling’s solution and ammoniacal silver nitrate. It gives various colonr-reactions characteristic of ‘sugars,’ and, after purification with alcohol, yields, with phenylhydrazine, a normal hexosazone, C1,H,2N,0, melting at 168-170”. Heated with water to 140°, it yields furfural. It is optically inactive, and appears to be incapable of fermentation hy yeast. The purified ‘sugar,’ when further heated in a vacuum to 100-106°, loses water and becomes hard and brittle, After 2-4 hours’ heating it has the composition C12H2201, and after 24 hours’ heating the com- position nearly approximates to C,H,,O,.The conditions under which tartaric acid may be converted into clihydroxymaleic acid by atmospheric oxygen exhibit close analogies with some of the essential conditions of vegetable grcwth; and it is suggested that the direct production of a ‘sugar ’ in the manner above indicated may possibly help to throw light upon the natural formation of carbohydrates. 39. (‘The dinitrosamines of ethylene aniline, the ethylene toluidines and their derivatives.” By Francis E. Francis, Ph.D., B.Sc. The dinitrosamine of ethylene aniline gives pdi-nitrosoethylene aniline hydrochloride on treatment with a mixture of glacial acetic and hydro- chloric acids, and the resulting tetramine yields quinone on oxidation, showing that it is a p-diamine, ethylenep-phenylene dialvine.The 64 di-nitrosamines of ethylene o-toludine and ethylene m-toluidine yield di-nitroso compounds, which on reduction pass into correspoiiding tetra- mines, whereas the di-nitrosamine of ethylene p-tolnidine is decomposed. This clearly shows that in the substances investigated the nitroso-group can only pass under the treatment described to the p-position in the benzene nucleus. 40. ‘‘Contribution to the knowledge of the P-ketonic acids.” Part V. By S. Ruhemann,M.A., Ph D., and A. S. Hemmg, B,A., M.Sc.Whilst studying the interaction between the sodium derivative of ethylic oxalacetate and ethylic chloi-ofumarate, the authors observed the formation of two isomerides of the formula C,,H,,O,. One of them, melting with decomposition at 200°, forms blue salts with alkalis which, by an excess of the reagent, become colourless. The other, which melts at 123O, does not yield coloured salts, but gives a dark red coloration with ferric chloride. The authors arrive at the view that in the forma- tion of these compounds, ethylic oxalacetate alone takes part, and they represent the constitution of the substance decomposing at 200” by the COOC,H, C==Y*COOC,H,formula, o&co-rr:c.COOC,H, (ethylicanhydro-oxalaconitate), COOEt*C* 0 COOEt the other by the symbol, H~.CO.~.cOOEt(ethylic pyronetricar- boxylste).41. LL Enantiomorphic forms of ethylpropylpiperidonium iodide.” By Clare de Brereton Evans. It has beep found that ethylpropylpiperidonium iodide (C,HloEtPrNI) may be obtained from its solution in absolute alcohol, in right-handed and left-handed crystals. The enantiomorphism, however, is of a purely crystallogenic order: due to the arrangement of the molecules in the crystal, and not to the position of the atonis in space. This is proved by the optical inactivity of the substance in solution, as well as by the fact that either variety may be converted into the other by recrystal- lisation, the behaviour being like that observed in the case of sodium chlorate and bromate, &c., &c.42. Further note on ketopinic acid-pinophanic acid.” By W. S. Gilles and F. F. Renwick. The further investigation of the acid obtained by oxidising the solid hydrochloride from pinene with the strongest nitric acid (Il?*u?as.,1896, 69, 1397), has brought to light a variety of interesting points. Although bromine alone does not, attack it, ketopinic acid is readily brominated if a small quantity of phosphorus be present ; the product has the formula C,oH130,Br. (C =46-18;46.06 ;H =4.96, 5.00 ;Br = 30.70. Calc. C =45.9s ; H =4.98 ; Br --30.66). Monobromoketopinic acid melts at 181O; it is readily soluble in ether, acetone, acetic acid, and ethylic acetate, but sparingly so in benzene, chloroform, and hot water. When heated with aniline or quinoline, it is reconverted into ketopinic acid.The hydroxime of ketopinic acid is merely hydrolysed when boiled with 50 per cent. sulphuric acid, being reconverted into ketopinic acid. When cautiously fused with caustic soda, or even when boiled with an alcoholic solution of sodium ethylate, ketopinic acid is converted into a clibasic acid, Pinophanic acid of the formula C,,H,,O,(C =60.14, 60.13 ; H= 7*86,8*02;Aginsilversalt =51*87,52*03;Calc. C=60*00; H=8*00; Ag =52.17). Pinophanic acid melts at 203" ; it is insoluble in benzene, light petroleum, and chloroform, moderately soluble in hot water and hot ethylic acetate, and readily soluble in alcohol, acetone, and ether. Like ketopinic acid, it does not combine with bromine.Although but slowly attacked, ketopinic acid is oxidised by prolonged digestion with neutral potassium permanganate solution. The product appears to be identical in composition with Kipping's camphotricar- boxylic acid and Marsh and Gardner's camphoic acid, but more closely resembles the latter. These acids are now being fully investigated. 43. I' A synthesis of citric acid." By W. T. Laurence, B.A.,Ph,D. Ethylic citrate was obtained synthetically by the condensation of ethylic bromacetate with ethylic oxalylacetate in the presence of zinc, as indicated by the following equations :-(1) COOEt*CH,Br +ClOOEt : CH,-CO*COOEt + Zn = COOEt*CH, *C(OZnBr) (CH,*COOEt)~COOEt ; (2) COOEt*CH,. C(0ZnBr) (CH;COOEt)*COOEt + H,O =COOEt* CH, *C(OH) (CH,*COOEt)*COOEt +ZnO +HBr.The yield of ethylic citrate is very poor, owing to other reactions proceeding simultaneously. To further confirm the formation of ethylic citrate, it was converted into the calcium salt of citric acid, and a substance obtained showing the charact<eristic properties of calcium citrate, The same salt was also obtained by heating the zinc compound formed in equation No. 1 with alcoholic potash and precipitating the calcium citrate from the hot solution, The results were all confirmed by analysis. The above synthesis of citric acid seems to be of interest as being more direct and simple than the synthesis from sym. dichloracetone or from ethyl y-cyanacetoacetate. 66 ADDITIONS TO THE LIBRARY. I.Purchase. Hintze, Carl. Handbuch der Mineralogie. Zweiter band, Silicate und Titanate. Pp. x+1841, mit 632 abbildungen im text. Leipzig 1897. Brauns, Reinhard. Chemische Mineralogie Pp. xiii + 460, mit 32 abbildungen im text. Leipzig 1896. Duclaux, E. Pasteur : Histoire d’un esprit. Pp. vii +400. Sceaux 1896. Engel, R., et Moitessier, J. Trait6 Eldmentaire de Chimie Biologique, Pathologique, et Clinique. Pp. vii + 615, avec 102 figures intercalkes dans le texte et 2 planches colorides. Paris 1897. Possetto, G. La Chimica del vino. Analisi, alternzioni, mani polazioni, adulterazioni. Pp. xvi + 496. Torino 1896. Register of the Associates a.nd old Students of the Royal College of Chemistry, the Royal School of Mines and the Royal College of Science, with Historical Introduction and Biographical notices, and portraits of Past and Present Professors by T.Q. Chambers. Pp. cxxii + 231. London 1896. 11. Donchtions. Arth. G. Recueil de Procdd6s de Dosage pour l’analyse des com- bustibles des minerais de fer, des fontes, des aciers, et des fers. Pp. iii + 313. Paris 1897. Two copies. From the Publishers. Fresenius’ Quantitative Analysis. Vol II.,part IV. Translated by C. E. Groves, F.R.S. London 1897. From the Publishers. 6’7 PASTEUR MEMORIAL LECTURE. The Pasteur Memorial Lecture will be delivered by Professor Percy Frankland, Ph.D., F.R.S., at an extra meeting of the Society on Thursday, March 25th, at 8 p.m. ANNIVERSARY MEETING. The Anniversary Meeting will be held on Wednesday, March 31st, at 3 o’clock in the afternoon.ANNIVERSARY DINNER. It has been arranged that the Fellows of the Society and their friends shall dine together at the Criterion Restaurant on Wednesday, March 31st, at ‘7 p.m. The.President, Mr. A. G. Vernon Harcourt, in the Chair. The Seeretavies will be gkad to receive early notiJiccction from those Fellows wlm intend to he present. 68 At the next Meeting, on Thursday, March 18th, the following Papers will be received. The authors of those marked with an asterisk have announced their intention of being present. a ‘l On the atomic weight of carbon.” By Alexander Scott, M.A., D.Sc. Q “On a new series of mixed sulphates of the vitriol group.” By Alexander Scott, M.A., D.Sc. * ‘6 The action of alkyl haloids on aldoximes and ketoximes.” By Wyndham R.Dunstan, F.R.S., and Ernest Goulding. _-. RICHARD CLAY AND SONS, LIMITED, LONDON AND BUNQAY.
ISSN:0369-8718
DOI:10.1039/PL8971300057
出版商:RSC
年代:1897
数据来源: RSC
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