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Proceedings of the Chemical Society, Vol. 26, No. 368 |
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Proceedings of the Chemical Society, London,
Volume 26,
Issue 368,
1910,
Page 49-64
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[Issued 11/3,:10 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 26. No.368. Thursday, March 3rd, 1910, at 8.30 p.m., Professor HAROLDB. DJXON,M.A., F.R.S., President, in the Chair. Messrs. A. J. Child, R. H. Cocks, H. H. Hughes, L. C. 'CV. Jenkins, and H. W. Southgate were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Oscar Lisle Brady, B.A., 51, Upper Bedford Place, W.C. Henry Leslie Farmer Buswell, B.A., 169, Queen's Gate, S.W. Thomas Patrick Cheetham, Vrijheid, Natal, S.A. Thomas William Dicksou, B.A., 153, Finborough lioad, South .Kensington, 8.W. Harold Albert Goldsbrough, Churchside, €€erne Hill, S.F. James Kenner, Ph.Z>.,B.Sc., 61, Marlborough Road, Slieffield. Sea-Kwain ICwoh, 125, Acomb Street, Manchester.Samuel Lamb, May Villa, Birmingham Road, West Eromwich. Knowles Preston, Newhaven, Cainden Avenue, Feltham, Middlesex. Certificates have been authorised by the Council for presentation to Ballot under Bye-law 1 (3) in favour of Atessrs.: Georges Baume, 44,Quai des Eaux, Vive, Geneva. Motilal Kashalchand Shah, Byculla Bridge, Bycullit, Bornbay. The PRESIDENYread the names of the Fellows recommended by the Council for election as Oflicers and Ordinary Members of Council of the Society. 50 It was stated that the Society had become indebted to Mr. Ernest de la Rue for a portrait of the late Dr. Warren de la Rue, who was President of the Chemical Society from 1S67 to 1869, and again from 1879 to 1580.The PRESIDENTannounced also that the banquet to the Past-Presidents who have completed fifty years of fellowship vould be held at the Savoy Hotel on Thursday, May 36th, 1910. Of the following papers, those marked * were rend : “54. cL Phenomena observed when potassium mercuri-iodide is dissolved in ether and water.” By James Ernest Marsh. The salt KI,HgT,,U,O dissolves in ether with evolution of heat, and this solution dissolves water with A further evolution of heat. On the other hind, water acts on the double salt with absorption of heat and with separation of pwrt of the mercuric iodide ; the addition of ether to this mixture brings about complete solution with evolution of heat. A solution of one molecular ptoportion of potassium and mercuric iodides in seventeen molecular proportions of ether and water separates, OK~warming, into three layers.As the temperature rises, the middle layer gradually diminibhes in quantity and disappears. On cooling, the middle layer reappears again, and increasing in quantity as the temperature falls, everitually absorbs the other two. A solution of less concentration than the above gives, on warming, two layers, the upper one increasing as the temperature rises and being re-absorbed as the temperature falls. With a solution of greater concentration, two layers are also formed on warming, but in this case it is the lower layer which increases with the temperature and is re-nbsorbed on cooling. When potassium iodide and mercuric iodide in molecular propor- tions are dissolved in cold ether with the addition of sufficient water to form the double salt KI,HgI,,H,O, the latter crystallises on warming the solution, but redissolves on cooling.In dry ether the two salts dissolve, forming a heavy liquid of the composition KI,HgI,,4Et20, which does not appreciably dissolve in excess of ether. DISCUSSION. Mr. MARSH,in reply to Ih. Caw, said that the salt 2KI+HgI, did not bring about the miscibility of ether arid water to the same extent as the salt KI+Hg12, nor was the effect of change of temperature so marked. 51 "55. '' The relation between absorption spectra and chemical con-stitution. Part XIV. The aromatic nitro-compounds and the quinonoid theory.'' By Edward Charles Cyril Baly, William Bradshaw Tuck, and Effie Gwendoline Marsden.It has been proved (Trans., 19OS, 93,1747) that the nitro-group possesses a free period of vibration, and it follows that if in any com- pound the nitro-group is in conjunction with a system which also has a free period of vibration, the substance will show an absorption band arising from the isorropesis which takes place. Such compounds are to be found in the substituted nitrobenzenes, where the substituent groups are of the so-called positive type. For example, the nitro- naphtbalenes, nitrofluorene and nitroquinol dimethyl ether 811 show well marked absorption bands. The position of the absorption bands depends on the position of the band of the group in conjunction with the nitro-group. The results described throw some doubt on the validity of the quinonoid theory, strong evidence being obtained froin the nitrodimethylanilines and the nitrobenzylideneanilines.The position of the absorption band in the nitro-compounds is found to vary with the residual affinity of the solvent. An increase in the residu;zl affinity causes a shift in the band towards the red. DISCUSSION. Dr. HEWITTagreed with Mr. Baly in so far as his results pointed to a similarity in constitution for the salts of p-nitrophenol and for free p-nitroaniline and its dimethyl derivative. He differed, however, in thinking that a quinonoid constitution for p-nitrodimethylaniline was not excluded ; a substance containing strongly positive and negative groups in the same molecule might well be an internal salt, and a structure such as 0 \XI/=\: IY ale2/ \dl0 was by no means improbable.Dr. LowRY'said that he was able to confirm from his own observations the migration of a band towards the visible region on displacing hydrogen by sodium, and in the opposite direction on displacing hydrogen by acetyl, and also the identity of the spectra of compounds containing the radicles *NH, and *ONa;but he did not believe that the nitro-group was capable of producing an absorption band except when acting in conjunction with other unsaturated groups. Such groups were present in nitrobenzene and in nitrostyrene, but not in nitromethane or in nitroethane ; the latter compounds were, how- 52 ever, very unstable, and the bands (which were not produced by nitro-carnphane) might be attributed to decomposition products.The quinonoid formula for sodium o-hydroxycinnamate did not necessarily involve the attachment of sodium to carbon, as the compound might be written : O:C,H,:CH*CH:CiONa),. Dr. MORGANsaid that one interesting point in the paper which had not been referred to by previous speakers was the fact, demonstrated by the authors, that the aromatic meta-nitroamines had absorption spectra quite similar to their ortho- and para-isomerides even when, as in the case of 2-nitrodimethyl-p-toluidine, the migration of a labile hydrogen atom could not take place. The colotir of these meta-nitroamines was often more intense than that of their ortho- and para- isomerides, and this circumstance negatived the view that the colour of the ortho- and para-series was due to the existence in these com- pounds of ortho- and para-quinonoid structures respectively.Another weak point in the quinone hypothesis as regards aromatic deriv- atives was the fact that the heteronuclear nitro-a-naphthylamines (I :5-and 1 :8-) were red, whilst the possibly quinonoid ortho- and para-nitro-a-napht hylamines mere less intensely coloured. The view that colour was dependent on unsaturation or residual a6nity was supported by the study of 6-aminocoumarin. This base and its alkyl and dialkyl derivatives were yellow; but when the nitrogen present passed from the tervalent to the quinquevalent con- dition, the colour disappeared, and the yellow 6-aminocoumarin yielded colourless salts, quaternary halides, and diazonium derivatives.Mr. BALY,in reply to Dr. Hewitt, said that it was not possible that the absorption curve obtained with an aqueous solution of o-nitro-phenol could be a summation curve of those given by o-nitrophenol in alcoholic solution and by sodium o-nitrophenoxide. In reference to the quinonoid formula suggested for the 0-and p-nitroanilines and their dimethyl compounds, namely (I): (1. UI.1 since the absorption spectra of the nitroanilines and the corresponding sodium nitrophenoxides were identical, it would be necessary to write similar formulae for the latter, for example (11),and, as Dr.Hewitt had agreed that this was improbable, it followed that it was equally improbable for the nitroanilines. With regard to Mr. Buttle and Dr. Hewitt’s work on picric acid and trinitroanisole, this was dealt with in the paper, where it was shown that their results were capable of n simple explanation. 53 In reply to Dr. Lowry, he did not understand the objection to the statement that the nitro-group had a free period of absorption, because there seemed to be no doubt whatever on that point as the result of the examination of a great number of compounds, "56. ('Action of ethyl cyanoacetate on 5-chloro-1 :l-dimethyl-h*-c~cZohexen-3-one."By Arthur William Crossley and Charles Gilling. It has been shown (Trans., 1909, 95, 27) that during the action of ethyl malonate on chlorodimethylcyclohexenone, a solid nitrogenous by-product melting at 141' is obtained, its formation being due to the fact that the ethyl malonate employed contained some ethyl cyano- acetate.When the latter substance is used instead of ethyl malonate in the above condensation, there is produced 75 per cent. of the theoretical quantity of the substance melting at 141', which has been shown by s detailed study of its properties and transformations to be ethyl hydroxydimethylcyclo'nexenylidenecyanoacetate, 57. (L The constitution of carpaine. Part I." By George Barger. Carpaine, the alkaloid from the leaves of the Papaw tree, Carica Papaya, L., was discovered by Greshoff, and has been further examined by Merck and by van Ryn (Arch.€'harm., 1897,235, 332), who found that it is a secondary base of the formuh C,,H,,02N.In the present investigation it has so far been shown that carpaine is hgdroljsed by acids and baryta to a substance, C,,H,70,N, soluble in water, which cont,ains a carboxyl group and is also a base. It closely resembles certain amino-acids, and the name cccrparnic acid is suggested for it. When heated with alcoholic hydrogen chloride, carpaine yields the hydrochloride of ethpl carpamate, C,,H,,ON *CO,Et,HCI. The hydrochloride of carpaine is transformed by chlorine into a very unstable, neutral substance, C,,H,,O,NCI,, insoluble in water and melting at 17" after crystallisation from methyl alcohol. The yield of all the above substances is quantitative.On oxidation by potassium permanganate in acetone solution, a nitrogenous acid results, from which ultimately a minute quantity of a crystalline dibasic acid, C8H1404,can be obtained, probably a6dirnethyladipic acid. The latter acid is also produced, in very much larger quantity, by oxidation of carpaine with nitric acid. 53. (‘Optically active glycols derived from I-benzoin and from methyl I-mandelate.” By Alex. McKenzie and Henry Wren. The preparation. of a number of optically active glycols derived from I-benzoin and from methyl I-mandelate was described. Whilst I-benzoin and certain of its derivatives, such as the methyl et’her, undergo racemisation with great ease in the presence of alkali, this racemisatiou is prevented when the cnrbonyl group in I-benzoin is displaced by the CRR*OHgroup.With one exception, the glycols described are dextrorotatory ; I-tri-phenylethylene glycol, for example, has [a], + 221.3O in acetone solution, and, since the same compound may be obtained either from I-benzoin or from methyl I-mandelate, the change of sign is probably not due to a Walden inversion. When I-triphenylethylene glycol is czlkylated by a mixture of methyl iodide and silver oxide, only one of the two hydroxy-groups is methylated. The monomethoxy-compound obtained in this manner has the formula OMe*CHPh.CPh,*OH, and not OH*CHPh*CPh,-OMe, and has [a]13+ 185.3’ in acetone solution. 59. “The colour and constitution of azo-compounds.Part V.” By John Theodore Hewitt and Ferdinand Bernard Thole. The authors have isolated benzeneazobenzenediazonium salts (chloride, platinichloride, and chromate or dichromate) in a solid form. Whilst the two former salts were analysed, the salt of chromic acid proved too explosive (compme Meldola and Eynon, Trans.,1905,87, 4). The chloride is characterised by great stability, and may be kept for months in a solid state without undergoing appreciable change, whilst its alcoholic solution does not undergo rapid decomposition. From a comparison of the absorption spectrum of this salt with those of sminoszobenzene hydrochloride and benzeneazophenyltrimethyl-ammonium iodide, no deductions are drawn as to its constitution, but attention is drawn to this further case of stability of diazonium salts being greatly increased by negative substituents in the para-position.Iodoazobenzene in alcoholic hydrogen chloride gives an absorption spectrum which renders it probable that an iodoniurn salt, C6H,.NH*N: C6H,:I*C1, is produced. Possibly the compound is formed with two niolecules of hydrogen chloride. 60. “The direct union of carbon and hydrogen at high temperatures. Part 11.” By John Norman Pring. In continuation of an earlier investigation (Pring and Huttori, Z’rcms., 1906, 89, 1591), the author has made a quantitative study of the reaction between carbon and hydrogen at temperatures ranging from llOOo to 2200’. The materials used were submitted to the most exhaustive purification, and the presence of moisture and nitrogen was carefully eliminated.The carbon mcts heated electrically, and out of all contact with any possible source of contamination. Direct uuion with hydrogen was found to occur at all temperatures, methane being fornied below 1800”, and methane, acetylene, and ethylene above this temperature. The formation of methane reached a minimum (0.16 per cent.) at about 1550’. Some experiments carried out on the decomposition of acetylene and methane showed that at 1775’ the former gas changes quickly into the latter, ancl the methane decomposes only very slowly. At 1200°, small percentages of acetylene in an excess of hydrogen were found to change slowly into methane and ethylene. In presence of platinum, the reaction between the carbon and the hydrogen was very much accelerated, and values were obtained which, at 1200°, amounted to 0.55 per cent., and at 1500’ to 0.30 per cent., of methane, On decomposing an excess of methane, an amount equAtl to 0.59 per cent.of the gas at 1200°, and 0.33 per cent. at 1500”, remained ; consequently, these numbers probably represent equilibrium values, in presence of platinum, at the temperatures mentioned. 61. “Affinity relations of cupric oxide and of cupric hydroxide ” By Arthur John Allmand. Crystalline cupric hydroxide is stable in ordinary moist air. When, however, it is shaken with alkaline or ammoniacal solutions at 25O, it loses water and becomes converted into cupric oxide. These two facts are apparently contradictory, and to explain them, tensimetric and electrometric experiments have been carried out, leading to the foilowing results.(a) Freshly-prepared cupric oxide ages with time, and its free energy content thereby falls. (b) This ageing is attributed to increasing molecular complexity- not to crystallisation or to surface changes-and is irreversible. (c) The explanation given accounts qualitatively for the electro- motive behaviour of samples of copper oxide which have been subjected to varying thermal treatment, and may perhaps throw some light on phenomena noticed in the determination of dissociation pressures of certain oxides at higher temperatures. (d) The tensimetric and electrometric evidence shows that crystal- line cupric hydroxide is stable with respect to freshly-prepared cupric oxide and unstable with respect.to aged samples of cupric oxide. A saturated solution of cupric hydroxide is unsaturated with respect to ‘‘fresh ” cupric. oxide, and supersaturated with respect to “ aged ” cupric oxide, which fact explains the apparently anomalous stability relations of cupric hydroxide, on the one hand, and cupric oxide and water on the other. (e) The free energy changes associated with a number of reactions at the ordinary temperature have been measured or calculated. (f)The dissociation pressure of cupric oxide at 1030’ has been deduced, and shows excellent agreement with the experimentally determined values. 62. L63-Aminoquinoline and the colour of its salts.” By William Hobson Mills and Walter Henry Watson.Quinoline-3-carboxylic acid has been prepared by a new method, and converted into 3-~cnainoquinoline,which exists in two forms, melting at 84O and 94O respectively. The salts of the base with one equivalent of acid are in sely yellow and fluorescent. The gradual addition of acid to the solution of a fixed amount of base is accompanied by remarkable variations of colour intensity, which are explained as being chiefly due to the formation of a semi-hydrochloride. In addition to a number OF salts of the base, the following compounds have been prepared ; q~inoline-3-carbox~~~~na~~~,3-cccet?/Zcc~~minoquinokirne, 3 -quinolineaxo -/3 -nupI~tho2, 3-hydroxyqui?toline, 2, -chloroquinoline-3-curboxt~lanaide,2-chZoro-3-amir~oquinoli?ze. 63.‘‘ The absorption spectra of p-toluidine, m-xylidine, and of their condensation products with acetaldehyde.” By John Edward Purvis. From an examination of the absorption spectra of the substances mentioned in the title, the author finds that (1) the absorption curves of p-toluidine and m-xylidine are very similar ; (2) the condensation products with acetaldehyde show a disappearance of the more refrang- ible band of the original bases ; (3) the isomeric a-and P-condensation products show very slight differences in the persistencies of the bands; and (4)the addition of hydrochloric acid to the condensation products has no effect on the form or the persistency of the band, 57 64.(‘A supposed case of stereoisomeric teroalent nitrogen compounds.” By Humphrey Owen Jones and Edward John White. Miller and Plachl (Ber., 1896, 29, 1462) found that the interaction of m-xylidine and acetaldehyde in acid solution gave rise to two compounds of the formula Cl,H170N:these were supposed to be stereoisomeric compounds containing tervalent nitrogen. This con- clusion is at variance with the views now held concerning nitrogen compounds, and these substances have therefore been re-examined. The method of preparation has been improved, and it is found that the more soluble a-compound melts at 103-104°, while the less soluble P-compound melts at 127-128”. The a-compound is not transformed into the @-compound by the action of heat or of solvents, but in acid solution each is transformed into an equilibrium mixture, containing two molecular proportions of the a-and one molecular proportion of the P-compound, and this mixture is gradually transformed into 2 : 6 :8-trimethylquinoline.Both compounds give the same oxirne, benzoyl derivative, phenyl- benzylhydrazone, methyl derivative, and condensation product with m-xylidine, but give different products with hydrogen chloride and with nitrous acid. It is clear that the compounds are not stereoisomerides, and it is suggested that the a-compound has the constitution C6H3Me,*NH*CHMe CH,. CHO, whilst the P-compound has the constitution in which the ring readily undergoes fission. Similar isomeric compounds have been obtained from p-toluidine and from $-cumidine.65. ‘‘ The isolation of stable salt hydrates, with special reference to the stable hydrates of sodium carbonate.” By Alexander Charles Cumming. If a mixture of hydrates is exposed to the dehydrating action of a large supply of the corresponding anhydrous salt, the hydrates lose water until the lowest hydrate is left in a pure state, after which no further dehydration occurs. The next lowest hydrate may be prepared in a similar manner by the use of the lowest hydrate as the desiccating agent. It is very probable that all the hydrates of a salt may be prepared in this manner. The process may be carried out in the reverse direction, that is, a hydrate may be prepared in a pure state by the hydrating action of the next higher hydrate, or in the case of the highest hydrate by the hydrating action of the saturated solution.These two methods have been applied to the isolation of the monohydrate, heptahydrate, and decahydrate of sodium carbonate. The rates at which these and other hydrates gain or lose water under certain conditions, and some incidental phenomena, such as a well-defined case of suspended transformat ion, were described. 66. ‘‘ Salts and ethers of 2 : 3 :5-trinitro-4-acetglaminophenol.” By Raphael Meldola and Harold Kuntzen. The trinitroacetylaminophenol described in 1906 (l’runs., 89,1935), which is a pale yellow substance, gives a series of highly coloured and beautifully crystalline salts with metals and certain organic bases.An account of the preparation and properties of these salts was given. The absorption spectrum of the free compound and of its sodium salt, for a study of which the authors are indebted to Dr. J. T. Hemitt, indicates a difference of constitution, and the “isonitro” form is suggested for the salts in explanation of this difference. It was thought possible, in view of the special character of the groups attached to the iminic nitrogen atom in this substance, C,H3O.NH*C,H(NO,),*0H, in which two acid radicles are associated with one hydrogen atom, that conditions might be favourable for the production of an asymmetric molecule containing a tervalent nitrogen atom. An attempt to resolve the compound by means of its brucine salt led, however, to a negative result, but the experiments in this direction are being continued. The silver salt on methylation gives a met/& ethei-(m.p. 194O), which on hydrolysis by sulphuric acid yields 2 : 3 : 5-trin‘itro-4-aminoanisole. The new trinitroanisidine crystallises in dull red, glistening scales melting at 13s-139”. 67. ‘‘The interaction of hydrogen and chlorine. The inhibitive effect of ozone and chlorine dioxide.” (Preliminary note.) By David Leonard Chapman and Patrick Sarsfield MacMahon. In their last communication on this subject (Ikccns., 1909, 95, 1717), the authors expressed the opinion that those substances which prevent or retard the photochemical interaction of hydrogen and chlorine take part in a chemical change with one or more of the constituents of the system hydrogen-chlorine-hydrogen chloride, and that the efficient energy of the chlorine derived from the light is dissipated in causing the change in which the inhibitor participates, thus being rendered incapable of bringing about the union of the hydrogen and chlorine.In complete harmony with this view is the recent discovery that very small quantities of ozone or chlorine dioxide-substances which can obviously react with hydrogen chloride- prevent for a considerable time the interaction of hydrogen and chlorine in light. These effects are being examined in detail, and the influence of other oxidising gases on the interaction of chlorine and hydrogen is being investigated.68. " Diketodiphenylpyrroline and its analogues. Part 111." By Siegfried Ruhemann. The colourless compound C23H,S03N2,which is formed together with diketodiphenylpyrroline by the action of sodiobenzamide on ethyl phenylpropiolate, was found not to have the formula N€€Bz* CPh :CH.CO*NHBz CPh: C Ph(Trans.,1909, 95,984), but NHBZ*C(OH)<~~-&~ , for, on boiling with potassium hydroxide, it yields deoxybenzoin besides ammonia, oxalic acid, and benzoic acid, and wibh cold concentrated sulphuric acid decomposes into diketodiphenylpyrroline and benxamide. The substance C,,H,,O,N,, therefore, is an additive compound of the diketopyrroline with benzam ide. Further, the d i ketopyrr oline unites with phenylmercaptan or piperidine to forrn'the compounds C,,H,,O,N,C,H,S and C,,H,,O,N,C,H,,N respectively ; it also condenses with phenol in a manner similar to isatin, and yields the compound The diketopyrrolines give the indopheuine reaction.69. '(Triphenyl-2-pyrone." By Siegfried Ruhemann. Whereas acetone or acetopheuone reacts with ethyl phenylpropiolate and sodium ethoxide to yield 4-pyrone derivatives (llrans., 1908, 93, 431, lZSl), such a condensatioii does not take place on using p-tolyl methyl ketone, propiophenone, or methyl ethyl ketone ; the only change which occurs is the hydrolysis of the acetylenic ester. Deoxybenzoin, however, condenses with ethyl phenylpropiolate with the formation of 4 :5 : 6-t~i~henyZ-3-pl/~.one, CO---CH>CphO<CPh:CPh (m.p. 245--246O). This compound is decomposed by potassium hydroxide in two directions, namely : (1) C:&*& +H,O =CO, + C,,H,,O, and yields an alkylidenedeoxybenzoin. On account of its behaviour on melting (it softens at 76'and is completely melted at go'), it is regarded as a mixture of stereoisomerides of methylbenzylidenedeoxy-benzoin, CPhMe:CPh*COPh, which could not be separated by crystallisation. Another part of the 2-pyrone compound decomposes thus : (2) C,,H,,O, + 2KH0 =CH,Ph*CPh:CH*CO,K +C,H,*CO,K to form a mixture of isomeric P-benzylcinnamic acids, one of which could be obtained pure and melts at 1.68-169'. This acid, on reduo-tion, yields P-phenyl-P-benzylpropionic acid (m. p. 95-96'), and with concentrated sulphuqic acid condenses to 3-phenyl-1-naphthol, (Ill.p. 100-1010). 70. ('The solubility of organic acids and bases in solutions of their salts." (Preliminary note.) By Nevi1 Vincent Sidgwick. Aniline is known to be more soluble in a solution of its hydro- chloride than in pure water. An attempt was made to determine how far this property was shared by other bases, and by phenols and acids. o-Toluidine beha.ves in the same way as aniline ;but the alkylamines examined (amylsmine, diamylamine, and dipropylamine) appeared to be less soluble in the salt solution. With phenols and monobasic acids an increase of solubility was found in every instance, whether they separated from the solution as liquids or as solids. The results are contained in the following table.Normsl-Ten~p- ity of Solubility in Substance. erature. salt. JYater. Salt Solution. Ratio. I% Aniline ..................... 25" 1 0.38 0-54 1.4'5 0.05 x lo-* 40" 1 0.42 0-65 1.5" 60" 1 0.50 0'81 1.6" 80" 1 0'61 1*07 1.7" o-'l'oluidine ............. 25" I 0'14 0.28 2-0 Phenol ................... 25" I 0.85 --50 x lo-* o-Cresol.................. 2.5 1 0.24 0.iO 2 9* 40 1 0 26 0.77 3 .o* 60" 1 0.31 0'91 3'0* SO" 1 0'39 1'26 3.2* o-Nitrophenol ............ 4s" 1 0'028 0 069 2.4" 750 x Benzoic acid ............... 25" 1 0.026 0'044 1.7 0.006 p-'l'olnic acid ............ 25" 1 0 0031 0.0054 1.8 0*006 p-Nitrobenzoic acid ...... 25" 1 0'0024 0.0046 1'9 0-040 Sa!icylic ,, ...... 25" 1 0.016 0.036 2.3 0-102 Ciiiiiainic ,, .....25" 0.5 0.0041 0'0105 2.5 0'004 #l-Phenylpropionic acid. 25" 1 0.050 1'15 22*9* 0.02s 11" tl 0'032 0.051 1'6 Hippuric ,, 25" 1 0'039 0.078 2'0 0'022 &Iodopropionic 25" 1 0'40 0.63 1-6 0'00977 Those cases where the substance separates in the liquid form are marked with an asterisk. 61 The table gives the solubility (in terms of normality) of the substance in the salt solution and in pure water, the ratio of the first of these to the second, and the dissociation constant of the acid or base. /3--Phenylpropionic acid at 25’ separates in a liquid form containing less than 50 per cent. of pure acid ;at 1l0 the solid acid crystallises out, but some of the salt with it. Phenol is miscible in all propor-tions with a normal solution of its sodium salt at temperatures above 13”.Where the substance separates as a liquid, the salt no doubt dissolves in both layers, and this may partly (and perhaps wholly in the case of the aromatic amines) explain the increase in solubility, since the mutual solubility of two liquids is always increased by the addition of a third substance, which dissolves more or less equally in both. Where the solid acid separates, this explanation cannot apply, and the phenomenon is probably due to the formation in the solution of a compound between the acid and the salt or its ions. This is con-firmed by the numerous instances in which acid salts of monobasic acids, of the type NaHA,, have been isolated in the solid state (see Farmer, Trans., 1903, 83,1440).The work is being continued. 71. <‘1 :4-Dichloroanthraquinone and its derivatives.” By Gertrude Maud Walsh and Charles Weizmann. An account was given of the condensation of 3 :6-clichlorophthalic anhydride with benzene and with the methyl ethers of o-, m-, and p-cresol. 72. The synthesis of A1-cyclopenteneacetic acid and of l-methyl-A2-cycZohexene-3-acetic acid.” By Victor John Harding and Walter Norman Haworth. The condensation of cyclopentanone and 1-methylcyclohexan-3-one with ethyl cyanoacetate, either through the agency of sodium ethoxide or piperidine, gives rise to cyano-esters containing the ethylene linking in the ring. These cyano-esters, FHz--cH>C*CH( CN) C0,Et and CH,<CHMe.cHcH2-cH2~~*~~(~~)o~~,~~, 011 hydrolysis yield the corresponding acetic acids : 62 73.‘‘Solubilities below and above the critical temperature.” By Dan Tyrer. The solubilities of sodium iodide in ethyl alcohol and of potassium iodide in methyl alcohol have been measured from the ordinary temperature to about 300’. In both cases the solubility in the liquid solvent at first increases and then decreases. Just below the critical temperatures of the saturated solutions the solubility decreases very rapidly, the curve being almost parallel to the solubility axis. It is found that above the critical point the salts dissolve to quite moderate extents. The solubility above the critical point, however, depends on the concentration of the solvent, that is, the amount of solvent contained in unit-volume.The effect of temperature on the solubility in a solvent of a particular concentration is very slight, but is greatest for the greatest concentrations, and for small concentrations it becomes immeasurably small. ADDITIONS TO THE I,IBRARY. 1. Donations. American Electrochemical Society. Transactions. Vols. XII-XV. Philadelphia 1907-1909. (Eefe‘ere?we.) From Dr. F. Mollwo Perkiu. Institute of Chemistry of Great Britain and Ireland. list of oficial chemical appointments compiled, ... by Richard B. Pilcher. 3rd edition, pp. 234. London 1910. (Reed. 15/2/10.> From the Institute. Lowe, Houston. Paints for steel structures. pp. 115. New Yolk 19 10. (Red 21/1/10.) From the Publishers : Messrs.John Wiley & Sons. Passon, Max. Kleines Handworterbuch der Agrikultnrchemie. 2 vols. pp. iv+454, 415. ill. Leipzig 1910. (Reed. 16/2/10.) From the Publisher : Wilhelm Engelmann. Sexton, A. Hurnboldt. Fuel and refractory materials. pp. x+ 364. ill. London 1909. (Reed. 15/2/10.> From the Publishers : Messrs. Blackie & Son. Watson, Richard. Institutionum chemicarum in Praelectionibus Acsdemicis explicatarum, Pars Metallurgica. pp. [viii] + 58. Cantabrigiae 1768. (Rffereme.) From Professor a. Carey Foster, LL.l)., F.R.S. 63 11. By PuivAme. Rape, IIms. Anleitung zum experimentieren in cler Vorlesung iiber organische Chernie. pp. x + 130. ill. Brauuscfiweig 1909. (Recd. 16/2/10.> Thibaut, P[ier~e].The art of chymistry : As it is now practised. Written in French by P. Thibaut, Chymist to the French King. And now translated into Englis’n, by a Fellow of the Roynl Society [W.A.]. pp. xxx + 279. London 1668. (Kefeyence.) ZII. Yasnphlets. Bredig, Georg, and Kerb, J. JK Uber die elektrische Reizschwelle katiilytischer Pulsationen. (From the Ve,*h. XcctudList. Med. Kweiw Heidclbery, 1909, lo.)Comessatti, Giussppe. L’azione rlello jodio e (lei suoi composti sull’ adrennlinh. (From the Arch. liicrntacol. sp~.Ski. afi)~i, 19\39, 8). Haensel, IIein?*ich. Bericht. April-September 1909. pp. 74. Pirna. Hellsten, A. 3’. Der Einfluss des Trainierens auf die (20,-hbgahe bei isometrischer Muskelarbeit. (From the Skand. B~chiw.Physiol., 1909, 22.) Herp, V.,and Wohler, P.Zur Kenntais der gebundenen schtvefligen Yauren. IV und V hbhandlung. (From the A9.b. Kais. Gesundheitsamte, 1909, 32.) Xremann, IZ. ber die Fortexisteuz vou Doppelsalzen, iin besotideren von Karnallit und Schonit in wasseriger L6snng. (From the Juhrb. I[. K. Geol. Reichsanstalt, 1908, 58.) Beitrage zur Kenntnis isomorpher Mischungen. (From the Jcdwb. K. K. Geol. ReichsmstaZt, 1908, 58.) Hremann, R.,and Xiittinger, K. Uber die Lcislichkeit VOII Aluminiumhydroxyd in hluminiurnsulfatliisungen und zur kunstlichen Darhtelliing von Alumian. (From the Jahrb. I{. K. Geol. ReichsanstaZt, 1908, 58). Lenormand, C. Ddtermination du degrk de pollution des eaux de mer par Ie dosage des matihres organiques. (From the BUZZ.SOC.Pharrn., 1909, 16) Mayerhofer, Ernst.Einiges zur Esbachschen quantitativen Eiweiss- bestimmung und iiber eins neue Kreatininverbindung. (From the Wien. Klin. Voch., 1909, 22.) Mingaye, J.C. H. Notes from the Chemical Laboratory. No. 2. (From the Records Geol. Sur. N. S. Wccles, 1909, 8.) Schimmel & CO. Bericht, Oktober 1909. pp. 236. Leipzig. 64 SzQki, Tibor. Ueber einige anormale Eigenschaften des Asaryl- aldehyds. (From the Naturw. Museumsheften, 1909, 4.) Thunberg, Torsten. Studien uber die Beeinflussung des Gasaus- tausches des uberlebenden Proschmuskels durch verschiedene Stoffe.. (From the Skand. Archiv. Physiol., 1909, 22.) Walter, L.W, The metal tungsten as ‘‘ valve ” electrode. (From the J. PTOC.Inst. Elect.Eng,, 1909, 43.) ANNUAL GENERAL MEETING The Annual General Meeting will be held on Friday, March lsth, 1910, at 5 p.m., when the President will deliver his address, entitled, ‘(The Union of Hydrogen and Oxygen in Flame.” At the next Ordinary Scientific Meeting on Thursday, March 17th,. 1910, at 8.30 porn., the following papers will be communicated : “Organic derivatives of silicon. Part XIII. Optically active compounds containing one asymmetric silicon group.” By F. Challenger and F. S. Kipping. “Studies of dynamic isomerism. Part X. The relationship between absorption spectra and isomeric change. Absorption spectra of camphocarboxylic acid and its derivatives.” By T. M. Lowry, C. H. Desch, and F. W. Southgate. “ Studies of dynamic isomerism. Part XI. The relationship between absorption spectra and isomeric change. Absorption spectra of the acyl derivatives of camphor.” By T. M. Lowry and H. W. Southgate. “The action of aromatic amines on malonic ester.” By F. D. Chattaway and J. M. D. Olmsted. R. CLAY AND SONS. LTD., BREAD S’I’REBT HILL, E.C., AKI) UUNGAY, SUFFOLR.
ISSN:0369-8718
DOI:10.1039/PL9102600049
出版商:RSC
年代:1910
数据来源: RSC
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