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Proceedings of the Chemical Society, Vol. 29, No. 417 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 417,
1913,
Page 179-214
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[Issued 14,'G/13 OF THE Vol. 29. No. 417. Extra Meeting, Thursday, May 22nd, 1913, at 8.30 p.m., Prof. WILLIAM LL.D., F.R.S., President, in the Chair. H. PERKIN, The Van't Roff Memorial Lecture was delivered by Prof. JAMES WALKER,D.Sc., F.R.S. A vote of thanks to Prof. Walker, proposed by Sir William Ramsay, K.C.B., F.R.S., and seconded by Sir William Tilden, F.R.S., was supported by Prof. H. E. Armstrong, F.R.S., and by Prof. F. G. Donnan, F.R.S., and carried with acclamation. Thursday, June 5th, 1913, at 8.30 p.m., Prof. W. €I.PERRIN, LL.D., F.R.S., President, in the Chair. Reference was made to the death, on May 16th, 1913, of Mr. Walter Shelley Spencer, of Farnworth, who was elected a Fellow on June 16th, 1887. Messrs. P. P. Phillips aiid A.G. Dix were formally admitted Fellows of the Society. Certificates were read for tlie first time in favour of Messrs. : Parmanaiid Mewaram Advani, M.A., B.Sc., Dayaram Jethmal Sind College, Karachi, India. Alan Hamilton Bateman, 12, Cliadwick Road, Leytonstone, N.E, 180 Norman Phillips Campbell, B.A., Trinity College, Randy, Ceylon. Mohamed Shams Eldin, B.Sc., The University, Manchester. Charles Huxtable, Devonia, Menlove Avenue, Liverpool. Benedict Hugh Rolfe, M.A., Wheatley, Oxon. Philip Howard Stott, Tottington Road, Harwood, Bolton. John Algernon Lacy Sutcliff e, 44,Broad Street, Birmingham. Messrs. H. Rogerson and E. Walker were elected Scrutators, and a ballot for the election of Honorary and Foreign Members was held. The following were subsequently declared duly elected : Prof.Dmitri Petrovitsch Konovaloff (St. Petersburg). Prof. Alfred Werner (Zurich). Of the following papers, those marked * were, read: *157. The relation between the absorption spectra and consti-tution of piperidine, nicotine, cocaine, atropine, hyoscyamine, and hyoecine.” By James Johnston Dobbie and John Jacob Fox. The absorption spectra of piperine, nicotine, cocaine, atropine, and hyoscyamine have been examined, and it has been shown that the spectrum in each case is practically identical with that of the unreduced nucleus of the molecule, namely, piperic acid, pyridine, benzoic acid, and tropic acid (compare T., 1911, 99, 1254; 1912, 101, 77). It has also been found that hyoscine (I-scopolamine), although differing in composition from atropine, gives the same spectrum, the difference between the two alkaloids lying only in the unreduced part, of the molecule.*158. (( The constituents of hops.” By Frederick Belding Power, Frank Tutin, and Harold Rogerson. A consideration of the literature, together with the results of the present investigation, has led the authors to conclude that most of the products hitherto obtained from hops were of a very indefinite nature. A coiisiderable number of well-defined substances, in-cluding some new compounds, have now been isolated and completely characterised. It has been shown that the bitterness of hops is not due to any single substance, but is to be attributed to a number of products, which are mostly amorphous.Some of these products are soluble in water, whilst others represent constituents of the resin. One 181 well-defined, new, crystalline substance, which possesses a bitter taste, has now been isolated from the resin, and designated humulol. This compound is phenolic in character, has the empirical formula C17H1804,and, when crystallised from 50 per cent. acetic acid, forms needles of a pale fawn colour, which melt at 196O. Another new, crystalline compound, of nearly the same percentage composition as humulol, but which has an orange-yellow colour and is devoid of bitterness, has been designated xanthohumol. This substance appears to possess the formula C1,H140,, and melts at 172O.The present investigation has furthermore shown that the resin of hops contains a large proportion of fatty acids and their esters, a fact which does not seem to have previously been observed or considered. It follows that such of the proposed methods for the valuation of hops as are based on the titration of extracts obtained by means of light petroleum and similar solvents are of very doubtful utility. DIScus SION. Mr. GRANTHOOPERcongratulated Dr. Power and his co-workers on the interesting and valuable results of this long over-due investigation. He understood that the volatile essential oil which was removed by steam distillation of the extract upon which the authors worked was disregarded, but he asked whether they could say, nevertheless, if the whole of the odorous character of hops was connected with this volatile essential oil.He realised, of course, that the flavour of hops was of a compound nature, but he would like to know whether the authors were of opinion that the bitter character was exclusively associated with one or all of the resinous substances which had been isolated. Mr. CHASTONCHAPMANsaid that so far as he was aware no one had ever supposed that the separation of the resin constituents into the so-called a-,p-,and y-resins represented a sharp chemical separation. It did, however, effect a certain degree of separation, and had done very good service from the technical point of view. He also thought that it had been very generally recognised for a considerable time that the bitter flavour of hops was due to a number of substances, and not to any one single constituent.The waxes and certain of the fatty acids were very general constituents of plants, and could not account for any of the characteristic properties of hops. In regard to fatty acids, he was interested in finding that Dr. Power had met with nonoic acid, since some years ago he (Mr. Chapman) had called attention to the fact that this acid existed in the form of an ester in the essential oil, and was obtained by the oxidation of that oil with chromic acid. He suggested that in the hop itself 182 that acid had probably resulted from the hydrolysis of the ester or from the oxidation of the oil. A number of chemists, who had made a special study of hops, both from the chemical and from the technological points of view, had described certain well-defined crystalline acids which were stated to be closely related to the true resius, and he (Mr.Chapman) did not see which of the constituents mentioned by Dr. Power corresponded with those so-called hop- bitter acids. It was evident that there was still a very great deal to be learned, and in the meantime it would be very interesting to know what light the work of Dr. Power and his colleagues threw on such a very important question as the preservative properties of hops, and how it explained the conversion (by simply boiling with water) of the petroleum-soluble and preservative constituents into products insoluble in petroleum, and possessed of little or no pre- servative properties.Unless the investigation helped to supply an answer to this and similar questions, its practical value would be considerably diminished. He would like to know from which constituent the valeric acid formed on oxidising the resin was derived. Dr. POWER,in reply to a question by the President, stated that humulol and xanthohumol contained no nitrogen, and did not combine with acids. In reply to Mr. Grant Hooper, it was stated that the aroma of hops could only be attributed to the essential oil. It was also explained that as the essential oil obtained in this investigation from an alcoholic extract of hops would naturally differ consider- ably in composition from a normal oil, as obtained by the direct distillation of hops with steam, it was not deemed desirable to record its characters. With reference to Mr.Chapman’s remarks respecting the character of the substances precipitated from a petroleum extract of the resin by alcohol, it was stated that, in view of tlie complexity of the extract, a product obtained by such a method would neces- sarily consist of a mixture of substances. *159. The nitrogenous constituents of hops.” (Preliminary note.) By Alfred Chaston Chapman. In 1910 the author published (Proc. Intern. Congress of Brewing, 1,93) the results of a preliminary investigation of the nitrogenous constituents of hops, and pointed out that he had commenced a detailed study of the various nitrogenous substances present, that he had already succeeded in obtaining certain crystalline bases, and that the work was being continued. As it has recently come to 183 his knowledge that Power has been engaged in the investigation of this subject, it appears necessary to give some account of the work so far as it has gone.This work is being continued, and a further communication will be made to the Society in due course. Owing to the presence in hops of large quantities of resinous materials, the isolation of the crystalline nitrogenous substances, which occur in relatively small proportions, is a matter of very considerable difficulty, and in the course of the investigation four different methods of obtaining these substances have been adopted.In some cases the hops themselves were extracted in the laboratory, but in other cases the extract prepared on the commercial scale was very kindly placed at the author’s disposal by the Hop Extract Co., Ltd., to whom his thanks are due. Sometimes the extract represented hops of one particular kind, whilst at other times the extract from hops of mixed growths was intentionally used. In the first method of working the concentrated aqueous extract of hops was precipitated with basic lead acetate, and the filtrate, after the removal of the excess of lead, was precipitated with phosphotungstic acid. The phosphotungstic precipitate was treated in the usual way, and to the solution containing the liberated bases, ammoniacal silver solution was added for the precipitation of purines.From this precipitate, histidine was obtained. The filtrate from the purines, after having been freed from silver, was evaporated to dryness, and the residue submitted to a process of fractional crystallisation from absolute alcohol, followed by fractional precipitation with mercuric chloride. By these methods betaine and choline were isolated, and another base, which is being examined, was obtained. From the filtrate from the phosphotungstic precipitate, nsparagine was isolated, together with another amino-compound, which has not, at present, been identified. In the second method the hops were mixed with lime, boiled with water, and the resulting mixture evaporated, dried, powdered, and extracted with alcohol.This extract was freed from alcohol, and precipitated with phosphotungstic acid. The solution of the bases thus obtained was precipitated with an ammoniacal solution of silver chloride, and from the resulting precipitate adenine and hypoxanthine were isolated. In the filtrate from the purine precipitate, betaine and choZi?ze were again obtained. In the third method the hops were extracted with ammonincal amyl alcohol, which was in turn extracted with water acidified with hydrochloric acid. The acid extract was treated with phospho- tungstic acid, and from the resulting solution of the bases adetlille 184 was again isolated. Betaine and choline were also again obtained. In this extraction a small amount of a definitely alkaloidal sub- stance was separated, but the quantity was insufficient for complete identification.With the view of obtaining confirmatory evidence as to the nitro- genous constituents present, a concentrated aqueous extract of hops was treated with a mixture of alcohol and acetic acid, filtered, the filtrate freed from alcohol, and the residue extracted with water. This aqueous extract was then treated systematically with various immiscible solvents. The residue from the amyl alcohol extraction, on treatment with an alcoholic solution of oxalic acid, yielded a precipitate from which hypoxanthine was isolated. From the aqueous extract, which is at present under investigation, a coloured nitrogenous substance was obtained, which is acid in charac- ter, and dissolves in alkalis, forming deep brownish-red solutions.The examination of this substance is still in progress. That portion of the hop extract which was not dissolved by the alcohol-acetic acid mixture was repeatedly extracted with water, and the combined aqueous extracts treated with lead acetate and lead oxide. The filtrate, after having been freed from lead, was evaporated, and the residue, after fractionation with alcohol and the removal of the greater part of the potassium by means of tartaric acid, was prel cipitated by copper acetate with €he addition of alcohol. From this precipitate, substances were obtained exhibiting properties which indicate that they are complex amino-acids or polypeptides, or more probably mixtures of these substances, and experiments are now in progress with the object of separating and identifying them.Although not a nitrogenous compound, it may be mentioned that the insoluble residue from the alcohol-acetic acid extraction, when extracted with hot glacial acetic acid, yielded on cooling a crystalline substance, melting at about YOo, which was almost insoluble in alcohol, and but sparingly so in acetic acid. This sub- stance, which is the ‘‘wax ” so frequently referred to in the literature of the subject, is being investigated. From one of the alcohol extracts of the aqueous hop extract, well- formed crystals separated, which on examination proved to be potassium nitrate. Results have been obtained showing the proportions in which the various groups of nitrogenous compounds are present in hops, and these will be given when the full communication is made.The author is also engaged in an investigation of the technological significance of these nitrogenous constituents, the results of which will be published in due course. 185 “160.‘(Anomalous rotatory dispersion. ’’ (Preliminary note. ) By Thomas Martin Lowry and Thomas William Dickson. By means of a photographic method the rotatory power of ethyl tartrate has been followed up to a point in the far violet region of the spectrum at which the ester produces a lzevorotation coin- parable in magnitude with the maximum of dextrorotation observed with a yellow light.The rotations €or 5 points observed plioto- graphically and for 13 wave-lengths observed with the eye can be expressed by the formula : k ka=L -2 X’L-X2 p-p‘ This confirms the view of Biot that anomalous rotatory dispersion is produced by the admixture of two substances differing in rotatory dispersive power as well as in the sign of their optical rotatory powers. Slow changes of rotatory power with time, comparable with those observed in methyl camphorcarboxylate, were found to take place in the liquid ester. DISCUSSION. Dr. LOWRY,in reply to a question by Mr. Walker, said that the effect of changing the temperature of ethyl tartra.te or of altering the solvent would probably be to alter the magnitude of the two ‘‘rotation constants ” without altering the corresponding (( dis-persion constants.” It would be quite impossible, however, to detect small changes of dispersive power by analysing a curve which involved four arbitrary constants.161. ‘‘Equivalent conductivities of sodium hyponitrite, calcium hyponitrite, and hyponitrous acid.” By Prafulla Chandra Rfy, Rajendralal De and Nilratan Dhar. Equivalent conductivities of sodium hyponitrite, calcium hypo- nitrite, and hyponitrous acid at various dilutions have been deter- mined at Oo. The ionic mobility of hyponitrosion is 38 (nearly) at Oo. Further, hyponitrous acid is found to be weaker than acetic acid, and stronger than carbonic acid. 162. ‘‘ Double carbonates of the alkaline earth metals and lead with potassium carbonate.” By Rasik La1 Datta and Haridas Mukherj ea.In a paper on the double platinic and cupric iodides (Datta, T., 1913, 103,426), it has been pointed out, t1ia.t the method of double decomposition in the presence of an excess of the substituted ammonium iodide was successful in the isolation of the double salts, and it was thought possible that such an indirect method might be usefur in the formation of double carbonates which cannot be prepared by direct means. Recently Barre (Compt. rend., 1912, 154, 279) tried to obtain some double carbonakes by directly boiling the precipitated carbonates in saturated solutions of the alkali carbonates. In the case of calcium, he succeeded in preparing two salts only, namely, CaC0,,Na2C03,2H20 and CaCO,,K,CO,, but he failed to obtain double salts with strontium carbonate and barium carbonate even after boiling them for twenty hours in a saturated solution of the alkali carbonates.The method of preparation of these double salts consists in preparing a saturated solution of potassium carbonate at the room temperature and adding to it the solutions of the metals, preferably the chlorides, when the double salts are at once precipitated. In this case, as in that of the double cupric iodides, the precipitates are unstable in the presence of water, as they dissociate into their constituents, and hence could not be washed freely with water. It is for this reason that a saturated solution of potassium carbonate has been used throughout, and the precipitated salt separated from the mother liquor by strong suction without washing with water.Barium and strontium carbonates combine with only one molecule of potassium carbonate to form the salts BaCO,,K,CO, and SrCO,,K,CO, respectively. Lead carbonate, on the other hand, combines with two molecules of potassium carbonate to form the salt PbC0,,2K2C03, and calcium combines with three molecules of potassium carbonate to form the salt CaC0,,2K,C03. The abnormality of the composition of double lead and calcium carbonates might be explained in the case of the former as due to its heavy molecular weight, and in that of the latter as due to a special tendency for salt formation, since it forms double carbonates with potassium carbonate even by the direct method.1’otassiu.m Barium Carbonate, BaCO,,K,CO, (compare Le Chatelier, Compt. rend., 1894, 118, 415). To a saturated solution of potassium carbonate, a concentrated Bolution of barium chloride is added, when the double salt is at once precipitated. This is triturated in a mortar with the mother liquor, and filtered with the aid of the pump. The salt could not be washed with water, since it decomposes into its constituents : 187 0.1802 gave 0.1242 BaSO,. Ba = 40.55. 0.7162 ,, 0.4906 BaSO, and 0.3536 K,SO,. Ba=40.27; K =22-11. BaC0,,B2C0, requires Ba =40.89 ; K = 23.28 per cent. Potassium Strontium Ca,rbonat e, SrCO3,K2CO3. When a concentrated solution of strontium chloride is added to a saturated solution of potassium carbonate, a transparent, jelly- like mass is obtained, which gradually becomes opaque, and finally, on continued stirring, assumes a granular appearance.After triturating in a mortar, it was collected as usual with strong suction, and allowed to dry in the desiccator. The salt could not be washed by water, since it is decomposed by air: 0.5393 gave 0.3287 SrSO,. Sr =29.07. 0.4365 ,, 0'2704 SrSO,. Sr=29*55. SrCO,,K,CO, requires Sr = 30.52 per cent. Potassium Calcium Carbonate, CaC0,,3K2C0, (compare Le Chatelier, loc. cit. ; Butschli, Verb. naturhist.-med. Ver. Heidel-berg, [iij, 8, 277). This is obtained similarly to the above salt, at first as a transparent jelly, which gradually becomes opaque, and is finally transformed into a fine, crystalline powder, which could be collected very easily. The salt was tested for water of crystallisation, which, however, could not be found : 1.0882 gave 0.176 CaO.Ca = 7-73. 0.4726 ,, 0.0544 CaO. Ca=7'85. CaC0,,3K,C03 requires Ca = 7.77 per cent. Potassium Lead Curbotzate, PbCO3,2K2CO,. This is obtained as an amorphous precipitate by adding a on-centrated solution of lead acetate to a saturated solution of potassium carbonate. After triturating in a mortar, it was collected by the aid of the pump, when it remained on the filter as a sticky mass, which was allowed to dry in the desiccator. The salt could not be washed for reasons previously assigned: 0.9268 gave 0.5174 PbSO,. Pb = 38.19. 0.5462 ,, 0.3018 PbSO,.Pb=37.73. PbC0,,2K,C03 requires Pb = 38.23 per cent. The authors are at present engaged in preparing other double carbonates of the series, not only with potassium carbonate, but also with the carbonates of the substituted ammonium bases. 188 163. ‘(The estimation of nitrites by means of thiocarbamide, and the interaction of nitrous acid and thiocarbamide in presence of acids of different strength.” By May Emily Coade and Emil Alphonse Werner. In continuation of work already published (T., 1912, 101, also), experiments have been carried out to test the value of thiocarbamide as a reagent for the estimation of various nitrites. The results have shown that thiocarbamide is a reagent superior to any of those which have been employed hitherto in the estimation of nitrites by the gasometric method.The advantages of the method are as follows: (1) The accuracy of the results are not affected by the presence of nitrates, even when in large excess. (2) Analyses can be completed in a few niinutes; no subsequent manipulation of the evolved gas is necessary as when carbamide is used ;the chances of experimental error are thereby reduced. (3) The gas can be read off with great accuracy; even after a large number of analyses the mercury in the nitrometer remains quite untarnished, which is not the case in other methods, (4) A much larger number of analyses can be made in a given time than by the other methods; two minutes suffice for the complete evolution of the gas (nitrogen) when acetic acid is used; by the carbamide method, twenty-eight minutes were required to complete the reaction.In the presence of a weak acid, the change takes place according to equation (a), in the presence of a strong acid according to equation (6) : (a) CSN,H, + HNO, =HSCN +N, +2H,O. (b) 2CSN,H, +2HN0, =C2S2N4H,+ 2N0 + 2H20. The total volume of gas evolved is the same in each case for the same weight of nitrite used. The influence of a number of acids on the direction of the change was examined. It was shown that reactions (a) and (b) proceed simultaneously according to the nature of the acid used, and the direction of the change on the lines of equation (6) was found to be directly proportional to the dissociation constants of the acid.164. ‘‘A case of isomerism in the methylated ferrocyanides.” By Ernald George Justinian Hartley. Further experiments on the preparation of tetramethyl ferro-cyanide by heating hexamethylferrocyanogen chloride show that 189 the former compound is thereby produced in two forms, having the same percentage, composition, and molecular weight, but exhibiting quite distinct properties. 165. ‘‘ Preparation of secondary amines from carboxylic acid. Part 111. Disecondary amines from dicarboxglic acids.” By Henry Rondel Le Sueur. The a-anilino- and a-1- and a-2-naphthylamino-derivativesof dicarboxylic acids, when heated above their melting points, readily lose two molecules of carbon dioxide, with the formation of the corresponding secondary amines. Thus, a 69 per cent.yield of s-diphenyloctamethylenediamine is readily obtained from ae-di-anilinosebacic acid : CO,H* CH(NHPh) [CH,],*CH(N HPh)*CO,H N11 Ph*[CH,]7-NHPh. The results obtained show that the method is of general appli- cation, and very suitable for the preparation of the alkyl derivatives of aniline and naphthylamine. 166. ‘‘ Guanidine thiocyanate : its formation from ammonium thiocyanate.” By Hans Krall. Guanidine is produced when ammonium thiocyanate is heated beyond the temperature at which thiocarbamide is formed. The equations usually given to explain the change appear to be purely hypothetical, and no careful experiments seem to have been made with the view of establishing the mechanism of the process.It was shown that the thiocarbamide first formed partly decom- poses into hydrogen sulphide and cyanamide, the latter uniting with unchanged ammonium thiocyanate to form the guanidine salt. The volatile products are hydrogen sulphide, ammonia, carbon disulphide, and the products of interaction of these. The carbon disulphide results from the interaction of hydrogen sulphide and thiocyanic acid : H2S+ HNCS =NH3+CS2. Since thiocarbamide dissociates into ammonia and thiocyanic acid in its reversion to ammonium thiocyanate (Werner, T., 1912, 101, 2186), the suggestion was made that at higher temperatures it tends to change partly into the isomeric form, NH:C(SH)*NH,, which could dissociate into hydrogen sulphide and cyanamide.It was found that the best conditions for the preparation of guanidine consisted in heating dry ammonium thiocyanate for four 190 hours at 200°, when a yield of 60 per cent. was easily obtained. The conditions usually stated, namely, 180-190° for twenty hours, are unduly tedious, and have no compensating advantage. 167. “ Silicon compounds. Part I. Rational nomenclature of complex silicon compounds and silicates, both organic and i~organic.,’ By Geoffrey Martin. The author explained a scheme for classifying the compounds of silicon on the basis of the number of linkings between the silicon atoms in the molecule. Compounds in which the silicon atoms are directly united are termed (‘silicoses,” whilst those in which the silicon atoms are joined up through oxygen, thus Si*O*Si, are termed (‘silicates.” 168.(I Silicon compounds. Part 11. Methylsilicoses derived from silicon hexachloride.” By Geoffrey Martin. The author described compounds derived from the action of magnesium methyl iodide on silicon hexachloride, which contain silicon atoms directly united in a chain, and dissolve in potassium hydroxide evolving hydrogen. They also evolve a mixture of hydrogen and methane when heated. 169. ‘‘The synthesis of o-aldehydophen ylglycine.” By Wilhelm Gluud. o-Aldehydophenylglycine,which the author considered might prove a suitable source for the production of indole or its derivatives, was synthesised in the following way. Starting with o-nitrobenzaldehyde, by reducing the corresponding oxime with ammonium sulphide, o-aminobenzaldoxime was obtained.The latter compound, when heated with cliloroacetamide and calcium carbonate, yielded the oxime of o-aldehydophenylglycin-amide, which, on boiling with alkali, gave the oxin2e of o-aldehydo-phenylglycine. The oxime group was removed by dilute sulphuric acid, yielding o-aldehydophenylglycine, CHO*C,H,*NH*CH,*CO,H. The pure dry compound consisted of aggregates of colourless crystals, melting at 176-177O. When heated with lime, either the aldehyde or the oxime of o-aldehydophenylglycinamideyielded indole or its derivatives ;this reaction will be further investigated. A crystalline compound, supposed to be o-cyanophenylglycine, 191 was prepared from the oxime of o-aldehydophenylglycinamide and sulphuric acid.By the fusion of the oxime of o-aldehydophenylglycine or the corresponding amide with potassium hydroxide, phenylglycine-o-carboxylic acid and indigotin were produced in quantities depend- ing on the experimental conditions. 170. ‘(Colonr and constitution of azomethine compounds. Part 111.” By Frank George Pope and Winifred Isabel Willett Unsuccessful attempts have been made to obtain azomethine compounds from pnitroaminoazobenzene. Various derivatives of aminoazobenzene were described, together with some compounds related to pnitroaminoazobenzene. p-Nitrobenzeneaaob eizzeneazo- phenol has been prepared, and the absorption spectra of the azo-methines derived from aminoazobenzene, together with those of p-nitrobenzeneazophenol and p-nitrobenzeneazobenzeneazophenol, have been observed.171. “Note on cupric malate and citrate.” By Spencer Umfreville Pickering. When alcohol is added to a solution of copper carbonate in glyceric, malic, or citric acid, it precipitates an emulsion, which dries to a pale blue solid, very soluble in water, forming a dark blue solution, in which the copper, on electrolysis, is found to be in the electronegative ion. The compound present is a cupri-compound metameric with the normal cupric salt, which latter, in the case of the glycerate, crystallises gradually from the solution, and is sparingly soluble. Normal cupric malate has now been obtained in the same way, and is insoluble, but the presence of some excess of acid is necessary to prevent the formstion of a basic salt.The normal citrate has not been obtained; a concentrated solution of the cupricitrate solidifies in ten minutes to a mass of blue, moderately soluble crystals of (probably) a basic cupri-compound, (R”12C~3)2,C~0,which, after thirty minutes, changes to an insoluble, amorphous, ordinary basic salt of the same empirical formula. 172. (‘Organic ferric salts.” By Spencer Umfreville Pickering. The quadrivalent character of copper in the cupri-compounds is supported by the similarity between these and the salts of quadri-valent iron. In the latter the iron is electronegative, does not 192 react as iron with ordinary reagents, and has a colour intensity about twenty times greater than that of iron in inorganic ferric salts.They are very soluble, and alcohol precipitates emulsions from them. Evidence as to the definiteness of their composition was given. In the case of the tartrate, malate, and citrate, the corresponding normal salts have not been obtained, but they each yield a highly soluble basic f erri-compound, R”3Fez,Fe203, and an insoluble, ordinary basic salt of the same formula, thus resembling the cupricitrate. Ferric oxalate is a normal salt, and the acetate appears to be dissociated in solution into acetic acid and colloidal ferric hydroxide. Attempts to prepare alkaline f erri-compounds have failed. 173. ‘(The colour intensity of iron.” By Spencer Umfreville Pickering. The molecular colour intensity of iron in solutions of ferric chloride, nitrate, and sulphate is practically identical (taken as unity), and is nearly constant throughout a considerable range of strength.It gradually rises to 2.5, after which further dilution causes it to fall; but these dilute solutions are not stable, and darken gradually, ultimately exhibiting a colour intensity of 140, which is that of iron in colloidal ferric hydroxide. This first rise to 2.5 is not due to the presence of colloidal iron, but to iron in some other highly coloured form, probably that in which it exists in organic ferric salts, where it is electronegative, and has a colour intensity of 24. This value is nearly realised in the case of the sulphate.As excess of acid in the case of the sulphate and nitrate render these salts colourless, it is probable that the true colour intensity of electropositive iron is nil, the yellow colour of the neutral salts being due to the presence of some of the compounds with the iron electronegative. 174. The conversion of a-amino-acids into a-ketonic aldehydes, and their relation to a-hydroxy-acids.” By Henry Drysdale Dakin and Harold Ward Dudley. The authors have recently shown (this vol., p. 156) that a-hydroxy- acids, in aqueous solution, yield a-ketonic aldehydes. Lactic acid, for example, gave methylglyoxal. It is now found that a-amino- acids behave similarly. Thus alanine, on digestion at low tem- peratures in faintly acid solution, with p-nitrophenylhydrazine may yield metliylglyoxaldinitrophenylhydrazone.Other amino-acids, such as glycine, leucine, aspartic acid, phenylalanine, behave similarly. The yields are relatively small : R*CH(NH,)*CO,H+R*CO*CHO+NH3. 193 The formation of a-ketonic aldehydes from a-amino-acids has interesting biological relations. It indicates, for example, a possible mechanism for the interconversion of alanine, lactic acid, and dextrose in the living cell, since each of these substances has been shown to be convertible into methylglyoxal, which in turn has been found by the authors to yield dextrose in the diabetic organism. 175. “The mode of combustion of carbon : the effect of drying the oxygen.” By Thomas Fred Eric Rhead and Richard Vernon Wheeler.It was shown that the results of experiments with well-dried oxygen do not conflict with the supposition that, in the burning of carbon, a ‘‘ physico-chemical complex ” is first formed ; and that any carbon monoxide and carbon dioxide that may appear to be the primary products of combustion arise from decomposition of this complex. It would seem that decomposition of the complex is accelerated by the presence of moisture. 176. ‘‘Cantharene, and other hydrocarbons allied to the terpenes.” By Walter Norman Haworth. An account was given of the synthesis of hydrocarbons of the dihydroxylene series, one of these being 1: 2-din2e thyZ-A2 :6-cyclo-hexadiene, CMeGCH. CH,CMe:CH>CH2, the properties of which agree with those described by -Piccard for the substance, cantharene, obtained from cantharidine by distillation with lime (Bey., 1878, 11, 2122).The physical constants of this A1 :5-dihydro-o-xylene, and of a corresponding meta-derivative, were compared with the data recorded by Auwers for A1 :3-dihydro-p-xylene, the gradation in the spectrochemical properties of the three hydrocarbons being analogous to that found for the three xylenes. A lower homologue of the terpenes, C9HI4,has also been syn- thesised, and its physical constants measured. This substance is $JH2*CIMeterie,l-~nethyl-2-isoprope~~yZ-A~-cyclopen CH,. CH,>C*CMe:CH,, and it differs in constitution from the terpenes only in respect of its containing a ring of five carbon atoms in place of the cyclo-hexene structure of dipentene. The above hydrocarbon is the fourth member of the group of terpenes derived from cyclopentane, three others having been already described by Haworth and Perkin (T., 1908, 93,573).194 177. ‘(The molecular condition of mixed liquids. Part I. Mixtnree of the lower aliphatic alcohols with water.” By William Ringrose Gelston Atkins and Thomas Arthur Wallace. From a study of the cryoscopic behaviour of mixtures of alcohols and water in aniline, no decided evidence could be obtained of any combination to form hydrates, even in the case of trimethylcarbinol, where the freezing-point concentration diagram shows the existence of a hydrate. Mixtures of the alcohols and water in equimolecular proportions show a decrease in the contraction on mixing, when the alcohols are arranged in the same order as are their association factors, deter- mined by Rainsay and Shields.Rise of temperature results in a decrease of the contraction on mixing in all cases except that of methyl alcohol, where, up to 43O at any rate, there is an increase of contraction. An explanation of this behaviour is offered in terms of the formation of hydrates. Calculation of the molecular volumes of these mixtures at various temperatures by means of Traube’s constants points to the formation of hydrates containing equimolecular proportions of alcohol and water. These problems are being studied further. 178. (‘The purification of acetone by means of sodium iodide.” By Kathleen Shipsey and Emil Alphonse Werner. It was recentiy shown (this vol., p.117) that sodium iodide can unite with acetone to form a crystalline compound having the com- position NaI,3C3H,O. Experiments have now been made which show that acetone in a high degree of purity can be prepared from the commercial article in a very simple manner by the aid of sodium iodide. The hydrated salt NaI,2H20 may be used with advantage on account of its ready solubility in acetone; the solution when cooled to about -8O gives a very good yield of the above compound, and it is possible to obtain 70 per cent. of the acetone in a pure state in a single operation. The purified acetone was found to be quite equal to that prepared by the rather tedious bisulphite process.179. 6b The absorption spectra of some thio-derivatives of benzene.” By John Jacob Fox and Frank George Pope. The absorption spectra of phenyl mercaptan and diphenyl sulphide were compared with those of phenol and diphenyl ether; and it was found that the substitution of sulphur for oxygen had resulted in an entire change in the character of both the vapour 195 and solution spectra. The characteristic bands of the benzene spectrum were suppressed by the introduction of the thiol group into the molecule. The spectrum of phenol vapour contained a large number of sharp, narrow bands which were absent from the spectrum of phenyl mercaptan. It was found that the position of the bands in the spectra of the solutions corresponded with certain groups of bands in the vapour state; and the extensions of the solution spectrum of diphenyl sulphide were definitely associated with the absorption bands in the spectrum of the vapour of this substance.180. ‘‘ The nickel salts of the benzildioximes.” By Frederick William Atack. It has been shown by Tschugaev that a-(syn)dioximes form nickel compounds, in which only one of the oxime groups has its hydrogen atom replaced by metal, but he has repeatedly stated that both &(anti-) and y-(amphi-)dioximes do not yield nickel salts. It is now shown that y-benzildioxime forms a definite and stable nickel compound in which both oxime groups are in-volved, giving a cyclic structure containing nickel.Tschugaev’e statement that only a-dioximes are capable of forming nickel compounds is therefore untenable. All attempts to prepare a nickel compound of the &modification have failed, nickel hydroxide being obtained in every case. It would appear probable from the results obtained that, of the oxime groups contained in 1: 2-di-oximes, in the a-(syn-)modification, one group is basic, the other acidic; in the &(anti-)modification, both groups are basic ; and in the y-(amphi-)modification both groups are acidic, 181. (L Preparation of secondary and tertiary acid amides from their metallic derivatives.” By Jitendra Nath Rakshit. When primary acid amides are heated with metallic sodium in indifferent solvents, they undergo condensation to secondary amides, which are isolated as sodium derivatives.Potassium under similar conditions gives, with formamide, potassium diformamide, but with acetamide and propionamide it yields only simple potassium sub- stitution derivatives. From sodium diacetamide, di-and tri-acetamide are prepared by the action of hydrochloric acid and acetyl chloride respectively. 182. The addition of negative radicles to SchifPs bases.” By Thomas Campbell James and Clifford William Judd. The authors have investigated the formation and decompositions of a large number of the additive compounds formed from Schiff’s bases with chlorine, bromine, iodine, and acyl haloids. In every case investigated, chlorine and bromine form dihalogen additive compounds, which are only sparingly soluble in non-ionising media, but dissolve readily (with partial decomposition) in alcohol, acetone, or ether.On treatment with water, acids, or alkalis, they undergo decomposition in two ways, (a) as indicated by Hantzsch (Bey., 1890, 23, 2773) in the equation: CHPh:NPh,Br, + H,O =Ph*CHO + C6H4Br-NH,(1: 4)-t-HBr, and (b) with elimination of halogen and production of the decom- position products of the Schiff’s base. Alkalis favour the former, acids the latter decomposition. The additive compounds with acyl haloids are of similar type, and are decomposed by warming with acids into aldehyde and acylamine. With Schiff’s bases iodine forms periodides, which, on heating gently, form red di-iodides.The compounds may probably be f orniulated as quinquevalent nitrogen derivatives, although the possibility of a quinonoid structure is not entirely eliminated. 183. (‘The preparation of some organo-selenium compounds.” (Preliminary note.) By Charles Weizmann and Henry Stephen. The authors have prepared scleti odiph etrylamine, which is obtained according to the two following methods: (a) byboiling a mixture of diphenylamine and selenium in a metal-bath for thirty hours until the evolution of hydrogen selenide ceased ; (b) by heating a mixture of the theoretical quantities of diphenyl-amine and selenium monochloride. In both cases the product is separated from diphenylamine by distilling it under diminished pressure, and crystallising the crude substance from ethyl alcohol.Selenodiphenylamine crystallises from ethyl alcohol in pale yellow plates, which melt and decompose at 189O. The crystals on exposure to air gradually darken to a green tinge, and in solution with concentrated sulphuric acid a violet coloration is produced. The research is being continued. 197 184. 6‘ P-Naphthol sulphide and iso-@naphthol sulphide ; and the constitution of P-naphthol.” By Thomas Joseph Nolan and Samuel Smiles. The results of previous experiments were used in discussing the constitution of the two sulphides. It was concluded that the normal sulphide is the true a-sulphide of @-naphthol (I),whilst the isosulphicle, which is formed by reducing naphthasulphonium-quinone, is representsd as in 11, and may be regarded as the hydro- sulphonium-quinone : (1.1 (11.) The constitution of &naphthol was also discussed, and it was concluded that in this substance, and probably also in naphthalene, the hydrocarbon nucleus exists in a symmetrical condition. 185.The nitrites of thallium, lithium, caesium, and rubidium.” (L By Walter Craven Ball and Harold Helling Abram. Thallous nitrite, TlNO,, is a bright, orange-red, soluble, crys- talline salt. Hydrated lithium nitrite crystallises with one molecule of water, as stated by RBy (P., 1908, 24, 75). Czsium nitrite, previously examined by Jamieson (Amer. Chem.J., 1907, 38, 616), closely resembles the potassiuni salt, as also does rubidium nitrite. 186. Note on the fat of the seeds of ‘Oncoba echinata ’;occurrence of chaulmoogric acid.” By Ernest Goulding and Noel Charles Akers.Samples of the seeds of the “Gorli” plant (Oncoba echinata, Oliver) have been received at the Imperial Institute from Sierra Leone, and have been examined with the f-ollowing results. The seeds contained 5.8 per cent. of moisture, and, on extraction with light petroleum, yielded about 47 per cent. of a hard, opaque, white fat of a crystalline appearance, and possessing a peculiar, characteristic odour. The fat furnished the following constants : D:S”;.-0.898, [a]$ +48.8O; acid value, 4.5 ; saponification value, 192.4 ; iodine value, 99.7 ; Hehner value, 96.5 ; Reicherf-Meissl 198 value, nil; unsaponifiable matter, 1.5 per cent.It had no definite melting point, but gradually liquefied above 35O, and was com- pletely melted at 45O. The fatty acids obtained by hydrolysing the fat had an iodine value of 105’1, [u]? +52*5O, and consisted of a mixture of a crystalline solid and a liquid. By pressing the mixture between folds of filter-paper, a large proportion of the solid substance could be separated, and on recrystallisation from warm alcohol it was obtained in thin, lustrous plates, melting at 69O. This acid gave an iodine value of 90.5, and [u]: +60’Oo; it was identified as chaulmoogric acid, C,,H,,*CO,H (Power and Gornall, T., 1904, 85, 846), by the analysis of the silver salt and the preparation of the methyl ester, which melted at 22O, and had [u]”d +55*8O.The liquid portion of the fatty acids, although saturated with chaulmoogric acid, gave an iodine value of 122, showing that the liquid acids are highly unsaturated; it darkened rapidly on exposure to the air. The investigation showed that the fatty acids consisted approxi- mately of chaulmoogric acid, 87.5 per cent., and liquid acids, 12.5 per cenh 187. A new model to illustrate the Walden inversion.’’ *L By William Edward Cfarner. This model consists of a wooden ball, divided vertically into three equal sections, which are bolted together so as to leave a space between each. Additional stability is conferred on the structure by rings situated at the top and the bottom of the model. To each of the bolts, which are placed as near the centre of the model as possible, is attached a steel arm, capable of being vibrated with an upward and downward motion.The three arms are connected by thin cord to the middle of a central glass or metal rod DDl, which passes through the two rings. The method of attachment is seen by reference to the diagram (Fig. 2). By the movement of the central rod upwards through the rings, the three arms are caused to move simultaneously, and if this movement is made sufficiently great, they pass downwards into the enantiomorphous position. The Werner model, constructed by the author (P., 1912, 28, 65), was utilised to illustrate the change of maleic acid into fumaric acid, without the destruction of the double bond, and its employ- ment in this connexion naturally suggested its use in the trans-formation of syn- into anti-oximes.In the latter case the inter- conversion of the isomeride may be demonstrated in either of two 199 ways, namely, (1) by the inversion of the valencies of the carbon atom, and (2) by the inversion of those of the nitrogen atom. If both the carbon and nitrogen atoms undergo inversion, no change in the oxime is produced. The three cases are illustrated below : 1. 2. C6H,*C*H -+ C H *OH /I II @OH HOSE 3. C H 9e-H H-fC7-CH ti 5Y -+ YG5 @)*OH H0.B The first method was easily carried out by means of the pre- viously described model (loc. cit.), but in order to illustrate the FIG. 1. FIG.2. 200 second case, it was necessary to devise a tervalent nitrogen model, the valencies of which could readily be inverted. The new model was constructed for this purpose.* The central rod is then made of glass, and the valency arms, A, B, and C, represent the nitrogen tetrahedron of Hantzsch and Werner.Two of the valencies of this model are connected by thin rubber tubing to two arms of a carbon model, and the transformation effected, as has been pre-viously described in the case of maleic and fumaric acids (Zoc. cit.). The appearance of the nitrogen model, when completed, suggested to thg author that it might be applied to represent some of the properties of the asymmetric carbon atom; the ends A, B, and C of the three arms, together with the end of the rod D,form the vertices of a tetrahedron, and consequently may represent the four groups attached to a carbon atom.The ease with which this tetrahedron is inverted renders the model suitable for the illustra- I. 11. 111. tion of racemisation and Walden inversion phenomena. Gadamer (Chem. Zeit., 1910, 34, 1004) had previously put forward the idea which it embodies, and had developed it fully to furnish an explanation of racemisation, and later has extended his theory to account for the differences in the behaviour of silver oxide and other bases on optically active chloro-acids (Frankland, T., 1913, 103, 722). If the model represent a chemical molecule the group D may be replaced by another group with a change of configuration. In order to accomplish this, according to the Werner theory (Ber., 1911, 44, SSl), the entering group must approach the molecule A, B, C, D from the side opposite to that occupied by the group D, and attach itself by means of its partial valencies at D'; if it is attracted to any of the other faces, no inversion would be obtained.Simultaneously with this addition, the group at D is gradually removed, and a corresponding movement of the other valencies * A model was first constructed in April, 1912. 201 occurs in a downward direction. The molecule will pass through an intermediate position 11,in which the three valencies A, B, and C lie in one plane, and the fourth valency is divided into two halves at D and D’,and in this position the entering and extruded groups are attached to the carbon atom with equal force.In other intermediate positions the length of the central valency above and below the ball will indicate the relative strength of the attachment of the two groups. Finally, the groups pass into the enantio- morphous position 111,in which the group, originally attached at D, is completely removed. Coloured balls or paper may be attached to the arms to represent the various groups. 188. ‘‘ The Baly-Krulla theory of fluorescence. A reply to A. W. Macbeth.” By Edward Charles Cyril Baly. In a recent paper (P., 1912, 28, 271) A. W. Macbeth criticised the theory of fluorescence which Dr. Krulla and the author advanced (T.,1912, 101, 1469). It seems that this criticism is based upon a misconception of the theory itself and of the processes which take place.According to the theory the condensed force fields surrounding the molecules of a substance may be opened up in stages by the influence of a solvent and of light. These stages may be called 1, 2, 3, 4, etc., and each one absorbs light of different wave-lengths, A,, A,, h4, etc. Whereas previously only two of these stages had been recognised, the existence of several definite stages in the opening up of the condensed field of force has now been proved, and it is hoped very shortly to communicate the results of certain observations, which clearly sho,w how by the use of suitable solvents several different stages can be produced absorbing different wave-lengths of light.Now it is obvious that in the absorption of these light waves considerable damping must be present. If this were not so it is evident that the whole substance would on prolonged exposure become diactinic. This is, however, absurd; owing to the damping that is present the light actually does work against the chemical forces, and is therefore changed, probably into heat, so that as the result a continuous and constant absorption of the light takes place. It would seem that Macbeth has not taken this damping into con- sideration. He states that if the substance can exist in stages 1, 2, 3, etc., these forms must be in equilibrium with one another. This is not a correct assumption. If the stage 3 were present in 202 equilibrium with 1 and 2, and if, according to hypothesis, 1+3 or 2-3 can be produced by absorption of light A,, it is absolutely certain that A, would be absorbed out of a light source containing these waves.It is an experimental fact that A, is not selectively absorbed as long as the solvent necessary is absent. In other words, if a fluorescent material which absorbs A, and emits A, is screened from A, no trace of selective absorption of hg can be detected. This rules out of court the assumption that stage 3 is normally present in simple equilibrium with 1 and 2. Under the influence of the light a photodynamic equilibrium is set up, which is a very different thing from the chemical equilibrium assumed by Macbeth. Macbeth's first criticism theref ore seems absolutely to fail, first, because he assunies? that stages 1, 2, 3 are in simple equilibrium; secondly, because he neglected the damping ; and thirdly, because he assumes that the substance when screened from A, must absorb hg.Macbeth states further that the theory, although it cannot explain fluorescence, is more capable of explaining phosphorescence. It is now generally agreed that the two phenomena are really the same, and only differ in the relative velocity of the two processes, absorption and emission. In any case of fluorescence or phos-phorescence there are two processes: the absorption of energy, and the emission of energy. If the velocity of the second process is equal to or greater than that of the first, then the substance fluoresces, but if the velocity of the emission is slower than that of the first, then phosphorescence takes place, namely, the persistence of the emission for an appreciable time after the exciting cause has been removed.In certain cases the velocity of the emission of the energy is exceedingly small, and in these circumstances the energy absorbed in the first process remains stored up in the sub- stance for a very long time unless the velocity of the emission is increased by some means, such as the application of heat, when bhe phenomenon is known as thermoluminescence. There seems, indeed, no reason to assume any difference between the two phenomena, and if a theory can explain one of them, it follows that it can explain the other.According to the theory, the stages 1, 2, 3, . . . n, inasmuch as they are stages in the opening up of the condensed system of a single molecule, are intimately connected with one another, and although the process by which A, is absorbed in the solvent is the only one which light itself is capable of bringing about, yet there can hardly be any objection to the probability that the disturbance to the whole system produced in this way will bring the next 203 possible vibration periods into play, namely, stage 3 followed in less degree by stage 4, and so on. It is known that, given the necessary external conditions, stages 3, 4, etc., are characterised by vibrations synchronous with wave- lengths A~, A,, etc.; if these vibrations are brought into play by means of some other vibration they will emit light of the same wave-lengt h.Macbeth seems to have fallen into an error as regards the relationship between the wave-length of the exciting light and the emitted light. In producing phosphorescence of wave-length A,, A, is not absorbed. There does not seem to be any difficulty in reconciling all observations as regards the relations between temperature and phosphorescence. In the first place, the conditions may occur when the process 2 +1 is very slow indeed, with the result that the process 1-2 will take place with absorption of hg. After some time the whole system will have absorbed considerable energy. On heating the system, or in many cases simply by rubbing or shaking, conditions are produced that enable the process Z+l to take place, with the result that a considerable amount of free energy escapes as heat, and the whole system gets disturbed, and some of the vibrations of stage 3 are called into play with emission of hg.In this process no A, is emitted. Care must be taken not to look upon processes l+Z, 2+3, or l+ 3 as being directly reversible, absorbing or emitting the same amount of light energy, for if this were so, it would simply resolve itself into a case of resonance phenomena. Macbeth has fallen into error here when he says that the reverse process 2 +1will be accompanied by the emission of light A,, as demanded by Kirchhoff’s law. Kirchhoff’s law has nothing whatever to do with the case, for it is not a case of black body radiation.The reverse process 2-1 is not accompanied by emission of A,, but probably by emission of heat, and the process is not reversible. The next point is: why do some substances fluoresce only at low temperatures when the free energy is less than before? The lower- ing of temperature will tend to produce a more completely closed system of force lines round the molecule. There must naturally exist a particular condition of this condensing together of the force lines for the particular type of fluorescence observed to take place, and it follows directly from the theory that this condition may be produced at low temperatures when it does not exist at higher temperatures. It has been shown (T., 1913, 103,91) that when a substance is opened up by a solvent and by light, the amount of light absorbed 204 increases with the dilution up to a maximum, after which further dilution tends to decrease the amount absorbed, which is then followed by the disappearance of the selective absorption.There is thus an optimum condition of concentration as far as absorption of light is concerned. This agrees with and explains Lenard and Klatt’s and Urbain’s observations on phosphorescence, for these authors have clearly shown that there is always a definite condition of concentration of phosphorescence in the diluent at which an optimum of phosphorescence is observed. Clearly at this con-centration the phospliorogen has its closed force field just sufficiently opened up, and in that condition best adapted .to respond to the exciting vibrations in such a way that the next stages, 3, 4, 5, etc., are called into play. This optimum condition only refers to one particular temperature.At a much lower temperature that con-dition will not necessarily give the optimum, and indeed, perhaps, may not give any phosphorescence at all. Some other concentration will be more suited for the new temperature conditions, and whilst this new concentration may not suit the old temperature, yet on cooling, the phosphorescence or fluorescence makes its appearance. A specific example may make this clearer, namely, the phos-phorescence of strontium sulphide. Becquerel (;1iiu. CAin2. I’hys., 1859, [iii], 55, 5) found that this material gives at ZOOo an orange phosphorescence, and as the temperature falls the colour passes through yellow, green, and blue until at -20° it is dark violet. This observation has been confirmed for a great number of sub-stances by Lenard and Klatt (A~~L.I’Aydc, 1904, [iv], 15, 225, 425, 633).The reason of this effect is that the phosphorescent spectrum consists of at leas$ five separate maxima having tlie above colours, and as the temperature is cliaiiged the relative intensity of the various maxima alters, and in the case of the strontium sulphide the tendency, with decrease of temperature, is for the maximum of the phosphorescence to move towards the shorter wave-lengths. If the sepzrate bands in the phosphorescent spectrum be called A, B, C, 3,E, then at the higher temperatures -4 will be the most intense, and as the temperature falls, B, C, D,6, in turn, show the greatest intensity.Each of these corresponds with a definite stage in the opening-up process, and the optimum condition for each stage, provided that the quantity of diluent remains the same, depends on the temperature. By varying the conditions of diluent, similar variations in the relations between the intensities of the different plicsplioresceiit maxima can also be obtained under constant temper at ur e conditions . This fact has an important bearing on tlie general theory. Since the whole phenomenon of phosphorescence is a property of diluted 205 matter, and since the fall of temperature allows more and more free energy to escape from the system, it follows that the lower the temperature the less is the phosphorogen opened up by the diluent.The observations on phosphorescence therefore run pari pcrsszs with the observations on absorption, for here the more a compound is opened up by a solvent the nearer the absorption maximum lies to the read. In other words, the more complex the solventsolute system, or, speaking generally, the more complex the system of the force field dealt with, the nearer to the red will be its absorption and also its phosphorescent or fluorescent maximum. Macbeth in his criticism, based on the fact that some substances do not phosphoresce or fluoresce at ordinary tem-peratures and do so at low imnperatures, has really advanced observations wliich strengthen and confirm the theory.Again, Macbetli attempts to draw an analogy between a spring in various stages of compression and the stages 1, 2, 3, etc. This analogy fails absolutely from the start, because it requires the same energy in different amounts to obtain the spring in the different stages of compression, wliile in the real case the stages 2 and 3, etc., require for their actilal production not only a different solvent, but light of different wave-length. He also contradicts himself here, because in order for the analogy to be complete from his point of view, the states of the spring when in different stages of compression must be in equilibrium with one another, an assumption he made for the stages 1, 2: 3, etc. Two further criticisms of Macbeth still remain to be dealt with.First, Nichols and Merritt’s observations that the position of maximum fluorescence is independent of the wave-length of the exciting light, and that the latter may be on the red side of the fluorescent maximum. Macbetli says the processes are now reversed, and hg is being absorbed and A, emitted. This is by no means the case. An inspection of the absorption and fluorescent curves shows that these extend considerably on each side of the maximum in each case. They frequently, indeed, overlap, and therefore the very fact of Nichols and Merritt’s discovery strongly supports the theory. The shape of the fluorescent curve is charac-teristic of the substance under the conditions of solvent and concentration.This fluorescence will be produced by any wave-length included in the absorption band, even if it happens by chance to be longer than those emitted. The substance responds to and absorbs the longer wave-length, and it is natural to expect that it would produce the same effect as any other wave-length in the same absorption band. Nichols and Merritt also observed in the same paper (Physical Review, 1904, 19, 18) that if the 206 fluorescent substance has a second absorption band of longer wave- length than the fluorescent light, the absorption of light in this second region does not produce fluorescence, which fact, of course, is in agreement with this theory.Finally, Macbeth quotes the observation of R. W. Wood, who showed that while fluorescing with light of definite wave-length a substance exerts no increased absorption of that light.. On a theory of optical resonance " fluorescence absorption " might be expected, and the fact that it has been proved absent argues strongly against any simple resonance as a basis of fluorescence and absorption. Nothing whatever in the theory makes it probable that fluorescence absorption should take place. A criticism based on the fact that it does not take place seems therefore somewhat irrelevant. The general conception may be made clearer by considering it in the following way. Light energy (A~)is absorbed and converted partly into heat and partly into light energy (h3).In ordinary circumstances this reaction is not reversible, because A, is not absorbed, but it might be considered that under certain special labile conditions it does become reversible. The absorption of A, during fluorescence would mean that the same reaction was taking place in opposite directions at the same time and absorbing energy on both counts. Whether the process is reversible or non-reversible, there is no reason why A, should be absorbed during fluorescence. ADDlTIONS TO THE LLBRARY. I. Donations. Cain, John Cannell, and Thorpe, Jocelyn Pield. The synthetic dyestuffs and the intermediate products from which they are derived. 2nd edition. London 1913. pp. xvii+423. 168. net. (Recd. 24/5/13.) From the Authors. Jellinek, Karl.Physikaliscbe Chemie der homogenen und hetero- genen Gasreaktionen unter besonderer Beriicksichtigung der Strah- lungs- und Quantenlehre sowie des Nernstschen Theorems. Leipaig 1913. pp. xivf844. ill. M. 30.-. (Recd. 6/5/13.) From the Publisher : S. Hirzel. Liebig, R.G. Max. Zink und Cadmium und ihre Gewinnung aus Erzen und Nebenprodubten. Leipzig 1913. pp. xvi +598. ill. M.301--. (Reccl. 15/5/13.) From the Publisher : Otto Spamer, 207 Lunge, George. The manufacture of sulphuric acid and alkali with the collateral branches, 4th edition. Vol. I. Sulphuric acid. [In three parts.] London 1913. pp. xxiv+ 1617. ill. &3 38. net. (Reference.) From the Author. Plmck, Max. Vorlesungen uber die Theorie der Warmestrahlung .2nd edition, Leipzig 1913. pp. xii+206. M. 7.50. (Recd. 15/5/13.) From E. Gardner, Esq. Shepherd, John William. Qualitative determination of organic compounds. London 1913. pp. xvi+348. ill: 68. 6d. (Recd. 14/5/13.) From the Author. Tables annuelles de constantes et donndes numdriques de chirnie, de physique et de t,echnologie. Publides sous le patronage de 1'Association internationale des Acaddmies par le Comitd international nommd par le VIP Congrks de Chimie appliquhe (Londree, 2 Juin, 1909). Volume 11. Ann& 1911. Paris 1913. pp. xl+759. (Refeyeme.) From the International Committee. II. By Purchase. Thorpe, Sir Edward. A dictionary of applied chemistry. Vol. IV. London 1913. pp. viii + 727. ill.$2 5s. net. (Rpfwence.) ITI. Pumphlets. Auerbach, Priedrich, and Pick, Hans. Die Alkalitat von Pankreassaft und Darmsaft lebender Hunde. (From the Arb. Kab. Gcsund., 1912, 43.) Eastick, John Joseph, Ogilvie, Jumes Pettigrew, and Lindfield, J. H. Rapid and accurate determination of traces of iron in cane and best sugar factory and refinery products. (From the Internat. Sug. J., 1912, 14.) Echols, William Holding. John W. Mallet : scholar, teacher, gentleman. (From the AZumni Bull. Univ. Virginiu, 19 13, [iii], 6.) Holloway, George Thomas. Notes on the valuation of ores and minerals, and on metallurgical calculations. (From the Trans. Inst. Min. Met., 1911-12.) Kanolt, C. !I? Melting points of fire bricks. (Tech. Papers, Bur. Stands., 1913, No.10.) Pusa, Agricultural Research Institute. Report, 191 1-1 2 (In-cluding Report of the Imperial Cotton Specialist), Calcutta 19 13. pp. 113. Schroder, F. Beitrag zur Kenntnis der olhaltigen Sitmen von Ximenia Americana. (From the Arb. Kais. Gesund., 1912, 43.) 208 At the next Ordinary Scientific Meeting, to be held on Thursday, June 19th, 1913, at 8.30p.m., there will be a ballot for the electioii of Fellows, and the following papers will be communicated: ‘IAbsorption spectra and chemical reactivity. Part 111. Tri-nitrobenzene, trinitroanisole, and picric acid.” By E. C. C. Baly and F. 0. Rice. ‘(Derivatives of o-xylene. Part V. 5-Bromo-o-4-xylenol and 6-bromo-o-4-xylenol.” By D. J. Bartlett and A. W. Crossley. “ The rotatory-dispersive power of organic compounds. Part 111.The measurement of magnetic rotatory dispersion.” By T. M. Lowry. “ The rotatory-dispersive power of organic compounds. Part IV. Optical and magnetic rotatory dispersion in some simple organic liquids.” By T. M. Lowry. “ The action of ozone on cellulose. Part IV. Cellulose peroxide.” By C. DorBe. “ The isomerism of p-azophenol.” By P. W. Robertson. “ Sylvestrene. The constitution of d-sylvestrene and its derivatives.” By W. N. Haworth, W. H. Perkin, and 0. Wallach “ Synthesis of pinacones.” By W. Parry. “ The refractivities of acenaphtliene and its monohalogen derivatives.” By H. Crompton and W. R. Smyth. 209 CERTIFICATES OF CANDIDATES FOR ELECTION AT THE NEXT BALLOT.N B.-The names of those who sign from " General Knowledge " are printed in italics. The following Candidates have been proposed for election. A ballot will be held ou Thursday, June 19tb, 1913. Biggart,William Love, Rossarden, Kilmacolm, Renfrewshire. Analytical Chemist. I am 47 years of age; a partner of McCowan & Biggart, Analytical and Consulting Chemists and Analysts to the Greenock and Lancashire Sugar Associations, etc. I am one of the public Analysts under the Food and Drugs Acts for the Counties of Ayr, Argyll, Bute, the Burgh of Greenock, and 23 (twenty-three) other Burghs. I am also Deputy Analyst under the Fertilisers and Feeding Stuffs Act for the Counties of Ayr, Argyll, Bute, and have been in the practice of chemistry for about 30 years.John Wm. Biggart. T. L. Patterson. A. Smith. Thomas S. Dick. Robert Mills. Brooks, Archibald Joseph, " Melrose," St. Lucia, B.W.I. Assist. Supt. Botanic and Agricultural Experiment Stations, St. Lucia, B. M7.Indies. Laboratory Assist. and Student, Swindon and North Wilts Technical Schools, 1896-1901. Lecturer in Agricultural Chemistry, Agric. School, Dominica, B.W.I., 1903-1911. Now engaged in work partly of an agricultural-chemical nature, and desirous of obtaining the Journal, and so keeping in touch with recent work, especially in Agricultural Chemistry. Francis Watts. Gilbert Auchinleck. A. T. Cameron. A. E. Collens. W. R. Bird. T. C. Davison. Joseph de Verteuil. Davies, William Rhys-, Swan Arcade, Bradford ;and at Ilkley, Yorks.Analytical Chemist, Sir Henry Mitchell Exhibitioner, Bradford 210 Technical College, 1899-1901. In public practice from 1902 to 1913. Analyst to the Bradford Chamber of Trades, and retained by many large Industrial Firms. A. G. Green. J. B. Cohen. A. G. Perkin. Walter M. Gardner. Barker North. Drummond, Jack Cecil, 8, Little Heath, Old Charlton, Kent. Research Assistant, Physiological Laboratory, King’s College, London. B.Sc. (Lond.), 1st Class Hons. Chemistry, Oct. 1912 (Internal);Research Assistant to Dr. W. Bain, M.D., Physiological Laboratory, King’s College, London, Nov. 1912-present time. J. T. Hewitt. R. W. Merriman. Clarence Smith. A D. Mitchell. F. G. Pope. W. D. Halliburton. 0.Rosenheim. Freeman, Horace, 1535, Robson St., Vancouver, B.C. Analytical Chemist and Assayer. Major Scholar, Birmingham (Eng.) Municipal Technical Day School, 1901-1905. Asst. Research Chemist, the British Cyanides Co., Ltd., Oldbury, England, 1905-1 910. Assayer-in-charge, The Canadian Bank of Commerce Assay Office, Dawson, Yukon Territory, 1911. .Chief Assayer, The Dominion of Canada Assay Office, Vancouver, British Columbia, 19 12. E. C. Rossiter. Douglas F. Twiss. T. Slater Price. Lionel M. Jones. Daniel Arkell. Glenday, Roy Gonqalves, Emmanuel College, Cambridge. Assistant Demonstrator, B.A. (Cantab.), 2nd Class Natural Science Tripos, Pt. 11. W. J. Pope, W. H. Mills. F. E. E. Lamplough. J. G. M. Dunlop. W. J.Sell. E. J. Holmyard. Hutchinson, James Joseph,‘‘ Cecilville,” Conquer Hill, Dollymount, Co. Dublin. Analytical Chemist and Lecturer. Devised Apparatus Measuring Vapour Pressure : Paper, Royal Dublin Society. Lecturer and Demonstrator, Organic and Applied Chemistry, City of Dublin Technical Schools (12 years) ; sometime Research Assistant, Royal 211 College of Science, Dublin (Sir W. N. Hartley); Chief Chemist, Messrs. W. aod R. Jacob & Co., Biscuit Manufacturers (6 years). Gilbert T. Morgan. James H. Pollok. Jos. Reilly. James C. Philip. P. Bertram Foy. Lefebure, Victor, 25, Belitha Villas, Barnsbury, N. Student in Research, University College. Graduate of University College, London ; B.Sc. Hons. Chem, ; Research Student holding Tufnell Scholarship ; Researching with Sir William Ramsay and Dr.Gray on some ‘(Adsorption ” effects. J.Norman Collie. H. E. Annett. Samuel Smiles. R. Whytlam-Gray. Irvine Masson. Macnaughtan, Duncan James, 31, Clonmel Road, Fulham, S.W. Metallurgical Chemist, Aero Metal Syndicate, 100-102 Victoria Street, S.W. 1906-1 909, general course of chemistry and engineering at South-Western Polytechnic, Chelsea. Obtained August, 1909, position as metallurgical chemist ;continued chemical studies at same institute. Examination results ; 1st Class Honours, Board of Education, Metallurgy, 1911 ; 1st Prize and Bronze Medal, Ordinary Grade, 1910, and 1st Prize and Silver Medal, Honours Grade, 1911, Iron and Steel Manufacture, City and Guilds Institute; 1st Prize and Bronze Medal, Electro Metallurgy, 191 2, City and Guilds Institute, At present engaged in metal research.Appointed Head Chemist to Aero Metal Syndicate, April, 1910. J. B. Coleman. F. H. Lowo. J. C. Crocker. J. Fl. Coste. E. T.Sltelbourn. Mahamadi, Ghulam Ali, (Elliehpur, Eerar, India.) Present address : 144, Jerningham Road, New Crose, London, S.E. Government of India Technical Scholar. Graduate of the Bombay University ;Training in the analytical work in the Chemical Labora- tory of the Imp. Ag. Research Institute, Pusa, India; Assistant Lecturer in Chemistry in the Ag. College, Nagpur, C.P., India; Special course of Oils and Fats Chemistry in Battersea Polytechnic, London; Special study of Oils and Fats and their products. John Wilson.W. H. Simmons. J. L. White. C. T. Bennett. C. DorBe. 212 Maxwell, Marius, Bettiah, India, or 77, Lawrie Park Koad, Sydenham, London. Technical Superintendent and Chemist of the United Provinces Sugar Factory, India. Certificated Analytical Chemist, Brunswick Sugar Institute, Germany ; Certificated Ingdnieur, Swiss Polytechnic, Zurich ; Membre de l’association des Chimistes de Sucrerie de France. Arthur Smithells. H. M. Dawson. J. B. Cohen. W. H. Perkins. W. Lowson. Oliver, Ralph Richard, Portsmouth, Virginia, U.S.A., Chemist and Paper Manufacturer, Southern Fibre Co., Portsmouth, Va., U.S.A. Completed the two years’ Paper-making Course at the Municipal School of Technology, hlmchester.Researdh in Cotton Seed Hull Fibre, with the result of its manufacture into a suitable absorbent paper. Harold Moore. F. S. Sinnatt. Stanley J. Peachey. E. L. Rheail. P.G’. Richards. Phillips, Percy Bernard, The London Hospital, E. Pharmacist, Having obtained the Minor and Major qualifications of the Pharmaceutical Society, I desire to keep in touch with Chemical Research. C. H. Hampshire. F. W. Crossley-Holland. Arthur W. Crossley. Herbert A. Mills. Chas. Horne Warner. Saunders, William Gilbert, 34, Hanover Street, Liverpool. Works Chemist. Associate of the Institute of Chemistry. Pharmaceutical Chemist. Edward C. Cyril Baly. A. W. Titherley. F. G. Donnan. C. 13. Hampshire. Arthur W. Crossley. Smith, Montagu George, 8, Cross Road, Bromley Common, Kentl. Dispenser and X-Ray Operator at the Infirmary, Lewishnm, S.E., 1894 to present date.I desire to keep in touch with modern chemical research. G. Stallard. C. Gerhid. H. Montague Heasman. H. E. Drgdsn. Frank H. Plews. C. J. Kegnn. W. Chas. Sayers. C. II. IIumpshire. 213 Thomas,Ebenezer Rees, Emrnanuel College, Cambridge. Research Student and Assistant Demonstrator in Chemistry at the University Laboratory, Cambridge. 3f.S~. (Wales) in Chemistry ; Certificate of Kesearch (Cambridge). Author of communications to the Society. IVilliam J. Pope. J. G. RI. Dunlop. W. J. Sell. W. H. hfilis. F. W. Dootson. J. E. Purvis. Thorne, Percy Cyril Lesley, Borough Road Training College, Isleworth.Tutor in Chemistry. Senior Science Scholar, Corpus Christi College, Cambridge; 2nd Class, 1st Pt., Nat. Sciences Tripos, 1911 ; 3rd Class, 2nd Pt., Nat. Sciences Tripos, 1912; Tutor in Chemistry, Borough Road College, Isleworth, 1913. H. J. H. Fenton. S. Euhemann. W. J. Pope. Charles T. Heycock. J. E. Purvis. Twomey, Jeremiah, 21, Onslom Road, Elm Park, Liverpool. Research Chemist in Flour Mills (W. Vernon 85 Sons, Birkenhead) ; also Consulting and Analytical Chemist to a Farming Co. (Shotwick Park Farming Co., Chester). B.Sc. Hons. Chem. (1st Class), Liverpool ; Le Btanc Medallist for Applied Chemistry. Researched under Prof. Donnan for one year on CaCO,,CO,,H,O equilibrium ; Osmotic Pressure of Soap Solutions. Awarded degree of M.Sc.Now in above position. F. G. Donaan. 9.W. Titherley. Edward C. Cyril Bsly. A. J. Allmand. R. E. Slade. Walker, John Stewart, Hiratsuka, Sagatni, Japan. Laboratory Superintendent of the Japanese Explosives Co., Ltd. Trained at Glasgom and West of Scotland Technical College (44 years) ; Antrim Iron Ore Co., Ltd., Belfast (3 years) ;Nobel’s Explosives Co., Ltd., Ardeer (2 years) ;Japanese Explosives Co., Ltd., Japan (5years). G. G. Henderson. Thomas Gray. F. J. Wilson. A. Campion. I. 31.Heilbron. Watson, Edwin Loogstsff, Nawabganj, C'awnpore, Indin. Works manager. Minor and Major Qualifimtious of the Pharma- ceutical Society. Arthur W. Crossley. C. H. Ihmpshire. Charles Gilling. Charles 1-1. Warner. James C. Philip. Wilson, Ernest John, M.A.(Cantab.),F.I.C., Osborne House, Wishech, Catrib-..Analytical Chemist. 1898-1908, at Magdalene Coll., Camb. ; took E.A. in 1901in Natural Sciences Tripos. 1902-1903, Junior As.cist,znt to J. T. Norman, Analyst., 23, Leadenhall Street, E.C. 1903-1006, at King's Coll., London, under Prof. J. 11. Thornson; pssed A.T.C. (Mineral Chemistry) in April, 1906. 1906-10, Senior Assistant to the late R. Barklie, P~blic~~Analyst for Belfast ; Lecturer in Chemistry for two yeas to Belfast Technical Institute (evening classes). 1911, private practice in Eelfast. 1913, Works Chemist to Wm. Wilson & Sons, Wis bech . Henry R. Ljell. Herbert Jilckson. Jolin 31.Thornson. Patrick H. ICirkaliiy. Henry L. Smith. Young, Thomas Howard, 118, Scotia Street, Winnipeg, Man., Canada.Analytical Chemist. Three years Demonstrator under Dr. Slater Price, Organic Chemical Laboratory, Jlunici pal Technical School, Eirmingham, England ; Three years Research Chemist under R. Threlfall, F.R.S., RIessrP. Albright st Wilson, Chemical Manufacturers, Oldbury, England ; Five years Chief Assistant Chemist, Canadian Pacific Railway (Western lines-Fort William to Vancouver). At present Acting Chief Chemist, Canadian Pacific Railway (Western lines). T. Skter Price. H. E.Bletclier. Matthew A. Parker. Douglas F. 'l'wiss. Lionel 31.Jones. R. CUT AND SONS, LTD., BRUNSWICK ST., STAMFORD ST., S.E., AND BUKGAY. SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9132900179
出版商:RSC
年代:1913
数据来源: RSC
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