|
1. |
Abstracts of the Proceedings of the Chemical Society, Vol. 4, No. 58 |
|
Proceedings of the Chemical Society, London,
Volume 4,
Issue 58,
1888,
Page 99-108
Preview
|
PDF (725KB)
|
|
摘要:
ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 58. Session 1888-89. November 15th, 1888. Mr. W. Crookes, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. Carl Duisberg, Ph.D., Farbenfabriken, vormals Bayer und Co., Elberfeld ; Lionel Remond Lenox, Ph.D., Lehigh University, South Bethlehem, Pennsylvania ; George Lloyd, 25, Kensington Gardens, Balsa11 Heath, Birmingham ; James Muir, Staunton Harold, Brank- some Park, Bournemouth ; Robert Hodgson Parker, 26, Harford Street, Norwich ; John Percival, B.A., 58, Harwood Road, Walham Green, S.W. ; Percy Andrew Ellis Richards, 44,Sinclair Road, Ken- sington ; Emanuel Roberts, Morataa, Ceylon. The following were duly elected Fellows of the Society :-Messrs.Walter Bromley Cooley, John Burke Fairley, Walter M. Gardner, Archibald Carlyle Mounsey Ingram, Prank Puliinger, A. Alexander Ramsay, Clement J. Rhodes, C. Heinrich Trinks. The following papers were read :-79. “ The Principles of Thermochemistry.” By S. U. Pickering. The author rejects the thermochemical principles enunciated by Thomsen, Naumann and Berehelot, not only on special grounds, but on the more general ground that they depend on an impossible dis-tinction between chemical and physical actions. A satisfactory ex-planation of all known thermochemical facts is derived from the recognitioii of the laws of dissociation and the hydrate theory of dissolution. Every act of combination must be accompanied by the evolution of heat, and in interactions where heat is absorbed this ab-sorption must be due to the fact that one or more of the agents being partially dissociated at the temperature of the interaction, the remo Val 100 OF one of the products of the dissociation necessitates a further decom- position of the agent. The heat evolved must also be a direct measure of the affinities saturated, and of two possible interactions that which evolves more heat must occur to the exclusion of the other.The cases of endothermic changes which present difficulties are those in which liquids and solids are concerned. The heat absorbed when ma8ny solids are dissolved in liquids cannot be explained by the fusion, but only by the volatilisation of the solid. A mass of water contains some fundamental molecules possessing an energy of 10,000 cal.greater than the average molecular aggregates const,ituting the mass. These can therefore combine with the salt, and effect its volatilisation with an evolution of heat, even if the heat of volatilisa-tion be nearly 10,000 cnl. ; other water aggregates then dissociate to supply the place of the free molecules thus removed from the sphere of act)ion. From theoretical considerat)ions the author arrives at the conclusion that Brrthollet's theory as to bhe division of a base between two acids is correct-that t,wo acids present in equivalent proportions should divide the base equally between them ; that, since sulphuric acid acts as a monacid in this respect, H,S04 should be compared with HCl and not, with 2HC1; and that, if one of the two acids form a dis- sociable salt, it would take none or very nearly none of the base.The facts observed, the author argues, are in accordance wit,h these conclusions, and are entirely opposed to the existence of the so-called "avidity " or " affinity '' constants advocated by Ostwald and others. The reason why sulphuric acid acts as a monacid in this respect, or, in other words, why H2S04and K2S04interact to form 2HKSa4 in spite of the absorption of heat accompanying the action, is that lower hydrates (especially of the acid) are present, and that with these lower hydrates the interaction is exothermic, and, therefore, necessarily occurs, the absorption of heat noticed being due to the dissociation of the higher hydrates to supply the place of the lower ones thus removed from the sphere of action.DISCUSSION. Professor RAMSAYsaid that it was merely a matter of nomenclature to distinguish p'hpsical attraction, in which each molecule present attracted every othvr molecule :teeording to some law comparable with the law of gravitation, from chemical attraction, in which selective attraction is exercised ; but that he preferred to draw the distinction, where possible, in order to save confusion, though it might, be di6cult in some cases to do so. He did not believe in the universal presence of complex molecules in liquids and solids: nor did he exclude the 101 existence of such ; the researches of Professor Young and himself, he thought, conclusively established the absence of a complex molecular structure in such liquids as ethyl alcohol and ether; while on the other hand Henry’s arguments testified to the complexity of the molecules of certain oxides such as silica.And with regard to water, which specially formed the subject of Mr. Pickering’s remarks, while the vapour-density pointed to molecular simplicity, other arguments drawn from its behaviour when examined by Raoult’s method were in favour of moderate molecular complexity. Dr. ARMSTRONGsaid that he agreed with Mr. Pickering, and thought that it would be necessary in tlhe future to attach a far wider signifi- cance to the term chemical action, and to greatly restrict the use of the term physical action-that, in fact, very many so-called physical changes would be found to involve a change in molecular composition or configuration.It was conceivable that in certain cases such as Professor Ramsay had mentioned molecule acted upon molecule chemically, but in such manner that the molecular aggregate was of the dimensions of the mass. By taking into account the action of water, Mr. Pickering had advanced what appeared to be a rational explanation of many facts which hitherto had appeared paradoxical. Mr. PICKERIRG,in reply to Professor Ramsay, said that the fact that gaseous water was of normal density appeared to him compatible with the existence of complex water molecules : probably a sudden change attended liquefaction or gasification.This argument might be of general application. 80. “Note on the mixture of Propyl Alcohol and Water.” ByProfessor Ramsay, F.R.S., and Professor Young. Chancel has called attention to the fact that a mixture of propyl alcohol and water in the proportions C3H80: H,O distils over to the last drop at 87.5” (press. = 738 mm.). Konowalow, however, determined the vapour-pressure of mixtures of the alcohol and water and arrived at results adverse to the conclusion that a definite hydrate exists, and the authors are of similar opinion. They found that’ the vapour-pressures of the mixture determined by the statical method were uniformly higher than those determined by the dynamical, but the difference is very small and far less than is observed with most dissociating substances, the behaviour being more nearly that of an imperfectly purified stable substance.The results of vapour-density determinations seemed to point to a rise of density with fall of tem-perature and increase of pressure, but it was afterwards found that the greater part of the rise was due to condensation, probably of water, on the side of the tube. A percentage contraction of 1.85was 102 observed on mixing the alcohol with water -71.46 per cent. alcohol to 28.54 per cent. water. The composition of the mixture of constant boiling point was found to vary with the pressure under which it was distilled. DISCUSSION. Mr. HOWARDexpressed the opinion fhat propyl alcohol and water formed a definite compound until vaporised; the behaviour of the various lower alcohols with water, and the fact that the solubility of amyl alcohol in water diminished as the temperature rose, all tended to prove that the alcohols formed hydrates.Professor YOIJFTG,in support of the opinion that the mixture was not a, hydrate, recapitulated the arguments which he and Professor Ramsay had advanced in previous papers in discussing the properties of various liquids and liquid mixtures. 81. “ Note on the Action of Nitric Acid on Amnionium Chloride.” By F. G. Mathews, Ph.D. The principal gaseous product of the action of nitric acid on ammoniuni chloride in solution is nitrous oxide, and not nitrogen, as has been previously stated ; the gas is mixed with small quantities of chlorine and oxychloride of nitrogen, from which it may be freed by washing with sodium hydroxide. The nitrogen of the nitric acid as well as of the ammonium chloride is concerned in the formation of the nitrous oxide.The interaction is of general application, and takes place in all cases in which a solution of an ammonium salt is heated in the presence of nitric acid and hydrogen chloride. 82. ‘‘ Ethylic Cinnamyldiethacetate.” By P. G. Mathews, Ph.D. A simpler method of preparing ethylic cinnamy ldiethacetate than has been previously known is to allow a mixture in molecular propor- tions of benealdehyde and ethylic diethncetoacetate saturated with hydrogen chloride to stand for about a month : the product separates slowly in crystals which are practically pure ethylic cinnamyldiethace- tate.On hydrolysis with barium hydroxide, cinnamic and diethacetic acids are produced, small quantities of a ketone only being formed. An atkempt to prepare the corresponding monethyl-derivative in a similar manner failed. On trying to prepare similar derivatives of ethylic mono- and di-methacetoacetate, no products could be isolated, the action appearing to be more complex than in the case of the corresponding ethyl compounds. 103 83. " The isomeric Sulphonic acids of Bekanaphthylamine.'' By Arthur G. Green. It is known that on sulphonating betanaphthylamine by means of ordinary sulphuric acid, amixture of a-and y-acids is produced at low temperatures, and at higher temperatures (160-170") a mixture of /3 and 6: according to the formub usually assumed for these acids, the first pair have their sulpho-groups in a-positions, the second pair in P-positions ; and their formation is exactly analogous to that of the a-and P-sulphonic acids of naphthalene.According to Dahl, the product at 100" consists of a-,p-and y-acids, but the author finds that as was to be expected, the &acid is also present. The four acids can be readily isolated by a slight modification of Dahl's process. The ammonium salts of the four acids were found to differ in a very characteristic manner : that of the p-acid is less soluble than the three isomeric salts, and by means of this salt, the @-acid was obtained in a pure state, and was found to crystallise in prismatic needles, not in nacreous plates, the formation of which is shown to be dependent on the presence of &acid.Although betanaphthylamine gives four isomeric acids on sulphonation, only two sulpho-acids are supposed to be formed by sulphonating betanaphthol; but bearing in mind the analogous behaviour of hydroxy- and amido-compounds, it would appear much more probable that four acids are formed in the latter case also, and hence a search was made for the 6-sulphonic acid in the product of sulphonation of betanaphthol at 100". As the separation of isomeric bstanaphtholsulphonic acids pyesents great difficulties, the method adopted consisted in converting the sulphonation product into the corresponding betaiiaphthyIaminesulphonic acids and separating these.By this means it was proved that the product formed at 100" is a mixture of the p-and 8-isomers. Hence at higher tempera- tures at any rate betanaphthol behaves on sulphonation like beta- naphthylamine; whether this is the case at low temperatures also remains to be seen. DISCUSS~ON. Mr. WYXNEasked whether Mr. Green had any evidence in favour of the formuls he had adopted for t,he a (Baclische) and y (Dahl) betansphthylaminesulphonic acids. The yacid was more usually represented by the formula ISH, : SO,H = 2 : 1'. With regard to the a or Badische acid, it was to be noted that Cleve had assigned the constitution adopted by Mr. Green to the dichloronaphthalene melting at 34"; that Forsling had assigned the constitutiou 1: 3 or 1: 2 to the dichloroiiaphthalcne melting at 61.5," obtainable from the Badische acids; and that Erdrnanii and Kirchhoff had obtained a dichloro- 104 naphthalene melting at 61.5"which was unquestionabIy heteronucleal.At present, therefore, Mr. Green's formula for the betanaphthylamine- a-sulphonic acid could not be accepted. Looking at the variation in the proportions of the four betanaph- thylaminesulphonic acids formed on sulphonating at different tem- peratures, Mr. WYNNEsuggested that the conversion of the a-and y-acids into the P-and &acids at 160" might be explained by suppos- ing that in the presence of the sulphuric acid the a-acid was convert& exclusively into the @acid, and that the yacid underwent a similar change into the &-acid, which itself at higher temperatures (or by it prolonged action of the sulphuric acid at 160") would undergo conversion into the &acid.Such a change, though perhaps different in its course, would be analogous in result to that described by Professor Armstrong and himself in the case of the monosnlphonic acids of the 6-halogen-derivatives of naphthalene having a constitution similar to that of the Badische acid. Dr. ARMSTRONGreferred to Emmert's observation that the beta- naphthol-a- sulphonic acid oorresponding to betanaphth ylamine- a-sulphonic acid is convertible into a dihydroxynaphthalene different from hydrobetanaphthaquinone, as incompatible with the conclusion that the a-acid was the 1 :2 compouhd; moreover, an acid in which the SO,H and OH groups were in the relative positions 1:2 would not, he thought, be capable of forming azo-colours.He then pointed out that the conclusions at which Mr. Wynneand he had arrived concerning the constitution of the dichloronaphthalene obtainable from the Badische acid were irreconcilable with Mr. Green's formula (cf. the following Abstract). Mr. GREEN,in reply, defended the view that the a-acid was the ortho-compound mainly on the ground that it and the corresponding hydroxy-acid differed so greatly in properties from their isomers, 84. ''The Constitution of the Dichloronaphthalenes, especially the ap-compounds." By Henry E. Armstrong and W.P. Wynne. The three possible oca-and the two possible heteronucleal p/1-dichloronaphthalenes are all known, and not only are they known, but there can be little doubt that the formula now ascribed to the several modifications (comp. Abstracts of Proceedings, 1888, p. 95) are correct expressions of their constitution. The object of the present note is to point out that the four possible ap-dichloronaphthalenes are also known, and to draw attention to the explanation of the somewhat discrepant statements on record relating to the so-called @-modification, melting at about 61". This was first prepared by Cleve, who obtained it from one of the three a-nitro-acids formed on nitrating naphthalene-p-sulphonia acid ; he subsequently 105 obtained a dichloronaphthalene having the same melting point from a, second of these three acids, but left it an open question whether two isomers of the same melting point existed, or whether an isomeric change took place on treating the nitrosulphochloride with phos-phorus pentachloride.Dichloronaphthalene melting at about 61" has since been prepared (1) by Arne11 from P-chloronaphthalenesul- phonic acid ; (2) by Cleve from dichloralphanaphthylamine; (3) by Claus from betanaphthol-a-sulphonic acid (Bayer's modification) ; (4) by Forsling from betanaphthylamine-a-sulphonicacid (the Badische acid) ; (5) by Erdmann and Kirchhoff from parachlorophenylparaconic acid. Forsling has quite recently stated (Berichte, 1888, 2802) that the moditication melting at about 61" is either 1: 2 or 1: 3 dichloro-naphthalene, his conclusion being doubtless based on Cleve's statement that dichloralphanaph t hylami 1.1e yields ph thalic acid on oxidation, and is therefore to be regarded as homonucleal.Now the authors have found (British Association Report, 1887, p. 231) that two distinct dichloronaphthalenes have been regarded as one, and that while that from dichloralphanaphthylarnine melts at 61*5",that from Arnell's 6-chloronaphthalenesulphonicacid and from the Badische or beta-naphthylamine-a-sulphonicacid melts at about 64" ; the chloride of the acid obtained on sulphonating the former melts at about 148", the isomeric sulphochloride obtained from the latter melting at 119". In support of Cleve's statement that dichloralphanaphthylamine is a homonucleal compound, they are able to state that it yields the same frichloronaphthalene (m.p. 92") as dichloralphanaphthol, an un-doubted homonucleal derivative. The dichloronaphthalene melting at 61.5" is, therefore, either the 1: 2 or the 1:3 homonucleal modification. That melting at 64" must be regarded as the 1 : 2' or 1: 3' hetero-ancleal modification, inasmuch as the dichloronaphthalene melting at 34" discovered by Cleve in 1887 is also a homonucleal compound. The dichloronaphthalene melting at 34"was obtained by Cleve from chlorobetanaphthylamine and from chlorobetanaphthol ; it may also be prepared from the chloralphn,naphthylamine which Cleve obtained by reducing dichloralphanaphthylamine.Cleve's statement that chlorobetanaphthylamine is a homonucleal compound, since it yields phthalic acid on oxidation, is confirmed by the observation that a sulphonic acid may be prepared from chlorobetanaphthol, which is converted on treatment with bromine into a bromhydroxyquinone- sulphonate, identical with that which may be obtained from Schaefer's betanaphtholsulphonic acid, in which the bromine is undoubtedly present in the quinone nucleus. The fourth ap and the second heteronucleal dichloronaphthalene is the 7-modification, melting at 48". This was originally obtained by Cleve from one of the three a-nitro-derivatives of naphthalene-/% 106 sulphonic acid; it has since been prepared by Forsling from beta- naphthylamine-v- sulphonic acid (Dahl's modification), and synthetically by Erdmann and Kirchhoff.The authors hare recently obtained it by distilling their ? P-naphthalenedisulphonic acid (Abstracts of Proceedings, 1886, p. 231) with phosphorus pentachloride ; attention is to be called to the fact that this had previously been stated to be a, method of preparing the &modification, melting at 61.5" (Brit. Assoc. Report, 1887, p. 232) ; how the mistake arose they are unable to explain, but a mistake was undoubtedly made, as a portion of the original specimen of the sulphochloride, melting at 150°,referred to in the British Association Report, gave on hydrolysis 9-and not 8-dichloronap hthalene. The sulphochlorides prepared from the two dichloronaphthalenes melting at about 48" and 61" respectively have the same melting point, and hence the mistake was overlooked until recently, when a large quantity of disulphonic acid was prepared and converted into dichloronaphthaiene. It being determined that the two modifications melting at 34" and 61.5" are the two possible homonucleal a@-dichloronaphthalenes, it remains only to ascertain which is the 1 : 2 and which is the 1:S compound ; the authors have succeeded in solving this problem some- what unexpectedly by studying so-called a-dichloronaphthalene, m.p. 38", which is obtained on heating naphthalene tetrachloride with alcoholic potash. On snlphonating this compound, two isomeric sul-phonic acids are formed, the chlorides of which melt at 133" and 148", but, as these are the melting points of the chlorides formed from the acids which result on sulphonating p-dichloronaphthalene (m. p.68") and 0-dichloronaphthalene (m. p. 61.5") reepectively, the two sulpho- chlorides from a-dichloronaphthalene were hydrolysed ; that melting at 148" gave 8-, and that melting nt 133" P-dichloronaphthalene, proving the supposed uniform a-dichloronaphthalene to be a mixture of 8 and p. From this it follows, as only a single C@ homonucleal dichloro- naphthalene can be obtained from naphthalene tetrachloride, viz., the 1:3 modification, that 8-dichloronaphthalene melting at 61.5" is the 1:3 derivative, and that melting at 34" must be regarded as the 1:2 derivative. This conclusion is supported by Widman's observation (Bull.Soc.Chirn., 28,506;Ber., 1882,2160) that a-dichloronaphthalene yields two tetrachlorides-one an oil yielding ytetracliloronaphthalene, the second a crystalline solid melting at 172", indistinguishable from that obtainable from B-dichloronaphthalene. It is also confirmed by the observation that on hydrolysing the dichloronaphthalenesulphonic acids prepared in accordance with Widman's directions from naph-thalene-a- and P-snlphonic chlorides, 8-dichloronaph thalene, melting at 61*5",is obtained from the &-acid, and p-dichloronaphthalene from the P-acid. 107 At present the data are not sufficient to determine whether the heteronucleal modification melting at 48"is the 1 :3 and that melting at 64"the 1:2 derivative, or *uice wersd.Erdmann and Kirchhoff have indeed put forward the view that 7-dichloronaphthalene is the 1 : 3 modification, but their method cannot be regarded as trustworthy, as the origin of the hydroxyl in their naphthol derivatives cannot be determined. The authors anticipate that the study of the sulphonic acids of the dichloronaphthalenes, in which they have long been engaged, will lead to results which will permit of the constitution of isomerides such as the 7 and the isomeric heteronncleal @-dichloro- naphthalenes being determined beyond question. 85. '(Piaeine-derivatives." By Dr. Arthur T. Mason. In this paper, which is an account of a contiiiuation of work described in the Berichte, 20, 267, the author adopts Widman's nomenclature (J.p.Chem., 38,135) : the "Ketines " (V. Meyer), ('Pyrazines " (Wolff, Masoy), '' Aldines " (V. Meyer), and all com- pounds containing a ring of four carbon-atoms and two nitrogen- atoms in para-position are now termed Parndiazines, or Piaxines. The author finds that the condensation product obtained from phenanthraquinone and ethylenediamine is not a diliydride as for-merly stated, but the base phenanthrapinzine. Dipheny~iazinedih2/dride,prepared from bend and ethylene-diamine, which is very unstable towards acids, gives on distillation a very stable base (2, 3) diphenyzpiazine; this crystallises from 50 per cent. alcohol in large colourless plates, melting at 118-119"; it is only a weak base.The chloroplatinate, C,6H,2N2,~JtC16, forms long, yellow, prismatic needles. By the action of sodium on a solution of 2, 3 diphenylpiazine in amyl alcohol, two hydrides were obtained of the formula Cl6H,,N2. a (2,3) Diphenylpiaxinehexlt ydride crystallises from light petroleum in long, slender, white needles, melting at 122-123", and possesses strong basic properties. The hydrochloride, C,,H18N;2HC1, forms long, glistening, white needles, melting at 310". The chloropzatinate, C16H18N2~,PtC16+ $H,O, forms golden-yellow prismatic needles. The nitroso-derivative, C16H16N604,crystallises in white prismatic needles melting at 142-143". Methyl iodide gives with the a-hydride the hydriodide of (1, 4) dirngthyl (2, 3) diphenylpiazine tetrahydride, C,,H,,N,HI, which forms long colourless needles ; the base of this salt crystallises from hot water in long colourless needles melting at 263-264" ; the chloroplntinate, (ClSH22N2)32HC1(PtC14)2+ 8H20, forms yellow prismatic needles./I (2, 3) DiphenyZ-piaziiiehexah$dride, which is found in the mother-liquors from 108 wbich the a-compound has separated, together with a third basic hydride, crystallises from 50 per cent. alcohol in long, silky, white needles, which on drying become dull white. It melts at 108-109”, and has strong basic properties. The hydrochloride, cuH,,N,2HCl, forms colourless prismatic needles, melting at 295”. The chloro-pZatinate, C,&f,&,*2BClPt!C& + 2H20, forms long light yellow needles. On oxidation (2, 3) diphenylpiazine yields a phenylpiaxine-carboxyZic acid, melting at about 202O, which yields well-characterised salts. The author, in conjunction with Mr.L. A. Dryfoos, is extending the research to the a-diketones of the fatty series. ADDITIONS TO THE LIBRARY. I. Donations. An Introdiiction to the Science and Practice of Photography, by Chapman Jones. London 1888. From the Author. Prnktische Metnllurgie, von A. A. Schnemann. Quedlingburg and Leipzig 1839. From B. H. Brough. New experiments and observations made upon the Icy Noctiluca, by R. Boyle. London 1681-2. From B. H. Brough. At the next meeting, on December 6th, there will be a ballot for the election of Fellows, and the following papers will be read :-“ A method of determining Vapour-densities applicable at all temperatures and pressures.” By Dr. W. Bott. “ Derivatives and some new Colouring Matters obtained from a-Plyrocresol.” By Dr. W. Bott and J. Bruce Miller. “ The action of Ammonia on Tungsten Oxychlorides.” By Dr. S. Rideal. fARBISON AND SONS, PEtIN’l’EHG 1N ORDINARY TO BXR MAJESTY, ST. MAltTllri S LANE.
ISSN:0369-8718
DOI:10.1039/PL8880400099
出版商:RSC
年代:1888
数据来源: RSC
|
|