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Proceedings of the Chemical Society, Vol. 21, No. 288 |
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Proceedings of the Chemical Society, London,
Volume 21,
Issue 288,
1905,
Page 1-16
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 21. No. 288. D.Sc.,Wednesday, January ZE;th, 1905. Professor W. A. TILDEK, P.R.S., President, in the Chair. Alessrs. T. R. Hodgson, J. K. H. Inglis, J. R. Johnson, aud G. F. Phillips were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : James Henry Ashwell, 117, Waterloo Crescent, Nottingham. Samuel Henry Clifford Brigs, B.Sc., Green Bank, Cleckheaton, Yorks. F. E. Clarke, Ph.D., B.Sc., Pennsylvania State College, Pa., U.S.A. Charles Richard Gardner, Grsen Cottnge, Brunswick Squl;we, Gloucest er. Frederick William Heely, 10, Ynrborough Street, Grimsby. James Alexander Russell Henderson, B.Sc., Clhihli Provincial College, Paotingfu, N. China.Percy Walter Jones, Toowong, Brisbane, Queensland. Joseph Lister, R.Sc., 50, Portland Street, Lancaster. Edward William Lucas, 3 7, Barton Street, Kensington, W. Frank Lee Pyman, Ph.D., I;.&., The Oaks, Hitchin, Herts. Fred Scholefield, B.Sc., 9, Lyndhurst Villas, Magdalen Road, Norwich. John Irwin Scott, B.A., Trent College, Long Eaton, Derbyshire. 2 William Dunham Seaton, 40, Argyle Roitd, Ilford, Essex. William Herbert Simmons, B.Sc., Oakleigh, Stoke Newingtoii Common, K. Eric H. Weiskopf, Modclerfon tein, Tranwd. gave notice that an EXTRAORDINARYThe PRESIDEST GENERAL MEETINGwill be held in the Society's Rooms on Wednesday, February 8th, 1905, at 5.30 p.m., to consider the proposal of the Council to make alterations in the Bye-Laws.The Council has ordered the following letter and report to be printed in the Journal and in the Proceedings of the Society : GOVERNMENTLABORATORY, CLEMENT'SJNN PASSAGE, STRAND, W.C.LOSDON, 6th December, 1904. GENTLEMEN, I beg to hand you the Report of the Interuatioiial Committee 011 Stomic Weights, 1905, to which I have appended the names of Professors Moissan and Seubert, as desired by t'hem. Since the Report was signed I have received, in cominon I presume with other members of the Committee, a communication from :I Committee of the Gerinan Chemical Society in reference to the adoption of only one table of numbers in which oxygen should be taken as 0 = 16, to the exclusion of a second table in which the values of the atomic weights were based on H=l.On my communicating with the Chairman as to what action should be taken in consequence OF the letter from the Berlin Committee I was informed that the Report as adopted had already been despatched to Japan, and was actually in print in America. In these circum- stances, and as the Sub-Committee had not had any opportunity of taking the communicatiou from the German Committee into considera- tion, he considered it desirable that the Report, as adopted, should be presented to the va~ious Societies concerned. I am, Gentlemen, Yonr obedient Servant, T.E. THORPE. 2Xe lion. Sewetaries, Y?ieChenticnl Society, Burlillyto 1t House, LOI Ld 0i I, IV. Report of the International Committee on Atomic Weights. The Interimtiounl (‘ominittee on Atomic Weights respectfully submits the following report, together with a table of atomic weights for use during 1905.Most of the values recommended in our table are identical with those reported in former years ; bwt a few changes seem to be needed. C)ther changes, which are suggested by recent investigations, are deferred until fuller inforniation regarding their desirability shall have been received. During 1904 there has been great activity jii the determination of atomic weights; and a suinmary of the more important researches may help to explain ow reasons for cliangiug or retaining hitherto accepted v;tlueb. The researclies to be consiclered art: as follows : (~Z‘EUciiiziriL.-*~toinicweight redeteriiiined by Parsons (J.Arizsr.Chew. S’oc., 1904, 26, 731). Sevcn analyses of the acetglacetonste gave, in mean, G1= ‘3.113. Nine analyses of the basic acetate gave exactly the same average. As the individual determinations range froiii ‘3.081 to 9.142, the figure 9.1 may evicleiitly remain unchanged. I?tdit~lll.--The iiivestigatioii by Thiel (Zeit.nr~o3.y.C‘hem., 1904, 40, 280) sbom that the atomic weight of iiiclium is higher than hacl beeii supposed. Xiialyses of the trichloride gave, in inean, In = 115.05. Aiialyses of the tribroinidc gnre 114.Sl. With the oxide, unsatis- factory results were obtained. For present purposes tlie ro~uicl number 115 iuay be adopted, although further investigation is pro-mised by Thiel, and a research by Dennis and Geer is in progress.~odi~zc.-In ow former reports we have noted tlie uncertainty in the accepted atoiiiic weight of iodine. Stas, by the synthesis of AgI, fomd I= 126.85. Scott, by the same general method, found I = 126.97 ; ant1 Ladeiiburg, by measuring the ratio AgI :AgCl, obtained the value 326.96, Koethner and Aeuer (L’er., 1904, 37,2536), froin data given by several methods, iiiclucling a repetition of Ladenburg’s process, coiiclucle that the atomic weight of iodine cannot be less than 126.963 ; bnt the full details of their investigation, at tlie date of writing this report, are still unpublished. A inor0 recent research by G. P. Baxter will soon appear, in which the higher value for iodine is completely confji-med, both by Ladenburg’s method and by that of Stas.Baxtei-’3 filial value is I = 126.975 ; and there can iiow be no reasonable doubt thxt the Stas figure is too lorn. The number 1216.97 is adopted in our table for O= 16, or 126.01 with hyclrogen as unity. LW~ogeiL.-The accepted value for the atomic weight of nitrogen, 14.04, is derived inainly from the work of Stas. Of late years, how- 4! ever, the study of gaseous densities has led several physicists, notably Rayleigh, Leduc, and Daniel Berthelot, to the belief that the true value is but little in excess of the round number 14. Guye (Compt. rend., 1904, 138, 1213) finds from the density of nitrogen the value 14.004. Still more recently, Guye and Bogdan (ibid.,138, 1494), by analysis of nitrous oxide, have found N = 14.007.Jaquerod and Bogdan (ibid., 139,49) have also studied nitrous oxide volumetrically, and obtained the figure 14.019. In view of the discordance between the volumetric and the gravimetric data, it seems undesirable to make my change at present in the number assigned to nitrogen. Further. investigation of this atomic weight is evidently needed. Rzcbidium-Atomic weight redetermined by Archibald (Tvaw., 1904, 85, 776) from analyses of the chloride and bromide. The final mean, derived from many concordant experiments, is Rb =S5.485. As some of the determinations are slightly higher than 85-5, that figure may be adopted as sufficiently accurate for all practical purposes. Xaiizarizc?iz.-Urbaiii and Lacombe (C'oq~t.Tend., 1904, 138, 116ci), by analyses of the octahydrated sulphate, find Sm = 150.34.A com-parison of this figure with the older determinations justifies the use of 150.3 as the most probable value for this atomic weight. The same authors (ibid., 138, 627) have also determined the atomic weight of europium, and give the figure En = 151.79. It is desirable, however, to await more complete information about europium before recognising it in the table. Tho~*iunz.-Evidence as to the complex nature of ordinary ''thorium " is steadily accumulating. According to Baskerville (J.Amer. Chent. ~oc.,1904, 26, 922), it is a mixture of at least three elements, which he calls carolinium, thorium, and berzelium. Their approximate atomic .weights are 256, 220, and 212.5 respectively, supposing them all to be tetrads.The value in our table is that of ordinary thorium, as it is found in mineral analyses ;and no change can safely be made until our knowledge has become more definite. Tu?&gste?z.-The figure conimonlg assigned to tungsten, W = 1S4, has been verified by Smith and Exner (PYOC.Amer. Phil. SOC.,1904, 43, 123). From twenty-seven measurements of the ratio WCl, :WO,, W = 184.04. From twenty-three syntheses of WO,, W =184.065. The individual determinations range from 183.94 to 184.14, which is a fair degree of concordance for so high an atomic weight. Changes, then, are recommended in the cases of indium, iodine, rubidium, and samarium. The column of atomic weights referred to blie hydrogen unit has also been carefully recalculated, and in it some small alterations appear.The latter modifications, however, are unimportant, except in so far as they help to bring the two tablesinto greater harmony. During the year there has been a revival of the agitation over the question of standards; and the policy of this committee, or rather sub-committee of the larger international body, in publishing a double table, has encountered some criticism. That criticism is perfectly legitimate, and we are glad to say that it has been expressed courteously, and in a truly scientific spirit. Professors Sakurai and Ikeda (C'hem. News, 1904,89, 305) have published an open letter upon the subject,* and, in response to a demand within the German Chemical Society, the committee representing that body issued a circular to the members of the larger International Committee, asking for an expression of opinion as to our procedure.We are not yet informed regarding the responses to that circular, and we therefore cannot base any action upon it. The Council of the American Chemical Society has also, by a formal vote, requested this committee to ask for instructions from the larger body, both as to the use of it double standard and as to the nomenclature and symbols of glucinuin or beryllium, and columbium or niobium. With this request we now comply, and hope that every inember of the larger liiternational Committee 011 Atomic Weights will send in his opinion upon the questions thus raised.Shall we continue to issue a double table 1 Can uniformity in symbols and nomenclature be obtained? And which names are preferable, in the light of history, evidence, and international usage, for the two elements under discussion ? That a single standard for atomic weights is most desirable, every chemist mill admit, but two standards actually exist, and each one is represented by earnest advocates who are unwilling to give way. Each side of the controversy is supported by eminent authorities in nearly equal numbers, and no agreement seeiiis to be possible either at present or within the near future. This condition of affairs the present committee has been compelled to face, and to deal with things as they are instead of as we should like them to be.Two tables of atomic weights exist,, and it has therefore seemed wisest to recognise the needs of both parties in the controversy, and to furnish each with trustworthydata for practical use. It is surely better to have oue committee prepare both tables, than to leave this work to be done in accordance with individual preferences. That there are difficulties in adjusting one table to the other is perfectly evident ; but the result- ing confusion is, we think, less serious than some of our critics would have us believe. The confusion is certainly less than it would be were the individual advocates of either standard to attempt the adjustment of one to the other independently. In short, the real question now before us seems to be this: Shall the present committee act in a quasi-judicial manner.recognising both parties in control-erq: or shall it assume a partisan position and represent one alone? . J$T. CLARIiK :. HENRI .MOISSAS-KARLSEGBERT. T. E. THORPE. International Atomic Weights. 0=16. R=l . 0=16. H=l. Aluminitim ......... A1 27.1 26.9 Neodyniiuin ...... Nd 113% 142'5 Antimony .........Sb 120.2 119'3 Neon ............... Ne 20 19.9 Argon ..............A 39.9 39% Nickel ............... Ni 58.7 583 Arsenic ............As 75.0 74.4 Nitrogeii........... N 14.04 13-93 Bariuni ............I31. 137'4 736'4 Osmium ............0s 191 169% Bismuth ........... Bi 208'5 206.9 Oxygen ............0 16.00 15'89 Boron .............. B 11 10.9 Palladium ........ 1'4 106.5 105.7 Bromine ............Br 79-96 i9.36 Phosphorus......... I' 31-0 30.77 Cadmium ......... Cd 112.4 111'6 Platinuni ........ I' t 194'8 193.3 Casiuin ............Cs 132.0 131.9 Potassium ....... I\. 39'15 38'85 Calcium ............Cn 40.1 39.7 Praseodymium ... I'r 140.5 139'4 Carbon ............ C 12.09 11.91 Railiam ............ Rtl 226 223.3 Cerium ........... Ce 140-25 139-2 Rhodiiuii ......... Rh 103*O 102'2 Chlorine ............C1 35-45 3;i.lS Rnbidiuin ......... Eb 855 84'9 Chromium ........Cr 52.1 51-7 Ruthenium......... Ru 101'7 100.9 Cobalt ..............Co 59.0 58.55 Saniariuni ........Sin 1503 149.2 Columbiniii ......Cb 91 93'3 Scandium ......... Sc 44'1 43'5 Copper ............Cn 63% 63.1 Selenium............ Sc 79'2 78% Erbium ............E!r 166 1642 Silicon...............Si 28'4 28'2 Fluorine ............P 19 18.9 Silver ............... A$ 107'93 107-11 Gadolinium ......Gd 156 15k-S Sodium ............Na 23.05 22'88 Gallium ............Gn 70 69 *5 Strontium ........Sr 8i-6 86'94 Germanium ...... Ga 72.9 72 Suiphnr ............ S 32.06 31'82 Glucinum .........G1 9.1 9-03 Taiitalani ........Ta 153 181'6 Gold ............... An 197'2 195'7 Tellurium .........Te 127 '6 126.6 Helium ............He 4 4 Terbinrii ..........Tb 160 158.8 Hydrogen .........H 1'008 1'000 Thalliruti .........T1 204'1 202'6 indium ............In 115 114.1 Tlioriuni ........... Th 232.5 230% Iodine ..............I 126'97 126'01 Thulimu ............Tm 171 169.7 Iridium ............ Ir 193'0 191.5 Till ..................Sn 119.0 118.1 Iron ..................Fe 55'9 55.5 Titanium ......... Ti 48'1 41'7 Krypton ............ Kr 81.8 81.2 Tungsten .........IY 184 182.6. Lanthanum ...... La 138'9 137.9 Uranium ........... U 238.5 236-7 Lead ...............Pb 206.9 205 *35 Tranadiuni ......... V 51'2 50*8 Lithium ............Li 7'03 6 *9s Xenon ...............Xe 128 121 Magnesium.........Blg 24'36 24'15 Ytterbiurrt ......... Tb 173'0 171.1 Manganese .........Mil 55 '0 54 *6 Yttrium ............Yt 89.0 88-3 Mercury ............Hg Molybdenum ...... 110 200.0 96.0 1985 95.3 Zinc..................zn Zircoiiiuiii ......... Zr 65'4 90.6 64'9 89'9 Of the following papers, t,hose marked * mere read :-*l. Nitrogen halogen derivatives of the sulphonamides.” By Frederick Daniel Chattaway. The nitrogen halogen derivatives of the sulphonamides, which are obtained by the action of hypochlorons acid on the sulphoqamides and the alkylsulphonamides, are remarkable for the great ease with which they can be prepared and crystallised, and for their comparative stability. The sulphondichloroamides all react with a1 kali hydroxides, forming the corresponding hypochlorite and the salts of the sulphon- monochloroamides.The latter salts, which are well crystallisetl and frequently contain water of crystallisation, only slowly undergo further hydrolysis. They have, in all probability, the iso-structure. The sulphondichloroamides, alkali sulplionmonochloroamides, and sulphonalkylchloroamides easily enter into a11 the reactions character- istic of nitrogen chlorides, and illustrate exceptionally well the be- liaviour of the nitrogen halogen linking, as the various types of simple interaction may with these substances be studied uncomplicatetl by the transformations which so readily occur with unsubstitnted ncylphen ylchloroamides. Sulphondibromoaiuides and sulphonalkylbromoamides are obtained most easily by a method andogous to that by which the corresponding sulphonchloroamides are prepared; that is, by the action of hypobromous acid on the corresponding aniides (compare Hoogewerff and van Dorl), Bec.Tmv. Chinz., 1887, 6, 373 ; 1889, 8, 173). They resemble the chloroamides in many of their properties, but are not so stable, and have a bright yellow or orange colour. The dibromoamides, which crystallise well and can be kept for some days unchanged, slowly decompose on longer keeping, bromine being generally liberated. When warmed with solutions of alkali hydroxides, they form salts, one bromine atom being replaced by metal. Thehe salts are beautifnlly crystalline, pale yellow substances frequently containing water of crystallisation, which is lost at 100”; when more strongly heated, tile!, decompose explosively. As in the salts of the chloroamides, the metal is probably attached to oxygen. A large number of typical examples of these compounds mere de’scribed. *2.‘‘ Electrolytic oxidation of the aliphatic aldehydes.” By Herbert Drake Law. The cliief product of oxidation of the lower iiiembers of the satiwatecl aliphatic aldehydes is the corresponding organic acid. To a simller 8 extent, the oxidation proceeds further, carbon dioxide and carbon mon-oxide being formed, aiid in the cases of acetaldehyde and propaldehrde small quantities of saturated hydrocarbons are also produced : RCOH + 0=RH +GO,. No corresponding reaction takes place in ilie cases of formaldehyde and isobntaldehyde.In these experiments, sulphuric acid was used as electrolyte. The gaseous products mere collected in Hofmann's electrolytic app,zratus fitted with platinum electrodes. The amount of acid formed was estimated in a porous pot fitted with a rotating platinum stirrer. DISCUSSIOS DF. F. M. PERKINsaid that one of the most interesting points brought out in the paper was the formation of small quantities of hydrocarbons in an oxidation process. It was remarkable how extremely stable the aldehydes were to electrolytic oxidation. This was shown most strikingly in the case of the aromatic aldehydes. Thus, if a mixture of toluene and benzaldeliycle was subjected to electrolytic oxidation, the hydrocarbon was oxiclised in preference to the aldehyde (Trans.Fmadcq Soc., 1901, 31). Some of the oxidations were best explained by supposing that the hydroxyl group and not free oxygen took part in tho reaction, as, for example, in the forma- tion of methyl alcohol in the electrolytic oxidat'ioii of an alkali acetate (Annalen, 1902, 323,304). "3. '' The diazo-derivatives of the benzenesulphonylphenylene-dianiines." By Gilbert Thomas Morgan and Frances Mary Gore Micklethwait. Ije~~xer~esul~~l~on~Z-p-137~e~aylenedicinziize,PhSO,*NH*C,H,*NH, (m. p. 173O), when diazotised in hydrochloric acid, yields R stable, colourless cliaxonium chloride, PhS02*NH*C6H,*N,C1, which, on treatment with aqueous alkalis or sodium acetate, condenses to forni a yellow diaxo-imicle, C,H,: [N,]*SO,Ph (in.p. 155'), this substance being produced directly when the base and nitrous acid int'eract in glacial acetic acid. The corresponding ortho-compound (m. p. 165-167'), when treated with nitrous acid either in hydrochloric or glacial acetic acid solution, at once gives rise to a colonrless cyclic diaminhids (m. p. 130') ; iri this case, the intermediate diazonium salt could not be isolated. When the iminic hydrogen atom of the PhSO,*NH group in t'he fore- going bases is replaced by methyl, the resulting compouiids, beneene-suZ~hon?/lmetlLyZ-p-(and-o-)-13?~enyle?aedinnzines,yield diazonium salts, PhS0,*NMe*C6H;N,C1, which do not condense to form diazoimides ; these products were characterised by the formation of their azo-/3-naphthol derivatives.Benxenesulp~onyl-mpheiLyZenediamine(m. p. 98-99') differs greatly from its ortho- and para-isoinerides in its behaviour towards nitrous acid; in hydrochloric acid, it yields a dinzonium chloride which, when freed from excess of acid or when treated with aqueous sodium acetate, evolves nitrogen and becomes converted into an azo-derivative ap- proxininting in composition to the formula PhSO,*NH*C,H,*N,*C6H3(O€€)=NH*SO,Ph. This change no longer occurs when the iminic hydrogen is replaced by methyl, and as-Beszxeizesulpl~on~Znzet~~Z-m-p~enyle~zedianziszep.(m. 96O), like its ortho- and para-isomerides, yields snccessively a normal diazonium salt and an azo-P-naphthol derirative (m. p. 129-131'). 1~SCUSSIOS. Dr. CAIN mentioned that he had diazotised large quantities of 21-aminoacetanilide in the manufacture of Coomassie Black, but had not noticed the formation of substances analogous to those described by the authors, Their failure to diazotise 211 amino-group in the ortho- position to a mono-substituted amino-group was in accordaiice wit'h the work of other investigators on such compounds.Dr. HEWITTagreed with Dr. R1organ respecting the probably essential difference in structure of thc compounds obtained by the action of nitrous acid on the monobenzenesulphonyl derivatives of 0-and p-phenylenediamiiies. Of the two cyclic formula: proposed for the ortho-compound, that in wliich a quinquevalent nitrogen atom was assumed seemed, however, very improbable ;nitrogen, as far as we know, only becoming quinquevalent in the case of salt formation.Dr. MORGAN,in reply, said that as benzenesulphonyl-p-phenylenedi-smine had been found to yield a new type of diazoimide, it became of interest to ascertain the behaviour of the similarly substituted ortho- and meta-diamines under comparable conditions. With reference to the alternative diazonium formula for the ortho- diazoimide, it seemed necessary to consider this possible configuration, inasmuch as, on account of the distinctly acidic nature of the complex C,H,*SO,*NH, the condensation of this substituent with the adjacent basic diazoniuin group might be regarded as involving the formation OF an internal salt. 10 "4. L6 The molecular condition in solution of ferrous potassium oxalate." By Samuel Edward Sheppard and Charles Edward Kenneth Mees.Ferroxs oxalate dissolves in alkali oxalates, forming double salts, such as K,Fe(C,O,) , which dissociate according to the scheme i --_ 2K + Fe(C,O,),. The complex anion, Fe(C1,0,),, is not very stable, and by solubility determinat,ions the value 0.8 was found for the constant at 20". Spectrophotometric ineasurements showed that the foimnt ion of ferrous ions at moderate dilutions was negligibly small. The action of acids is to precipitate ferrous oxalate by removing free oxalate ions, thus disturbing the equilibrium indicated above. The absorption-spectrum was measured at three concentrations- The absorption is unilateral, increasing nniformly toward the violet end of the spectrum. "5.'' A further analogy between the asymmetric nitrogen and carbon atoms." By Humphrey Owen Jones. In the present state of our knowledge of the stereoisomerism of quinquevalent nitrogen compounds, any definite knowledge about the similarity and diff ereiice between them and asymmetric carbon com- pounds is of value. The author has proved that, during the formation of an asymmetric nitrogen atom in a compound cont,aining an asym- metric carbon atom, two isomerides, which are called the a-and p-corn-1)ouiids, are produced. Methyl-I-amylaniline has been combined with ally1 and benzyl iodides. The dextrorotatory a-ally1 compound can be isolated by crystallisa- tion from alcohol ; [a], in chloroform = 21*8', gradually falling to 3.1' a2.i the a-isomeride changes into the P-derivative until equilibrium is at t ainecl. The two benzyl compounds caiinot be separated in the same way, because the difierence in solubility is not great, and they are very labile.They have therefore been separated by means of their cainpliorsnlphonates. a-Phenylbenzylmethyl-Z-aniylammoniumiodide melts at 144-145' and has [a],, in chloroform = 65'; the p-coili- pound melts at 131-132" and has [a]D= -1S.s'. The cliloroform solutions of both compounds change rapidly until equilibriuiii is attained with [.ID =2.8'. 11 6. (‘The formation of magnesia from magnesium carbonate by heat and the effect of temperature on the properties of the product.” By William Carrick Anderson.Magnesia prepared from different substances and by different methods is known to vary greatly in properties, and it is generally supposed that this is clue either to variation in the size of the molecule of the oxide, or to a difference in the grouping of the magnesium and oxygen atoms in the molecule, 01’ to both of these causes. In the absence of a method of deterinining the niolecular weights of solid substances, evidence in support of the view that the magnesia is polymerisecl must be indirect. Experiments were conclucted on the native magnesium carbonate (magnesite) and on three forms of artificial carbonate with the view of ascertaining (1) the lowest temperature at which the evolntion of carbon dioxide could be distinctly recognisecl ; (2) t’he cornparatjive rates at which the expulsion of the gns takes place at higher ternper- ;Ltiwes under atmospheric pressure ;and (3) the extent to which the samples of initgnesia thus obtained dissolve in water after being kept at different known temperatures for :I fixed period.This solnbilitg was determined after leaving an excess of the specimen in water for 2 hours at 20’. In 20 hours at 350°, native magliebite yielded a quantity of carbon dioxide equal to 0.40 per cent,. of its weight,, and the rate of evolution increased rapidly with rise of temperature. Complete expulsion T.F;I% reached at about 750’ with two at least of the artificial carbonates, but only above 810’ in the case of the third (“ heavy carbouate ”).The rate of solution of the magnesia obtained by heating tlie “ heavy carbonate ” mas found to be greater than that of the samples obtained from ‘‘light ” and “ crystal ” carbonate under the same conditions, so long as the heating was little more than that needed for complete decomposition of the carbonates. As tlie teiiiperatnres of prepnration were increased, the rate of solution diminished in every instance, but much inore rapidly in the case of the “heavy” oxide than in those of the other two. It is inferred from these results that polyiiierisation takes place when magnesia is heated, anll that this goes oil faster in the dense ‘‘heavy ” oxide than in the 1ightc.r specimens of magnesia. The rate of solution as determined in the experiments is believed to be a measure of the rate of hydration, and this appears to be inost rapid in the molecnle (MgO)l, obtained by heating the heavy cayboilate at 810’.12 7. LL Transformations of derivatives of 8-tribromodiazobenzene.” By Kennedy Joseph Previte Orton. The discrepancy between the results obtained by the author (PYOC. Koy. Xoc., 1902, 71, 153; Trans,, 1903, 83, 796) and by Hantzscli :Hantzsch and Pohl, Ber., 1902, 35,2964 ; and Hantzsch, Ber., 1903, 36, 2069) with respect to the transformations of s-tribromobenzenedi-azonium salts and s-tribromobenzenediazotates has led the author to reinvestigate these react ions. According to the author, in solutions of the diazonium salts of weak acids, that is, solutions in which the ions (C,H,Br,*N,) and (Oh) are simultaneously present, a replacement of a bromine atom by hydr- oxyl takes place, bromine ions appearing in the solution, and 3 : 5-di-hroino-o-beiizociuiiiouecliazide (3 :5-dibromo~liazophenol),0:C6H2Br2:NP, being formed.A siiiiilar decomposition takes place when a solution of the corresponding s-tribromobenzenediazotate is treated with quantities of an acid insufficient to convert the diazo-compound into the diazonium salt, the free diazohydroside, C,H2Br,*N:N*OH, thus formed, probably now cleaving into tlie groups (C,H,Br,*N,)’ aiicl (OH). According to Hantzsch, on the other hnncl, under both conditions the primary product of the change is s-tribl.oinophenyliiitrosoainilie, G,H,Br,*NH*NO, a substance which, although at first thought to be readily capable of isolation (Ber., 2902, 35, 2964), is now stated (Be?.., 1903,36,2069) to be unstable and, at any but low temperatures, liable to decompose into the quinonediazide with the elimination of hydrogen bromide.The difference between these two results is ascribed by Hantzsch to the fact that tlie anthor carried out his experiments at the ordinary temperature and not at as low a temperature as possible. In the new experiments, the solntions have been kept partially frozen during the reaction, and the primary product has been examined in order to ascertain if any decomposition, which was accompanied by the formation of quinonediazide and the eliiniiiatioii of hydrogen bromide, could be detected. The author’s earlier observations, namely, that the primary product was a mixture of a complex condensation product with the quinonedinzide, were completely confirmed.The proportion of the quinonediazide in the primary yellow product was estimated by conversion into the azo-P-naphthol derivative, and found to represent about 12 per cent. of the cliazonium hydrogen sulphate, when 2 gram-mols. of hydrogen carbonate were used for each gram- mol. of diazonium salt ; at the same time, it was shown that the quinone- cliazide did not arise during the operation from the decoinposition of s-tribromophenylnitrosoamine,as no simultaneous formation of hydrogen bromide could be detected. 13 In the yellow aqueous extract of the primary product, which, accorcl- ing to Hantzsch, contains the nitrosoamine in solution, the author was unable to find any substance but the quinonediazide.On keeping or on heating, no decomposition accompanied by the elimination of hydrogen bromide was observed ;the diazophenol could be completely extracted from the solution by chloroform and then coupled with alcoholic P-naphthol; lastly, when exposed to light, the solution behaved in the manner characteristic of diazophenols. Experiments showed that between the limits of O’and 15’ temperature has but little effect on the extent of the decomposition of the s-tribromo- cliazobenzene ;as the author has previously stated, the prime factors appear to be the concentrations of the ions (C,;H2Br3*N2).and (OH).The author sees, therefore, no reason for modifying the views expressed by him in former papers rts to the inechanism of this re- action, and thinks that at pesent there is not sufficient evidence for supposing that a nitrosoarnine is the primary product, which sub- sequently decomposes into quinonedinzide and hydrogen bromide. 8. “The addition of sodium hydrogen sulphite to ketmic com-pounds.” By Alfred Walter Stewart. The statement made by Beilstein in his IIasztZbuch (3rd ed., I, 999). that pinacoline forms no addition product with sodium hydrogen sulphite, when taken in conjunction with the current idea that ‘‘bisulphite ” compouiicls are formed only with those ketones whicli contain the acetyl group, suggests that the introduction of methyl groups into tlie ketonic chain has a tendency to prevent the formation of an additive product.With the view of testing tlie correctness of this idea, and in order to estimate the relative amounts of the double compounds formed with diff ereiit ketones, advantage was taken of the fact that iodine solution does not oxidise the S0,Na group of a ketonic bisulphite compound. Thus, if two solutions, one of pure sodium hydrogen sulphite and the other containing a niixture of this salt and a ketonic compound, are titrated, the difference in the number obtained on titration indicates the ainouiit of additive product formed. This method was applied to several compounds containing the acetyl group and the principA1 results are shown in the following table : Percentage of bisiilphite cornpound foriiiecl in 10 niiiiutes.30 minutes. 50 minntes. 70 minntes. Acetaldehyde .................. Acetone .......................... 85.O 28.5 88.0 47 ’0 88.i 55 .9 88-7 58 0 Methyl ethyl ketone ......... Methyl propyl ketone......... Methyl isopiopyl ketone...... Pinacoline ........................ 14.5 8.5 4.Y 4“‘ 25.1 14.8 7.5 5.6 32.1 19% 11% 5.(j 38’4 25 ‘5 13.0 6% 14 9. “The reduction products of anisic acid.” By John Scott Lumsden. When anisic acid dis.;olved in amyl alcohol is redaced by sodium, the prodnc ts of yeclnc tion are hesalipdrobenzoic acid and 8-ketohexa-IiyVdrobenzoic acid. The formation of the former acid is explained 1))-the removal of the methosy-group of anisic acid and the complete hydro genntion of the ring, but the production of the %ketonic wid is more dificult to understand, beiiig probably due to foiw hydrogen atoms he-coming attached, and then, by the agency of one molecule of water, the iiietliyl group is removed as methyl alcohol, and the hydrogen of tlie wnter is added to the y-carbon atom.By analysis of the ketonic. acid and its salts ancl from the melting point of the semicsrbazone, it ih proved to be identical with the acid recently prepared synthetically by Perkin (Trans., 1904, 85, 416). 10. ‘ The physical properties of heptoic, hexahydrobenzoic, and benzoic acids and their derivatives.” By John Scott Lumsden. From hexahydrobenzoic acid, which was obtained pure from anisic i\cid, the methyl, ethyl, and propyl esters, the acid chloride ancl anhj-dride, aiid the nude aiid anilide were prepzred andatheir properties compared with the corresponding compounds of heptoic and benzoic acids.It was foniicl that the properties of hexahydrobenzoic acid and its derimtives were in general intermediate between those of the other two acids, the inelting points, boiling points, specific gravities, and rc-fractive inclices being higher than those of the heptoic, and lower than those of the benzoic acid series. The solubilities of the three acids are nearly alike, but the afiinitJ- constant of the hexahydro-acid is lower than that of benzoic acid, and is like the value of that of an acid of the fatty series.The boiling points of the liexali3’dro-CoHipouiids are regularly 9’ higher than the heptoic, ancl 15’ lower than the corresponding benzoic derivatives. A comparison of the molecular volumes showed that a hexamethylene ring and a benzene nucleus have identical volumes, while measurements with a Pulfrich’s refmctometei* proved that the hexamethylene struc- ture has no influence on tlie refraction of light, but that a beiizeno nucleus retayds light to an amount equal to that due to six hydrogen atoms, thus making the molecular refractions of the correspoiidiiig derivatives of beiizoic and 1ies;~hydyobeuzoic acid identical. 1.5 11. ‘( The influence of solvents on the rotation of optically active compounds. Part VII. Solution-volume and rotation of menthol and menthyl tartrates.” By Thomas Stewart Patter- son and Francis Taylor.The authors have exaininecl the rotation of menthol, I-menthyl d-tartrate, and I-menthyl diacetyl-d-tartrate in ethyl alcohol, benzene, and nitrobenzene: and have compared the vdnes obtained with the corresponding values for molecular-solution-volume. The results were considered, on the whole, to confirm the suggestion that rotation in solution and molecular-solution-volume are closely related phenomena. For menthol, the facts are in complete agreement n-ith theory. With menthyl tartrate, the results for alcohol and nitrobenzene are in good agreement, although the relationship between the two variables in benzene is anomalous. Difficulties are met with also for menthyl diacetyltartrate ; but although in alcohol and benzene the relationshil) is not a quantitative one, it is in accordmce with theory in so far as, in both cases, contraction brings about increased rotation.Out of the nine examples studied, seven are in agreeinelit with the relatiun- ship suggested. ALTERATION OF LIBRARY RULE 4. Instead of :-“ New Books are not available for circulation till two months after their names have appeared in the Proceedings.” The Rule now reads :-‘‘ A Book may not be taken out of the Library until one month after it has been received.” ADDITIONS TO THE LIBRARY. I. Donchons. Internationaler Kongress fur angewandte Chemie (V). Berlin, Juni 1903. Bericht erstattet vom Prasidenten des Kongresses Otto N.Witt, und dem wissenschaftlichen Sekretar des Kongresaes Georg Pnlvennacher. 4 Binde. pp. xii + 795, xii + 1021, xii + 1075, xv+ 1156. ill. Berlin 1004. (Recd. 7/1/05.) From the Congress. Wardle, Sir Thomas. Kashmir : its new silk industry, with some account of its natural history, geology, sport, etc. pp. xx + 363. ill. London 1904. (Recd. 12/1/05.) From the Author. IT. Bp Purchase. Bunsen, Robert. Gesammelte Abhandlungen. Im Auftrage der Deutschen Bunsen-Gesellschaf t fiir angewandte physikalische Chemie, herausgegeben von Wilhelm Ostwald und MRXBodenstein. 3 Bande. pp. cxxvi + 536, 660, 637. ill. Leipzig 1904. (Recd. 14/12/04.) Gay-Lussac, Louis Joseph. Untersuchungen uber das Jod. (1814). Herausgegeben von Wilhelm Ostwald. (Ostwald‘s Klussikeg*,No. 4.) Leipzig 1889. (Recd. 29/12/04.) Kayser, 13. Handbuch der Spectroscopie. 2 Bande. pp. xxiv + 781, xi + 696. ill. Leipzig 1900-1902. (Recd. 21/12/04.) At the next Ordinary Meeting, on Thursday, February 2nd, 1905, at 8 p.m., the following paper will be communicated :-‘6 Studies in the camphane series. Part XVI. Camphorylcarb-imide and isomeric camphorylcarbamides.” By 31.0. Forster and H. E. Fierz. R. CLAY AND sms, LTD., BREAD svr. HILL, E.c., AND BUNGAY, SUFFOLL
ISSN:0369-8718
DOI:10.1039/PL9052100001
出版商:RSC
年代:1905
数据来源: RSC
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