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Proceedings of the Chemical Society, Vol. 12, No. 162 |
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Proceedings of the Chemical Society, London,
Volume 12,
Issue 162,
1896,
Page 53-66
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摘要:
Xssuctl 17/33/1896. PROCEEDINGS OF TRE CHEMICAL SOCIETY. EDITED 13Y THE 8ECRE:TARIE:rS. No.162. Session 1895-96. March 5th, 1896. Xi*,A. G. Vernon Harcourt, President, in tbe ch;tir. Xlessrs. Alexnndw Simpon, Joseph John Rawleg, Tvalter A VOSS, and William A Bone were formally admitted Fellows of the Society. Certificates were read fox$the flrst time in favour of IkIessrs, John Perciyal Jenkins, 30, St. John’s Rond, Clifton, Bristol j Tom Mitchell, Cemetery House, Shaw, near Oldham ; Raymond St, George Ross, 30, Britannia Squqre, Worcester, Of the follotv~ngpapers t,lioae marked * were read :-‘29. “The explos’on of Cyan6Efen.’9 By H.€3. bhn, M.A., F.R.S., E. H. Strange, B,SG., and E.GEaham, kS(3, Since it has been rlhoizfn by previoirs iiirestiqaticm~that cyanogen probably liurns fillst to carhi,i~oxide, and secondly tn carboh diokide, b(tli in ordinary flames and in the explosion wave, and since the burning of carbonic oxide to carbon ciiokidc appears to be generally conditioned by the presence of water vapoui-, it, seemed of interest to invcstipte the eoiirse of the chemical changes occurrhg in the coma plvte conilunatio~iof cganogcn.The authors firnt mensiircd the rate of explosion of cyanogeh witli an excens of oxygen. The c~ncliisiondrawn is that when cyanogen is exploded with its own volume of oxygen it burns directly to carbonic oxide ; on adding a second volume of oxygen to ihc mixture, cmbonic: oxidc is formed ih the wave-front, and the heated (mibonk oxide and uxygeu combine behind tl)e wave-front ; on acldiiig more 0x3 gm tlie formation of carbon dioxide is auEciently rapid to affect the velocity of the wave itrself, when one volume of cyanogen is exploded with four VoIumerJ of oxygea, the rate is 5 per cent.faster than the rate ualcu- lated on the supposition that the cyanogen is only burning to car- bohic oxide in the wave-front. The formation of carbon dioxide, although without influence on the velocity of the wave in the faster explosions, is found to exert an influence in the slower explosions. In order to study tfhe intentity and duration of the flame following the exploaion mve, photographs were taken of the jets of flame pro-jected from the ends of long tubes filled with the explosive mixtures of cyanogen and oxygen.Since the wave travels faster than sound in the unburnt gas the wavezfront mnst reach the end of the tube before any other disturbance can be propagated through the gas; the jet of flame whicb ig drives from the tube must accordifiglv be part of the column oE burning gases following in the wake of thc wave. When cyanogen is burnt with its own volume OE oxygen to carbonic oxide, the intensity of the explosion is very great, but only vepy slight jet of ffarne is projected from the tube. The length of column of highly heated gases must be short,. But wlieii cyanogen is burut with twice its volume of oxygen to carbon dioxide the explosion is less intense, but the jet of flame projected from the tube is long and of considerable brightness.The column of highly heated gases must therefore be 1011g~ If the extra oxygen is inert in the wave-front it accounts €or the superior brilliancy of the unimpeded reaction C,N, + O2= 2CO $; PI;, over the impeded reaction C,N, + 20, =2CO + 0, + NZjand if the formation of carbon dioxide mainly occurs behind the wave, it accounts for the brightness of the jet of still burning gases thrown from the tube in the second case. To obtain a direct record of the intensiiy and length of flame in the two cases, the explosion wave wa8 photographed on a very rapidly moving film as it passed a short window in a long tube. Tho sensitive film was fixed round a light iron drum driven by a high speed electric motor. Two tubes, each provided with a window, wcre iixed side by aide, one being filled with one mixture, the second with the other.The gases being fired simultaneously, the two flames were photographed on the same film. On developing the film in a long trough each image received precisely the same treatment, and one could be compared witli the other. The fiont of the flame in all cases UYCS sharply defined, but the rear of the flame dies ;:way in a tail which grdu:-llly tLins out. When cyanogen is exploded with its own volume of oxygen, an intense image of the window is pi-oduced, only slightly drawn out by the revolution of the drum, followed by a faint and short tail. When, howcver., cyanogen is exploded with twia; its volutnr: of oxygen, the 55 image is not so bright and there is no abrupt fall in int,ensity ; the tail is much brighter and longer. These photographs accord with the view that cyanogen burns first to carbonic oxide, and that the fornia-tion of carbon dioxide is a secondaiy action, Photographs were then taken with the same apparatus of the flames produced by mixtures of cjanogen with two vols.of oxygen (1) well dried, and (2) moist. No difference could he detected in the images of the flames. Water-vapoar, therefore, does not seem to affect the reaotion between oxygen and the just-formed carbonic oxide. Similar photographs of the flames produced in mixtures of carbonic oxide and oxygen in the dry arid moist state showed a marked difference : in the presence of steam the flame is intonser and sliorter. *30, On the mode of formation of carbon diaxide in the burning of wrb~n-wrnpouudri.” By H,B.DlxQn, MA.,F.R,S. Assuming that in tlie combustion of carbon compounds the carbon burns first to carbonic oxide, the author discusses the views that have been advanced concerning the function of steam in promoting the union of carbonic oxide and oxygen. Professor Armstrong coiisiders that the moisturg acts as an elec. trolgte, and that cheriiical change only takes place when carbonic oxide, steam, and oxygen are in contact. ‘l’he chief difficulty in this theory is to account, for the great velocity with which tho explosion wave is piopagated though a, dawp mixture of carbonio oxide and oxygen, In gaseous mixtures the rate of explosion npproxiinates to the rate of the forward movement of the reactiug rnoiecules, i,e., the ware is transmitted like sound from molecule to molecule, According to the electroly ti0 theory, the chemical change could only occur on the siniultaneous collision of at least three mole-cules ;yet the explosiou wave is propagated in carbonic oxide, steam, niid oxygen at a rate of 1738 metres per second, In the explosion of’cyanagen, carbon dioxide is formed without the intervention of steam.‘l’his theory, which has the advantage of’ including a nnmber o€ cognate phenomena, seems better suited to explain reactions at ordinary temperatn res than those occurring in the explo- sion wave. A similar difficulty OCCLII‘S in Professor J.J. Thomson’s theory, according to which the steam, by forming liqiiid particles, produces dissociattvn of the oxjgen molecules, and thus facilitat-es the oxida- tion of the carbonic oxide, It is hard to understand how steam, which is far below the saturation point at ordinary temperatures, can he condensed in the explosion wave. lllendeleef considers that carbonic oxide cannot combine directly with oxygen because all combination between gases takes place according to the law of equal volunies. Caibonic oxide aid steam react in equal VOIUM~S, and therefore tlie chnnge begitis by the car- bonic oxide taking the oxygen from the steam. The liberated hydrogen unites with its OWLI volutiie of os~geiito foim hydrogen peroxide, and this in turn reacts with its own voliirne of carbonic oxide to form carbon dioxide sud watcbr.The spark will not, bow- ever, kindle a mixture of dried cui.bonic oxide and nitrous oxide (mixed in equal volumes), but the aclditidn of a trace of steam renders the mixture explosive. Lothar Meyer and Beketoff attribute the influence of the steam to the fact that the direct action of cltrboniu oxide on oxygcu requires a vory high terriperature, whereas carbonic oxide decomposes steam much more readily. But although it may be true that eteaiu faciIitatcs the oxidation of carbonic oxide on account of the low temperature of the reaction, this does not account for the non-unioti of carbonic oxide and oxygen at the intensely high temperature produced in the wave-front in the explosion of cyanogen.The author shows that a dried mixture o€ carbonic oxide and ozonised oxygen is not inflamed by the spark; here tlie resistance cannot be attributed to the stability of the oxygen. The author has repeated Bcketoff's experiment of explodirig together a mixture of cyanogen, carbonic oxide, and oxygen in tlis dry stake. With quantities of cyanogen below 12 per cent. the flame causes an incomplete combustion of the carbonic oxide. The mme results were obtained when carbon bisulphide was substituted for cyanogen. The more intense the exciting flame, the larger was the amount of carbonic oxide burnt. The dissociation of carbon dioxide, held by Bungen and by Deville to limit the combustion of carbonic oxide tLnd oxygeu, may be the reason why carbonic oxide and oxjgen do ilot unite in the wave- front, but can combine as the gases cool down behilid the wave.The reaction between steam and carboiiic oxide gives out littie heat, so carbonic acid might be fornicd indirectly, and the liberated hydrogen tnight re-form steam, which could exist at a temperature at which carbonic acid would be broken up. The union of dry carbonic oxide and oxygen, without flame, on the surface of platinum may be due partly to the power of the metal to conduct away heat. The dissociation theory explains home of the facts obstrved concern- ing the combustion of carbonic oxide, but probably some other cause exists which limits the union of carbonic oxide and oxygen at lower tern peratures.The Rontgen rays do not appear to makc a dried mixture of car-bonic oxide and oxygen inflammable. 57 "31. '' On the explosion of chlorine peroxide." By H. B. Dixon, M.A,, F.R.S.,and J. A. Harker, D.Sc. The decomposition by shock of endothermic compounds, discovered by M. Berthelot, and the explosion of carbon bisulphide vapour described by Dr. Thorpe, led the authors to determine whether a true explosion. wave was transmitted through these compounds. It was found, however, that when a charge of fulminate was fired in a steel bomb attached to a long tube filled with cyanogen or acetylene, the detonation w-as not transmitted through the gas in the tube except for a short distance. With carbon bisulphide the flame extended for some distance, but gradually died out.&I.Maqnenne has recently obtained similar results. A mixture of chlorine peroxide and oxygen (with a trace of chlorine) was prepared by warming potassiuni chlorate with sulphuric acid. The gases were passed up through a long, glass tube, 33 ft. long, inclined at an angle of 30". When the tube was full, " bridge-pieces " were clamped on at each end. The explosion was started by igniting a mixture of hydrogen and oxygen in one bridge-piece-The explosion wave set up in this was comniunicated to the chlorine peroxide. Ry making the explosion break a silver bridge (coated with paraffin) at each end of the tnbe, the rate of the explosion was determined on the electric chronograph.A sample of the gas for analysis was collected at the end of the tube. In two experiments the folloming resnlts were obtained. of mixture. I Rate of explosion in metres per second. ..... 64 '03 ....... 36 '() j ..........1 1126 It would appear, therefore, that a true explosion-wave is propagated through chlorine peroxide. "32. "Note on the use of certain phosphorescent substances in rendering x-rays visible." By Herbert Jackson. In a former paper on " Obserratioiis on the Nature of Phos-phorescence " (Trans., 1894, 734), the author drew attention to the similar nature of the phenomena of phosphorescence obtained with rarious substances placed either inside or outside of a T-acuum tube. 58 Since tlie publication of that paper, the ~orkhas bceu continued, mainly with a view to studying the relation oE phosphorescence to the chemical structure, and more especially to the spectra of the sub-stances which exhibit the phenomena.The pibeseut note is put for-ward because the author’s experience has cnablecl hiiii to obtain useful resnlts in the attempt to iaencler certain structures, &c.. visible by iiieans of the radiations, the effect of which on photographic plates has latterly attracted so much attention. The existence of somethiiig proceeding froin a \~aeuuintube capable of penetrating imny otherwise opaque bodies was first made public by 1,enarcl. The author employed at the time, aucl has since iisecl, such substances ;LS obonite, metals, nut1 otlier opaque sheets as win-clo~s01’ covers to vacuum tubes in studying pliospliorcsceiice with snch receptivc substai~ce~ as tlie platiiiicjanides, the oxides and carbonates of many metals, and the soiliuin, potassium, and litliiuni lialoids.The kno~vIeclge of the nature of the mcliatioiis n-liich intlace phos-phorescence in many substances outside a vacuum tube has recently been very greatly added to by Professor Riiiitpn’s discovery tlia18 they exhibit none of the phenomena of refraction, cliffraction, and interference. To this important discovery lie has added the inierest- ing observation of hlie iaelative transparencics of bone and flesh. The vacuum tube most suitable for showing the phenomena, in the writer’s experience, is a slight modification only cjf one inveiited by Mr. Ci-ookes to illustrate the heating effect of focussed radiant matter.It consists of a concave aluminium cathode and a platinum anode. The latter is inclined at an angle of 45O, arid spreads the rays from the cathode in every possible direction, nppai*eiitly by scattered reflection. Such a tube has been regularly employed by tlie stutlior iii experi-ment’s upon the phosphorescence of the platinicyanides, and of‘ some 300 other substances, and was first used by him in January, 1894. About 70 tubes were made in the attempt to obtain the best results, but so far the one described has proved to be tlie lllost actile. To obtain good results the vacuuiii must be high. Apparently the nature of the residual gas does not affect the working of the tube in any marked manner.Both Dr. Norman Collie and the author have tried a nuniber of gases without noticing any marked difference. This may be largely due to the fact that if a niercnry pump be used a very considerable percentage of the residual gas is the vapour of that metal. The most brilliaiitly phosphorescent substance yet obtained is potassium platinicj-anicle. This salt crjstallises with th~ee molecnlar 59 proportions of water, and is most nctirt! ill its frilly hydi*akect stafp. lt effloresces, and should tliercfore be usetl in such n way that either it cannot lose water or can be readily moistened. If this platini- cyanide be painted on to black cardboard, or thin vulcanite, &c., its phosphorescence will enable transparent and opaque objects to be clearly differentiated.The particular potassium salt was chosen from considsratious of the brilliant expanse of blue seen in the spectrum of compounds of that metal. Many of the other plntinicyanides have been tried as well as a number of the platosamine salts. With none of them is the amount of light equal to that OF the potassium salt. A study or' the phenomena during the exhaustion of the tube shows that tlie rays (it is convenient to speak of rap) proceeding from the conca1ve cathode meet apparently at tlie centre of curvature and diverge in a solid cone. As the vacuum becomes higlier this cone narrows until, when the exhaustion reqnired for the maximum phosphorescence outside the tube is attained, it apparently hecomes a stra,ight line.If,as at present observation seems to indicate, the rays froin the cathode are still brought to a focus at the centre of curvature, the fact that they proceed thence in a straight line gives a material aspect to the phenomenon, as this would be the behaviour of particles coming at right angles from the surface of a concave disc, and collid- irig at the centre of cnrvature. This, however, would require the assumption that the particles are non-elastic. it is possible that only the cenlre of the electrode is iniplicated at high exhaustions. The author is conducting experiments with a view to settle this question of the path of the mjs. It does not seem probable that the radiation is confined to the centre, because a straight cathode gives none of the effects observed when the concave forni is used.When the rays meet the reflecting platinum plate, which is conveniently, but not necessarily, niade the ariodp, they are scattered by the relatively coarse surface of the metal, a very small circle upon which becomes the radiant. This is shown by experiments with phosphorescent sub-stances placed upon tJhe platinum, and by examining the tube through a pinhole in an opaque metal sheet by ineacs of it phosphorescent screen. The results obtained are only consistent with the source of illumination being a point or a very small circle. The alternative to the view that the cathode is the truc origitial source of the exciting cause, and that the rays proceed from the glass is disproved by using flat and curved tubes.A point as the illuminative source would be obtained if rays proceedcd at right angles froin the surface of 3 curved glass but not from a. flat one. In his previous paper the author attempted to show that all the phenomena of phospLlomscence, uithei-i11,4idt! or ouhide R VMXU.IIU tube were best explained on the assurliption that the exciting cause proceeding from the cathode was of the nature of light, or was capable of setting into vibration the residual gas particles so as to give rise to undulations of the nature of light. Professor Rontgeii has expressed an opinion in favour of loiigitudinal vibrations. The author adheres at present to the notion of transverse vibrations, and hopes before long to bring further experimenhal evidence before tlie Society in dealing with his work on the relation of the spectra of substances to their phosphorescence.D1scuss1oIz‘. LLSTER,Sir JOSEPH reninrked on t lic pi*ol,ahle importance to medicine and surgery of the discovery that the shadows produced by the Rontgen rays could be rendered visible to the naked eye in the manner which had been demonstrated by hilr. Jackson. Dr. ARKSTRONGthought it would be found, when Ah. J~C~SOII’S full communication was stcdied, that he liad not only materially advanced the application of Roiitgen’s nimt remarkable discovery, but also added much to our knowlcdge of the plieiiomena coil- cerned. His success was due to no chance observations, but was the outcome of prolonged, thoroughly scientific study of phosphor-escent phenomena, and a development of his previous work.Tt mas certainly very startling to see, with the aid of a Inere screen held before the eyes, tlie bones in the foot right through t,he boot, and to learn that a photograph could be secured in the merest fraction of a second with the aid of such a screen, He believed that Mr. Jackson was of opinion that there were a great variety of Rontgen radiations, and that different) objects wwe opaque to these in different degrees ; so that it might ere long be possible, by properly selecting tlie radiations, to distinguish objects in ucli more closely related thm bones and flesh.“33. “ The union of carbon and hydrogen.” By William A. Bone, M.Sc., Ph.D., and David S. Jordan, M.A., B.Sc. Two years ago, one of the authors, iii conjunction with J. C. Cab (Proc., 1894, 56), observed that when a iiiixture of cyanogen and hydrogen is fired in a long lead coil witli a volume of oxygen insuf€i- eient to burn all the carbon present to carlm~~monoxide, a small umoant of methane, varying from 1.0 to leipe~cent., according to the composition of the original mixture, was found among the pro- ducts of explosion. This seeiiiecl to indicate the possibility of the f;ormatzionof methiiiie b,y the union of its elements at the high tern- 61 pemture of the explosioii wave, and the anthow undertook the following experiments, with a view of testing this hypothesis.They have iiivestigsted (1) the effect of heating carefdly purified carbon (obtained by heating sngai. charcoal in chlorine and snbseqnently in hyclrogeii until all tl,e chlorine was expelled) in a glazed Berlin poi~elain tube to white lieat in an atmosphere of dry hydrogen free from hydrocarbons ; and (2) the action of carbon upon hydi-ogen at tlie temperature of the electric arc. In the first series of experimeiits the porcelain tube was heated in n Fletcher injector furnace by means of a11 air-coalps blow-pipe. In ordei-to avoid tlie possibility cf the diffusion of furnace gases through the poiwlain tube, it was placed inside a wider tube of the same niaterizl, and a cnrrent of liydrogen was passed thr~ugh the amiular space between them.Several blank experiments were per- formed, iu which hydrogen f I ee from hydrocarbons was passed through the inner tube and through the jacket, whilst the tubes were main-tained at a m-hite heat; samples of hydrogen taken from the inner tnbe duriiig the course of an experiment were fonnd, on analysis, to contain no cwbon compouiid. The purified carbon, after being dried over phosphoric anhj-cli*ide for two months, was strongly heated in a hard glass tube attached to a Sprengel air-pump, and was theu sealed up in a vscuuni with quicklime. This carbon was introduced into the inner porcelain tube, and was heated to white heat in a current of hydrogen free from Iiydi*ocai~boiis,whilst simultaneously a current of the same hyclrogen was passed through the space between the inner am1 outer tubes.Samples of the exit gases from the inner tube were afterwards carefully nnslysed ; they were found to contain no acetylene or other unsaturated hydrocarbon, but about I per cent. of methanc. In aiiotlier experiment, a volume of hydrogen was enclosed ill the inner tube, hcatecl for three liours in contact with the carbon ; 011 subsequently analjsing the gas, it mas found to contain nearly 2 per cent. of methane. In tlie second sevies of experiments, the electric ai'c was formed between termiii:ils of purified gas-carbon in an atmospheiae of dry hfdrogeii free from hjdrocnrbons, coiitained in a glass globe standing in a trough over inercury.Nach of the carbon terminals, which had been previously strongly heated for several hours in a hard glass tube connected with a Sprengel air-pump, was attached to a stout copper mire, whicli in turn was fixed into a piece of narrow glass tubing bent into U shape and filled with mercury. The limb of the U-tube bearing the carbon was then thrust into the globe froni below the surface of the mercury in the trough. The t,op of the globe was drawn out and sealed to a thyee-nay tap, by means of which connec- tions could he made, on the one hand, with an air pump or the supply 62 of hydrogen, mid, oil tlie other liwnd, to a nitrometer fnll of inei*ciiry, which served to collect samples of the gas in the globe at intervals during an experiment.At the outset of an experiment, the globe wits exhausted of air by attaching it to a working air-pump until it mas coiiipletely filled with mercury. Then dry hydrogen was introduced, and the arc passed between the terminals for about a quarter of ail hour. The globe was again exhausted, and finally filled with the dry purified hydrogen. The arc was then passed for a period of time varjing from 30 minutes in tlie first experiment to two hours in the last, and at the end of 5, 15, 30, etc., minutes in each experiment, samples of the gas were drawn off for analysis. Cowposiitiou cf the Gcms.-The gases were always found to contain small amounts of hydrocyanic acid, due no doubt to the presence of a little nitrogeii iu the liydi-ogen employed.Acetylene was also present in considerable quantity, and was detected by passing the gas through an ammoniacal solution of silver chloride, when a copious precipitate of silver acatylide was formed. A detailed analysis of the gases showed, howerer, that, in addition to acetylene or other un-saturated Iiydrocarbou, they invariably contained an appreciable amount of some saturated hydrocsybon, most probably methane. BIinutcs. Experi. -111ent. I Gases clrawu off after .. 3. 15. 30. 43. GO. 1 '30. 120.II-----l--. -------I Absorption by solid potadi 020 1-01 1*51 [lirdrocjaiiic acid]Absorption by friiniiig sul-5 *lo 8 -43 0 -85 -A.... { phuric acid and caproiis chloride solatioii, i.e., ethylene, acetFlene Methane ...............1'32 2 90\ Absorption bp solid potash 0 '11 0 $20 3 -20 [hydrocyanic acid] -1-Absorption by fnming sul-2 '13 4-99 3 -08 B.... { phuric acid and cuprous I-chloride solution, i.e., ethylene, acetylene I-Methaiie ............... 0 -64 1-38 2-26 -I -----__ trace 0.10 1-00 0-39 4TO 6-16 6.42 7.59 I acetylene ~Methane ............... 1-00 1-63 2 '37 j 63 Tlie gases mcre analysed in n modified form of the AlIcLcod apparatus. A large volnme of the gas was successively treated with solid potash, fumiiig sulpliuric acid, AC cl solution of cullrous chloride, and a dilute solution of potnsli, iii order lint all liydrocyanic ad, nnsaturnted hydrocarbon, 2nd ariy traces of csrbouic oxide might be removed ; a poition of the residual gas was then exploded with excess of air, f-ee froto carbon d;oxide, aticl the cont,rac.tioii arid ahsorptioti hy posash solution after the explosion dctrrniiiied.Filially the excebs o€ oxygen was absoybed hg means of alkLline pyrogallate, and the residual nitrogen mensui3ed. Tlie results of the analyses are tabulated in percentages. In :ill three experiments sn alternating curleiit from a dpamo was used. In Experiment A, the voltage was 160, and in B and C‘, between 40 and 60, bnt it wag extreiiiely dit-fcult to maintaiii ;I con-stant voltage throughout a long experiment. 34. ‘I Note on the aql-dimethylglutaric acids.” By William A. Bone, MSc., Ph.D., and W. H.Perkin, junr., F.R.S. The authors are now able to con61.m the observation of Thorp and Au wers (Uw.,28, 623j that the acid melting at 105-107” which they debcribed in a paper published iast year (TLans., 1895, 416) is really an eqniniolecular misture of trans- and cis-dimetliylglutal.ic acids melting at 140-141” and 127” respectively.This equinioIeculxr niisture which in many respects behaves like a homogeneous sul~ stance, having, for example, a fairiy sharp and constant melting point, rnay be resolved into its constituent acids by careful treatmerib with acetgl chloride, when the cis-acid xields an anhydride, M liilst the trans-acid is uuchanged, or by fractional precipitation of the acid calcium salCs, that of the tran~-acid being leabe soluble. 35. The symmetrical dimethylsuccinic acids.” By William A.Eone, M.Sc,, Ph.D., and W. H. Perkin, junr., F.R.S. During the course of their investigations on trimethjlsuccinic and aa,-dimethylglutaric acids last year, the authors obtaiiied a ( onsider-able quantity of ethylic dimettiylc~-anosuccinateas a bye-product of the action of potassium cyatnide ou ethy lie a-bromopropionate in alco- holic solution (Trans., 1895,416). On hydrolysing this ethereal salt by means of concentratcd hydrochloric acid they obtained a mixture of trans- and cia-dimethylsuccinic acids? 11hich they were able to separate either by fraclional crjstallisation from water or by a, fractional pre-cipitatiou of their. calcium salts. After studjiilg the literature of t1.e subject, the authors found that the properties of the dimethyl- succinic acids which they had obtaiilccl differG-cl coiisiderably frai those assigned to them by previous inrest,igators, and thej tliercforo submitted these acids and their sntiydr-ides to a carefill examination.They also prepared tho dimetliyIsuct*inic acids by the action of ethylic a-lorornopropianate on the sodium compound of ethylic iiietII y1ma1onate, su1) sequent 11J droIJ sis of t he resuIting etherea1 sA 1t by means of alcoholic potash, and then heating the tribasic acid so ob-tained to 200" until all evolutiou of cjsrbonic anhydride had ceased. The resulting acids \vwe in all respects identioal with those obtained by the first method, Trans-dimethylsucoirii~ wid when pure molts at 209",and is very much less soluble in water than tho cis-acid, which melts at 129'.The calcium szlt of the trans-acid is, however, much more sohible in water than that of the cis-acid. Each acid, when treated with acetyl chloride or Scetio anl-iydride, yields its own ankydride, a fact first, ob-served by Octo and Riissing (Bey,, 28,2736)and confirmed by Risnhoff ; the trans-anhydride melts at $3" (not 38' as given by Bischoff) and is less stable than the cis-anhydride, which melts at 88*, and is com-pletely transformed into the last-named Rubstance on prolonged liratiag with acetic qnhydride. Both acids, on distillation at atrno-spheric pressure, jield tho ois-anhydride. Each anhydride dissolves in hot water yielding its own acid, not, as some autharities have stated, mixture of cisc and trsns-acids, 36.The cis-and trans-methyliaopropylsueoinicaoidd' By William Henty Bentley, William Henry Perkin, junr., and Jocelyn F, Thorpe. The authors hare studied tlie action of ethylic a-bromoisovalerste on the sodium compound of ethylic rneth~l~-nalonate in alcoholic and in xylene solution, and find that in both cases the product of the reaction consists of etbylic iso~"0pylrnethylef~~ar(t.ti.icai.boxylate, COOC,H,*CH(CsHi).C(CH3) (*COOC,H5>2, a colourless oil, whioh boils at 2c)0--809" (80 mm,). This oil, on hydrolysis and subsequent elimination of carbon di- oxide, yields n mixture of cis-and trltnff-methylist,prc,py7succinicacids, which art: separated by methods described in detail is the paper.CB3 *VH*COOHCis-methylisopropylsucciizic acid, C3B7*CH-COOH'melts at 125-li16", and, when heated with hydrochloric acid at' 180a, is partially cotii.erted into the trans-modification ; when distilled or digested with acetic anhydride, it yields a liquid anhydride bailing at 1S8--140° (35 mm.). The uniZic acid, C0OH.CHa (C,H, 1*CH(CH3)4 CONHC,H, (?),mcl ts at 15;3O, and, at R somewhat higher temperature, loses mater with -CHsiYH*COformation of tlie corresponding a?LiZ, >NCsH,.CsHi*CK*CO ti5 CH,-7H.COOH , melts at 174Trans-met hy1 isopropylsti.cciuic acid, CO0H-CH*C,H, -175", and is much less soluble in water than the cis-acid ; when distilled under diminished pressure, or wheu digested with acetic anhydride, it is converted into tt solid anhydride melting at 46'; and this, when repeatedly distilled at ordinary pressures, is converted into the anhydride of the cis-acid, Tlie a~rilicacid obtained from the trans-anhydride by treatment with aniline melts at 160°, and a few degrees above this tempera- tuie loses water and is converted into the anil of the cis-acid.The authors have also prepared the metlr~lisopropylsuccinicacids from ethyvlic isopl.opylethanetricai,boxyl;lte, which Roser (Anr~aZejl, 220,272) first synthesised by the action of et!hylic aabromisovalemte on the sodium derivative of ethjlic nialonate, When this ethercal salt is acted on with %odium ethoxide and methylic iodide, ethjlic niethyli~opropglethaiictricai.boxylate is pimluced, and from this ethereal salt the inetliylisop~opyls~i~ca;inicwida liiay be obtained by the method described abovg.ADDITIONS TO THg LIBRARY. I. B~JPwchase. @arpenter,ySt, B, The llicrclscope aiid its &evel~tiona. Seventh edition in which thrj firat seven chapters have been entirely rewrittt~n and the text thro~~ghoutreconstructed, enlarged, and revised by the Rev. W. H. ballinger, LTLD., P.R.8., with 21 plates and 800 wood engravings, xviii.+ 1099 pp. London 1891. avo. Redwood, Bovei*ton, and H~llu~ay, c;?. T. Petroleum A tkeatise 011 the geogr aphid distrgibutioii and geological occui-rence of petw-leurn and natural gas; the physical and chemical propertiesj pm-duction, and reflriing of petroleum aiid ozokerite ; tlie characters aiid uses, testing, tiianaport, and stornge uf petpoleurn-products, ad the lcgisiative enacttnentn idelating tlieretu ; tugether wit,h a descriptiuu of the ahale oil and allied ilidustries.Vol I. xxviii+ 1-4.0i1 Vol, 11. 404-9900 pp. tvith 2 frontispieces, 15 plates, and 327 figures. London 1896, 8vo. Rey, Jean, Essays of deaH Rey, lloctoid of Mediciile: On un enquiry into the cause wllercforc tin and lead increnrse in weight on Calcination. ( 1630.) 54 pp. Ed inlmrgh 1895, 8\70, (Alembic Club RepriiitB. No. 11.) Wiley, Harvey W. Principles arid Practice of Agricnltnral AD^-1ysit.l: A maIlLiill for the eetiirlatidu trf soils, fgytlli&rs, and atgr.icraltura1 products foi. the use of analjsts, teachers, and stndents of agriculturJ cbeiniutry.Vol. 1. Soils. x +607 pp., with 93 figures. Vol. 11. Fevtilizers. viii fS;32 pp. with 17figures. Eastcri 1894-5. 8vo. At tlie next meet’iug on Thursday, 3ftti.ch 1‘3th, the following papr~will be read :-“ The conatitation of :L new acid ~*~siilti~igfrom the oxidation of tartaric acid.” By €1. J. H, Fenton, M,A. “ The volume and optical rclatior.ships of the potnssiam, rubidium, atid cmium salts of the monoclinic series of double mlphatca, R,M(SO,),*T.H,O.” By A. E, Tatton. “ The hydrioriides of hjdroxylamine.” By Professor Dunstan, P.R.S., and Krnest Gouldiiig, “ An analysis of the water from the Dripping Well RC Knares-borougli, in Yurkshire.” By B. A. Burrell. ANNIVERSARY MEETING. Tlic Anniversary Meeting will be held un Thursday, March 26t11, at 8 IJ‘M., tvlien the Presidelit) will deliver ail addrws, and the electivli of Officers and Council for the ellsuing year will take pla8ce.
ISSN:0369-8718
DOI:10.1039/PL8961200053
出版商:RSC
年代:1896
数据来源: RSC
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