摘要:

850 RUHEMANN AND ELLIOTT THE LXXL-The Isonitrile of PhenylhydTazine. By S. RUHENANN Ph.D. and W. J. ELLIOTT. ISONITRILES derived from hydrazines have not been carefully ex-amined and as such an investigation seemed desirable me under-took their examination and now communicate to the Society tlie results of our experiments on the isonitrile of phenylhydrazine. For the preparation of this isonitrile phenylhydrsziiie is dissolved in alcoholic potash and chloroform is carefully added to the solution. After heating in a water-bath for half an hour the flask is cooled the product diluted with water and shaken with ether. The -Lulaltered phenylhydrazine is removed from the ethereal solution of the iso-nitrile by shaking with very dilute sulphuric acid. On craporating the ethereal solution a brown oil remains which has a penetrating odour of isonitrile and partially solidifies on cooling.The crystal-line mass thus obtained is dissolved in alcohol from -which spherical aggregations of pale-yellow needles devoid of odour separate. The alcoholic filtrate almost entirely loses the odour of isonitrile on stand-ing for a few days and on evaporating the greater part of the alcohol deposits a small quantity of the same crystals while the fjltrate from these contains an uncrystallisable resin. The crystals thus obtained become quite white on recrystallising several times from alcohol. The pure substance melts at lSO" is easily soluble in chloroform carbon bisulphide and acetic acid as well as in alcohol and in ether but is insoluble in water and is not T-olatile in steam.The results of analysis indicate the empirical formula C7HGNZ :-Fonnd. 7 Calculated f o r r-dL-CiIIGN,. I. 11. C 71-08 - 71.19 5-46 - H 5.08 N 2373 - 23.89 100*0 ISONITRILE OF PHENPLHYDRAZINE. 831 Hence this substance has the percentage composition required for the isonitrile of phenylhydrazine C6H,*NH*NC ; but it is shown not to have this composition by the absence of the characteristic odour of the isonitriles and by its chemical behaviour. It is very probable that the crystals which melt at 180" are the result of a change which the initially formed isonitrile undergoes ; for in some preparations crystals did not separate out from the oil immediately after evapora-tion of the ether but only OD. standing for some time.It is possible that the stable Compound consisted of the normal cyanide C6H5*NH*CN and in that case me should have had the molecular transformation of an isonitrile into a normal nitrile taking place at a lower temperature than the corresponding change of the isonitriles of aniline and its homologues. In order to determine whether the substance obtained from phenylhydrazine was the normal nitrile its behaviour with acids and particularly with hydrochloric acid was studied. The compound when heated at 200" with hydrochloric acid in a sealed tube is only slightly altered. The tube contains bluish crystals which are soluble in alcohol leaving behind a small quantity of a blue residue with metallic lustre. White needles are deposited from the alcoholic solution which were proved to be the original compound by their melting point and by a nitrogen determination, which gave 23.94 per cent.of N. The substance undergoes no change on heating at 100" with alcoholic potash. Hofmann ( B e y . 17 1914 ; 18 1825) failed to convert the cyanides of tetra- and penta-methylaniline into the corresponding acids. Hence the stability of this compound towards hydrochloric acid does not conclusively prove that it is not a cyanide. Further investiga-tion however showed that we are here dealing with the representa-tive of another class of substances. We next proceeded to find the molecular weight ol the compound. This cannot be done by a vapour-density determination because partial decomposition takes place at the high temperature required for vaporisation.In consequence we employed Raoult's method of de-termining molecular weights and used for the purpose hhe sirnplc apparatns described by Holleman (Ber 21 860) which gave very satisfactory results. The solvent used was glacial acetic acid the freezing point of which was 14.39". 0.2931 gram of the substance dissolved in 18.9784 grams of acetic acid depressed the freezing point by 0*25", which corresponds to the molecular weight 240. It follows from this determination that the empirical formula derived from directl analysis should he doubled. The formula C14EI12N4 thus obtained requires a molecular weight of 236. Furthe 852 THE ISONITRILE OF PHENYLHTDRAZINE. confirmamtion of this formula is furnished by the behaviour of the substance with nitric and sulphuric acids.When a solution of the compound in glacial acetic acid is treated with fuming nitric acid a lemon-yellow crystalline precipitate forms at once. This is insoluble in water but soluble in boiling glacial acetic acid from which it separates on cooling in microscopic needles which melt at a temperature lying above 300". A nitrogen determination shows the compound to have the formula C I * H ~ N ~ * N ~ ~ -Calculated for Cl,HllN,.NOz. Found. N . 25.10 24-91 When the substance formed from phenylhydrazine is heated with concentrated sulphuric acid it dissolves ; if the heating is continued till no precipitate is formed immediately on the addition of water to a drop of the solution and the cold solution is then poured into water, tufts of white needles crystallise out on long standing.These crystals which contain sulphur are insoluble in alcohol benzene and chloroform only sparingly soluble i n cold water. After cry stailisation from hot water they give on analysis numbers which correspond to the formula CIIHllN4.HSO3. Found. CtLlculated for +7 CI4Hi1N,*HSO,. I. 11. - N . 17.36 17.72 s - 10.20 10.126 This substance therefore is a sulphonic acid. It forms an am-monium salt and a barium salt not easily soluble in water. The molecular weight as determined by Raoult's method together with the formation of the nitro-compound CIIH1lNI*NOZ and the sulphonic acid Cl~Hl1N4*HSO3 prove that the compound obtained from phenylhydrazine i n the manner described above has the formula c 14 H,,N*.When we consider the mode of formation and the chemical behaviour of the compound CI4Hl2N4 there can be scarcely any doubt that its constitution is expressed by the formula-CGH,*NH*N:C C :N*NH*C,H,. The pentad nitrogen of the isonitrile passes into the triad condition by the union of two molecules of the isonitrile CGH,*NH*NC ; whereas in all aromatic isonitriles known up to the present time the corre-sponding change takes place by the molecular transformation of the isonitrile into the normal nitrile SILICOY COMPOUNDS AND THEIR DERIVATIVES. 853 Further experiments with secondary as well as primary hydrazines are in progress in order to determine whether they show the same behaviour as phenylhydrazine. It is a pleasant duty for one of 11s (S. R.) to express his best thanks to Mr. R. H. Adie for the valuable help received from him at the commencement of the research. Uwiu e rsity Laboratory , Cam6 ridge

ISSN:0368-1645    

DOI:10.1039/CT8885300850

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

SILICOY COMPOUNDS AND THEIR DERIVATIVES. 853 LXXI1.-Researches on Silicon Compounds and their Derivatives. Part 111. The Action of Silicon Tetrabromide on Allyl- and Phenyl-thiocnrbainides. Part I V . The Action of Ethyl Alcohol o n the Corn-pound ( H4N,CS)sSiBrd. By J. EMERSON REYNOLDS M.D. F.R.S. Professor of Chemistry, University of Dublin. IN a former paper (Trans. 1887 51 ZOZ) I gave an account of the results obtained when silicon tetrabromide is made t o act on the primary thiocarbamide in presence of benzene. I t was shown that 8 mols. of the amide withdraw but 1 mol. of the tetrabromide from its solution even after moderately prolonged heating with excess of it t o the boiling point of benzene. In this paper are described the results afforded by allyl- and phenyl- thiocarhamidcs when similarly treated.The Action of Silicon Tetyabronaide on Allyl-thiocarbamide. The allyl-thiocarbamide used was prepared by the action of ammonia on the corresponding thiocarbimide. It was perfectly pure and dry and readily fused under benzene to a clear liquid since its melting point. is 74". A quantity of the smide was fused under boiling benzene in which it does not dissolve and an equal weight of silicon tetrabromide gradually added. The mixture was t'lien digested in a flask provided with a reflux condenser and this treatment was continued for about two hours. The allyl-thiocarbamide gradually changed from a clear, mobile liquid to an opalescent viscid mass insoluble in benzene 854 REYNOLDS OX SILICON COXPOUNDS The latter which contained much unaltered silicon tetrabromide at the end of the operation was poured off and the mass digested with successive quantities of boiling benzene in order to wash away any adherent tetrabromide.The product when cooled to the ordinary temperature %-as a very viscid liquid having a slight yellow colour. It held fine flakes of a white substance in suspension. The latter were partially removed by filtration under pressure at lOO" as a t that temperature the liquid flows about as freely as pure glycerin does at the ordinary tempera-ture. It proved to be impracticable to wholly remove the white substance in this way and since the latter seemed t o be a product of decompo-sition another preparation was made exactly as above described save that t'he excess of silicon tetrabromide was not allowed to act on the allyl-thiocarbamide for more than half an hour a t the boiling point of benzene ; but even under these conditions an opalescent product was obtained and the benzene poured off had a distinct alliaceous odour.Each preparation was found to contain silicon bromine and the proximate constituents of allyl-thiocarbamicle. The following are the results of the analyses of No. 1 specimen,-the product obtained by the action of excess of tetrabromide during two houm; and of KO. 'L,-the corresponding product obtained by heating for only half an hour. The results are compared in the table with thc calculated percentage composition of (A) an octothiocarbamide compound with silicon tetrabromide and (B) the same substance minus one atom of sulphur :-Theory.Pound. 7 T-h-. r--A--A. 13. No. 1 product. 50. 2 product. Si 2.19 2.25 1.95 1.83 Br 24.10 25-78 26-20 24.76 s 20.06 18.06 16.26 17-47 N ,. 17.55 18-06 - 1S.36 The conclusions drawn from these results were (1) that allyl-thiocarbamide quickly withdraws sufficient silicon tetrabromide fi-om its benzene solution t o form an octo-compound but ('2) that the product is decomposed by the continued action of excess of bromide, accompanied by greater or less loss of sulphur according to the duration of the action the white substance which rendered the viscid liquid somewhat turbid being probably one of the results of the secondary change. Such decomposition is analogous to that already traced analytically in the case of the primary thiocarbamicle though it is possible t o prepare the nearly pure octo-compound of that bod AND THEIR DERIVATIVES.855 in presence of benzene. The allyl-thiocarbamide however always afforded more or less decomposed products in presence of benzene, hence I discarded benzene altogether and found i t easy to prepare any quantity of the allylic octothiocarbamide compound vith silicon tetrabromide in the following way :-9.28 grams (8 mols.) of perfectly dry allyl-thiocarbamide were poured into a pressure tube which had been previously filled with dry carbon dioxide gas 3.5 grams (01- slightly more than 1 mol.) of pure silicon tetrabromide were then added and the tube sealed. When the tube was heated in B current of steam the amide melted and evidently combined with a portion of the tetrabromide but much of the latter found its way to the bottom of the vessel and remained there under the 1a-j-er of fused amide.By occasional agitation of the contents of the tubes combination of the two substances m-as gradu-ally effected in less than half an hour and all but a minute trace of tetrabromide disappeared. The product was a very pale-yellowish perfectly transparent liquid a t looo and about as viscid as pure glycerin is a t ordinary tempera-ture ; when cold the liquid became so viscid that the slowly moving liquid required two days to partially adapt itself to a reversed posi-tion of the tube. This liquid is perfectly transparent and homogeneous ; moreover a specimen of i t which has now been prepared for a considerable time (nine months) does not exhibit the slightest tendency to alteration.It is scarcely dissolved by benzenc but is readily dissolved and decomposed by alcohol and water. The direct production of this remarkable compound thus confirms one of the conclusions arrived a t by the study of the action of the benzene solution of silicon tetrabromide on allyl-thiocarbamide. An experiment was now made in order to ascertain whether an excess of the tetrabromide would attack the octo-compound. 4-64 grams of allyl-thiocarbamide (4 mols.) and 3.5 grams of silicon tetrabromide (1 mol.) were sealed up in a tube which had been previously filled with dry carbon dioxide gas. The tube was heated in a current of steam as before. Combination quickly took place and the volume of tetrabromide diminished as the action proceeded.At first a perfectly transparent viscid liquid was formed from which the heavy tetrabromide readily subsided ; but when sensibly half the latter had disappeared the whole became opalescent and an hour's continued heating sufficed to render the liquid as turbid as the first product obtained when excess of tetrabromide was made to act f o r two hours on the amide in presence of boiling benzene. The tube was now heated at 100" for three days but at the end of that time a very sensible quantity of tetrabromide remained free while th 856 REYNOLDS ON SILICON COMPOUSDS opacity a i d viscidity of the amidic compound had much increased ; moreover it completely solidified when cold. It is evident then, that when excess of tetrabromide is allowed to act on the first product TI further change is established which probably leads to the partial formation of a tetrathiocsrbaniide compound as well as other products which remain for detailed examination, Hence the primary product of the action of silicon tetrabromide on allyl- thiocabamide is the remarkably viscid liquid, SiBr4( SCN2H3C3H5)8.The similarity of this allylic compound in composition and some of its characters with that derived from the primary thiocai-bamide indicates probably similarity of structure. The Actio?t of Silicon Tetrabromide o n Phertyl- and D&Jt,enyl-th iocarbamides. Phenyl-thiocarbamide or thiocarbanilamide dissolves to a moderate extent in boiling benzene though much quickly separates in crystal-line condition i f the temperature of the saturated solution be slightly reduced below its boiling point.In consequence of this solubility of the amide in hot benzene it was hoped that silicon tetrabromide would precipitate an octothiocarbamide compound from the solution. Silicon tetrabromide mixed with benzene was added hot to a boiling solution of phenylt hiocarbamide in benzene. A yellowish, clotted mass quickly separated ; this was repeatedly washed with hot benzene and allowed to cool ; it then became a translucent somewhat brittle solid a t the ordinary temperature. This substance proved on analysis to contain more of the thiocarb-amide than was required for the ccto-compound with silicon tetra-bromide ; the first preparation contained nearly 12 mols.of the amide for one of the tetrabromide. Further investigation showed that the octo-compound in precipitating carried with i t more or less free arnide which could be only partially removed by boiling benzene or changed by excess of tetrabromide ; since either treatment speedily set up decomposition of the octo-compound which latter appears to be even more prone to alteration than the analogous allylic product. The following mode of operating however enabled me to obtain the octo-compound in nearly pure condition. 12.16 grams of pure and dry phenyl-thiocttrbamide (8 mols.) were spread over the bottom of a small conical flask which was heated on a water-bath. 3.5 grams of silicon tetrabromide (1 mol.) were poured over the amide so as to moisten it as completely as possible and the mixture was heated to 100" for about half an hour in a slow current of dry carbon dioxide.It quickly became a viscid opalescent mass and continued in this con AXD THEIR DERIVATIVES. 857 dition while over the water-bath. On removal from the latter the flask was very cai-efully heated over the naked flame when the suhstance almost immediately became a nearly transparent yellowish liquid which was more viscid than the allylic compound a t the same temperature. On cooling the new substance solidified to a hard, translucent' vitreous mass containing but few entangled white particles. Although the mode of preparation left no reasonable doubt as to the composition of this substance the ratio of bromine to sulphnr was determined in it and proved to be 1 2.035 or 4 8.14.It therefore contains SiBr4( SCN,H,C,H,),. It is slightly soluble in hot benzene and is easily dissolved and decomposed by boiling anhydrous ethyl alcohol. I n another case it mas found that obvious decomposition ensued when even a slight excess of tetrabromide was used above that emplored in the experiment just described. When clipheizyl-tl2iocarbalnide was warmed with silicon tetrabromide, combination also took place and a yellowish viscid liquid resulted, which solidified in a rather hard substance on cooling. The product dissolved in water and alcohol with evident decomposition and generally resembled the monophenylic octothiocarbamide compound with silicon tetrabromide. PART IV.-Tlhe Actio?z of Efhyl Alcohol on the Compound (SCN,H,),SiBr*.It lias been already mentioned that the octothiocarbamide silicon bromide is dissolved by anhydrous ethyl alcohol and that it undergoes decomposition during solution. The products obtained in the course of this treatment include representatives of two new gronps of thio-carbamide compounds which will be described in t h i s paper. A large quantity of material for this branch of the inquiry was prepared in the following way :-lo0 grams of finely powdered thio-carbamide were treated as before with 90 grams of silicon tetrabrom-ide in benzene solution. The product when thoroughly washed with benzene and dried weighed 154 grams. 100 grams of thiocarbamide are capable of affording 157 gram of the octothiocarbamide com-pound hence the conversion of the thiocarbamide into its silicon bromide compound was practically complete.The product was then dissoIved in boiling anhydrous ethyl alcohoI ; 900 C.C. were sufficient for the solution of the above weight of sub-stance. A small quantity of light flocculent matter which separated, resembling gelatinous silica was rapidly filtered off and the alco-holic solution allowed to cool in a well-closed flask. Rapid cooling o a5s REYNOLDS ON SCClICON COXPOUXDS such a solution leads to the separation of small spheres like those of leucine but; which grow t o a considerable size in the liquid. By slow cooling 11 owever beautiful stellate groups of fine silky crystals were formed some of which closely resembled sea anemones in appearance. One of these groups as seen from above is shown in the annexed sketch.When quite cold the solution became an apparently solid felted mass of crystals. This material was drained by means of the filter-pump and washed with a little cold alcohol. The mother-liquor and washings afforded on distilling off much of the alcohol second and third crops of crystals which latter were also washed drained and dried. The several crops were mixed and then completely purified by repeated crystallisation from absolute alcohol. The alcoholic distillates obtained in the course of this treatment were found to contain some ethylic thiocyanate and a little bromide and sulphide. The residual alcoholic solution from which the ssveral crops of crystals had separated was preserved for further examiria-tion the results of which will be described later on.A. Zxamination of the Pure Crystals.-These proved to be quite free from silicon but contained much bromine and the constituents of t'hiocarbamide. The aqueous solution gave the galena reaction for thiocarbamide* freely and was not coloured by ferric chloride. The complete analysis of the compound led to the results stated below. I may mention however that the determination of hydrogen proved to be of exceptional difficulty owing to the large proportion of sulphur nitrogen and bromine present. I. 0.3545 gram burned with lead chromate and copper gauze in front gave 0.1561 gram of CO and 0.1704 of H,O. Percentage of C = 12 ; of H = 5.34. * '' The Synthesis of Galena," by J. Emerson Reynolds.Trans. 1884 45, 162 AND THEIR DERIVATIVES. 859 11. 0.3849 gram gave 0.1718 gram of CO and 0.1848 of H,O. Percentage of C = 12.17 ; of H = 5.33. Percentage of C = 11.98; of H = 5.17. "111. 0.3708 gram gave 0.1.634 gram CO and 0.1716 of H,O. 1V. 0.3561 gram gave by Dumas's method 95 C.C. of N at i0*So and 750 mm. Percentage of N = 31.24. V. 0.3492 gram gave by Will and Varrentrapp's method, 0.1092 gram of N. Percentage of N = 31.27. Percentage of S = 31.75. Percentage of S = 31.82. VIII. 0.5041 gram gave 0.236 grain of AgBr. Percentage of Br = 19.89. IX. 0.466 gram gave 0.2186 gram AgBr. Percentage of Br = 19.95. fVI. 0.6232 gram gave 1.441 gram of BaS04. VII. 0.7671 gram gave 1.776 of BaS04. The analytical data lead to the formula-C4E€20N,S4Br.I n the following table the calculated and experimental values are compared :-Found. Calculated. 7- \ C,. . 11.94 12.00 12.17 11.98 N,. . 32.34 31.24 31.27 -SL 31'84 31-75 31.82 -Br 19.91 19-89 19.95 -H2". 4.97 5.34 5.33 5-17 The new compound is therefore a derivative from 5 mols. of thio-cay ba mid e. The pure substance melts at 173-174 and begins t o decompose a t 178-180". It is easily soluble in boiling anhydrous alcohol ; but is so much less soluble in the cold liquid that the hot saturated solution * In this combustion e-very precaution was taken to eliminate possible traces of The lead chromate mas first The copper gauze was reduced in hydrogen but t The sulphur and bromine determinations were made by improved methods, An account of the processes carbon liydrogcn and moisture from the materials.strongly heated in pure oxygen. was subsequently heated to redness in an atmosphere of pure and dry hydrogen. which afforded very concordant results as seen abo-re. will shortly be published 860 RETICOLDS OK SILICON COJiPO~TXT?S becomes almost solid at the ordinary temperature. It is almost inso-luble in ether chloroform and benzene. Water dissolves the com-pound but a t the same time partially decomposes it. The composition and properties of this beautiful product led me to suspect that it might be regarded as (H,N,CS)lHINBr or (H,N,CS),NBr consequently that its synthesis should be affected by the union of thiocarbsmide with amrrionium bromide ; hence the fol-lowing experiment was made :-One gram of ammonium bromide mas dissolved in as little absolute alcohol as possible and the solution was added to a boiling and nearly saturated alcoholic solution of 3.04 grams (4 mols.) of pure thio-carbamide; the solution was again boiled for some time and then allowed to cool in a flask.On standing the contents of the flask solidified to a beautiful crystalline mass identical in appearance with the product obtained from the silicon compound. The substance was drained from mother-liquor by the pressure pump then purified by recrystallisation from alcohol dried and examined. The synthetic product melts a t the same temperature as the original substance and begins to decompose in the same way a t 178-180". Its other characters are the same. 0.2866 gram gave 0.135 AgBr = 20.04 Br.Theory for (H5N,CS)JBr requires 19.91 of Br. There is therefore no doubt that the synthetic product is identical with that obtained by the aid of silicon bromide and is a well-defined corn-pound of a tetmthiocarbanzide group or is tetrathiocarbamidammonium bromide. This result obviously raised the question whether analogous com-pounds could be obtained with other bromides and considerable time was occupied in examining varioiis products which were formed by the union of certain bromidcs iodides and chlorides with 4 mols. of thiocarbamide. The following among a number of other similar compounds were obtained by the synthetic method and will be described in detail in a separate paper. The formula of the original bromide is given a t the head of the list for reference.(H5NzCS)4NBr or ( H4N,CS),H4NBr, (H~N~CS)IH~NI, (H3,C S ) 4H4N C1, (H~N~CS)~H:,(CHS)NB~, (H,N,CS)JL( CzH,)SBr, (H4NZCS)1H( C2H5)3NC1, (H4NzCS)1(C,H5)aNBr. All the above compounds resemble the first in appearance and mode of crystallisation AND THEIR DERIVATIVES. 861 The converse question that is whether other amides than thiocarb-amide would unite with ammonium bromide was answered in the nega-tive for the most part as neither allyl- phenyl- diphenyl- nor acetyl-phenyl-thiocarbamides united with the bromide under the conditions which led to the formation of the fine compound with the primary thiocnrbamide. It will appear laber on that t h i s is a point of some theoretical interest even though we should succeed in effectiiig union under other conditions.The action of various metallic salts on tetrathiocarbamidammonium bromide have been examined but the most interesting results were obtained with silver nitrate. One milligram-molecule (0.402 gram) of the bromide was dissolved in 25 C.C. of very strong alcohol and an alcoholic solution of silver nitrate (containing 0.01 gram of the salt in each c.c.) was gradually dropped into the bromide. A precipitate formed at each addition of the silver solution but quickly redissolved until 17.5 C.C. had been ad.ded that is 0.175 gram of AgN03 or slightly more than 1 mgrm.-molecule. On continuing the addition of the silver solution a granular white precipitate formed and separated until 66 C.C. more (nearly 4 mols. in all) had been added.Near the end of the precipitation blackening occurred owing to the formation of silver sulphide by secondary action. In this case silver bromide was first formed by double decom-position with the new compound and was momentarily precipitated, but the silver !*,omide was redissolved in consequence of the forma-tion of a soluble compound (H4NzCS)zAgBr which can be crystal-lised out from the solution at this stage of the treatment. The granular precipitate produced on the addition of silver nitrate to the argento-bromide solution is probably a mixture of monothio-carbamide compounds with silver bromide and nitrate. The above results led to a general examination of the relations of silver haloid compounds to thiocarbamide. It was found that solutions of thiocarbaniide dissolved or acted upon silver bromide chloride, iodide cyanide &c.directly and the following among other sub-stances were formed and analysed :-( H4N2CS)2AgBr, ( HaN2C S ) AgBr, (H4N2CS) 2AgC1, (&NzCS)AgI, (HaN,C S) ZAg CN. The results of +he detailed study of the above and other similar compounds will form the subject of a separate communication. I may mention however? that they have afforded the clue required €or VOL. LlII. 3 862 REYNOLDS ON SILICON COMPOUSDS the interpretation of some obscure facts recordedin one of my earlier papers on the metallic compounds of thiocarbamide. B. Examination of the Residual Lipid from Crystals of the Tetra-thiocarbamide Compound.-This has led to the recognition of an interesting firithiocarbavzide derivative the 6rst of its class.The liquid from which successive quantities of the crystals were separated as already described was reduced by distillation to 180 c.c., which hed the sp. gr. 1.108. When this yellowish residual liquid was treated with twice its volume of anhydrous ether the mixture separated in two layers. The heavier layer was removed shaken up with fresh quantities of ether and the ethereal solutions were mixed and preserved for further examination as the ether was found to hold an ethylic silicate in solution. The heavy liquid separated from ether slowly deposited a consider-able quantity of short transparent prismatic crystals. These closely resembled dithiocarbamidethyl bromide in appearancc and like the htter afforded a fine yellow precipitate of Zead rnercaptide when the solution was treated in the cold with alkaline lead tartrate.On boiling with excess of the lead solution the galena reaction was also obtained. The compound when purified by three crystallisations from anhy-drous alcohol was carefully dried and analysed. Its formula proved t o be C5H&,&Br2. The following are the data obtained :-I. 0.484 gram of substance gave 0.2118 gram of H,O and 0.2535 of GO,. Percentages of C = 14.28 ; of H = 4.86. Percentages of C = 14.38 ; of H = 4.55. Percentage of N = 20.17. Percentage of Br = 38.07. Percentage of S = 23.11. Percentage of S = 23.13. 11. 0.4 gram gave 0.164 of H,O and 0.211 of CO,. 111. 0.3525 gram gave 0,4935 of Pt. IV. 0.7461 gram gave 0.6675 of AgBr.V. 1,4775 gram gave 2.484 of BaS04. VI. 0.35 gram gave 0.589 of BaS04. The percentage composition of the substance is AND THEIR DERIVATIVES. 863 Found. Theory. r- -7 C5 14-29 14.28 14.38 H, . 4-76 4.86 4.55 Ng 20.17 - 20.00 S3 22.85 23.11 23.13 Brz 38.08 38.0 7 -The experimental values therefore fairly agree with those calcu-lated from the formula. The elements nitrogen sulphur and bromine, when present together in large proportions in a compound as in the present instance render the precise determination of hydrogen some-what uncertain ; hence in the case of a substance which has so high a molecular weight (420) as that in question analysis alone cannot decide between such expressions as H, and H?, for the probable number of hydrogen-atoms in the molecule.But the choice in this instance lies rather between H, and H,, as any intermediate expression would present greater theoretical difficulty than either. Analysis readily decides in favour of the higher value viz. :-Calculated Calculated for H16. for Found (mean). Percentage of hydrogen 3.846 4.762 4.705 Moreover the formula deduced best accords with the mode of derivation of the compound and with the following facts which indicate its nature. The new substance readily affords lead mercaptide or mercaptan itself (ethyl thiohydrate) when boiled with caustic potash conse-quently it contains the ethyl-group directly united with sulphur. It also easily yields up bromine to alkalis. In so far as it is analogous to the dithiocarbamidethyl bromide, H,NZCS*CJIS I 9 H,N,CS.Br which acts in a similar manner and is therefore a sulphinic compound of ethyl bromide also.Further the composition of the body and the fact that it gives the galena reaction on heating for some time with alkaline lead solution indicate the presence of three groups derived from 3 mols. of thiocarbamide. These facts point to the following as the formula for the compound (H5N,CS),BrCzH,Br. I f this be confirmed by synthesis it will materially strengthen the evidence of the unsymmetrical structure of the thiocnrbamide itself, and even suggest an expression for the latter ; but it would be prema-ture to discuss this subject at the present stage of the inquiry 864 SILICOX COMPOUNDS AKD THEIR DERIVATIVES. C. The Ethwenl solution that separated from the liquid which afforded the compound last described was distilled from the wat'er-bath as long as any ether passed over.The residue which was a thick liquid was poured into a tube and hermetically sealed as it waq found to mpidly hydrate and gelatinise on exposure to air. After standing for three months a mixture of crystals had separated con-sisting of the two thiocarbamide-derivatives (which are not quite in-soluble in ether containing alcohol) and the usual gelatinous product from diethylic silicate. The investigation of the action of ethyl alcohol on the compound (H4N,CS),SiBr4 has therefore shown-(1) that ethyl bromide thio-cyanate and silicate are formed ; ( 2 ) that but one of the thiocarbamide-groups undergoes actual resolution ; (3) that the remaining 7 mols. of the amide afford the tri- and tetra-thiocarbamide compounds described. Only two classes of thiocarbamide :products have hitherto been known namely those derived from 1 mol. or 2 mols. of the amide ; but it has been shown in this paper that 3 and even 4 mols. can unite in forming more highly condensed compounds under the influence of silicon tetrabroniide and even less pomerf ul agents. Ethyl alcohol also dissolves and decomposes the compounds of allyl-and phenyl-thiocarbamides with silicon tetrabromide but the pro-ducts have not been examined in detail. I desire to acknowledge the valuable assistance received in the analytical part of the work recorded in this paper from my friend and former pupil Emil A. Werner F.C.S. University LaEoratoqt, Trinity College Dublin

ISSN:0368-1645    

DOI:10.1039/CT8885300853

出版商:RSC    

年代:1888

数据来源: RSC

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LXXLI1.-The Heat of Dissolution of Substances in diferent Liquids, and its bearing on the Explanntion of the Heat of Newtralisation, and on the Theory of Residual A$nity. By SPENCER UMFREVILLE PICKERING M. A. Professor of Chemistry at Bedford College. A SHORT time ago I drew the attention of the Society to the fact that the thermal results of neutralisation proved the existence of an equality represented by-M,R,aq - M',R,aq = M,R',aq - M',R',aq (1) in which M and R represent metallic and non-metallic radicles and I pointed out that unless we could assume the existence of a similar equality as regards the constituent parts of these terms namely the heat of formation of the salt molecules from the atoms-M,R - M',R = M,R' - M',R', and the heat of dissolution of these molecules in water-MR,aq - M'R,aq = MR',aq - M'R',aq, an assumption which I regarded as most improbable these two con-stituent actions must be integral parts of one and the same reaction, namely the perfect saturation of the affinity of the radicles M or R ; and that as the first action is chemical so also must be the second one the dissolution of the salt molecules (Trans.1887 593). My explanation of the facts of the case was subsequently reproduced almost verbatim by Dr. Nicol in a paper read before the British Association in 1887 (see Chem. News 56 162) and he suggested, though on very weak grounds in my opinion,* that this equality did hold good of each of the two constituent actions. The parmiount importance of the conclusions drawn from the heat of neutralisation renders it necessary to examine any possibility however improbable, of its being interpreted in a sense consistent with the so-called physical theory of solution.* The grounds were that a fern very imperfect determinatione seemed to show that the difference in the extent to which the vapour-pressure of water is lowered by the addition of salts of two different acid8 is independent of the nature of the metal present. But even if further experiments prove this to be the case we should stmill have to prove the proportionality between the lowering of the vapour-pressure a.nd the heat of disolution (see Chem. News 66 191). VOL. LIlI. 3 866 PIcKERING THE HEAT OF DISSOLUTION It appeared that the possibility of the equation-MR,aq - M‘R,aq = MR,aq - M’R‘,ay (which represents be it noted the heat of combination of single molecules with excess of water not the heat of dissolution of masses of the solid salts) holding good might be settled in the following manner.During the dissolution of a snbstance three forces must come into operation whether these forces be chemical or physical :-(I) the attraction of salt moleciile for salt molecule ; (2) the attraction of the moleculc s of the solvent for each other ; (3) the attraction of the salt molecules for the solvent molecules. The first o€ these is inde-pendent of the nature of the solvent and the second is independent of the nature of tlie dissolved substance the third only is dependent on both substances. Now by taking a sufficient excess of the solvent we shall have the attraction of salt molecule for salt molecule practically entirely over-come ; and we shall also have the attraction of the molecules of the solvent for each other overcome to the same extent whatever salt be dissolved in it.This is obviously true when the proportion of the solvent is infinite for then not only will the dissolved molecules be entirely separated from each other but the solvent molecules will be less united with each other than they are when no dissolved snbstance is present by only an infinitesimally small amount which infinites-imally small amount will differ according to the salt dissolved by a still more infinitesimal amount. We cannot of coiirse use an infinitely large proportion of solvent hut by taking some 500-1000 mols.of it we obtain values which as I will show can differ by but very little from those referring to infnite dilution. Now let the heat evolved in the satisfaction of the various attrac-tions concerned be (MR)c (M’R)c &c. for the attraction of the salt molecules for each other; let w and a represent that due to the combination of the solvent molecules with each other where the solvent is water and alcohol respectively and let (MR)w (M’R)w, (MR)a (M’R)a &c. represent the heat of combination of the various salt molecules with the tm70 soJvents; then the heat evolved in the dissolution of the solid MR in infinity of water will be [- (MR)c -w + (MR)w] and in alcohol [- (MR)c - a + (MR)n] and so 011 with the other salts M‘R MR’ &c. On the physical theory of solution the same relation must exist between the heat of dissolution of various salt molecules in alcohol as in water ; if with water we have-MR,aq - M‘R,aq = MR’,aq - M’R‘,aq OF SUBSTANCES IN DIFFERENT LIQUIDS.867 or in the above notation-(MR)w - (M‘R)w = (MR’)w - (M’R’)w, so with alcohol we must have-(MR)u - (M’R)a = (MR’)a - (M‘R‘)u, which two equations may be combined into-(MR) (ZU - U) - (M’R) ( w - U) = (MR‘ ) ( w - U) - (M’ R ’ )( LU - u) ( 2) and the observed heat of dissolution of the various solid salts in water and alcohol must show the following relations :-Diss. of solid MR in water - Diss. of solid MR in alcohol. [ - (3IR)c - w + (MR)w] - [- (MR)c - u + (MR)a] - Diss. of solid M’R in water + Diss. of solid M’R in alcohol. -[-(M‘R)c - w + (M’R)w] + [-(M’R)c - (7 + (M’R)u] = Diss.of solid MR’ in water - Diss. of solid MR’ in alcohol. = [ - (MR’)c - w + (MR’)Lo] - [ - (IMR)c - u + (MR’)a] - Diss. of solid M’R’ in water + - [ - (M’R’)c - w + (M’R’)w] + because this equation simplifies into (2). This would moreover hold good even if the alcohol contained water; for in such a case (MR)c would still have the same value and for the complete separation of the particles of this mixed liquid we should have a‘ which would cancel out in the same way a s does; while for the results of‘ the action of the salt molecules on those of the dilute alcohol containing l / x t h of its weight of water we should have (1 - x)(MR)a + z(MR)w instead of (MR)a since (still according to the physical conceptions of solution) the salts would in each case exert their influence on the alcohol and water (in the dilute alcohol) in direct proportion to the relative masses in which these were present and our equation would still simplify into equation (2).The determination of the heat of dissolution of the four suitable salts in water aiid alcohol became therefore necessary. The salts selected were the anhydrous chlorides and nitrates of lithium and calcium but in addition to these other salts were also examined for purposes to be mentioned below. The determinations in alcohol were attended with considerable difficuhies. It was found t?iat milny of those salts which were said to dissolve in alcohol did so to a scarcely appreciable extent when the alcohol was anhydrous or at any rate not in sufficient quantities for calorimetric purposes.In the case of several of the salts which were Diss. of solid N’R’ in alcohol. [ -(M’R’)c - a + @f’R’)a], 3 0 868 PICKERING THE HEAT OF DISSOLUTION eventually taken over 1000 mols. of the alcohol had to be used for each molecule of the salt and even then the dissolution took a very considerable time necessitating the application of a large correction for the loss of heat by cooling during the determination I n one or t w o cases the salt was not entirely dissolved and the amount which had dissolved had to be subsequently estimated in the liquid. Owing to the comparatively high molecular weight and small density of alcohol the volume of this liquid which should he taken to give the same molecular proportions between the solvent and salt as in the case of water should be four times as great as with water but for economical reasons the volume of 600 C.C.generally used was reduced t o 270 c.c. and consequently the weight of salt taken was very sniall, often but a fraction of a gram so that .the observed evolution of heat had to be multiplied by some hundreds to give the so-called molecular heat of dissolution. Most of the salts moreover are of an extremely hygroscopic nature and some of them such as ZnC12 CaBr2 and CaI, especially this last could not be obtained in an anhydrous condition without experiencing a certain amount of decomposition. But the chief source of error in such determinations is that the rate of cooling is a t least 10 times greater than in the case of water, owing to the volatility of t'he alcohol.The results are given in Table I (p. 875). For the open calorimeter holding 270 c.c. used in the earlier determinations a calorimeter holding 600 c.c. and covered with a thin copper lid with an opening in it for the introduction of the salt was substituted in the later determinations the rate of oooling being thereby greatly reduced. I n the case of the determiixttions with the chlorides and nitrates of lithium and calcium the later determinations gave considerably higher results the difference is greater than can be accounted for by the errors in the thermometric measurements and is probably due to the fact that in the earlier determinations the tubes in which the salts were weighed out before dissolution had not as far as I can remember been specially heated immediately before the introduction of the salt and the 2 or 3 mgrms.of moisture adhering to the surface of the glass would have produced a considerable amount of hydration of the small quantity of salt taken. This explanation is rendered all the more probable by the fact %hat with the less hygroscopic sodium iodide the difference is scarcely appreciable and with the non-hygroscopic mercuric chloride there is no difference a t all. At any x-ate the esrlier and later determinations are consistent in themselves, and whichever are taken for the purposes of our equation the result obtained is practically the same. The alcohol taken was dehydrated by exposure for a week or two in a vacuum over freshly burnt lime OF SUBSTAKCES IX DIFFEREST LIQUIDS.869 f n this and the subsequent tables-w = the weight of salt taken, W = that of the solvent, w”c” + w’c’ = the heat capacity of the solution and apparatus, (t’ - t)” = the corrected rise of tempemture, D7n = the heat of dissolution for one gram-moleculm proportion and the probable error given in the last column is the difference which would have resulted from an error of 0.002” in the deterniinatiori of the rake of cooling per minute half this amount only is taken iri calculating the probable error in the later determinations. The heat capacity of the solution is taken as being equivalent to the sum of those of the solvent and the dissolved salt. In the case of the three later determiriations with calcium chloride, Borne variation is noticeable this is probably due to the different amounts of solvent taken and in taking the mean it will be well to omit the one with only 440 C2HI,0 and take the other two which do not differ from each other by more than the amount due t,o the error of reading the thermometer.The determiriation of the heat of dissolution of these same salts in water is given in Table 11 where the results are compared with those obtained by ‘l’hornsen. With these they agree very well except in ttie case of CaI, where the specimen used by myself was known to be considerably decomposed. With CaCl, Ca(N0,)24H,0 Nal, Na(C2H302) and Mg(NO3),GH,O my results are appreciably higher than Thornsen’s whereas with CaCl,t;H20 LiC1 CaBr, ZnC1 (the last two being both known to be partly decomposed) the reverse is the case.Whether evolution or absorptioii of heat occurs those result,s which give the highest numbers are probably the most correct. The experimental error is here much less than in the case of alcohol, generally abodt 5 cal. Taking now the values here obtained (the later and more accuratt. determinations with alcohol being alone considered) and substitutirig them in our equation above we get-c = the heat capacity of the solvent, of the salt, Dise. of solid CaC1 in water. -18,i‘L3 - 17,555 + - 16,312 + 23,486 = -3,943 - 8,710 Diss. of solid CaCI in alcohol. -Disc. of solid 2LiC1 in water. Diss. of solid 2LiC1 in alcohol. = Ilks. of solid Crt(N03)= in water. Diss. of solid Ca(h’O& in alcol~ol 870 PICKERINJ THE HEAT OF DISSOLUTION -Dim of solid 2LiN0 in water.+ Dim. of solid ZLiNO in alcohol. - 662 + 9,310 or 8,342 = 3,881. numbers showing a difference of 4461 cal. where if Dr. Nicol’s view be cori*ect there should be equality. I do not feel sure whether according to his view an eqnivalent of the calcium salts should be compared with a double equivalent of the lithium salts as above but i f riot the discrepancy becomes still greater giving us 4755 = - 443 for the two sides of the supposed equation. For the absolute validity of our argument the proportion of solvent should as I have already mentioned be infinite but the further dilu-tion of these very dilute solutions gives such feeble calorimetric results that the values obtained for infinike dilution would differ by very little from those taken here.By performing a series of experi-ments with different proportions of solvent and plotting out the results against the percentage instead of the molecular composition of the solution we get a curve which can easily be extended to the zero point that is to infinite dilution. This has been done with series of determinations which I have made with calcium nitrate and chloride in water and thus it was found that infinite dilution of Ca(N0,)2400H,0 would absorb 120 cal. and of CaC1,400H20 would evolve 550 cal. If we admit a possible error of 350 cal. from tliis source in each of the values used in our equation and that the sign of this error is always of a character favourable to rendering the two sides equal we should obtain for the sum of the errors only 2800 cal.which would still leave an irreconcilable difference of 1661 cal. ; it is however far more probable i f not indeed certain that the sign of the corrections would be the same with each salt whether water or alcohol were the solvent, and in this case they would. exactly or nearly counterbalance each other according as they were exactly or nearly the same in value with the two solvents. Though it would be advisable before drawing too rigid a conclusion to examine other sets of salts still as it does not appear possible to obtain any other suitable sets we must take these resnlts as showing conclusively as far as they go that no such relationship exists between the heat of dissolution of salts in water and in alcohol as would exist i f the equation MR,aq - NR’,aq = M’R,aq - M’R‘,aq were true; and hence that this so-called physical explanation of the thermal results of neutralisation is opposed to experimental evidence OF SUBSTANCES IN DIFFERENT LIQUIDS.871 According to my explanation of the heat of neutralisation the residual affinity of one of the radicles composing any salt molecule becomes entirely saturated when it is dissolved in excess of water, and it appeared probable at first sight that since the amount of this residual affinity is independent of the nature of the solvent the lieat of dissolution of a salt must be the same whatever the solvent be. The other determinations given in Tables I and I1 were made with a view of investigating this point.The general results are col-lected in the following table the numbers in brackets referring to the order of magnitude of the quantities. Salt. CaBi.2 . CaC1 Car ZnC1 . LiCl Ca(NO,) NaI Li N 0 . CaCl26H,0 Ca(NO3),PH20 Na ( C2H302) I-IgCl Mg (NO,) ,61120 I n water. 23,293 18,723 15,937 (3) 15,220 8,156 3,948 3,943 1,404 33 1 -2,116 - 4,251 - 4,547 - 8,354 In alcohcl. 21,47 1 17,555 19,833 (3) 9,767 11,743 1,274 8,710 4,587 4,655 0 - 2,563 936 - 1,835 Difference. - 1,822 -1,168 + 3,896 + 3,587 + 3,183 + 4 334 + 2,116 + 1,688 + 5,483 + 6,419 - 5,453 - 2,674 + 4,767 That the heat of dissolution is the same in the two cases is a t once disproved.There is a rough similarity in order of magnitude in the two series but beyond this no other connection is noticeable. The diBerence between the heat of dissolution in the two liquids ranges between -5500 and +6400 cal. though with alcohol the numbers obtained are generally the higher of the two. To these we may append the following :-ZnClz in water 15,220 cal. , NH,C1 sol . 15,091 ,, , KCI , 14,895 ,, HgCl2 in water -2,116 ,, , NH4C1 S O ] . . . -1,623 ,, where the values though more nearly the same than in the case of alcohol are certainly not identical. On further consideration however it does not appear that the heat of dissolution of a salt should according to my views be independent of the nature of the solvent 8 72 PICKERIKG THE HEAT OF DISSOLUTION The equation-M,R,,aq - M,R',aq = M',R,aq - M',R',aq, holds good (1) if one of the radicles only in each case be saturated by the solvent and (2) if this radicle be saturated by the free affinity of the solvent.If the heat evolved in saturating it were counter-balanced in part and to different extents in different cases by any alteration in the force with which the molecules of the solvent were united with each other or with which the atoms are combined together in the molecule or if any of the residual afEnity of both ra,dicles of the salt were saturated by the solvent then the equation would no longer hold good. I n the case of water we are dealing with a substance composed simply of one metallic and one non-metallic substance the atomic constitution of which is very simple and very stable and such a solvent may well act so as to fulfil the two neces-sary conditions above mentioned," whereas other less simple arid less stable Solvents would not do so.This appears at any rate to be the case with alcohol. It is impossible with the means a t our disposal to get other solvents as simple as water in order to prove the truth of this view but it seemed probable that some approach to constancy in the heat of disso-lution might be obtained by simplifying the substance dissolved instead of the solvent. By taking an elementary substance instead of a salt we do away with the possible saturation of the two different radicles and the second of the above-mentioned conditions will then be the only one too be fulfilled in order to produce this constancy.Table 111 contains the results obtained on dissolving iodine, bromine and sulphur in various liquids the numbers in columns 3 and 8 referring to gram-atomic proportions of the substances. Many of these liquids being more volatile than alcohol the diffi-culties of the determinations were proportionately greater and although the 600 C.C. calorimeter with its corer was used in every case the cooling produced by evapopation was very great. The iodine used had been precipitated from an alcoholic solution and dried by exposure in a vacuum this treatment rendering it more finely divided and hence more easily soluble. The bromine however was ouly a commercially pure specimen. I n dissolving the latter it was enclosed in a sealed bulb which was eventually broken under the surface of the liquid.To break such a bulb a t a particular moment in a liquid which is being continually stirred in which there is sus-pended a very delicate thermometer and which i s cont,ained in a * Some of the many exceptions to the constancy of the heat of neutralisation are, no doubt due to these conditionp not being always fulfilled even in the case of water OF SUBSTANCES IX DIFFERENT LIQUIDS. 873 calorimeter supported on points only is not a very simple operation. The following apparatus was devised €or the purpose and found to act well :-The bulb was kept in position at the bottom of the liquid by means of a small inverted platinum cone with jagged edges fixed on to a long platinum rod which extended to the top of the calorimeter, and which was united by a vulcanite connection to a longer brass rod.this brass rod being held by means of a screw and socket to an arm projecting from the jacket of the calorimeter. As soon as the temperature was constant the screw was loosed and a tap on the top of the brass rod was sufficient to drive the cme on t’o the bulb and break it. I t is well to make the bottom of the bulb somewhat con-cave and place under it a spiral of thick platinum wire with a pro-jection in the middle the projection getting driven against the concave bottom of the bulb facilitates its being broken. A false bottom consisting of a disc of very open platinum gauze is placed in the calorimeter so as to cover the bulb and prevent the broken glass from being driven against the thermometer by the stirrer.The present experiments were only intended to be preliminary in their character. The solvents used though commercially “ pure,” were far from being so in reality ; their heat capacity (specific heat) more-over is known with no degree of certainty yet the results obtained are eminently suggestive. With iodine the heat of dissolution f o r 126.54 grams is as follows :-In benzene , chloroform , carbon tetrachloride , ammonium chloride sol , alcohol , ether carbon disulphide pocassium iodide sol. . -3957 cal. -3007 ,, -28g1 ,, -22504 ,, -1538 ,, -857 ,, -768 ,, -546 ,, With the first three solvents none of which contain oxygen the heat of dissolution is practically constant within the limits of experi-mental error ; with carbon disulphide there is an appreciable rise in the heat developed which attains still greater proportions in all the solvents containing oxygen alcohol and ether giving near17 the same results.The amount of iodine dissolved in the ammonium chloride solution was so small that the value obtained is only a rough approxi-mation. With bromine (79.76 grams) where only a small number of sol-vents could be tried the results axe 874 PICKERIXG THE HEAT OF DISSOLUTION I n water -754 cal. , carbon tetrachloride -265 ,, , carbon disulp hide. -7 9 , water (Thornsen). . +539 ,, , potassium bromide sol. . +lo90 ,, showing the same fact as with iodine that the sulphurised solvent gives slightly higher values and the oxygenat'ed ones give consider-ably higher values than the others.The results with water how-ever are exceptional iu this respect. This may be due to moisture or impurity in the bromine and it is noticeable that my value differs considerably from Thornsen's which comes in the position we should expect it to from the results with iodine.* With benzene and ether, the values obtained are much higher than in the other cases for here we get ordinary chemical actions occurring. With sulphur (octohedral) the values for 31.98 grams are as fol-, chloroform -323 ,, . lows :-f In ether -1499 cal. , chloroform . -697 ,, , benzene -690 ,, , carbon tetrachloride -624 ,, , carbon disulphide -469 ,, Here as in the case of iodine the chloroform and benzene give identical numbers and as in the cases of both iodine and bromine the values with carbon tetrachloride are slightly smaller and those with carbon disulphide considerably smaller.The results with ether how-ever are different from those in the case of the halogens showing a larger instead of a smaller absorption of heat than with the other solvents and this difference is I think far too great to'be accounted for by experimental error due to the great rate of cooling and the smallness of the quantity of sulphur dissolved. Considering the very large experirneiital error in determinations with these volatile liquids the impurity of the majority of them, and * Thom$en however gives no details ns to the preparation of his bromine or as to the method by which he obtained his results.With such a volatile liquid, special precautions must be taken to prevent the bromine vaporising and giving the heat of dissolution of bromine Tapour a quantity which xould be considerably greater than that of liquid bromine. Berthelot (Me%. Chim. 1 511) misquotes Thomsen's number as bpplying to gaseous bromine. t Alcohol was found to dissolve sulphur in proportions too small (0.075 p. c. a t 18') to render a determination with it practicsble. 5 The solution of iodine in carbon bisulphide and benzene showed signs of con-Pitierable action after being kept for six days so also did the solution of bromine in chloroform I w* I Salt . - Earlier Determinations . CaC12 CaCI26H2O . Ca(NO& . Ca(E03)24H20 Cah2 CaL ZnU2 . LiC1 LiNO NaI HgC1.Mg(NOZ)26H20 . NaC2H302 . ZnC12 . HgCl2 Caa . . C a ( NO3) . LiC1 LiN03. NaI . Irgci 0 *549 2.643 1 *066 2 *a55 0'535 0.439 1 -908 0 -382 1 *579 1 -007 3 -168 3 *331 0 '338 11 -502 11 -354 8 -529 11 -631 2 . 6 1 a 1.9350 1 * 6387 2 '3312 2 -2419 0 -6201 1 -8359 1 -8939 2 * 954 2.928 930C. H60 400 750 400 . 1740 3270 330 500 200 750 400 360 1100 3NH4 C1hOH20 3KC1400H20 6 KCl8C OH 0 7'5NIT4 C11050Ef2O . . Later Determinations . M'OC2ReO 600 700 700 7 50 700 390 380 520 9 to 122 -94 123 * 69 123.12 123 -61 122 '91 122 -88 122 -90 122.96 123 '33 122 *94 123)'75 122.90 607 *69 603 *06 607 *69 603 -06 295 9 1 295 -84 295 -85 296 .01 295 *99 295 -67 295 * 92 295 -93 295 -99 296 -0 876 PICKERING THE HEAT OF DISSOLUTION 0 . n u I u W 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Q . . . . . Q . . . .B ;z TABLE 111.-Determination of the Heat of Dissolution of Iodine Bromine, at 18" & 0.1. Substance. --Iodine , . . Bromine . , Sulphur W. -3 *0230 3 2484 2 *5857 1 -8941 1 *4085 2 -0102 7 '9532 0 * 2429 0 *8488 1 -6281 2 '8991 1 W10 2 * 2591 1 '7450 1 -7684 5 -140 4 *235 4.419 0 '743 3 -20s ~~ Solvent. 440czB'60 . 390CSz 37OCHC13 4OO(C286)2O . 6UOC,H,j 350CC1 1Z4NH4C115,50OI~,O 2700H,O 8.5K Br1400H20 3.8KI555HiO 22ocsz 3OOCHCI~ L60CCl4 23O(CZHj).O. . 27oc~H6 48CS2 35CC1 . 40C6HG 200(C,H,),O . 6OCHC1 . d. 476 *70 762 *ll 897 '4 434 '37 530 -1 860 *1 630 -0 604 -09 51 1 -86 534.35 600-35 764.55 '707 -75 367 * 60 460 -20 584 -00 502 6 io 413.50 368 '10 672 -2 -c.-0 -597 0.239 0 -234 0 * 537 0 *436 0 *201 0.868 0.952 0 999 0.938 0 -239 0 -234 0 *201 0 -537 0.436 o 289 0 -201 0.436 0.537 0 -23 878 DISSOLUTION OF SUBSTANCES IN DIFFERENT LIQUIDS. our imperfect knowledge of their heat capacity the results are strongly in favour of the conclusion that the heat of dissolution of an elementary body in a solvent of simple constitution is a constant quantity as must be the case if the heat evolved is due to the coin-plete saturation of residual affinity." I may take the present opportunity of mentioning one point of in-terest in connection with the heat of neutralisation.The equation (1) (p. 865) applied to the case of any two alkalis gives us-K,OH,aq - Na,OH,aq - K,Cl,aq + Na,Cl,aq = 0, showing that K may be represented by hydrogen as well as other radicles. In the case where two different acids are treated with the same base we find that M may be represented by hydrogen as well as by other metals ; but if the hydrogen is associated with hydroxyl the constancy no longer obtains. The neutralisation of an acid by an alkali gives-H,OH,aq - Na,OH,aq - H,Cl,aq + Na,Cl,aq = 13,750 cal. instead of 0. From which we must conclude that the heat of forma-tion of H20 from H and OH? and the subsequent union of the various H20 molecules thus formed into aggregates is greater by 13,750 cal.than the heat of formatiori of the other bases (K,OH) and the union of these bases with excess of water. As the heat of formation of the water aggregates from the fundamental molecules cannot be greater than the heat of volatilisation of the water some 10,000 cal. at IS" it is evident that the heat of combination of OH with H is several thousand cal. greater than it is with any other metallic atom. * Berthelot (Me'c. Chim. 1 546) gives some approximate values for the heat of dissolution of naphthalene (128 grams) in alcohol ether and acetic acid which are confirmatory of the constancy observed by me j they are -3700 -3900 and - 4,300 cal. respectively

ISSN:0368-1645    

DOI:10.1039/CT8885300865

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

8 i 9 LXXIV.-The Gonstitutiola of the Terpmes and of Benzene. By WILLTAX A. TILDEN D.Sc. F.R.S. THE idea that turpentine and lemon oils consist of a hydride OE cymene is due to Oppenheim (Ber. 5 94 and 628). This view has been supported by KekulB (Bey. 6 43&) and very generally adopted down to the present time. Nevertheless I believe it to be incon-sistent with many of the most prominent characteristics of these hydrocarbons and so long ago as FebruarT 1878 I laid before the Chemical Society a statement of some of the difficulties which beset this hypothesis. The formulae which I then proposed for the terpenes I do not now pretend to sustain inasmuch as they involve the mistaken assumption that these compounds are sexvalent cr contain three double linkings of carbon.Nevertheless my opinion is not only unchanged but is fortified by all that I have since learnt of these hydrocarbons that whilst the terpeness almost certainly contain a nucleus of six atoms of carbon these are not disposed in the manner in which they ai-e assumed to be in benzene whatever constitutional formula is adopted for that substance. The publication of a number of papers on the chemistry of the terpenes more especially the very important researches of Wallach (Annulen 225 227 230 238 239 241 245 246) hasattracted my attention again to the subject and I desire to state in the first instance the grounds for my belief that the terpenes are not consti-tuted as benzene derivatives. The hypothesis commonly received originated in the experiments of Oppenheim Barbier and KekulB upon the production of paracymene from turpentine.C. R. A. Wright afterwards examined the action of bromine upon a number of terpenes from various sources and found that they all gave the same cymene in different proportions. Nevertheless the importance of this fact must not be exaggerated, for it must be remembered that the yield in the most favourable case is much below the theoretical arid cymene cannot be reconverted by any known process into a terpene. Moreover the known hydrides of benzene toluene &c. are totally unlike terpenes in character. The hypothesis also accounts only for three dihydrides assuming the propyl-group to remain the same or six if there be a cymene con-* Using this term to include all the liquid members of the group natural 01.artificial but not the solid “ camphenes,” which hare lotally different characters. I shall generally use Wallach’s nonienclature 880 TILDEN THE CONSTlTUTION OF taining isopropyl. The isomeric terpenes already recognised exceed this number. A second point upon which great stress has been laid is the nature of the oxidation products of the terpeiies and their derivatives terpin hydrate &c. As the impression seems to preva>il that the terpenes when acted upon by dilute nitric acid form a productive source of para-toluic acid I have made a few comparative experiments with the object of determining the proportion of this acid obtainable under exactly the same conditions from several terpenes from cymene and from paraxylene. A weighed quantity of the hydrocarbon was in each case boiled in a flask with reflux condenser with a quantity of nitric acid slightly in excess of that theoretically required for its oxidation to toluic acid.The nit& acid was diluted with four times its volume of water. When the hydrocarbon had disappeared the mixture was allowed to cool the crystailised acid filtered off dissolved in boiling dilute solution of ammonia then reprecipitated by dilute nitric acid, t+nd after some hours collected dried and weighed. The acid thuR obtained was white ; it melted a t about lXO and was therefore nearly pure. Quantities of hydrocarbon varying from 15.9 to 17.1 grams were taken. The following proportions are calculated from the results :-100 parts (by weight) give of paratoluic acid-Cyrnene (fiwm turpentine) .80.1 Cymene (from cummin oil Kahlbaum) 73.1 Psraxylene (Kahlbaum's pure) . 77.2 Australene (from American turpentine). . Terebenthene (from French turpentine). . 1.2 1-9 0 Hesperidene b. p. 175" (from orange oil) . . The hesperidene having failed to give any recognisable quantity of toluic acid an experiment on a larger scale was tried. About 85 grams of the hydrocarbon gave by similar treatment an acid liquid which when concentrated to a smdl bulk deposited 0.15 gram of an insoluble acid (probably terephthalic acid). The chief products of oxidation were a yellow resin which by protoracted action of strong nitric acid gave a viscid nitro-compound and oxalic acid (7.07 grams of anhydrous H,C,OJ) and a small quantity of terebic acid.A comparison was also made between the products of oxidation by chromic acid solution upon cymene and australene with the following result :-Cymene 17 grams gave 7 grams ferephthalic acid or 41 per cent THE TERPENES AND OF BENZENE. 881 Australene 16.3 grams gave a trace only insufficient to weigh, together with a minute quantity of a camphor in the conderiser. Wright (Trans. 1873 553) in oxidising pure hesporidene by chromic acid mixture obtained no terephthalic acid acetic acid being the only product. My contention has always been that the natural terpenes do not yield appreciable quantities of aromatic acids by oxidation ; that they do yield by isomeric change under the influence of heat o r of reagents, compounds which must be regarded either as direct derivatives of benzene or closely connected with it must of course be admitted.Thus not only is cymene obtainable by the removal of 2 atomfi of hydrogen but t,he dipentene (terpilene) obtained from the dihydro-chloride got from turpentine doubtless contains a nucleus of six carbon atoms which either has assumed partly the structure of benzene or possesses a stmwture which is easily transformed into that of benzene. I found that when oxidised by nitric acid as already described, 100 parts of it gave 27-6 of toluic acid although the turpentine from which it was derived gave practically none. The characteristics of the terpenes as a class may be stated as follows. The terpenes are polymerised very readily by the action of heat or of small quantities of sulphuric acid and other agents.All the terpenes combine instantly and eagerly with chlorine and bromine whilst benzene and cymene behave save under exceptional circumstances as saturated compounds. All the terpenes unite with hydrochloric hydrobromic and hydr-iodic acids. Some of the terpenes (the pinene-group especially) also unite slowly with the elements of water forming two alcoholic bodies terpineol, C,,H,,OH and terpin CloH,,( OH),. All these characters are precisely those which are exhibited so plainly by the olefines but in no case by hydrocarbons directly derived from benzene. A few other facts deserve notice. No natural terpene is recoverable from its compound with bromine or hydrochloric acid. A new hydrocarbon of the same composition, Cl0HI6 is always formed namely a camphene dipentene terpinene, or terpinolene according t o circumstances.Again the terpenes are resolved when heated to a temperature of 400" to 500' into a pentene, C5Hs which may be retransformed into a dipentene Cl0H16 the relation between these two compounds being exactly similar to the relationship subsisting %etween amylene and diamylene. If we recall the existence of the sesquiterpenes and the constituents of colophene which are polymerides of terpene the persistence of the YOJI. LIII. 3 882 TlLDEN THK COSSTITUTION O F factor 5 in the number of carbon atoms C5H8 C,,H:,, CI5HZ4 C,,H,?, &c. is remarkable. The combining capacity of the majority of the terpenes appears t o be pretty definitely indicated by the formation of compounds with 2B C1 and in four cases namely limonene (citrene) dipentene sylves-trene and terpinolene with Br4.These tetmbromides which were d l discovered by Wnllzch are crystalline and stable. Nevertheless, it occurred to me as just possible that these hydrocarbons might after all possess a greater combining capacity though the products of their combination with bromine niiglit not be stable enough to admit of their being isolated. A new estimation of their capacity f o r bromine seemed also very desirable in view of the conclusion arrived a t by Gladstone (Trans. 1886 p. 609) from the refraction equivalent and recently restated by Briihl ( B e y . 21 156) to the effect that the pinenes (australene terebentllene &c.)? contain only one double bond, or in other words are only bivalent.T o determine the capacity for bromine a solution of hypobromite of sodium was used. The pure hydrocarbon diluted with twice its volume of chloroform mas mixed with diluted hydrochloric acid in a bottle and the hypohromite solution added in small qiiantities shaking after each addition till the hydrocarbon which settled clown exhibited a faint yellowish colour. This plan being not quite satisfactory it was found better to add at once a slight excess of the hypobromite 80111-tion shake well f o r a minute and then add some potassium iodide, and estimate by thiosulphate solution the amount of liberated iudine. Four to five grams of the hydrocarbon were taken for each experiment. By this method 136 parts or 1 molecule of hydrocarbon took in each case the following quantities of bromine :-Australene (from American turpentine) Terebenthene (from French turpentine) Hespericlene (from orange oil) Dipentene (from dihydrochloride).. 297 77 Br4 EO x 4 320 313 307 326 Calculated for Br 80 x 2 . . . . . . . . . . . . 160 There can be no doubt in t'hese cases that the hydrocarbon fixes four atoms of bromine and no more. One molecule or 154 parts of terpineol C,,H,,OH combined with 185.6 parts of bromine which is only a little more than is required on the assumption that it unitfes with Br2 or 160 parts. An aqueous solntion of tcrpin CI,H,,(OH), does not decolorise bromine-watey even after some t,inie. We have therefore Quadriralent. Bivalent. Saturated THE TERPENES AND OF BENZEKE.883 So far the terpenes. It is well known however that there exists another class of compounds the camphenes CloH,, which are iso-meric with the terpenes and derivable from them. It is unfortu-nate that these compounds should be so commonly classed with the t,erpenes and apparently regarded by many writers as pmsessing a, simiiar structure for t'heir chemical characteristics are very different. When American o r French turpentine oil free from water is satu-rated with dry hydrochloric acid gas a solid compound is formed con-taining CI,H,,HC1. From this the elements of hydrochloric acid may be withdrawn though with difliculty by the action of alco-holic potash or of sodium acetate &c. The resulting hydrocarbon is camphene optically active or inactive according to circumstances.It is a solid melting a t 48" arid boiling a t 160". The same substance is formed in considerable quantity among the products of the action of sfrong sulphuric acid upon turpentine (Arnistrorq arid TiIden Trans. 1879 7 3 3 ) . It is also formed by the ackion of sodium upon the hydrochloride C,,,H,,HCI from turpentine aiid i s obtainable through the chloride from borneol and hence from camphor. Camphene differs notably from the terpenes in its chief proauct of oxidation for it yields neither toluic nor terephthalic acid but acetic acid and camphor. It does not combine with bromine but forms an ill-defined liquid monobromo-compound C,,H,,Br (Wallach, Ann. 230 235). It does unite with 1 mol. of hTdrochloric acid forming a com-pound which is very similar in appearance to the monohydrochlo-ride CIOH:IGHCI prepared from turpentine oil but differs from that compound in dissociating into a hydrocarbon and HC1 when heated' (Ehrhardt Chem.Netos 54 239) and in. yielding up readily the elements of HCl when boiled with water or alkaline solutions regene-rating the camphene. There are three varieties of this hydrocarbon which a p e e com-pletely in all physical and chemical characters except in their action on polarised light the one possessing right-handed rotatory power, another being left-handed whilst the third is inactive. When turpentine unites with dry hydrochloric acid therefore a change is induced manifestly more profound than that which occurs when it combiiies with 2HC1 as it does in the presence of water or alcohol.This latter compound when heated alone or with aniline readily yields liqiiid dipentene which in general characters is veiy similar to the original hydrocarbon and is probably identical with the optically inactive product of the action of heat upon turpentine. We must therefore recognise the following chemically distinct isomerides (see also Wallach Ann. 239 45). 3 r 884 TILDEN THE CONSTITUTIOK OF I. NATURAL TERPENES (optically active liquids). 1. Pinene (australene and terebenthene). 2. Limonene (citrene). 3. Sylvestrene (from Swedish turpentine). 4. Phellandrene (from Phellandriurn aquaticunz &c. Pesci, Gazz. Claim. 16 225). 11. ARTIFICIAL TERPENES (optically inactive liquids). 1.Djpentene (from the dihydrochloride CloHf1162HC1 m. p. 2. Terpinolene (from the action of sulphuric acid on terpin). 48'). 3. Terpinene ( 7 7 9 7 9 ) 1. ITI. ARTrFrCrAL CBMPHENES (solids-two optically active in opposite directions-one inactive). The combining capacity of none of these exceeds four units. Con-sequently it is not possible to represent the nucleus of six carbon-atoms which undoubtedly they all contain as forming an open chain. They must be united into a closed chain containing a t the most two double bonds. Hence we are driven to such formule as those which have been proposed by Oppenheim (Bsr. 5 98) by Goldschmidt and Z:ii&er (Ber. 18 1729 and 20 486) by Wallach (Annalen 239 46), and more recently by Briihl (Bey. 21 165). Goldschniidt and Zurrer derive the formula of lirnonene (= carvene or citrene) from that of carvol in consequence of the relations which they have cstab-lislied between these t w o compounds.Thus :-Limonene. Carvol. QsH7 c3137 c c' C H / ~ H CH+H cH\ c IT CH+ HC*CH3 HC.CLI, Unfortunately the constitution of carvol as a benzene-derivative is not fully established for its conversion into carvacrol is attended by :a very energetic reaction in the course of which we may well believe that a profound alteration of structure occurs. Wallach has shown in a very plausible way how the polymerisation of isoprene C,H (assumed to be CH,:C(CH,)*CH:CH,) into dipen-tene may be accounted for by a similar formula. I do not agree with him in some points of detail for example in his statement that pinenes contain only one double bond for as shown on R previous page the pinenes combine with the same amount of bromine as the citrenes and they form with hjdrochloric acid the same dihy THE TERPENES ASD OF BENZESE.885 drochloride. Neither can I accept his formula for solid camphene, which certainly contains no double bond at all as testitied by its i n -difference to bromine. But I am glad to observe that he adopts the view which I have so long maintained that pinene (turpentine oil " keiu gewohnliches Hydrocymol ist " (Ann. 239 48). The formulae for the terpenes range themselves under sevcral t,ypes, which represent them all as containing two double bonds such as are conveniently called ethylenic bonds. The most probable of these are represented as follows in which R and R' stand for the t w o groups methyl and propyl.Of course okhers may be conceived as for example by exchange of position by R and R' in 1. A t present however we do not know whether all the different species have yet been recognised. There may be other isotnerides which must hereafter be taken into account and there is very lithle to guide us in assigning to each known hydrocarbon its appropriate formula. It will be sufficient therefore if I indicate the manner in which they may be used by rcference to one example. Adopting a formula of type I for turpentine-and indicating the asymmetric atom of carbon which it contains by ,z black-faced letter its transformation into the monohydrochloride and t h i s subsequently into camphene and campbor may be represented by the following formule : 886 TILDEN THE COXSTITUTIOS OF But it will naturally be remarked that such formule as these, which have been proposed for the terpenes are the accepted formuh for derivatives of benzene.Oppenheim’s formula ‘or turpentine which is identical with that given above except that the positions of the methyl and propyl are reversed was deliberately contrived for the purpose of exhibiting the relation of turpentine to barizene as indicated by its conversion into cymene. The conclusion t o which we are impelled is that Kekul6’s formula for benzene must be abandoned. If the evidence for this con-clusion rested solely upon our present imperfect knowledge of the terpenes it would of course possess but little value.This however is not the case. The chief objection which has been raised against Reknl6’s formula, namely that the positions 1 2 and 1 6 are not identical has been met by a well-known hypothesis due to Kekul6 himself. That hypothesis has very little probability in its favour but whether that explanation is now generally accepted is not of great importance in the presence of anot’her objection which has not been so generally recognised as I think it deserves to be. KekulB’s formula represents benzene as containing three times over the same kind of linking of the carbon atoms which we must admit in the case of ethylene, VIZ. :- -c=c-. It is characteristic of this grouping that it is associated with the capacity for instantaneous combination with bromine with tjhe liydracids &c.In benzene we have a compound which exhibits no trace of this character. Bromine dissolves in benzene without form-ing addition products after the mariner of the olefines and other hydrocarbons in which we assume the existence of double or treble linking and only under exceptional circumstances are these addition products formed. In the formuk of many aromatic compounds the same symbol is used to represent two distinct functions. Thus in cinnamic acid for example THE TERPESES AND OF THE BESZENES. 887 CH CH/\C-CH= CH -CO~H CAI ICH ‘.c//H the atoms of carbon united by two bonds in the side-chain combixe instantly with HBr or HI with Br2 or with HC10. They are in fact strictly et’hylenic in character. The two double bonds in the hexagon correspond to nothing of the kind for they do not unite in the same way under similar circumstances.Doubtless most chemists have been in the habit of indulging in a mental reservation as to the significance of the double bond in a closed chain. This however, does not justify the employment of the same symbol to express two different things. Again when benzene and its homologues are submitted to oxidation, the six carbon atoms remain very persistently united and a series of acids containing a nucleus of Cs results. I n other cases where double linking unquestionably occurs i t seems very often to be a point of weakness the carbon atoms thus united separating more readily than those which are united by single bonds. Ally1 alcohol for example, gives by the action of dilute nitric acid formic (or carbonic) and oxalic acids.Now this splitting up of the double bonds in a forniuln like that which Kekulh attributed to benzene ought to yield abund-ance of oxalic acid. This is what the terpenes do but which benzene and its homologues do not. v. Baejer in some important papers (Bey. 19 1797 and more recently Anrcalen 245 103) describes the remarkable properties of the hydroterepht,halic acids and points out that these compounds no loriger possess the character of benzene derivatives but in spite of the ring-like arrangement of the carbon atoms their chemical nature indicates that they must be regarded as compounds of the fatty series. There is in fact the same sort of relation between the properties of terephthslic acid and dihydroterephthalic acid that there is bet ween cymene and the terpenes.I n order to explain the peculiarities of the hydroterephthalic acids, v. Rae-yer proposes a theory which seems to be nearly identical with that enunciated by Armstrong about a year previously (Phil. Mag., Feb. 1887). I n benzene and its immediate derivatives he assumes that the six carbon atoms form a symmetrical figure. One unit of valency of each draws the carbon atoms towards the centre of the ring but v. Baeyer expressly states that they must not be assumed to be free in the ordinary sense neither are opposite carbons united together the central unit’s of valency are only to be regarded as passive. It seems to me as already pointed out by Ladenbur 888 TILDEN THE CONSTITUTION OF THE TERPENES ETC.(AnnuZen 246 382) very difficult if not impossible to distinguish this formula from the diagonal formula of Claus. I do not tliink tlie present state of knowledge in regard to this matter enables us to state more than the following propositions :-1. The six atoms of carbon in benzene form a very stable group, which is not easily broken up by heat or by chemical agents. 2. The carbon atoms are all in the same condition and the hydrogen is distributed equally among them. 3. The carbon atoms are not united together by ethylenic bonds. 4. There are three and only three disubstitution-derivatives. Either of the formulae of Claus of v. Baeyer of Armstrong or the prism of Ladenburg satisfies these conditions but a t present there seems no solid reason for preferring one before the other.With regard to the Claus formula v. Baeyer has already pointed out that in any ring-like arrangement the carbons in the pya-position must be further apart than those in the oi-tho-position and hence the existence of three isomeric diderivatives may be accounted for. Briihl’s two recent papers on the terpenes and their derivatives (Bey. 21) contain suggestions as to the constitution of the terpenes, based upon the observation of their refraction equivalents. These p,ipers have been already very severely criticised by W allach (Annulen, 245 121) and I need only add that I agree with the latter in thinking that much reliance cannot be placed upon the recorded values of the refraction equivalents in this group of compounds by reason of the more than doubtful puritly of many of the substances operated upon.And when the conclusions are in direct conflict with those derived from the most obvious chemical properties as for example when the saturating power of camphene which is untouched by bromine is represented as being the same as that of terebenthene, which instantly combines with four atoms of bromine all we can do is to wait for further information as to their optical properties and the relation in which these stand to chemical constitution. Evidence from other sources so far as it is available supports the view that I have adopted. Thus Hartley (Proc. R o y . Soc. 1879, 29 290) found that australene terebenthene and hesperidene gave none of the bands which are exhibited in the spectrum of tlie ulf ra-violet by cymene and other undoubted benzenoid compounds. And from Abney and Festing’s (Phil. Trans. 1881) observations at the opposite extremity of the spectrum the crucial line 867 with its attendant band characteristic of benzene-derivatives is not seen in the absorption-spectrum of turpentine

ISSN:0368-1645    

DOI:10.1039/CT8885300879

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

889 LXX V.- Combustion by 3Ienn.s of Chromic Aizhydyide. By C. F. CROSS and E. J. BEVAN. SONE time since we published a preliminary note of results obtained on the combustion of carbohydrates with chromic anhydride and sulphuric acid as a method of ultimate analysis (Chem. News Octo-ber 23 1885). Having observed that carbonic oxide was formed and evolved with the carbonic anhydride we found it necessary to abandon gravimetric methods and to measure the volume of the evolved gas the proportion of carbon per unit of volunie being inde-pendent of the ratio CO CO,. We have employed mercury as the confining liquid and an apparatus consisting of a U -tube graduated in the one limb which is in connection with the combustion flask the other limb being open to the air and connected with a reservoir of mercury by means of which the levels are adjusted for reading (Rep.A n d Chern. 1887 37). In some cases we have employed a Lunge's nitrometer but the particular form of apparatus to be employed for the purpose is rather a matter of detail. Before proceeding to deal with the results obtained we must briefly notice a well-known paper of Ladeiiburg's published in 1865 ( A r m a h , 135 l) on the subject of ultimate analysis by the few methods other than incandescent combustion which are available. In this paper we find chromic acid mentioned but dismissed as unavailable by reason of its decomposition on heating with sulphuric acid with evolution of oxygen. This decomposition was specially studied by one of us (Cross and Higgin Trans.1882 113) with the result of showing that it took place only at high temperatures the evolution of oxygen being imperceptible up to a temperature some degrees above loo" and becoming brisk only as the boiling point of the acid was reached. At the same time it was noticed that) the course of the de-composition differed somewhat when potassium dichromate was snbstituted for the chromic anhydride taking place more readily and yielding a sulphate of different character and composition. Laden-burg having dismissed chromic acid apparently as a result of a general impression of its instability finally selected iodic acid added in the form of silver iodate to the sulphuric acid used as the liquid auxiliary. His combustions were performed with this mixture in sealed tubes, and his estimations consisted in determining the loss of weight after complctely removing the gaseous products and the total oxygen consumed.The results he obtained leave nothing to be desired in point of accuracy and we can only conclude that it is the trouble an 890 CROSS AKD BEVAN COMBUSTION risk attending operations wit,h sealed tubes which have deterred chemists from adopting this method. On the other hand with an open combustion such as that we have employed the operation is a very simple one completed in a few minutes and if proved to be accurate would be a useful addition to our laboratory methods even if its applications were limit,ed. But apart from any question of application the results of such combns-tions partial for certain groups of compounds complete in others, cannot fail to throw some light on the problems of the molecular coiistitution of carbon compounds.We shall therefore in the mean-time content ourselves with recording the results obtained and leave it to the progress of research to determine their value. The proportion of carbonic oxide formed i n the combustion of the carbohydrates depends very much upon the conditions of the decom-position. We have found under those which we have perhaps arbitrarily selected that it is reduced to a minimum ; this being so, and a strict uniformity in the conditions being observed the “ error of the apparatm ” we find satisfactorily constant. The conditions we may note here are :-(1) A quantity of substance to be used yielding from 90 to 100 C.C.of gas; (2) the same volume of sulphuric acid, namely 9 c.c. must be employed ; ( 3 ) an excess of chromic acid of about 30 per cent. beyond that required for complete combustion. The substance cellulose for example being dissolved in the acid, and the chromic anhydride introduced in a small tube into the neck of the flask the latter is connected in the horizontal position with the U -tube and after a suitable interval the level of the mercury is brought to zero The thermometer having been read off the tube containing the chromic anhydride is allowed to fall to the bottom of the flask, and is well shaken with the acid solution. The combustion proceeds rapidly the temperature rising to 60-70” ; after about two-thirds of the gas has been collected it is necessary t o apply heat the remainder of the gas being rapidly expelled a t 100”.The conclusion of the combustion is well marked by the cessation of the frothing which ac-companies the evolution of the gas in the viscous medium. The flask is allowed to cool and the gas volume read off with the usual pre-cautions. If again heated and a second reading taken after cooling, it will be found identical with the first. We may take this together with the numerical results about to be described as sufficient evidence of the stability of the chromic anhydride under the conditions of the combustion. But we shall revert subsequently and more specifically to this point. I n order to “standardise” the apparatus and to determine the error due to the absorption of carbouic acid we made several series of combustions of oxalic acid.We may cite the results of one of these BY MEAXS OF CHROMIC ASHTDR1L)E. 891 consisting of 16 experiments. The weight of substance taken varied from 0.05 gram to 0-2s gram. The mean percentlage of cmbon caleu-lated from the gas volume obtained was 26.0 (C2H20 = 26*6) with a probable error for a single observation of The absorption of GO by H2SOa is 0.75 vol. at ordinary tempera-tures. After reading off and allowing an interval of some minutes before taking a second reading we found that the latter showed no perceptible difference. But after half an hour a difference of level was matnifest; in two hours the diminution of volume amounted to from 3-5 C.C. This is no doubt attributable to a gradual absorption of the gas by the acid.The absorption therefore under the con-ditions of observation adopted is only a fraction of the theoretical maximum and as we find about 217. Supposing this absorption constant and the quantity of substance weighed for combustion to 0.2 per cent. --Cellulose. Swedish filter-paper . Oxalic A c i d . Citric Acid. . Qly cerim Phthalic Acid Salicylic Acid. . Phthalic Anhydride . . Benzoic Acid Weight taken. { 0'1341 0 *1143 U -1147 0 '1280 (0 '1344 0 '1305 0 -1750 0 * 2080 0 a2020 0.1625 0 '1337 0 * 0962 0 -0966 0 -0945 0 *0881 0 -0922 0.0895 0 -0860 1 i { { Gas Polume cor-rected to 0" arid 760 mm. 94'6 C.C. 94.1 ,, 94.5 ), 93.5 ), 94-0 )) 94.9 ) ) 104.3 ), 66.1 )) 64-0 ,, 86.2 ), 102.2 )) 98 *O .>, 108-9 ,, 92.6 ), 101'6 ,, 108% ,, 104.8 ,, 105'0 ,, 109 -0 )) 113-1 ), 107 '5 )) Percentage carbon.Found." 44 -0 43 -6 43.4 43.9 44 .O 44 -3 43 -6 26.3 26 *2 26 -3 26 - 2 26 -0 35-9 37.1 56 *6 60 '2 59 -4 63 -8 63 -8 67 -8 67.8 * The correction t o be applied to these calculated numbers will be dealt with subsequently 892 CROSS AND BEVAN COMBUSTION vary the error in defect should vary in inverse proportion. We found the evidences of such a variation in our numbers but the pro-portion was not sufficiently strict to be made the basis of a correction. We therefore found it necessary to eliminate the variation of the gas volume. Keeping this within the limits of 80-110 c.c.and com-paring substances of varying carbon percentage we find that the error is with sufficient approximation directly proportioned to the carbon percentage. We give a selection of results (p. SSl) obtained in series showing the degree of approximation attainable in combustion according to t.his method. A very large number of our earlier determinations were made with quantities of substance yielding gas volumes varying from 50-120 C.C. We do not think it necessary to reproduce these since they merely serve to indicate the conditions necessary to secure a constant error. Under these conditions already defined the error may be empirically expressed by the following fmction : x 0.4 Carbon percentage of substance 25 _ l _ l _ _ ~ . that is the percentage calculated from the gas volume must be in-creased by this amount to give the true percentage.I n order to in-vestigate the process from the point of view of the oxidising substance the following combustions of cellulose purified bleached cotton were carried out under the above conditions but with a weighed quantity of pot'assium dichromate in excess. The residual chromic acid was determined by titration with ferrous sulphate in the usual way. The chromic acid used is expressed as the equivalenf, of oxygen ; the quantity necessary for complete combustion to COz is given side by side for comparison:-Weight of Oxygen Oxygen to eel lulo ye. consuined. burn to C02. CO coa. 0.1805 0*2010 0.21U7 0.01.69 0.2630 0.1803 0.2060 0.2106 0.0080 0.2770 0.1~40 0.2126 0 2297 0.0294 0.2865 (a.) 0.1164 0.1350 0.1387 0.0065 0.18C5 (6.) 0.1120 0.1300 0.1325 0.0044 0.1755 I n the two latter the combustion-was carried out in connection with the gas collecting apparatus ; the following were the volumes estimated corrected to 0" and 760 mm.(a) 94.5 = 43.5 C per cent. (b.) 91.4 = 43.6 , BY MEANS OF CHROMIC ANHYDRIDE. 893 Taking the mean of these we may apply the correction as above described :-43-55 + 7 43*.55 x 0.4 = 44.25 per cent. carbon. 2a These numbers indicate a complete cornbustion to gaseous products, in which t8he proportion of carbonic oxide is very small. The forma-tion of carbonic oxide we had verified at the time of publishing our first communication by finding a combustible gas burning with the characteristic blue flame left after absorbing the carbonic acid by potash; the quantity of cellulose treated for the purpose being sufficient to yield 500 C.C.of gas. We have since made two observa-t,ions on the gases evolved (u) in the earlier stages ( b ) in the latter stages of the combustion under the conditions obtaining in our quantitative experiments :-(a) 40.5 C.C. treated with Cu2Cl in HCl gave a contraction of (b.) 30.8 C.C. treated with KOH gave a contraction of 30.4 C.C. The corresponding ratio by weight are ( a ) 1 24 The proportion of CO therefore varies with the conditions of the combustion. We have now briefly to notice those cases in which our investiga-tions have shown that the combustion is partial these are more particularly acids of the fatty series and compounds containing nitrogen.Combustions of palmitic and stcaric acids with chromic anhydride yielded from 60-70 per cent. carbon in t'he form of gaseous products, and the results are variable. The partial nature of the combustion is referable t o molecular structure rather than to the relatively large pro-portion of carbon far we have obtained good results with rromatic compounds containing as much as 90 per cent. of carbon. The second group of compounds which only partially burns is that of the organic bases. We propose to investigate this subject further : i t is probable that useful information will be pined by a study of the residual products of combustion. It is worthy of note that under the conditions we have described urea is not attacked.In the course of this research we have made a number of observa-tions on the behaviour of chromic anhydride and potassium dichromate when heated with sulphuric acid. 2.5 C.C. co. co,. co. co,. ( b ) 1 117. We may cite the following :-(a) 0.010 gram G O 3 heated at 100" with 9 C.C. sulphuric acid for three hours. No appreciable reduction 89.2 CROSS ASD REVAX COMBUSTION (b.) 0.300 Cr03 heated with 9 C.C. H,SO1 a t 100" one hour flask connected to gas apparatus. Increase of vol. a t 16" (corr.) 0.75 C.C. ( c . ) 0.300 K,CrzO7 heated with 9 C.C. H?SO two hours a t 105"; residual K,Cr,O,-estimated with FeS04-0.286 ; 0.014 decom-posed in two hours. (d.) 0,590 K2Cr2O7 heated with 9 C.C. H,SO1 two hours a t 105". Residual KZCr,O7 determined 0.5700.( e . ) 1.574 K,Cr,O7 heated with 9 C.C. H2S04 two hours a t 105". Cr,O formed 0.101. (f.) 1-904 CrO? heated with 9 C.C. H,SO two hours at 105O. Cr,Os formed 0.085. Eqt. of 0 evolved 0.0023. 0.020 decomposed. These results are sufficient to show that the instability* of the chromic anhydride begins to be manifest a t 105" ; the decomposition however even at this temperature is extremely slow. It is more rapid with the dichromate than the anhydride and in both cases, increases with the mass. The explanation of this we take to be that the portion remaining undissolved is more liable to decomposition than that dissolved in the acid. It i H t o be observed however that the conditions in the blank experiments above cited differ from those in the combustion process by the absence of the sesquioxide and the presence of a large proportion of undissolved trioxide.The sesquioxide is peroxidised by the ttrioxide as is well known and its presence therefore is an additional element of stability. Finding no mention of investigations of the oxidation of the sesquioxide in presence of sulphizric acid we made observations on this po!'ntl. We find that it is rapidly oxidised to the trioxide by permangannte under this condition ; also though lcss rapidly by manganese dioxide. The comparative stability of the trioxide under the conditions of the combustion is probably therefore due in part to the presence of the sesquioxide as also to the relatively small mass of residual trioxide, and its being dissolved in the acid solution.We made observations on the stability of t'he acid mixture which remained a t the conclusion of a combustion of 0.14 gram of cellulose. (9.) The combustion having been finished by raising the tempera-ture to go" and agitating until no rncre frothing appeared the acid solution (9 c.c.) was sealed in a tube of 20 C.C. capacity. This as heated at 104" for 1 hour. The tube after cooling, was opened in gas-tight connection with a U-tube of mercu1.y. A difference of level of 6 mm. was observed. The total rolume * The anhydride heated by itself begins to decompose at 250" BY NEANS OF CHROMIC ANHYDRIDE. 895 between the sulphuric acid in the tube and the mercury in the U-tube being 30 c.c. the increase of gas in the tube is 0.3 C.C. at 15". (h.) The tube was again sealed and heated for two hours a t 100" The difference of level in the U-t'ube on opening it after cool-ing was 40 mm.; the corresponding increase of volume in the tube 1.6 C.C. (i.) Again sealed and heated for two hours a t 190" the gas evolved in the tube amounted to 2.3 C.C. G.) A similar mixture of sulphuric acid chromic sulphate and chromic anhydride was heated in a flask connected with a gas apparatus as in a combustion for 14 hours a t 105". The in-crease of volume was 3 C.C. These experiments are sufficient to show that the error due to de-composition of the chromic anhydride during the compnrat'irely short period of heating necessary to complete the combustion is so small that it may be neglected. We wish to express oui- thanks to our friends Mr. R. Merrirnan for his assistance in the research and to Mr. A. Green for kindly supplying pure preparations for analysis

ISSN:0368-1645    

DOI:10.1039/CT8885300889

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

INDEX OF AUTHORS’ NAMES, T R A N S A C T I 0 N S. 18 8 8’. A. Adie R. H. Armstrong H. E. note on electrolytic conduction and on the evidence of a change in the constitution of water, 125. See M. M. P. Muir. B. Bailey 8. H. and 8. J. Fowler, some reactions of the halogen acids, 755. Ball E. J. the alloys of copper and antimony and of copper and tin, 167. Bevan E. J. Bloxsm C. L. obituary notice of, 508. Bothamley C. H. reduction of potas-sium dichromate by oxalic acid 159. Bothamley.C.H.,and G.R. Thomp-son estimation of chlorates by means of the zinc-copper couple 164. Boussingault J. B. J. D. obituary notice of 509. B r a u n e r B. density of cerium sul-phate solutions 357. B r a u n e r B.,and F. TomiEek action of hydrogen sulphide on arsenic acid, 145.Brown H. T. and Gt. H. Morris, determination of the molecular weights of the carbohydrates 610. See C. F. Cross. C. Carnegie,D. J.,actionof finely divided metals on solutions of ferric salts : rapid method for the titration of the latter 468. Carnegie D. J. See S. Rnhemann. Carnelley T. and A. Thomson, the solubility of isomeric organic com-TOL. LIIT. pounds and of mixtures of sodium and potassium nitrates and the relation of solubility to fusibility 782. Carnelley T. and J. Walker the dehydration of metallic hydroxides by heat with special reference to the polymerisation of the oxides and to the periodio law 59. Col 1 ie N. action of heat on the salts of tetramethylphosphonium 636. - on a new method of preparing tertiary phosphines ’714.Collie N. Colmau H. Gt. and W. H. P e r k i n , jun. synthetical formation of closed carbon-chains. Part 111 (cofit.). Some derivatives of pentamethylene, 185. Couldridge W. interactions of nitro-gen chlorophosphide 398. C r o m p t on H. an extension of Mend-el6eff’s theory of solution to the dis-cussion of the electrical conductivity of aqueous solutions 116. Cross C. F. and E. J. Bevan com-bust,ion by means of chromic anhy-dride 889. See C. M. Thomp-son W. Shenstone. See also A. Lawson. Cundall J. T. D. Day T. C. new method of estimating nitrites either alone or in presence of nitrates or chlorides 422. D e bu s H. chemical investigation of Wackenroder’s solution and explana-tion of the formation of its constitu-ents 278.Divers E. and M. Eawakita on the composition of Japanese bird-lime, 268. D i x on A. E. action of isothiocyanates on the aldehyde-ammonias 411. Duff y P. obituary notice of 513. 3 898 INDEX OF AUTHORS. Dunstan W. R. and T. S. Dymond, on the alleged existence of a second nitroethane 134. Dymond T. S. See W. R. Dunstan. E. E a s t F. J. Edeleanu L. some derivatives of phenglmethacrylic acid 558. E l l i o t t W. J. See S. Ruhemann, C. M. S t u a r t . E l s w o r t h y H. S. note on a modifica-tion of Traube’s “ capillarimeter,” 102. See R. Meldola. F. Fowler G. J. F r a n k l a n d P. F.,a gasometric method of determining nitrous acid 364. - action of some specific micro-organ-isms on nitric acid 373. Freer P.C. and W. H. Perkin jun., synthetical formation of closed carbon-chains. Part V. Bxperiments on the synthesis of heptamethylene-deriva-tives 215. - synthetical formation of closed carbon-chains. Part IV. Some de-rivatives of hexamethylene 202. See G. H. Bailey. G. Gladstone J. H. and W. H i b b e r t , the optical and chemical properties of caoutchouc 679. G o t t B. S. and M. M. P. Muir bis-muth iodide and bismuth fluoride, 137. H. Hamblv F. J. See Thorpe. H a r t l e i W. N. proof of the identity of natural and artificial salicylic acid, 664. - researches on the rehtion between the molecular structure of carbon com-pounds and their absorption spectra. Part IX. On isomeric cresols di-hydroxybenzenes and hydroxybenzoic acids 641.H i b b e r t W. See J. H. Gladstone. Humpidge T. S. obituary notice of, H u n t l y G. N. 513. See F. R. J a p p . J. Ja.pp F. R. and G.N.Huntly,action of phenylhydrazine on an unsaturated y-diket,one 184. J a p p F. R.,and F. Elingemann the constitution of certain so-called mixed azo-compounds 519. K. Kawakite M. See E. Divers. Kigping F. S. synthetical formation of closed carbon-chains in the aromatic series. Part 11 21. Klingemann F. See F. R. J a p p . L. Laurie A. P. the constitution of the copper-zinc and copper-tin alloys, 104. Lawson A. and N. Collie the action of heat on the salts of tetramethyl-ammonium 624. Lewkowitsch J. the rotatory power of benzene-derivatives 781. Loeb M. the niolecular weight of iodine in its solutions 805.-. the use of aniline as an absorbent of cyanogen in gas analysis 812. M. Marshall W. See T. Purdie. Meldola R. and F. J. East re-searches on the constitution of azo- and diazo-compounds. Compounds of the naphthalene @-series 460. Meldola R. and E. H. R. Salmon, some amines and aruides derived from the nitranilines 774. Meldola R. and F. W. S t r e a t f e i l d , researches on the constitution of azo-and diazo-derivatires IT. Diazo-amido-compounds (cont.) 664. Morris G. H. Muir M. M. P. and R. H. Adie the interaction of zinc and sulphuric acid, 47. See also B. S.Gott. See H. T. Brown. Muir M. M. P. N. Nef J. U. carboxyl-derivatives of benzoquinone 428 INDEX OF AUTHORS. 829 Nilson L. F. and 0. P e t t e r s s o n , on two new chlorides of indium and on the vapour-density of the chlo-rides of indium gallium iron and chromium 814.P. Perkin A. Gt. and W. H. P e r k i n , jun. on some derivativea of anthra-quinone 831. P e r k i n W. H. sen. chlorofumaric and chloromalei'c acids and the mag-netic rotatory power of some of their derivatives 695. - magnetic rotatory power of some of the unsaturated bibasic acids and their derivatives also of mesityl oxide 561. - on an apparatus for maintaining a constant pressure when distilling under reduced pressure 689. P e r k i n W. H. jun. synthetical for-mation of closed carbon-chains. Part I. On some derivatives of hydrindo-naphthene and tetrahydronaphthsl-ene 1. See also H. G. Colmau P. C. P r e e r .P e r k i n W. H. jun. P e t t e r s s o u 0. See L. F. Nilson. Pickering S. U. heat of dissolution of substances in different liquids and its bearing on the explanation of the heat of neutralisation and on the theory of residual valency 865. P u r d i e T. and W. M a r s h a l l action of alcohols on ethereal salts in pre-sence of small quantities of sodium alkyloxides 391. R. Ram s ay W. the molecular weights of nitrogen trioxide and nitrogen per-oxide 621. Reynolds E. J. the action of bromine on potassium ferricjanide '767. R ey n o Id s J. E. researches on silicon compounds and their derivatives. Part 111. The action of silicon tetra-bromide on allyl- and phenyl-thio-carbarnides. Part IV. The action of ethyl alcohol on the compound (H,XN,CS)&3iBr4 853.Rodger J. W. Riicker A. W. on the range of mole-See T. E. Thorpe. cular forces 222. Ruhemann S. and D. J. Carnegie, action of acetone on ammonium salts of fatty acids in presence of dehydrat-ing agents 424. Ruhemann S. and W. J. E l l i o t t , the isonitrile of phenylhydrazine, 850. See also 8. Skinner. Ruhemann S. S. Salmon E. H. R. Schunck E. on the supposed identity of rutin and quercitrin 262. Shenstone W. A. and J. T. Cun-d a 11 the influence of temperature on the composition and solubility of hydrated calcium sulphate and of calcium hydroxide 541. Skinner S. and 8. Ruhemann ac-tion of phenylhydrazine on urea and some of its derivatives 550. See R. Meldola. S m i t h W. J. S t r e a t f e i l d F.W. SeeR. Meldola. S t u a r t C. M. action of phosphorus pentachloride on salicylaldehpde 402. - halogen substituted deriratives of benzalmalonic acid 140. S t u a r t C. M. and W. J. E l l i o t t the action of chromium osychloride on ortho-substituted toluenes 803. See T. E. Thorpe. T. Thompson C. M.,and J.T. Cundall, the action of potassium on tetralk-jl-ammonium iodides '761. Thompson G. R. See C. ZI. B o t -hamle y. Thomson A. See T. Carnelley. Thorpe T. E. and F. J. Hambly, note on Chatard's method for the estimation of small quantities of manganese 182. - on manganese trioxide 175. - the rapour-density of hydro-fiuoric acid '765. Thorpe T. E. and J. W. Rodger, thiophosphoryl fluoride 766. Thorpe T. E. and W. J. S m i t h on morindon 171. Tilden W. A. the constitution of the terpenes and of benzenes 879. TomiEek F. See B. B r a u n e r . T u r n e r T. the influence of silicon on the properties of iron and steel. Part 11 844 900 INDEX OF AUTHORS. w. W a l k e r J. See T. Carnelley. Wayd W. S. obituary notice of 518. W ar i n g t 0 n R. the chemical action of some micro-organisms 727. W e r n e r E. A. chromorganic acids. Part 11. Chromoxalates. Red sel ies, 404. - oxidation of oxalic acid by potas-sium dichromate 602

ISSN:0368-1645    

DOI:10.1039/CT8885300897

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

INDEX OF SUBJECTS. T R A N S A C TI 0 N S. 18 8 8. A. Acetanilide aclion of beiizoic chloride on 780. Acetic acid electrical eonductirity of solutions of 122. Acetoacetic acid action of diazobenzene chloride on 538. Acetone action of on the ammoniiim salts of fatty acids in the presence of dehydrating agents 424. Acetopropyl alcoLlo1 constitution of, 189. AcetylpyruvaldehSdrazoiie 526. Acids bibasic magnetic rotatory power Action moleculai* the radius of 226. Alcohols action of on ethereal salts in presence of small quantities of sodinm alkploxides 391. Aldehyde-ammonia action of isotliio-cyanates on 411. Aldehydrazone action of heat on 542. Allyltliiocarbamide action of silicon Allylthiocarhimide action of aldehyde-Aluminium group valency of elements - hydroxide dehydration of by Aniides derived from the nitranilines 774.Amines derived from nitranilines 774. Ammonium chlorof umarate 699. Anliydracetophenonebenzil action of Aiinual General Meeting March 28th, Anthraquinone derivatives of 831. Anthraquinonemonosulphonate exam-ination of the products obtained in the dry distillation of the sodium salt of 831. Antimonious acid dehydration of b y heat 72 86. of 5G1. tetmbromide on 853. ammonia on 41 5. of the 825. heat 74 87. phenylhjdrazine on 184. 1888 479. Antimony-copper nllops 167. di*abinose molecular weight of 619. Arsenic 'wid iwtion of hydrogen sul-dzo- and diazo-derivatives constitut,ioii Azo-compounds mixed constitution of dzo-deriratires researches on the con-pliicle on 1435.of 460. certain so-called 519. stitut,ion of 664. B. Bacillus$fEoccu.s 729. - intestini 729. - szdplmrezis 730. - tardewesceias 731. - toruliformis 730. Balance Sheet o+ the Chemical Society from March 21st 1887 to RIarcli 21st. 1858 506. - of the Research Fund from March 21st 1887 to March Zlst, 1885 507. Eenzalninlonic acid chloro- broino- arid iodo- 141. - orthonitro- reduction of 143. - - substitution derivatives of, Benzene constitution of 870. Benzene-azo-acetone introduction of monad radicles into 525. Benzeneazo-/3-naphthol metanitro-, acetyl-derivatives of 464. Benzeneazo-P-naphtliyl acetate 4G6. Benzeneiizo-P-naphtli~-lain~iie nietani-tro- action of nitrous acid on 463. Benzene-cieriratives rotatory power of, 781.Benzene-a-hydrazobutpric acid 53s. Benzoyuinone carboxyl-derivatives of, Benzylacetanilide '780. 140. 42s. 3 Q 902 INDEX OF SUBJECTS. Beiiz~lacetyl.lparaiiitraniiilide 779. Benzylbenzo ylpamnitranilidc iS0. Beiizylsuccinic acid 10. BenzSlthiocarbiiiiidc action of aldehgde-- action of raleraldchycle-ammonia Bird-lime Japanese composition of 265. Bismuth fluoride 138. - hydroxide dehydration of by heat, - iodide 137. Bisiiiuthgl fluoride 139. Bromine heat of dissolution of in ammonia on 411. on 413. 72 86. various solvents 874 877. C. Calcium hydroxide influence of tem-perature on the composition and solu-bilitj of 550. - sulphate influence of temperature on the cornposition and solubility of, 554. Caoutchouc action of l.~alogcns on 6S2..- acbtion of heat on 686. - from Japanese bird-lime 270. - optical and chemical properties of, Capillarimeter modification of 102. Carbaiiiide and its derivatives action of Carbohgdmtes cleterniinatilm of tlic Carbon-chains closed syiithet ical for-- sjnthetical forniation of in Catechol absorption-spectra of 650. Cerium dioxide hydrated dehydration - sulpliate solutions density of 357. Cl:lorates estimation of by the zinc-Clrroniic anliTdr'icle conibustioii by Chranii~uiii dichloride vapour-density - trichloride rapour-density of 529. Clironi-organic acids 404. Chromoxalates red series 404. Citmconic acid magnetic rotatory power - anhj dricle magnetic rotatory p o ~ er Cobaltic hj droside dehydration of b j Conibnstion by means of chroniic anhy-C'oppcr pentathioriate 300.679. plienylhgdraziiie 011. 550. inolecular weights of. 610. ination of 1 21 185 202 215. the aromatic series 21. of by heat 70 84. copper couple 164. niediis of 889. of 830. of 580 591. of 576 596. heat 78 90. drldc 889. Copper-antimony and copper-tin alloys, Copper-tin and copper-zinc alloys con-Cresol phosphate dichlorortho- 403. Creaols absorption-spectra of 643. Cyanogen use of aniline as an absorbent 167. stitution of lo&. of in gas analysis 812. D. I) ehydro triacetoniniine 426. Dextrose molecular weight of 614. Diacetylparat olylosazone. 543. Diazoamidobenzene dinitrodibromo-, - paradichloro- and its ethyl-deriva-Diazoamidobenzenes meta- and para-Diazottmido-compounds 664.Diazo-derivatives researches on the con-Dibenzylethjlphosphine 725. Diethylbenzylphosphine 723. Diethyldibenzylpliosphonium chloride, ~jetligliso:~~iiiylpliospliine 722. ~ietli~lrnc~tliylpliosphine 719. Dietliylpropylpliosphine 721. IMiydroxydur~-lic acid 435. 1)iliyrlroxy~~yromellitic acid 453. Diketone y- unsaturated action of I)iiiietliyldietliylphosplionium chloride, Dinietliylethylphosphine 720. Diphenylcarbazide 551. Diphenylthiocarbamide action of silicon tetrabromide on 857. Distillation under reduced pressure ap-paratus for maintaining a constant pressure during 689. 669. tivc 670. dinitro- methylation of 666. stitution of 664. action of heat on 724. phenylhydrazinc on 184. action of heat on 720. Duroquinone 430.Dnrylic acid diamido- 433. DurSlic-acid-quinoiie 434. E. Electrical conductivity of aqueous solu-Electrolj-tic conduction 125. Ethacetoucetic acid action of diazo-bmzcne chloride on 540. Ethane nitro- con-existence of a second, 134. Ethereal salts action of alcohols on in presence of sinall quantities of socliuin dioxides 391. tions 116 INDEX O F SUBJECTS. 903 E t h j l acetate reaction of with isoamyl - reaction of with isobutyl - acetoacetate action of diazo-salts - action of methylpentamethyl-- acetylmethylhexametlqlenecarb-- hydrolysis of 213. - acetylmethylpentamethylenecarb-- hydrolysis of 198. - alcohol action of on the com-- broniomethylpentamethyleneaceto-- chlorofumarate 700. - action of ammonia on 702. - chloromaleate 708.- citraconate magnetic rotatory power of 581 591. _- diacetyldiamidopyroiellitate 446. - diainido pyromellitate 443. - dihydroxydurylate 437. - dihydroxypyromellitate 447. - 1-’a‘adiketohesamethylenetetra-- din itropy romellitate 4 42. - disodisolieptanetetracmboxylate, action of bromine on 220. - etliacetoacetate action of diazo-benzene chloride on 535 537. - fuinarate magnetic rotatory power of 574 592. - glntarate magnetic rotatory power of 567 589. - isolieptanetetracarboxylate 217. - itaconate magnetic 1.0ti1tOl.j power of 584 591. _I- maleate magnetic rotatoi-y power of 572 591. - mesaconate magnetic rotatory power of 585 592. - methacetoacetate action of diazo-benzene chloride on 532. - action of ortho- and of para-diazotoluene chloride on 535, 53’7.ate 206. ate 192. alcohol 395. alcohol 395. on monalkyl-derivatives of 532. ene dibromide on 197. oxylate 212. oxylate 197. pound (SCN,H,),SiBr, 857. acetate 211. carboxylate 455. - metliylhesame thylenedicarboxyl-- methylpentame thylenedicarboxyl-___ plienglenedipropionate (nieta-) 32. - phe nylhy drazoneacetoglyoxylate, iiction of phenjlhydrazinc on 529. - q~iiiioltetracarboxylate 447. - quinonedurjlate 5%. - q~~inoiiepyromellitate 446. - quinonetetracurboxjlate 446. Ethyl sebate magnetic rotatory power of 567 589. - sodacetylenetetracarboxylate ac-tion of benzoic chloride on 10. - xyl~lenedichlorodimalonate (meta-) 26. - (orth-) 14. - (para-) 35. - xylylenedimalonate (meta-) 27. - (ortho-) 16. -- - (para-) 35.Ethylacetylparanitranilide 778. Ethylbenzoylparanitranilide 779. Ethylthiocarbimide action of aldehyde-Ethyltrimethylphosphonium chloride, ammonia on 414. action of heat on 717. F. Ferric hydroxide dehydration of by - salts action of finely divided - rapid method for the titra-Ferrosoferric ferricyaaide 773. Ferrous chloride vapour-density of, Films thin table of properlies of 260. Forces molecular range of 222. Fumaric acid amido- diamide of 703. chloro- 697. ___ chloride chloro- 696. Fumaryl chloride magnetic rotatory Fusibility relation of to solubility 733. heat 76 89. metals on 468. tion of 468. 827. -power of 575 592. G. Gallium clichloride vapour-density of, - t~ichloride mpour-densit,y of 823. Gas analysis use of aniline as xi? ab-Glutaric acid magnetic rotatory power 825.sorbent of cyanogen in 812. of 566 589. H. EIalogeri acids some reactions of 755. Heat of dissolution of substances in Heptamethylene-deriratives experi-Hexamethylene-derivatives 202. Hydrazones of a-ketonic acids forrna-different liquids 865. ments on the synthesis of 215. tion of 532 904 INDEX OF SUBJECTS. HJ d rind onaph thenecarboxy lic acid 9. Hvdi,ii7Clonaphtliene-derivatives 1. Hydrindonaphthenedicarboxy lic acid 7 . Hydrofluoric acid vapour-density of, 565. Hydrogen chloride action of on phos-phorous pentoxide 756. - peroxide explanation of the de-coinposition of 326. Hydroxides metallic dehydration of, by heat with special reference to the polymerisation of the oxides and to the periodic law 59.Hydroxybenzoic acid meta- and para-, absorption-spectra of 658. I. Ilicyl alcohol 274. Indium dichloride and its vapour-density 818. - hydroxide deliyhation of by heat 74 88. - monochloride and its papour-density 820. - trichloride and its vapc nr-density, 816. Iodine heat of dissolution of in ~arious soh-ents 8’73 877. - molecular weight of in its solu-tions 805. Iron influence of silicon on the proper-ties of 844. Isonmyl acetate reaction of nitli ethjl alcohol 395. - reaction of with nietliTl al-Isobutyl acrtate reaction of n ith ethyl -__ reaction of with niethjl al-Isoplitlialic arid note on the prepara-Isopropjl alcohol hydrate of 42’7. cohol 394. alcohol 395. COhOI 395. tion of 45.K. Ketonic acids action of diazo-salts on, 538. L. Lead dioxide hydrated dehydration of, by heat 70 85. M. Maleic acid chloro- 706. Maleic acid magnetic rotatoq power of, - anhydride chloro- 703. - magnetic rotatory power of, Mnlonic acid magnetic rotatory power Maltose molecular weight of 617. Manganese Chstard’s method for tile estimation of small quantities of 182. - heptoxide 177. - trioxide 175. Maiinitol molecular weight of 620. Mercuric hydroxide dehydration of bJ heat G4 80. Mercury action of ligdrogen elrloridr, bromide and iodide on in presence of oxygen 759 760. Mesityl oxide magnetic rotatorJ power of 586 591. Methacetoncetic acid action of diazo-benzene chloride 0 1 1 539. Met lioxybenzal cliloi*ide. ort1io- 404.Methoxj benzalmalonic acid 142. Methyl acetate reaction of with iso-- reaction of mith isobntj 1 - citraconate magnetic rotatory - isobutyl ketone magnetic rotatory - mesnconate magnetic rotator? - phenylene~ipropionate (meta-) 33. (para-) 40. Methylacetylmetanitranilicle 777. RIethjlucetylparnnitranilde 776. Methylazelaic acid 218. Methylbenzoj lmetanitraiiilide 7’78. Metli~lbenzoylparanitrsniiilide 776. Methylhexamethylene methyl ketone, Methylhesamethylenecarboxylic acid, Methylhexamethglenedicarboxylic acid, Methylliydl.ocarbostSri1 560. Methylmetanitraniline 777. Methylnitranilines action of diazotised Methglparanitranilinc 775. Methylpentamethylene dibromide 205. - action of sodium on 214. - methyl ketone 198. Metli~lpentamethylenecarbox~lic acid, Methylpeiitamet~ylenedicarboxglic acid, lKethgltetramethylene dibromide 190 -I - action of sodium 011 201.572 591, 56’7 596. of 562 587. amyl alcohol 394. alcohol 395. power of 583 591. power of 586 591. power of 586 592. -213. 208 213. 207. nitranilines on 667. 194. 198. 193 INDEX OF SUBJECTS. 905 Micrococcus gelatinosus '731. Micro-organisms chemical action of - specific action of on nitric acid, Milk chemical action of micro-organisms Milk-sugar molecular weight of 618. Mochyl alcohol 274. Molecular action radius of 226. - forces range of 222. - magnitudes 260. - weight of iodine in its solutions, Morindon 1'71. some 727. 373. on 734. 805. N. Naphthalene (I- azo- and diazo-deriva-Nickelic hydroxide dehydration of by Nitranilines some amines and amides Nitrates reduction of by micro-Nitric acid action of some specific - electrical conductivity of Nitrification 751.Pr'itrites method of esbimating either alone or in presence of nitrates and chlorides 422. Nitrogen chlorophosphide interactions of 399. - peroxide molecular weight of, - trioxide molecular weight of 621. Nitrous acid a gasometric method of tives of 460. heat '79 91. derived from 774. organisms '742. micro-organisms on 373. solutions of 121. 621. determining 364. 0. Organic compounds isomeric solu-Oxalic acid oxidation of with potassium Oxalurhydrazide 556. Oxides polymerisation of 59. Ozone explanation of two properties of, bility of 783. dichromate 159 602.324. P. Pentamethylene-derivatives 185, Pentathionates action of hydrogen sul-phide on 328. Petathionates action of sulphurous acid - characteristic reactions of 297. Pentathionic acid influence of time on the formation of 333. Periodic law in reference to the dehy-dration of metallic hydroxides by heat 59. Phenylenediacetic acid meta- 42. Phenylenediacrylic acid ortho- 14. - para- 41. Phenylenedipropionic acid meta- 32. - ortho- and its tetrabromo-derivative 18. - para- 39. Phenylhydrazine isonitrile of 850. - parabanate 555. Phenylhydrazine-alloxan 557. Phen ylh y drazoneace tog1 y oxy lic acid, action of phenylhydrazine on 530. Phenylhydrazonepyruvic acid action of heat on 541. Phenylisobutyric acid nitramido- 660. Phenylmethacrylic acid derivatives of, Phenylnethjlnitrosamine paranitro,-Phenylpiperyl tliiocarbamide 558.Phenylthiocarbamide action of silicon Phenylthiocarbimide action of alde-- action of valeraldehyde-ammonia Phenyltrimethylammonium iodide ac-Phenylurazole 554. Phosphines tertiary mixed new method Phosphoric acid electrical conductivity Phosphorus pentoxide action of hy -Polythionates action of sulphurous acid - forrnulae of 351. - general reactions of 298. Potassium chlorofumarate 698. - chromoxalate 405. - dichromate reduction of by oxalic - ferricyanide action of bromine on, - hexathionate 303. - hydroxide electrical conductivit,y of solutions of 123. - pentathionate 291. - decomposition of an aqueous on 331. para- 44. -paranitro- 558. -558.775. tetrabromide on 856. hyde-ammonia on 416. on 417. tion of potassium on 763. for the preparation of 714. of solutions of 122. drogen chloride on '756. on 331. acid 159. '767. solution of 311 906 INDEX OF SUBJECTS. Potassium polythionates behaviour of, in aqueous solution 319. - reactions of solutions of with acids 316. - tetrathionate decomposition of an aqueous solution of 311. c_ thiosulphate reaction of with sul-phurous acid 343. - trithionate decomposition of an aqueous solution of 313. Pressure constant apparatus for main-taining when distilling under reduced pressure 689. Propionglacetylhydrazone 540. Propyl succinate magnetic rotatory Propyltriethylphosphonium chloride, Pseudocumoquinol nitro- 438. Pseudocumoquinone nitro- 438.Pyromellitic acid dinitro- 439. Pyrotartaric anhydride and chloride, magnetic rotatory power of 564 589. Pyruvaldehydrazone action of phenyl-hydrazine on 531. - introduction of monad radicles into 525. power of 562 587. action of heat on 720. Q-Quercitrin and rutin supposed identity Quinol absorption-spectra of 654. Quinolt etracarboxy lic acid 453. of 262. R, Racemic acid action of phosphorus Radius of molecular action 226. Raffinose molecular weight of 619. Resorcinol absorption-spectra of 652. Rutin and quercitrin supposed identity pentacliloride on 695. of 262. S. Salicylaldehgde action of phosphorus Salicylic acid absorption-spectra of, - natural and artificial proof of Salts heat of dissolution of various in pentachloride on 402.656. the identity of 664. different solvents 871 875. SiIicic acid dehydration of by heat 66, Silicon compounds researches on 853. -influence of on the properties of Silver hydroxide dehydration of by Sodium hydroxide electrical conduc-Solubility of isomeric organic com-- of mixtures of sodium and - relation of t,o fusibility 783. Solutions aqueous electrical conduc-tivity of 116. Spectra absorption- relation between the molecular structure of carbon compounds and their 641. Stannic acid dehydration of by heat, 68 83. Steel influence of silicon on the pro-Succinyl chloride magnetic rotatory Sugar cane- molecular weight of 615. Sulphur a new allotropic modification - action of sulphurous acid on 347. - chloride and sulphurous acid, - heat of dissolution of in various Sulphuric acid and zinc interaction of, - electrical conductivity of solu-80.iron and steel 844. heat 64 79. t i d y of solutions of 123. pounds 783. potassium nitrates 783. perties of 844. power of 563 590. of 282. interaction between 345. solvents 874 877. 47. tions of 118. T. Tartaric acid action of phosphorus Terpenes constitution of 879. Tetrahydronaphthalciie-derivatires 1. Tetrahydronaphthalenedicarboxylic acid - anhydride 12. Tetralkylarnmonium iodides action of Tetramethylammonium iodide action of - salts action of heat on 624. Tetramethylphosphonium d t s action Tetrathionates action of hydrogen sul-- action of sulphurous acid on 333. Thallium hydroxide dehydration of by Thiophosphoryl fluoride 766.pentachloride on 695. (p-p-) 11 20. potassium on '761. potassium on 761. of heat on 636. phide on 328. heat 76 88 ISDES OP Tin-copper alloys 167. - constitution of 104. Titanic acid dehydration of by heat, Toluenes ortho-substituted action of Tolylhydrazone para- 544. Tolylhydrazonepyruvic acids action of Tolylthiocarbimide ortho- action of Tribenzylphosphonium chloride action Triet hylbenzjlphosphonium chloride, Triethylisoamylphosphonium chloride, Triethylmethylphosplionium chloride, Trit,hionates action of hydrogen sul-66 81. chromium oxychloride on 803. heat on 543. aldehyde-ammonia on 418. of heat on 725. action of heat on 723. action of heat on 721. action of heat on 719. phide on 329.U. Urea and some of its derivat,ives action - hydrolysis of micro-organisms 732. of phenylhydrazine on 550. V. Valency of elements of the aluminium-group 825. Vapour-densities of indium gallium, iron and chromium chlorides 814. SUBJECTS. 907 Vapour-density of hydrofluoric acid 765. w. Wackenroder's solution chemical in-vestigation of and explanation of the formation of its constituents 278. - preparation of 281. - spontaneous decomposition of 317. Water evidence of a change in the con-stitution of 125. X. Xylylene bromide meta- 26. - para- 34. - cyanide meta- 41. - para- 44. - dibromide 5. - diethyl ether meta- 45. Xylylenedimalonic acid meta- 31. - para- 38. Z. Zinc and sulphuric acid interaction of, - dust action of on ferric salts, - pentathionate 299. Zinc-copper alloys constitution of 104. Zirconium hydroxide dehydration of, 47. 468. by heat 68 82. HARRISON AND SONS PRINTERS IN OI~DINABY TO HUE MAJESTY ST. MARTIN'S LANE

ISSN:0368-1645    

DOI:10.1039/CT8885300901

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ISDES OF SUBJECTS. 907 ERRATA. VOL. LI. Page Line 749 20 from bottom f o r “ hulled ” vead “ unhulled.” VOL. LIII. 119 13. , , , ‘‘ - 758.97~ ” read (‘ + 758.9727.” 476 8 from , , ‘( H. H. MacMunns ” read “ IF. H. McMinnies.” 723 top line , “ triethylbenzoylphosphonium ” read “ triethylbenzyl-plzosphoniurn.” 752 12 from top , “Dr. Tilden” read ‘‘ Tilden and Shenstone.” 814 13 , , insert “ Chlorides of ” before “ Indium.” 125 top line >> ‘(P )’ , ‘I PI.

ISSN:0368-1645    

DOI:10.1039/CT8885300907

出版商:RSC    

年代:1888

数据来源: RSC