摘要:

QUARTERLY JOURNAL OF THE CHEMICAL SOCIETY. Anniversary Meeting March 30 1850. THEPRESIDENT in the Chair. The following Annual Report was read by the President. WE are now arrived at the Tenth Anniversary of this Society; and the steady though not rapid advance which has marked its existence from the formation to the present time must be considered as auguring well for its prosperity and permanence. It appears by the last Report that the Society then consisted of one hundred and twelve resident and one hundred and twelve non- resident Members three Associates and nine Foreign Members. In the present session there have been elected twelve Members of whom four are resident and eight non-resident ; three resident and three non-resident Members have withdrawn and we have lost two Members by death.Twelve Foreign Members have been elected comprehending as you cannot fail to observe names of philosophers of the highest reputation. The Foreign Members elected are MRI. Boussingault Chevreul Gay-Lussac Gmelin Kopp Laurent Mitscherlich Pelouze Regnault Rose Th&nard and Wohler. The Society therefore now consists of 101 Resident Members 120 Non-resident Members ,,r 2 Associates 20 Foreign Members. I have already stated that we have lost two non-resident Members by death namely Mr William Crawhall and Colonel Thomas VOL. III*-NO XI H PRESIDENT’S ADDRESS. Moocly. The former gentleman was a native of Allendale in Northumberland where he was born in 1784. After a school education under a neighbouring clergyman he was placed in his father’s office who was agent to the lead mines of Sir Thomas Blackett.In this situation he paid considerable attention to the stratification of the rocks of the lead-mining district; and of the mines he drew plans and sections so as to acquire an accurate knowledge of the mineral products of the country the results of which were highly beneficial to Colonel Beaumont and to himself. In 1812 on the death of his father bfr. Crawhall succeeded him as superintendent of thc mines of Colonel Beaumont and his attention was naturally drawn to the process of lead smelting as the operation was then conducted and the injurious effects which the vapour escaping produced on vegetation and the loss af metal which attended it.To remedy these evils he constructed long horizontal ehimnies one of which is two and a half miles in length and his plans were attended with great; success. It may be stated without any diminution of the credit due to MY.Crawhall that the same plan had been previously proposed by Bishop Watson,* but it does not appear that it was ever carried into effect. In the year 1845 owing to the declining state of his health he retired to his house near Hexham where he died on the 28th of March 1849. Colonel Moody obtained his commission in the corps of Royal Engineers while in the West Indies where he was employed on active service. He was for many years engaged in the Colonial Office and subsequently held the appointment of Inspector of Gun-powder at Waltham Abbey.The following are the titles and names of the authors of the several Memoirs which have been read before the Society since the last Anniversary. 1. “Analysis of Gold Dust from the Coast of California:” by E. IF. Teschemacher. 2. “Analysis of the Thames Water at Greenwich:” by Edward T. Bennet. 3. “Analysis of a Mineral Water from the Neighbourhood of Bristol :,,by Thornton J. Herapath. 4. “On the Sulphitea of Potash Chromium Lithia and Bismuth :” by Joseph Danson. * Watson’s Essays Vol. 111 Essay 8. PRESSDENT’S ADDRESS. 5 cc Notes on a Singular Substance resulting from Cloves :” by Dr. R. Scott 6. ‘<An Analysis of Plate Glass :’’ by Messrs. J. E Mayer and J. 8.Brazier.7. “Researches on the Amy1 Series :” by El6Medlock. 8. “On the Carbonate of Alumina :” by J. S. Muspratt. 9. rr On the Manufacture of Soda and the Composition of @tilt- cake Black-ash Soda-ash and Soda-waste :” by Frederick Mus- pratt and Joseph Danson. 10. c‘ On Chromate of Copper :” by H Sugden Evans. 11. “ On the Quantitative Estimation of Cyanogen in Analysis :” by Charles Heisch. 12. cc Examination of some Slags from Copper-mnelting Furnaces :” by Frederick Field. 13. “On the Relative Expansion of Mixtures of Alcohol and VVater under the influence of a certain rise of Temperature and on a New Instrument for taking the Specific Gravities of the same :” by G. N,Makins. 14. ‘(On some New Acids contained in the Oil of the Bussk Latifilia :” by T,F.Hardwick. 15. c( Researches on Strychnia:” by E. C. Nicholson and F. A. Abel 16. “On the Isolation of Organic Radicals:” by E. Frank-land. 17. (‘On a New Series of Organic Bodies containing Metals and Phosphorus :” by E. Frankland. 18. “Researches on the Volatile Organic Bases ?’by A. W. Hof-mann. 19. ‘‘On the Water of the Dead Sea :” by Thorntofi J. Hera-path and William Herapath. 20. “Analysis of the Well Water at the Royal Mint :” by W. T. Brande. 21. “On Titanium :” by Prof. Wohler. 22. ‘‘Continuation of the Researches on the Volatile Organic Bases:” by A. W. Hofmann. 23. ‘‘ Analysis of a Deep Well Water :” by J. Mitchell. 24. “On the Prevention of Incrustation in Steam Boilers :” by J.Anderson. 25. “On the Action of Sulphur on the Pentachloride of Phos-phorus:” by J. R. Gladstone. 26. “On the Gaaes Eliminated from Sewers :” by M Scanlan and 3. Anderson HZ 100 PRESIDEXT’S ADDRESS. 27. ‘‘On the Action of drsenious Acid on Albumen :” by J. B. Ed wards. 28. “ On the Composition of Mesitilole :” by M. Cahours. 29. “On the Identity of Bisulphethylic and Hyposulphethylic Acids and of Bisulphimethylic and Hyposulphamethylic Acids :” by J. S. Muspratt. 30. Ir On some of the Salts of Carbonic Acid:” by ill. N. Saxnuelson. 31. ‘‘Observations on Etherification :” by Thomas Graham. 32. “On a Natural A4110yof Copper and Silver from Chili :” by Frederick Field.33. “Researches on the Organic Radicals :” by E. Fi*ankland. 34. ‘I On some Salts of Chromic Acid :” by 5. Danson. 35. On the Relations of Animal and Vegetable Life :” by Re War in g ton. 36. “On the Precipitation of the Colouring Matter of Sugar by a Metallic Oxide :” by Henry War burton 37. On the Relations between Chemical Composition Boiling Point and Specific Volume :” by Hermann Kopp. 38 “On the Composition of the Ashes of the Cactus :” by Frederick E’i el d. 39. On the Application of Liquid Diffusion to Produce Decoin- tC position :” by Thomas Graham. The laborious investigations of which the above-named communi- cations are the results it would be a pleasing task to dilate upon ; but such an occupation of your time woiild be needless since most if not all of them are or will be printed in your Journal which I trust will ever be regarded as indicative of the zeal and ability of the Members of this Society.It will now be proper for me to state the various specimens and books which have been presented to the Society since the last Anni-versary ; and it may not perhaps be here out of place to express a hope that as we have now the means of placing and arranging books and specimens their numbers will augment with the oppor-tunity of placing them in safe and convenient situations. The presents received are 1. ‘(A Phial containing a Curious Film of Gun Cotton which had becn formed in the interior by the Spontaneous Evaporation of the Et,ler from a Collodion Solution :” presented by George Phillips.2. I‘ The Pharmaceutical Journal :” from the Editor. 3. I’he Journal of the Franklin Institute :” from the Institute. 4. “The Address delivered at the Anniversary Meeting of the PRESIDENT’S ADDRESS. Geological Society;” by Sir H. T. de la Bech e from the Author. 5 ‘‘ Report of tbe Smithsonian Institution and Smithsonian Con- tributions to Science Vol. I. :” from the Institution. 6. ‘‘ Contributions to the Science of Agriculture;” by J. T. W. Johnstone from the Author. 7. ‘‘De Saliva;” by Nicholaus Jacuboowitsch and “Die Diagnostik verdachtiger Flecke in Criminal€allen:” by Karl Schmidt from Dr. Schmidt. 8. (‘On the Motion of Gases Part 11.trby Thomas Graham from the Author.9. “Proceedings of the Royal Society of Edinburgh No. 33 and 34:’’from the Society. 10. the Use of the Blowpipe:” by Professor Plattner; translated by S. Muspratt from the Translator. 11. ‘(Taylor’s Calendar of the Meetings of Scientific Bodies :” from the Author. 12. “The New and Admirable Arte of Setting of Corne 1601,” being a reprint from H. Nesbitt. 13. “ On the Composition and Money-value of different varieties of Guano ;” by J. T. Way from the Author. 14. ‘{Transactions of the Royal Academy of Stockholm;’’ ‘c An Introductory Lecture on the Importance of Chemistry ;,t Annual Report of the Progress of Science;’’ by Dr. Svanberg from the Boyal Academy of Sciences at Stockholm. 15. ‘<Onthe Nitro-prussides;” by Dr.Playfair from the Author. 16. Proceedings of the Philosophical Society of Glasgow Vol. 111 No. 1 :” from the Society. 17. cc Experimental Investigation of the Amount of Water given off by Plants durinp their Growth;’ by J. B. Lawes; and “Agricul- tural Chemistry,” by the same presented by J. H. Gilbert. 18. ‘‘Address Delivered at the Anniversary Meeting of the Geo- logical Society of London on the 16th of February 2849;” by Sir H. T. de la Beche from the Author. 19. “Orr Benzole ;” by C. B. Mansfield from the Author. 20. “Transactions of the Royal Society for 1848-9;” from the Royal Society. 21. “Regnault’s Trait6 de Chimie :” from the Author. 22. ‘‘ Miscellaneous Results for the Laboratory and on the Pro- perties of Linseed Oil Cake;” by J.T. Way from the Author. 23. u The Quarterly Journal of the Geological Society :” presented by the Society. PRE~IDENT’S ADDRESS. Tho following Gteiitlemen were elected Offiearsand Council for the ensuing year PREBIDENT. Richard Phillips F.R.S. VICE-PRESIDENTI. W. T. Brmde F.R.S. W. A. Miller M,D. F.R,@. Thomas Graham F.R.S. Lyon Playfair F.B.S. SECRETARIES. B,C. Brodie F.R.S. Robert Warington Esq. FOREIGN SECRETAW. A. W. Hofmann YhD. TEEASURER. Robert Borretb F.R.S. COUNCIL Thomas Andrews M.D. J. P. Joule Esq. John Blytb M.D. G. D. Longstaff’ M.D William Ferguson Egq. Theopbilus Eedwood Esq Edward Franklasd PbrDt 1E;dward Schunak Fq. J. J.Griffin 88s. E,F. Teschemachw Esq H. B,Joqea M.D. A. W. Williamson Ph,D. The Hecretary read a list of the:Contributions towards the expenses ef the Charter when Professor Graham proposed and Dr. Iltong-ataff secondei a vote of thanks to the Contributors. The following audited Report of the Treasurer was submitted to the Society AUDITED REPORT OF THE TREASURER. UP. ROBERT PORRETT (TREASURER) IN ACCOUNT WITH THE CHEMICAL SOCIETY OF LONDON. Cr. -__. --6;. 6 d. 1850. s. 8. a7. To Balance from old Account . . 67 2 4 March 25 By Payment for a Silver Candelabrum presented to W. Tooke Esq. in acknowledgment of his , 3Year Dividend on $300 Consols to 5th Jan. services in obtaining the Charter . . . 30 0 0 1849 . ..... 5 16 6 ,) Ditto to Dunn and Duncan for Engrossing and , 1Year Ditto on S2;O Consols to 5th Jan.1850 7 5 8 Binding the Charter . . . . . 5 5 0 , Subscriptions received for Arrears prior to 1849 73 7 0 , Ditto for Book-binding . . . . . 6 13 5 , Ditto for the Years 1849 and 1850- . .. 301 1 0 , Ditto for Printing and Editing Journals 5 6,7 , Ditto for the Year 1851 (anticipated) .. 4 0 0 and8 . . . . . . . . 165 4 5 25 0 0 , Composition from a resident Member .. 20 0 0 , Ditto for Rent to Society of Arts . . ,)5 Ditto from non-resident Members . .. 50 0 0 ,) Ditto for Priiiting . . . . . . 1-1-1 10 , Adtnission Fees . . . . .. 22 0 0 ,) Ditto for Stationery and Postage Stamps . . 3 16 6 , Donations towards Charter expenses . .. 14 2 0 ,? Ditto for Books and Journals . . . . 10 6 6 , Ditto towards a Library Fund .. .. 2 2 0 , Ditto for Subscription to Calendish Society . 1 1 0 , Sale of ‘(Memoirs,” &c. . . . .. 6 13 8 ) Ditto for Tea and Coffee . . . . . 8 10 9 , Ditto for Servants and Doorkeeper (Society of Arts) . . . . . . . . 1 10 0 ,? Ditto for Collector’s Poundage. . . . 17 9 0 . 2 7 7 1l Ditto for Carpenter’s Work . . . 282 2 Balance carriedtonew Account . . -4 -6; 573 10 2 6; 573 10 I2 London 25th March 1850. R. PORRETT, Treasurer to Chemical Society. We have examined the Accounts of the Chemical Society of London presented by Robert Porrett Esq. the Treasurer and find the same correct showing a balance of A282 46 ad. and 6250 Three per cent. Consols in his name as Treasurer $238 14s.5d. being in the hands of Rfessrs Coutts and Co. and 4‘43 9s. 9d. in the hands of the Treasuer. EDW‘AILD J CHAPMAN PROFESSOR KOPP ON April 1 1850. THOMAS GRAHAM,EsQ. V.P. in the Chair. The following presents were announced The Pharmaceutical Journal for March :” from the Editor. “Outlines of Qualitative Analysis for Laboratory Practice,” by J Muspratt from the Author.

ISSN:1743-6893    

DOI:10.1039/QJ8510300097

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

PROFESSOR KOPP ON April 15 1850. THE PRESIDENT (Richard Phillips Esq.) in the Chair. Joseph Danson Esq. Edward S. Tudor Esq. and Alfred Anderson Esq. were elected Fellows of the Society. The following presents were announced cc Journal of the Franklin Institute :” from the Institute. “On the Diffusion of Liquids,” by Professor Graham from the Author. The following papers were read XILI.-On the Relations between the Chemical Composition and the Boiling Points and Xpecijc Volumes. By PROFESSOR KOPP. HERMANN I had formerly established the fact that with analogous coin-pounds a difference of C H in their composition corresponded to a constant difference of about 19O in their boiling points and likewise to a constant difference in their specific volumes.I determined the latter finally* to be about 21.8 for the boiling points of the substances in question ;e.g. the specific volume of alcohol being 58.5 that of methyl-alcohol was found to be 38.6 difference 199.-Dr. Miller+ has since made use of Pierre’s observations to put these statements to the test and bclieves himself warranted in concluding that they are contradictory to facts because the numbers obtained by Pierre’s observations which according to the above statements * Ann. Ch Phaim. L 21. t Chem. SOC. Qu. J. I 363. BOILING POINTS AND SPECIFIC VOLUMES. 105 should be constant are found in reality to exhibit too many discrepancies. I cannot believe this conclusion to be correct. The results of Pierre have been contradicted in part and I believe corrected by some researches conducted by myself with the greatest possible care.* The following table shows a comparison of the numbers arrived at by the observations of Pierre and myself for the boiling points and specific volumes rhe difference C H in br the boiling the specific points.volume. ?ierre KOPP. ?ierre Alcohol and methyl-alcohol . . . . 120.0 12O-9 19 -3 19 09 Iodide of ethyl and iodide of methyl . . . . . 26 *2 -17 a5 -c_ Bromide of ethyl and bromide of methyl . . . . 27 -7 -20 -0 Acetate of oxide of ethyl and acetate of oxide of methyl . 15 -6 18 *O 14 *7 23 -6 Butyrate of oxide of ethyl and butyrate of oxide of methyl. 16 -9 18 *9 36 9 23 *5 Acetate of oxide of ethyl and formiate of oxide of ethyl .21 *2 19 *4 20 -0 22 *7 Acetate of oxide of ethyl and butyrate of oxide of methyl . 27 09 21 *6 7 *o 18 *8 Butyrate of oxide of ethyl and acetate of oxide of ethyl . 17 *4 20 *2 13 *5 21 -1 Butyrate of oxide of methyl and acetate of oxide of methyl. 21 03 19 *8 10 4 21 -2 Butyrate of oxide of methyl and formiate of oxide of ethyl. 24 -6 20 *5 13 -1 20 *8 Butyrate of oxide of ethyl and formiate of oxide of ethjl 22 so 20 *o 21 -0 21 07 Butyrate of oxide of ethyl and acetate of oxide of methyl . 19 *8 19 *5 19 03 22 *o Hydrated oxide of amyl and alcohol. . . . . 17 *8 17 *6 20.3 20 *3 Hydrated oxide of amyl and methyl-alcohol . . . 16 03 16 *4 20 -1 30 *2 It will be seen from the above that many of the numbers which were found by Pierre's researches and exhibit the greatest dis- crepancies from my statements are very different from those arrived at by my determinations which agree very nearly with the laws. The existence of ai kind of law cannot be denied even if the numbers which should be constant are found by experiment to exhibit discre- pancies. * Pogg. Ann. LXXII 223.

ISSN:1743-6893    

DOI:10.1039/QJ8510300104

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

106 PROFES/OR CALVERT ON THE PREPARATION XIV.-On the Preparation of certain Chlorates particularly of Chlarate of Potash. Owing to the importance which chlorate of potash has acquired within the last two or three years in our manufacturing districts due principally ta its application as an oxidizing agent in steam colours to raise their intensity and increase their beauty and also in conse-quence of the high price which commercial potashes have attained during the last two years without any prospect of becoming cheaper I was indlrced a few months back to try if any other chlo- rate could be introduced as a substitute for that of potash; and also whether a cheaper method could not be devised for manufacturing that important commercial product of which the useful application as an Oxidizing agent is greatly impeded by its high price.For it is well known that potashes have averaged for the last two years from &2 to BEa. 5s. a hundred weight which quantity does not contain above 39 to 41 per cent of potash the remaining amount of alkali often quoted to exist in the salts being soda. It may be stated that in all the potashes which I have analysed I have uniformly found from 10 to 12 per cent of Bods. My attention was first directed to the preparation of the chlorate of lime which I produced by passing a current of chlorine gas into a thick milk of lime nearly boiling. It appeared after several expe- riments that heat had great influence in assisting the oxydation of the chlorine. For whilst at ordinary temperatures I could only obtain hypochlorite of lime at about 200' or 212' F.little or no hypophlorite was formed but a large amount of chlorate of lime. It will be seen immediately that it was the observation of the remarkable influence of a temperature of about 212' F. to increase the degree of acidification of chlorine which led me to the discovery of a new method of preparing chlorate of potash. I tried for some time to find a mode of separating chlorate of lime from chloride of calcium. But the chlorate is not to be separated with facility from the highly deliquescent chloride of calcium. A curious chemical reaction was observed to take place several times during the numerous trials which were made on this point. It was that large amounts of pure oxygen were often given off; OF CHLORATE OF POTASH.107 and on every recurrence of such an action no eblorate was pro-duced. I next directed my attention to the preparation of the chlorate of baryta the commercial manufacture of which would haye been greatly enhanced by the recent opening of an extensive mine of car-bonate of baryta at Pride Hill in Wales near Shrewsbury. The mineral referred to yields on an average 90 per cent of pure carbonate in fqct its high degree of purity has caused its success- ful application at the potteries and also in the finishing of calicoes as a substitute for carbonate of lead in the glazisg of cgrds &c. I at first followed the process described in chemical works namely the passing of a current of chlorine gas through water holding car- bonate of baryta in suspension Iqstead of forming chlorate I only produced a hypochlorite; but when a heat of from 200 to 212O F.was communicated to a thick milk of carbonate of baryta one of the neatest chemical reactions took place for the whale mass was transformed into chlorate of baryta and chloride of barium. It appeared to me at the time that a cheap substitute for chlorate of potash was thus obtained. But I was deceived; as it was found impossible to separate in a satisfactory manner the chlorate of baryta from the chloride of barium even by seven or eight consecutive crys- tallizations from water. Though certainly the chlorate was becoming gradually purer still it was impossible to free that salt completely from chloride of barium.Although this coincidence in the solu-bility of these two salts had been remarked by Chenevix still a% in most works the chlorate of baryta is stated to be employed to prepare chloric acid I persevered but regret to say in vain. I even tried to separate these two salts by treating them with rectified spirits and wood-naptha or the hydrate of oxide of methyl but without success. I next directed my efforts to discover a cheaper method than those hitherto known of preparing the chlorate of potash. It is necessary here to mention that the chloratr of potash is not now generally manufactured by passing chlorine into a concentrated solution of carbonate of potash but that the useful process recom- mended by Professor Graham namely of carrying a current of chlo-rine through a mixture of sulphate of potash and lime has been generally adopted and has given satisfactory results.I placed myself in the best circumstances for ascertaining the relation of this process to the one hereafter described. One equiva- lent or 97 parts of sulphate of potash dissolved in a sufficient amount of water and mixed with six equivalents of lime or 168 PROFESSOR CALVERT ON THE PREPARATION parts was submitted to a current of chlorine at 212O I?. Although chlorate of potash was formed in this experiment yet its quantity was inferior to the theoretical amount naniely 122.5 parts. From this and other experiments and also from information which I have obtained I find that commercially 122.5 parts of chlorate of potash are never produced from 97 parts of sulphate of potash.No doubt this result is due to the formation of a certain amount of chloride of potassium in addition to the imperfect decomposition of the sulphate of potash by the lime. A mixture of chloride of potassium with lime was also submitted to experiment but yielded no satisfactory results. It was several months after my researches were completed that I learnt from Professor Graham himself that he had published in the lCTransactions of the Chemical Society,J’ (Vol. I. p. 5) a short notice on the production of the chlorate of potash by means of a mixture of carbonate of potash and lime. Still this chemist has not inquired into the precise bearing of his interesting observation as to the best mode of conducting the process commercially and the amount of chlorate produced.I was led by a series of consecutivc trials to examine what would take place by passing chlorine gas at ordinary temperatures through a solution of caustic potash containing caustic lime in suspension. Under these circumstances I only produced the hypochlorites of potash and lime and the chlorides of potassium and calcium; but if the chemical action was assisted by heat chlorate of potash was formed in large amount instead of hypochlorite. It is certainly interesting to see in this series of experiments how a comparatively small increase of temperature (from 60° to 180O) modifies chemical action and assists the fixation of an additional amount of oxygen by the chlorine.Having been successful so far niy attention was next directed to the best means of producing by this method the largest amount of chlorate of potash an object which I arrived at by examining thc influence of solutions of caustic potash more or less concentrated upon the quantity of salt produced. For my first experiment a solution of caustic potash of specific gravity 1.040 at 60°F. was taken containing 34 grains of real potash in 1000 fluid grains of liquid. In order aIso to act always on the same proportion of potash a constant bulk of fluid was taken nhich contained exactly 100 grains of oxide of potassium. In this case therefore 3000 fluid grains were made use of containing 102 grains of potash.I then took 6 equivalents of good quick lime or OF CIILORA'PE OF POTASH 109 358 grains which after being slaked mere added. The mixture being heated to about ZOOf) F. a rapid current of chlorine was passed through as long as the gas was absorbed. The whole was thrown on a filter and the small deposit washed with boiling water. The liquor in cooling yielded a fair amount of chlorate which was slightly increased by the concentration of the mother-liquor. The quantity was 130 grains of chlorate or 3 times as much as potash alone would have given. A second experiment was made with a solution of caustic potash of specific gravity 1.050 and containing 40 grains of potash in 1000 fluid grains; consequently 2778 grains of this caustic solution were taken and contained 100 grains of oxide of potassium.After being mixed with the required proportion of slaked lime they were submitted to the operation above described and gave 140 grains of chlorate of potash exclusive of a small amount of that salt left in the mother-liquor. As an increase in the quantity of caustic potash for a given bulk of fluid appeared therefore favourable a third trial was now made with a solution of specific gravity 1.070 containing 58.75 grains of oxide of potassium in 1000 fluid grains; or 1750 grains contained 102 grains of oxide of potassium. In this trial 158 grains of chlorate were produced. Such details on the action of chlorine on solution of caustic potash at different strengths may be excused as they afford an interesting illustration of the modifications which chemical actions may undergo in consequence of the influence of small changes either in the mode of operating or in the medium in which the reactions takes place The results perfectly corroborate the facts which I formerly observed respecting the action of ammonia on the nitrate of lead as well as the remarks vhich I then made on the formation of the salts resulting from the action of these two compounds.It was necessary to proceed very cautiously with this series of ex- periments as I had remarked that if a particular strength in the solution of caustic potash was exceeded I then produced chloride of potassium and less chlorate. Another serious impediment was also created by the liquor becoming so thick by the amount of lime re-quired for a given weight of potash that the free passage of chlorine gas was prevented.In a fourth experiment I took a solution of caustic potash of specific gravity 1.090 at 60° F. A quantity of liquor containing 100 grains of potash gave 172grains of chlorate. In a fifth trial a liquor of specific gravity 1.099 being used 100 grains of potash gave 185 grains of chlorate besides some left in 110 PROFESSOR CALVBRT ON CHLORATE OF POTASH. the mother-liquor. This last quantity already exceeded more than faur times that which potash alone would have furnished. In a sixth experiment an enormous amount of chlorate was pro- duced amounting as it will be seen to nearly the theoretical propor-tioh namely 260 parts of chlorate for 100 parts of potash ; and I have no doubt that in manufactures the amount produced would be still nearer as the portion left in the mother-liquor would be com- paratively less.A solution was finally employed of caustic potash of specific gravity 1.110 or containing 105333 per cent of real potash ; conse-quently the quantity of fluid operated upon 1000 fluid grains con-tained 102-83 grains of oxide of potassium. To this liquid was added 358 grains of quick lime previously slaked. The whole being slightly heated a rapid current of chlorine gas was passed through the temperature rising very fast to 180° F. owing to the intensity of the chemical action. The operation was considered complete when the liquid refused to absorb any more gas; the whole was then eva- porated nearly to dryness the residue dissolved in boiling water and the liquor filtered.After washing the slight deposit left on the filter the whole of the liquors were evaporated for crystallization. The amount of chlorate of potash obtained in this experiment was equal to 220 grains with some salt still left in the mother-liquors. The last no doubt amounted to nearly 20 grains owing to the rather large bulk of mother-liquors which were reserved so as to prevent the chlorate from being soiled with chloride of potassium. It is certainly remarkable that there should be a determinate spe- cific gravity where the chemical reaction is brought to bear to its fullest extent or where in other words the whole of the potash is transformed into chlorate while in solutions of greater or less speci- fic gravity a smaller quantity of chlorate is produced with a corres-ponding increase of chloride of potassium.This chemical reaction is rendered still more worthy of notice by the influence of the above fact in modifying the action of chlorine relatively to its affinity for potassium or calcium. Thus in a liquor of specific gravity 1.110 we find that calcium takes precedence of potassium in combining with chlorine and preserves the latter metal almost entirely from the action of chlorine ; while the oxygen disengaged from the calcium applies itself to the chlorine to transform the latter into chloric acid which neutralizes the potash only. This so far as I am aware is the only example which chemistry affords where in the presence of two bases the chlorine applies itself almost entirely to one of the metals whilst oxygen attaches itself to the chlorine converting it CAPTAIN REYNOLDS ON PROPYLENE into an acid which neutralizes exclusively the second base namely the patash.The commercial advantages of the above process over the old one will be easily conceived when we reflect that in the latter 100 parts of oxide of potassium yielded only 43 parts of chlorate whilst treated by the method here recommended 100 parts of the same oxide give nearly 260 parts of chlorate of potash. The chlorate may be produced by the new process at about seven- pence per pound and might therefore be supplied on terms which are greatly below the present market price. Before concluding I have much pleasure in acknowledging the valuable assistance which I have received in this inquiry from one of my former pupils Mr. Charles O’Niel of thi- 3 town.

ISSN:1743-6893    

DOI:10.1039/QJ8510300106

出版商:RSC    

年代:1851

数据来源: RSC

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CAPTAIN REYNOLDS ON PROPYLENE XV.-On ‘‘ Propylene,” a new Hydrocarbon of the series C H,. By CAPTAINJOHNW. REYNOLDS,F.C.S. The formula C H, represents a numerous group of bodies con- taining an equal number of equivalents of carbon and hydrogen of which the well-known olefiant gas C H, may be taken as the type* For many years this latter stood alone till Mr. Faraday in a research upon compressed oil-gas published by the Royal Society in 1825,* showed the existence of another substance of like percentage- composition but distinguished from it by the number of carbon and hydrogen equivalents condensed into the same space ; since that time the progress of science has made us acquainted with a numerous series of similar bodies. The dehydration of the alcohols C Hn+20, or C H, 2 HO has been the chief but by no means the only source of these hydro-carbons which are also formed in several processes of destructive distillation and in the metamorphoses of various compounds con-nected with the alcohols.The consequence of this diversity of origin and the propensity of each alcohol to give rise in addition to a hydrocarbon containing the same number of carbon equivalents as itself to several rnetameric bodies is that the series C H exceeds in number that of the alcohols C H,+ O, though it does not reach to that of the acids C H 0,,with which both are associated. * Phil. Trans. 1825. CAPTAIN REYNOLDS The result of the experiments detailed in the following pages has been to supply a term hitherto wanting in the series the position of which will be best understood by inspection of the subjoined table in which all the members of the series C H, at present known are given together with the corresponding alcohols so far as we are acquainted with them.Methyl-alcohol . . C H4 0 Methylene . c H, Ethylene . Ethyl-alcohol C H6 0,{Bthene . Olefiant gas . YY 3 Y , Yt I) Butylene 11 9) , { Ditetryl . . Amyl-alcohol . . C,,H,,O Amylene . . . C, H, Caproylene , YY 2 1) ,> IY { Naphthene *) C16 a 59 Paramylene . . C H, J3 fl $1 J> Jt J Cetylene . Cetyl-alcohol . + . { Cetene *... C32H3402 19 97 9 ,? , Metamylene . C, H,o f> 1 ,J >Y 7 ..> Cerotyl-alcohol .Cerotylene . Cerotin . . . . Cerotenc . . . >Y , Y ¶J > $Y } c 60 H 0 Melissyl-alcohol . . Melissylene . Melissin . 69 2 { Melene . . In this table are not included a number of isomeric hydrocarbons said to be contained in coal-tar naptha and present in the various kinds of petroleum and also obtained by the distillation of the fatty acids because their position on the scale has not been sufficiently well established ; even the table contains some terms concerning which doubts still exist. Methylene* has been obtained only once by Dumas and Peligot and as appears from their account not in a state of absolute purity. * Ann Ch.Phgs. [2] LVLII 1. ON PROPYLENE. 113 Ethylene ethene or olefiant gas is obtained as is well known by the de-hydration of ordinary alcohol.The alcohol corresponding to the next term in the table C HS is not known but the hydrocarbon itself was obtained originally by Faraday,s as before mentioned from the liquid condensed from oil-gas; the same body according to Bouchardat,? appears to exist among the products of the dry distillation of caoutchouc; and Kolbel has also lately obtained it as a product of the decomposition of valeric acid by the battery. Amylene has been studied by Balard,$ who obtained it by the action of chloride of zinc upon amyl-alcohol or fusel-oil.11 The reaction with chloride of zinc gives rise also to the formation of paramylene originally obtained by Cahours,v in the corresponding prc cess with phosphoric acid and metamylene whose formulze have bet n controlled by the determination of the density of their vapours.(hproylene is one of the hydrocarbons obtained by Fremy,** in the destmstive distillation of several fatty acids ; it was originally described under the name oleene. Among the various hydrocarbons separated from naphtha by Pelletier and Walter,?? one has been studied with particular attention. This substance called by the discoverers naphthene is very probably the term CI6H,,. Cetylene is the hydrocarbon of the cetyl-alcohol discovered by Dumas and Peligot,f$ in their researches on spermaceti. Cerotylene and melissylene are derived from the interesting wax-alcohols discovered by Mr. Brodie.@ The formulz in the * Phil. Trans. 1825. t J.Pharm. XXIII 454. 2 Chem. SOC. Qu. J. 11 157. § Ann. Ch. Phys. [3] XII 294 11 The same body is formed together with various substances in the decomposition of iodide of amyl by zinc ; for on comparing the composition and properties of the corn- pound lately described by Frankland (Chem. SOC. Qu. J. 111. 30) under the name of valerene there cannot be the slightest doubt that it is nothing but Balard’s amylene. Both substances contain the same amount of carbon and hydrogen and exhibit the Same state of condensation. Their physical properties are absolutely identical ;and if MI:Frankland has observed a boiling-point a few degrees lower than Balard this is perfectly intelligible on the supposition that his substance still contained traces of the more volatile hydride of amyl.Valerene was observed to boil at 350; the boiling- pint of Balard’s amylene is 39O which has lately been verified by Mr. Medlock who has prepared this body on a large scale. 7 Ann. Ch. Phys. [2] LXX 81. +* Ann. Ch. Pharm. XX 50. -fj-Compt. Rend. IX 146. $$ Ann.Ch. Phys.[2] LXII 1. $5 Phi?. Trans. 1849. VOL. III.-XO. x. I CAPTAIN REYNOLDS table are the same as those given by Mr. Brodie although there is still some doubt as to whether they are actually the correct ones ; the doubt arising from the fact of the substances in question being metamorphosed by the action of heat and consequently not admit- ting of density-determinations. The first term missing (the alcohol of which is likewise unknown) in the above series is that which should occupy the place between olefiant gas and butylene.It is this hydrocarbon whose composition must be represented by the formula C6 H, that the succeeding experiments have supplied and to which I propose to give the name of Propylene. This name is like those of the rest of the series derived from the corresponding alcohol in this case still unknown and for which the appellation of Propylic alcohol has been suggested by Dr. Hofmann. PREPARATION OF PROPPLENE. It is well known that the vapour of alcohol is entirely decomposed on passing through a red-hot tube and that the products of decom-position are principally olefiant gas and marsh gas C H and C H, together with several fluid and even solid bodies which have not yet beeii more closely investigated.Amyl-alcohol or fusel-oil under similar treatment might have been expected to yield analogous results in the production of the bodies It was the investigation of this point that gave rise to the dis- covery of the hydrocarbon C H, which is the object of the present communication. The arrangement employed was as follows A long tube of hard German glass was placed in a combustion- furnace one end being connected with a flask containing fusel-oil and the other after passing through a Liebig’s condenser bent so as to dip into a TVoulfe’s bottle partly filled with water which latter was furnished with a flexible tube to convey the evolved gas into a gasorneter. When the tube was red-hot the fusel-oil in the flask was made to boil briskly whicli caused an abundant evolution of gas and a quantity of ON PROPYLENE.liquid collected in the Woulfe’s bottle which appeared to consist of un-decomposed fusel-oil though it is possible further examiuation might show tbat liquid products of decomposition are also present The quantity and quality of the gas evolved were greatly influenced by the temperature of the tube. When the heat was too great little besides ordinary marsh gas was obtained ;on this account an iron tube could not be employed. If on the other hand the tempe- rature was not sufficiently high the greater portion of the fusel-oil passed over undecomposed arid but little gas could be collected. When the operation was properly conducted the resulting gas burnt with a highly luminous flame and when brought into contact with chlorine or bromine gave rise to an abundant formation of oily drops in a manner similar to that of olefiant gas.Some preliminary experiments showed that the gaseous product thus obtained was a mixture of different substances the proportions cof which appeared to vary considerably even in operations which were considered successful ;hence there appeared but little chance %of obtaining satisfactory results from eudioinetrical analysis; I there-fore decided to submit to closer examination the product obtained by the action of bromine upon the crude gas by which alone a consider- able separation was effected. BROMINE-COMPOUND. This compound was formed in the following manner The gas was collected in bottles and bromine added in small portions the bottles being shaken at the same time till the bromine ceased to be deco- iourized.In this manner a quantity of a heavy oily liquid was obtained which was mshcd with water dried over chloride of *calcium and subsequently purified by repeated distillations off quick lime. It is not advisable to prepare this compound by passing the gas directly into bromine as experiment showed that under these circumstances a large quantity of substitution- bodies was formed diminishing considerably the amount of the chief product of the reaction. The limpid oil obtained as above described began to boil at 136O C. the boiling-point rising rapidly to 143O where it re-mained stationary for a considerable time and subsequently rose slowly to 160° when a quantity of a brown liquid remained in the retort which at that temperature began to decompose with evolu- tion of hydrobromic acid; a portion more than three-fourths of the I2 116 CAPTAIN REYNOLDS whole was ultimately separated by rcpeated distillation; its properties are as follow It is a colourless oil of an ethereal odour slightly alliaceous and very similar to that of Dutch liquid.Its boiling-point is 143' (3. It does not solidify at -200 C. Its specific gravity is 1.7. It is decomposed by concentrated sulphuric acid. Combustion with chromate of lead and oxidized copper-turnings gave the following results I. 0.5709 grm. of substance gave 0.3839 , , carbonic acid and 0.1526 , , water.11. 0.4811 , , substance gave 0.3170 , , carbonic acid and 0.1346 , , water. 111. 0.6305 , , substance gave 04095 , , carbonic acid and 0.1729 , , water. The bromine was determined by combustion with lime in the usual manner IV. 0.7934 grm. of substance gave 1.4974 , , bromide of silver. V. 0.5115 , , substance gave 0.9640 , , bromide of silver. Percentage-composition I. 11. 1x1. IV. V. Carbon . 18.33 17.97 17.73 -- CI Hydrogen 2-96 3.10 3.04 Bromine -L -78.58 79.07 The simplest expression to wh,Gh these numbers leal is the for-mula c3 H3 Br as may be seen from the following comparison of the theoretical and experimental values Theory. Mean of -Experimeat, 3 equivs.Carbon . 18-00 18.13 1890 3 , Hydrogen . 3.00 3.02 3.04 1 equiv. Bromine . 78-26 78-85 78.83 99.26 100*00 99-87 ON PROPYLENE. 117 The determination of the density of the vapour however proves that this formula must be doubled if we admit that the elements are condensed in a manner similar to that which obtains in the cor- responding member of the olefiant gas series. Weight of flask with dry air . . 33.2504 grms. Temperature of balance case . . 22.25' (3 Height of barometer . . . 759.4 mm. Temperature at time of sealing . . 198O C Weight of flask with vapour . . 34.0879 grhs. Height of barometer . . . 759.0 'mm. Volume of air remaining in the flask . 4.0 cc. Volume of mercury filling flask .. 204-5 cc. The density of the vapour deduced from the above data is 7-3098 which on comparison with the following theoretical value will sbow that the formula of the compound in question must be c6H6 Br,. 6 equivs. Carbon = 6 vols. = 49920 6 , Hydrogen = 12 vols. = -8316 2 1j Bromine = 4vols. = 22.1776 28.0012 On dividing this total by 4,we have Theory. Experiment. 2'"O'fL = 7.0003 7.3098 4 The excess above the theory is probably due to the partial decom- position of the vapour which caused a small quantity of carbon to be deposited in the flask. If we adopt for the analogous body in the olefiant gas series the term hydrobromate of bromide of acetyl we may call the present compound hydrobromate of bromide of propionyl c6 H Br.H Br. On digesting the oil just described with alcoholic solution of potash very energetic action took place with abundant deposition of bromide of potassium and a liquid distilled over from which on the addition of water a heavy colourless and very mobile fluid separated extremely volatile and of a peculiar odour resembling that of rancid fish. This substance was dried over chloride of calcium and rectified by 118 CAPTAIN REYNOLDS distillation off quick lime. Its boiling-point not being stationary it was treated several times with alcoholic solution of potash which however only appeared to increase the variableness of the tempera- ture of ebullition. The product was therefore separated by fractiozal distillation into portions boiling between 45O and 56O 56O and 60° and 60° and 70°.Analyses of these distillates gave the following results I. 0.6495 grm. of substance boiling from 45O to 56O gave 0.6893 , , carbonic acid and 09348 , , water. 11. 0.4207 , , substance boiling from 56O to 60°gave 0.4516 , , carbonic acid and 0.1580 , , water. 111. 0.4543 ) , substance boiling from 60°to 70°gave 0.5134 , , carbonic acid and 0.1891 ) , water. Percentage-composition I. 11. 111. Carbon . . 29.06 29.26 30.88 Hydrogen . 4.03 417 462 The first of these results will be seen to approximate closely to the formula c H Br as may be seen from the following comparison Theory. Experiment. r-y 6 cquivs. Carbon. . . 36 30.18 29-06 5 , Hydrogen * 5 4-19 4.03 a 1 equiv.Bromine 78.26 65.62 ...-119.26 99.99 As the boiling-point rises the proportion of carbon and hydrogen increases thereby leading to the conclusion that the action of the potash produces in the first instance the body c6 H Br and that afterwards a substance containing more or less oxygen in the place of bromine is formed The formula of this second body may probably be or oxybromide of propionyl which would contain Carbon . . . 42-78 Hydrogen . . 5.94 ON PKOPYLENE. 119 The great loss caused by repeated distillation in the hope of obtaining a constant boiling-point previous to the above hypothesis suggesting itself left me so little substance that I was unable to determine this point more accurately.CHLORINE-COMPOUND. This compound was formed by allowing the crude gas obtained from fusel-oil to meet chlorine in a quilled glass globe when combi- nation took place with evolution of heat; and a heavy oily liquid similar to the bromine-compound collected in the receiver. This liquid was dried over chloride of calcium and distilled repeatedly off quick lime and finally a portion was obtained which boiled at loo0 and 103O. Two chlorine-determinations* gave the following numbers I. 0.4618 grm. of substance gave 1.1694 , , chloride of silver. 11. 0.3659 , , substance gave 0.9256 ,) , Percentage 1. 11. Chlorine . . . . 62.64 62.55 which agrees with the formula c H CI, as may be seen from the following comparison Theory.Mean of -Experiment. 6 equivs. Carbon . . 36.0 31.85 -6 , Hydrogen . 6-0 5-30 -2 , Chlorine 35.5 62.83 62-59 ____I 77.5 99.98 On treating this compound with alcoholic solution of potash 8 decomposition similar to that wliich took place in the case of the bromine-product appeared to result. The perfect analogy in composition and deportment of the com-pounds described with the corresponding terms of the olefiant gas series * The fraction boiling at a constant point was much smaller than in the ease of the bromine-compound a larger quantity of substitution-products being formed. CSPTAIN REYNOLDS ON PROPYLENE. appear to warrant the conclusion that the substance which conibines in the present cases with bromine or chlorine is the hydrocarbon c He In successful operations the proportion of propylene in the gas derived from fusel-oil was about half the original gas.The residue obtained by passing the gas through bromine till the latter ceased to absorb it appeared to consist chiefly of marsh gas; but this point demands a more particular investigation which I intend shortly to make. I also propose to try whether by the use of solvents such as benzol or oil of turpentine it may be practicable to obtain the hydrocarbon C H pure so as to examine it eudiornetrically. On considering the composition of the bodies c6 H Br and c 13 c1 it will be seen that they may be regarded as belonging to the allyl- series; and it may therefore be anticipated that the action upon either of sufphide of potassium and sulphocyanide of potassium will produce respectively oil of garlic and mustard oil sulphide and sulphocyanide of ally1 C H Br -I-K S = C H S + KBr C6 H Br + K C N S = C H C2 N S2 + K Br.I intend to make these reactions the subject of further investiga- tion as well as to complete what is deficient in the experiments already detailed and I hope to have the honour of submitting the results to the Society. I may mention in conclusion that the above inquiry was con- ducted in the Laboratory of the Royal College of Chemistry and I take this opportunity of expressing my thanks to Dr. Hofmann for his kind assistance and advice in the performance of these experiments

ISSN:1743-6893    

DOI:10.1039/QJ8510300111

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

DR HOFNANN ON VALERIC ACID. XVX.-Note upon the Action of Heat upon Valeric Acid; with some remarks upon the forrnut~eof the Alcohol-Radicals. By A. W. HOFMANN, Ph.D. F.C.S. The interesting experiments which Capt. Reynolds has just now communicated to the Society have pointed out the existence of a gas long anticipated by theory but which had hitherto escaped observation. This body will most likely be found a very frequent product of the dry distillation of sLzbstances rich in hydrogen. The gases hitherto obtained in various reactions of this kind and con- sidered as olefiant gas may possibly have contained together with the latter some proportions of this hydrocarbon c6 He and it is by no means improbable that the luminiferous properties of common coal gas far from entirely arising from olefiant gas may be partly due to the presence of propylene of butylene and even of amylene.The method used by Capt. Reynolds in treating his gas with bromine might be followed with advantage in order to settle this point. By adopting this plan I have been able to trace the evolution of propylene in a reaction which has lately engaged my attention. The vapour of valeric (valerianic) acid when passed through a red-hot tube yFlds a considerable volume of gas together with a quantity of liquid products the amount of which varies with the temperature at which the action is performed. Without entering into details respecting the liquid products it may at once be stated that the gas consists chiefly of hydrocarbons of the formula C H, together with the oxides of carbon.After having removed the carbonic acid by means of an alkali these hydrocarbons were absorbed by bromine- vapour ;the residuary gas then burned with a blue flame and was found to consist of carbonic oxide. On passing it into pentachloride of antimony it was at once converted into phosgene gas readily recognized by its nauseous odour and by disappearing when con-ducted into water with formation of carbonic and hydrochloric acids. In several operations the gas after having passed successively through potassa bromine pentachloride of antimony and water was no longer inflammable consisting now of accidental atmospheric air ; in other? a mere trace of inflammable gas was left which may have been a member of the marsh-gas family-most likely marsh gas itself; in contact with chlorine it yielded oily drops doubtless of chloride of carbon.On submitting the oily fluid obtained in the absorption of the DB. HOFMANN ON THE ACTION series C 13 to ebullition the thermometer rose at once to 130° C. The main bulk of the liquid passed over between 136O and 156O,when hydrobromic acid wa3 evolved arising from the decomposition of the small quantity of substitution-products the formation of which can never be altogether avoided. On redistilling the resulting liquid the therniometer became tolerably stationary between 143O and 145O when about half of the compound passed over. As I was unable to subject the product which had been prepared on a small scale only to an elaborate purification I could expect from analysis but approximate results.I. 04696 grm. of oil gave 0,3245 ,,,,carbonic acid and 0.1350 ,,,,water. 11. 0*2805 ,,,,oil gave 05276 ,,,,bromide of silver. These numbers lead to the following percentage Carbon ......18934 Hydrogen ..... 3.19 Bromine ......80.00 These numbers although evidently incorrect nevertheless so closely approach the percentage of Capt. Reynolds' hydrobromide of bromide of propionyl that I do not hesitate to assume that the bromine-compound examined actually consisted chiefly of this sub- stance contaminated most likely with a small quantity of a substi-tution-product and possibly of the corresponding terms in the ethylene-and butylene-series.For the sake of comparison I adduce the percentage of these several substances C H Br C H Br C N,Br Carbon ...12.77 17.82 22.22 Hydrogen . . 2.12 2.97 3.70 Bromine ...85.11 79.21 74.08 I ooooo 100~00 100*00 Of the oil distilling at a lower temperature I have only made a bromine- determination. 0.3237 grm. of oil gave 0.6455 , ,,bromide of silver. Percentage of bromine 84-83. This number as well as the boiling-point sufficiently showed that this substance consists chiefly of the bromine-compounds of olefiant gas. OF HEAT ON VALERIC ACID. 123 The chief bulk then of the hydrocarbons evolved in the decom- position of valeric acid by heat would appear to consist of propylene accompanied by small quantities of olefiant gas and possibly of butylene.I could not however affirm the presence of the latter. The experiments of Capt. Reynolds on the action of heat on arnyl-alcohol were made on a sufficiently large scale to prove that in this reaction in addition to propylene no other term of the same series is formed in considerable quantity. I was unable to devote so large a quantity of valeric acid to the attainment of an equal degree of precision and therefore leave it doubtful whether butylene is actually formed in this reaction. The results obtained in the dry distillation of valeric acid were far from what I had anticipated when I undertook the experiment;. 1 had hoped to see this acid imitate the deportment of acetic or benzoic acid under similar circumstances ; these acids being converted with the loss of 2 equivs.of carbonic acid the one into marsh gas the other into benzol. A similar behaviour of valeric acid would have given rise to the formation of a compound c8 H, C,o HI0 0,-2 Cog = c8 HIO. The experiments which I have just now detailed show that the compound in question is not found among the gaseous products of the decomposition of valeric acid. It appears that this term,* unable to exist at the prevailing temperature is broken up into the more stable compounds of the series C H, the excess of hydrogen being eliminated either in the form of marsh gas or as water formed by the reduction of carbonic acid to carbonic oxide. Several experi- ments in which the temperature was so far lowered as to allow a considerable quantity of valeric acid to distil undecomposed yielded sensibly the same results; nor was much difference observed when the tnbes were filled with pumice-stone or when in order to fix the carbonic acid valeric acid was distilled with an excess of baryta.In the latter experiment together with the hydrocarbons C Hn pure hydrogen gas appeared to be evolved. * The members of this series appear to be far less stable than the hydrocarbons con- taining an equal number of carbon- and hydrogen-equivalents. The rapid distillation of margaric acid with and without lime appears to yield hydrocarbons of the family C H only ;this subject however is by no means sufficiently examined. The instabi- lity of these substances would also explain why we have not hitherto obtained a member of the marsh-gas-series derived from the fatty acids in the various tars and naphthas which have been examined whilst the more stable corresponding terms derived by loss of carbonic acid from the acids of the benzoic series viz.benzol toluol xylol cumol cymol have been found to be present in considerable quantities in coal-oil (Mansfield) and in the oil precipitoted from wood-spirit on addition of water (Cahours). 124 DR. HOFMANN It would be interesting to repeat the same experiment with butyric acid and propionic acid; it is possible that the greater simplicity in the construction of the terms C H and C H, will protect them from being broken up into inferior groups. The preparation under the above circumstances of the marsh- gas term of valeric acid acceptable as a contribution towards the completion of this hitherto apparently scanty family would have commanded additional attention by the decision which it appeared to promise of a very important question which is pending at this moment.Chemists have read with unusual interest the highly rcmarkable researches published within the last two years in the Journal of this Society by Drs. Kolbe and Franlrland. Dr Kolbe in his admirable investigation of the products formed in the electrolysis of valeric acid first pointed out the production of a hydrocarbon represented by the formula C H, for which from theoretical views peculiar to himself he proposed the name Vatyt. The above formula represents the radical of the missing alcohol of butyric acid.Kolbe leaves it undecided whether this body actually is the radical in ques- tion but remarks that its vapour-density exactly coincides with this assumption. The next step was the isolation of the radical of a known alcohol of methyl. In treating cyanide of ethyl with potassium Drs. Kolbe and Frankland obtained together with a beautifully crys- talline alkaloid cyanathine isomeric with the mother-compound a permanent gas which exhibited exactly the composition and the condensation of the hypothetical radical methyl The mine being once opened discoverics followed each other with rapidity. Dr. Frankland in pursuing by himself this line of inquiry arrived by acting with zinc upon the alcohol-iodides suc- cessively at the isolation of ethyl c H5 and lastly of amyl c, %I* The details of these beautiful researches performed with remark-able experimental skill are yet fresh in the recollection of the Society.An unusual interest is attached to these investigations; the isolation of the radicals presenting in their compounds so great an ON THE ORGANIC RADICALS. analogy to hydrogen and replacing this element when in a state of mobility both in acids and bases,-the isolation of these elementary groups appeared to be the key-stone of the theoretical edifice in the construction and elaboration of which the finest discoveries of the last twenty years had been made. But notwithstanding the deep interest excited by these discoveries all chemists were not perfectly satisfied with the general character exhibitect by the new radicals.Nobody expected that ethyl like zinc would disengage hydrogen from sulphuric acid and water or that like iron it would precipitate copper or antimony. There were however many who thought whether rightly or wrongly that these substances would under certain circumstances like hydrogen combine directly with chlorine ; that they would combine with other elements without giving rise to phenomena of substitution; and reproduce like other of the isolated radicals as cyanogen or cacodyl some terms of their own series. The great difficulty with which free hydrogen combines with chlorine and the powerful affinity exhibited by the latter element for hydrogeii when in the combined state militates it is true to a certain extent against this assumption; but we have on the other hand in olefiant gas and its congeners well known instances in which this direct combination actually appears to take place.Up to this present moment none of the supposed alcohol-radicals have been observed to combine like cyanogen or cacodyl directly with any of the elements; none of them have been found capable of reproducing a methyl- ethyl- and amyl-compound. The first doubts respecting the interpretation of the experiments in question were raised by some of the French chemists MM. Laurent and Gerhardt,* in reporting upon the investigatioii of Dr. Frankland have pointed out that the bodies described under the names of methyl and ethyl might with more probability be considcred as homologues of marsh gas.In fact if we double the formulze of the substances in question 2 C H = C )I Aeetene. 2 C H = C H, Butene we arrive at a series of substances the analogy of which becomes evident by the following equations C H 0,-2 C02 = (32 H, w w Acetic acd. Marsh gas of acetic acid (Formene). * Compt. Rend. Trav Chim. 1850. 126 DR. HOFMANN Propionic acid. Marsh-gas of propionic acid ( Acetene). Cl HI 0,-2 CO = c H, -J + Valerie acid. Marsh-gas of valeric acid (Bdene). The experiments upon the action of heat on valeric acid which I have communicated to the Society had been undertaken chiefly in order to decide between the two views. If this reaction had given rise to the formation to the body hitherto called ethyl or of a substance having the same compositioii but endowed with different properties we should have been enabled to adopt either the one or the other of these views.Unfortunately this experiment has led to results reconcileable with both opinions the reaction evidently going too far and inferior terms of the family C H being produced. Unable then as I have been to bring forward any experimental evidence of my own in favour of either view I must limit myself to adducing a few considerations in order to raise a discussion of this very important subject which will not decide the question pending but may lead to new experiments and contribute to a more perfect understanding of what is meant by the often somewhat loosely employed term organic radical.If we assume the existence of compound radicals which by their justaposition to chlorine bromine and iodine give rise to the forma- tion of the chlorides &c. of methyl ethyl and amyl we are com- pelled to represent their molecules by 2 volumes of vapour. In this manner the constitution of the vapours of these conipounds becomes perfectly analogous to that of hydrochloric hydrobromic and hydri- odic acids in fact of the compounds of these elements in which the radical is replaced by hydrogen 2 vols of hydrogen + 2 vols. of chlorine = 4 vols. hydrochloric acid. 2 , , ethyl + 2 , , chlorine = 4 , chloride of ethyl. 2 , , amyl -+ 2 , , iodine = 4 , iodide of amyl. The condensation of the vapour of the radical hydrocarbons re-presented as it is by 2 volumes of vapour is very different from that exhibited by ordinary hydrocarbons.The equivalents of these sub- stances have been found to be invariably represented by 4 volumes of vapour. In some cases doubts have been entertained; but it is remarkable that whenever a hydrocarbon has been well studied especially by a careful examination of its metamorphoses the equiva- ON THE ORGANIC RADICALS. lent has been found to correspond to the condensation which I have mentioned. The only hydrocarbon mesitilol the vapour of which appeared to have a different constitution has ceased to form an exception since M. C ahours’ careful density-determination lately communicated to the Society.* The peculiar mode of condensation which we have to assume for the substances called methyl ethyl and aniyl if we consider them as the radicals C H, C H and C, HI1 disappears if we double these formulze.The expressions C €I6 C Hl0 C, H, correspond like all the other hydrocarbons to 4 volumes of vapour. In the absence of any decisive experiments upon the metamorphoses of the substances in question it would be hazardous to adopt the latter formulae in preference to those proposed by Drs. Kolbe and Frankland unless some of the properties of these substances were found to countenance this change. Now I believe that the boiling-points of the eornpounds in question are certainly in favour of formulze representing 4 volumes of vapour.H. Kopp first pointed out the regular differences between the boiling-points of homologous liquids. As an average result from the observations made at the time when he wrote upon this subject he has fixed upon the number 19 as the difference in the boiling temperatures of two analogous substances differing by C H,. The numbers observed are often somewhat lower but frequently also higher benzol (C, H16)boils at 80° toluol (C14H12) at l0S0 the difference being 28O; cumol (Cls HI,) boils at 148O cymol at l75O difference 27O. I readily admit that our knowledge respecting boiling-points is still very deficient ;yet the existence of a regularity like that observed by Kopp for a certain range of the thermometer cannot be denied. Now let us consider the boiling-points of the radicals hitherto observed.Methyl and ethyl being gases at the ordinary temperature may be left out of consideration. Valyl obtained in the electrolysis of vderic acid boils at 108O; amyl as originally produced in the reaction of zinc upon iodide of amyl and lately obtained by Messrs. Gosleth and Brazier in the electric decomposition of caproic acid boils at 155O; and lastly caproyl if we may represent by this term a substance likewise produced by Messrs. Gosleth and Brazier in the analogous decomposition of aenanthylic acid boils at 202O. Name. Formula. Boiling-point. Difference. Valyl . . . cs H 108O 47 Amy1 . . . C,,Hll 155O Caproyl . . . C, N, 2020) 47 * Chem SOC. QII. J. 111 17. 128 DR. HOFMAXN The anomalous differences exhibited by the boiling-points in question amounting actually in these instances for an elementary difference of C H to nearly the double of the niaximuni ever ob- served disappear at once if me adopt formu18 representing 4 volumes of vapour as may be seen from the following conspectus in which the boiling-points of the missing terms are assumed to be half way between those of their neighbours.Name. Formula. Boiling-point. Difference. Valyl . 23 Amy1 . 23 . 23 Caproyl . . 23 I The boiling-points are certainly in favour of the higher formuliR so much indeed that I believe had these substances first been met with in coal-gas naphtha or in the tarry liquids obtained in various processes of distillation few chemists would have adopted other than 4-volume forinulE unless they had been in the possession of additional informa- tion respecting their deportment.The formulze representing 2 volumes of vapour derive in fact their chief support from the re- markable circumstances under which these substances originate. Hydriodic acid and zinc yield iodide of zinc and hydrogen ;in the same manner it would appear the iodide of an alcohol-radical gives rise to the formation of iodide of zinc and the alcohol-radical. There is decidedly a most striking parallelism ;nevertheless there is a certain deficiency in the analogy inasmuch as we do not by the action upon zinc of the hydrogen-acids obtain a compound of zinc and hydrogen corresponding to zinc-methyl.* However nobody will deny that the mode of formation of a compound must always be considered as a most important element in the construction of its formula and in the case before us that mode of formation appears to be certainly in favour of the lower formulae.* The existence of other metallic hydrides as exemplified in the hpdrogen-com- pounds of arsenic and antimony induced me to study the action of dry hydrochloric acid upon zinc exposed in a combustion-tube to the lowest temperature at which the reaction took place ;hydride of zinc if it followed the deportment of zinc-methyl would when coming in contact with water yield hydrogen and protoxide of zinc C If Zn -+ €30= C H4 + Zn 0 EI Zn -+ I10 = H2+ Zn 0 and might in consequence of this decomposition have escaped observation ;hoxerer the gas obtained in the above reaction even when collected in perfectly drg vessels was found to be free from zinc.ON THE ORGAXIi! RADICALS. Nevertheless it would not be difficult to adduce many cases in which an entire reliance upon the mode of formation has led to thc construction of formuh which had subsequently to be rejected when other methods of investigation were applied to the same question. Shortly after the discovery of amyl-alcohol 81. C ahours* examined the action of anhydrous phosphoric acid upon fmel-oil; he obtained a hydrocarbon boiling at 160° which was immediately con- sidered as the olefiant-gas term of the amyl-series C, €Ilo. Nothing appeared siinpler than the formation of this body The density-determination made by the same chemist proved that the hydrocarbon in question was represented by 2 volumes of vapour ; and M.Cahours characteristically remarked at that period that the evident parallelism of the ethyl- and amyl-series was interrupted by the anomaly presented in the condensation of the elements in this hydrocarbon olefiant gas the corresponding term of the ethyl-series being represented by 4 volumes. However only a few years elapsed when &!I. Balard in studying this reaction on a larger scale and using chloride of zinc as an agent of dehydration discovered the actual olefiant-gas term C, Hlo the true amylene boiling at 39O and corresponding like olefiant gas to 4 volumes of vapour. M. Balard showed that C ahours’ hydrocarbon which now assumed the name of paramylene might be represented by c20 H309 (corresponding to 4 vols of vapour) a forinula agreeing perfectly with its boiling-point.The same chemist found that in this reaction in addition even a third member of the same family metamylene c40 H40 is formed the formula of which is likewise represented by 4 volumes of vapour. A series of perfectly analogous remarks applies to the hydrocar- bons derived from acetone by the elimination of water under the influence of sulpharic acid. Mesitilol is far from being represented by the formula which its discoverer assumed who Tvas guided by the supposed analogy of his product with olefiant gas. The boiling- point of the body being far too high for the assumed formula the study of a series of its metamorphoses readily showed that its equivalent is actually treble that represented by the original formula.In the same mannei; I might adduce the change which has been * Ann Ch Phys. [25 LXX 81. To:,* 111.-NO* ‘X B 130 DR IZOFMANN made in the formula of acetone itself,-the original expression of which was doubled in consequence both of its deportment with reagents and its vapour-density. It would not be difficult to quote a great number of cases exhibit- ing in a similar manner the tendency possessed by atoms of inferior order to be polymerized into molecules of a higher equivalent ;and in no group of bodies perhaps does this inclination prevail to a greater extent than among the alcohol-compounds.Hence it would not appear a very unusual mode of decomposition if we assume that under the influence of zinc 2 atoms of the hypo- thetical radical amyl unite to produce the hydrocarbon C, HZ2 This equation in fact would be satisfactory in every respect ;it would be in accordance with the observed deportment of the body with the usual mode of condensation of hydrocarbons with the boiling-point,-and lastly it would be even more in accordance with the formation of the secondary products of decomposition namely of amylene and hydride of amyl. Of the two equations c20 H22 =ClO H12 +c,o HlO 2 GoHI =CIO H12 +ClO HI07 the former is certainly better supported by analogy although I do not lay much stress upon this point The admission of the doubled formule would moreover remove another difficulty the discrepancy exhibited by the boiling-points of amylene hydride of amyl and amyl.Boiling-point. C, Hlo 390 Amylene . Clo H, 155O Any1 Hydride of amyl . C, H,2 30° It appears strange at the first glance that the boiling-point of C, H, should be raised more than looo by the assimilation of 1 equivalent of hydrogen whilst we usually find that the addition of hydrogen depresses the boiling-point; and again that in amyl the boiling-point should be depressed even in a more striking manner by its combining with the same amount of hydrogen. But I do not attach great importance to this point inasmuch as the formukc of these bodies corresponding to different volumes cannot well be compared with each other.nloreover it is but right to state that tye are not very well acquainted with the influence of hydrogen on boiling-points ;thus the boiling-point of bromine is considerably ON THE ORGANIC RADICALS. higher than that of hydrobromic acid whilst on the other hand hydrocyanic acid boils at a higher temperature than cyanogen itself. The metamorphoses of the radicals from which the most decisive evidence in favour of one or the other formula might be obtained have as yet been studied but very imperfectly. The facts however with which we have hitherto become acquainted are by no means in opposition to the higher formuhe. DF. Kolbe believes that the product obtained by distilling vaIy1 with nitric acid contains nitro-butyric acid ; the liquid resulting from the action of nitric acid on am$ presents according to Dr.Frankland a powerful odour of valeric acid. These observa- tions are perfectly in accordance with theory. The respective radicals pass over into the hydrated oxides of amyl and valyl which under the continued influence of the powerful oxidizing agents yield their correlative acids. Admitting that these acids are actually generated-which is still to be proved by more decisive experiments-I think that their formation is perfectly reconcileable with the doubled formulz We know that the action of nitric acid upon oleic acid gives rise to all the acids CnH 0, from capric downwards. We have no difficulty in eon- rerting the higher terms of this series into lower ones e.9,pelargonic acid into caprylic cenanthylic and even caproic acid.There is no reason why the carbohydrides G, H2, or c16 HIS should not yield all the acids containing a smaller iiumber of carbon-equivalents and among these valeric and butyric acids. Cymol and cumol are converted uiider the influence of nitric acid the former C, H, into tohylic acid c, H O, the latter C, HI2 into benzoic-acid c1*H 0,. The- action of chlorine which affords perhaps the simplest method of controlling formulae has been studied as yet only in one individual case. The results which Kolbe and Frankland obtained by acting with chlorine upon methyl derived from the decomposition of cyanide of ethyl with potassium are highly remarkable This gas yields under these circumstances hydrochloric acid and a new chlorinated body represented by the formula C H C1 which coincides with that of chloride of ethyl.The following equations represent the reaction according as we take either the formula C H, or C H,. 2 C H + 2 C1 = C €1 C1 + HC1 c 9-16 + 2 c1 = c H c1 3-H c1. The far greater simplicity of the second equation is evident it has not escaped Mr Frankland dmsuggests that the methyl obtained K2 by the above process is different from the true methyl obtained by acting with zinc upon iodide of methyl or in the electrolysis of acetic acid with which it wouid be only isomeric. An actual diffe-rence between the two substances is not yet proved by experiment. As the question stands at present two views have been enunciated respecting the bodies obtained by Drs.Kolbe and Frankland. The one view assumes the existence of two groups of bodies one emnbrac- ing the alcohol-radicals and another containing the homologues of marsh-gas the former corresponding to 2 the latter to 4 volumes of vapour. According to this view we haw the fdlowing series Metlzj-1 c H Forinene C H Ethyl c* H5 Acetene C H Pro]$* C6 H c H* Valpl (Butyl) C €1 C f40 Amyl c, III Caproelie Cio H, Caproyl C, HI3 c, Hl The other view considers all these substances as members of the same group as homologues of marsh gas (formene) and arrives at the following series Forniene c2 H4 Acetene c Hii Methyl ? C6 H8 Valerene c HI Ethyl ? Caproene C, HI2 Hydride of Amyl.c, % CI Hl Pelai*geae CI6 HIS Valyl ? c, H*0 Caprene C,o H, Amyl? c, H, Laurene c, H26 Caproyl ? In the preceding pages I have pointed out that the boiling-points of the radicals appear to me to speak for formuh with 4 volumes of va-pour; it now remains to be seen whether other experiments will come to the assistance of this view I an? howevei; by no nieans prepared to say whether as represented in the second table the so called radicals are actually bodies of the same properties as marsh gas; that they * This name might be &en to the hydrocarbon obtained by Dr. Kolbp in the electrolysis of hntyric acid ; its urnination is not 1et completed. ON THE ORGANIC RADICALS are homologues of that body as is assumed in &11Srl[.Laurent and Gerh ar d t ’s interesting suggestion.If we bear in mind the endless isomerisms prevailing in the department of organic chemistry and especially among the hydro- carbons witness the large family CZ0 H16 we may perhaps assume that the so-called radicals although presenting the same state of condensation are only isomeric with the homologues of niarsh gas that they may exhibit an isomerism similar to that of cumol and mesitilol. The latter view receives some support from the fact that methyl (acetene) when treated with chlorine yields not chloride of ethyl but a compound isomeric with it whereas if viewed as an homologue of marsh gas it might be expected to give rise to the production of the former. This importaiit experiment should be repeated.If the preceding considerations lead us to adopt a view respecting the substances described under the names of methyl ethyl &c. which to a certain extent differs from that of their discoverers if we cannot admit that the bodies in question actually represent the niolecules which as conceii-ed by the electro-chemical theory by the assimilation of 1 equivalent of chlorine bromine iodine &c. give rise to the formation of the corresponding ethers we are far from denying a most intimate relation of these compounds to the alcohols from which they are derived. This relation is sufficiently indicated by their mode of generation. These radicals it would appear stand to the alcohols in a similar position as benzile and stilbene do to the benzoyl-group or as the acetones stand to their mother-acids.All these substances are formed by the fusion of several organic mole- cules which split again under the influence of powerful agents corn- pounds of the original order being reproduced. The benzoyl-type when passing into benzile or stilbene is polymerized into C, H, ?* and C, H12 which under the influence of oxidizing agents again return to the original series oil of bitter almonds and benzoic acid being formed. Similarly by converting acetic acid into acetone we pass into a higher series from which we step down again by acting with oxidizing agents upon the latter compound which is reconverted into acetic acid. In an analogous manner the so-called alcohol-radicals might give rise to the reproduction of the acids belonging to the original alcohols.Should experiment however prove that the so-called alcohol- radicals are actually the homologues of marsh gas as supposed by Messrs. Laurent and Gerhardt these substances although losing the prestige of radicals in the conception of the electro-chemical 134 DRI HOFMANN ON THE ORGANIC RADICALS. theory would certainly not present less interest. Chemists know the remarkable manner in which the researches of Dumas Regnau 1t and Melsens have linked the methyl-series to marsh gas and thc facility with which we pass from marsh gas over to chloride of methyl. We have a right to expect that the higher hornologues of marsh gas will exhibit a similar deportment.If this be actually the case the action of chlorine upon ethyl would place the whole series of the butylic alcohol at our disposal; in fact we should have discovered a general method of forming the homologues of common alcohol and this series presenting as yet so many gaps would ere long be as complete as the parallel group of the fatty acids May 6 1850. THE PRESIDENT in the Chair. J S Brazier Esq. W. F. Doyne Esq. and Henry Deane Esq. were elected Fellows of the Society. The following presents were announced “Transactions of the Royal Scottish Society of hrts Vol. 111. Part IV :” from the Society. ‘(The Pharmaceutical Journal for April :” from the Editor. C‘Baunian’sMedical Chemistry :” from the ,4uthor “The Quarterly Journal of the Geological Society for May 1850 :” from the Society.A Paper by Professor Vi’ohler was read “On the Nitride of Boron.” See p. 167. May 14 1850. ROBEET PORRETT, EsQ. Treasurer in the Chair. The following presents were announced “An Account of certain Chemical and Microscopical Researches on the Blood Excretions and Breath in Cholera,” by Thorntou J. Herapath Esq. from the Author. I‘The Collected Works of Sir Hurnphry Davy :” from Dr A. TV. ?Vi 11i a m son, ‘‘ The Pharmaceutical Journal for May :” froni the Editor. The following Papers were read

ISSN:1743-6893    

DOI:10.1039/QJ8510300121

出版商:RSC    

年代:1851

数据来源: RSC

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DR. GLADSTONE ON CBLOROPHOSPHURET OF NITROGEN. 135 XW.1.-On C~~oro~~os~~ure~ of Nitrogen and its Products of Decomposition. By J. H GLADSTOKE, PH.D. PART.I. A crystalline body containing phosphorus nitrogen and chlo- rine was discovered by Wiihler and Liebig during their investiga- tion of the compounds of nitrogen and phosphorus.* It was slightly examined by its discoverers and a partial analysis was made from which was deduced the probable formula P N Cl,. cc Chlorphos-phorstickstoff” was the name given to this substance which has been translated by Kan e :-<; Chlorophosphuret of nitrogen.” 1 am not aware that any chemist has since even prepared the body in question ;but I have lately submitted it to a complete investigation and shall now detail a portion of my results.In the paper upon the compounds of phosphorus and nitrogen which I had the honour to read before this Society last year,? chlorophosphuret of nitrogen was mentioned as invariably formed when pentachloride of phosphorus is saturated with ammoniacal gas. That its production does not depend upon any trace of moisture accompanying the ammonia I established by passing the gas through tubes five feet in length filled with sticks of potash when exactly the same result was obtained. I found it also produced when penta- chloride of phosphorus containing some terchloride was subjected to the action of ammoniacal gas; as also when the chloride was but imperfectly saturated with the gas. Thus it seems an invariable concomitant of the action of dry ammonia upon pentachloride of phosphorus.When the terchloride of phosphorus is saturated with ammoniacal gas no trace of this substance is produced. When thus prepared it is mixed with a large amount of chloride of ammonium and Gerhardt’s cc Chlorophosphamide.” In order to separate it from these the dry mass may be agitated with ether which dissolves out the chlorophosphuret of nitrogen leaving the other bodies. The ethereal solution will again yield crystals on evaporation; but as a secondary reaction is liable to take place be- tween the ether and the chlorophosphuret the following method of purification is to be preferred. The white mass resulting from the action of ammonia upon the pentachloride of phosphorus is placed in * Ann Ch,Pharm.XI. t Chem. SOC. Qu. J. 11,121. 136 DR. GLADSTONE a capacious retort half filled with water and the whole is brought into brisk ebullition ; the chlorophosphuret of nitrogen melts rises to the surface of the liquid is volatilized along with the vapour of water and condenses again in the neck in a state of purity. As it requires a long time to saturate the pentachloride of phos-phorus and as the amount of the crystalline body produced is very small proportionally this is a tedious process. Liebig found that the same could be effected by passing the vapour of pentachloride of phosphorus over chloride of ammonium heated almost to the point of sublimation in a glass tube three feet long in a coinbustion furnace. Impure phosphuret of ni trogeii is formed torrents of hydrochloric acid are given off and chlorophosphuret of nitrogen condenses in a receiver attached to the combustion tube.This is the process which I prefer ; but I have found it expedient to modify it in some degree. One part of pentachloride of phosphorus is mixed with 2 parts of well dried chloride of ammonit& in a Florence flask which may be half filled with the niixture. A series of two or more receivers is attached by means of tubes arid perforated corks. The first receiver should be dry and kept cool; the last should contain a considerable quan- tity of water. IIeat is then applied to thc flask either by means of a large flame of a spirit lamp or by glowing charcoal. The penta- chloride of phosphorus gradually sublimes combining with the chloride of ammonium which becomes red at first and is afterwards converted into a light brown substance wholly free from soluble chloride but retaining the original shape of the pieces.Chlorophos-phuret of nitrogen sublimes. In the first receiver condenses a limpid liquid with perhaps a small quantity of a white powder; whilst the hydrochloric acid gas is absorbed by the water in the last receiver and a little chlorophoephuret is also deposited there. When no more pentachloride of phosphorus remains undecomposed the flask may be suffered to cool and the chlorophosphuret of nitrogen contained in it may be separated from the other matters by either of the processes above detailed. The liquid condensed in the first receiver is colourless and fumes in the air emitting a pungent odour.When poured into water it does not mix but sinks to thc bottom; after the lapse of a minute or two violent chemical action ensues the liquid disappears chlorophos- phuret of nitrogen remains iii its place and the water holds in solu- tion hydrochloric aid phosphoric acids. No permanently elastic gas insoluble in water is evolved during this reaction. If the liquid under consideration be heated a large quantity of hydrochloric acid ON CHLOltOPHOSPHURET OF NITROGEX. is given off. A portion was taken and heated in a water-bath till the gas ceased to be evolved; the temperature was then raised and at 116O C. (240*8OF.) the liquid distilled over. When the thermo- meter began to rise rapidly the distillation was stopped and a liquid remained which deposited a quantity of crystalline chlorophosphuret of nitrogen on cooling.The distilled liquid was decomposed by water only a minute trace of the crystalline body was left; and the hydrochloric and phosphoric acids were precipitated in the ordinary way. 1.2025 grnis. of substance yielded 3.402 , , chloride of iilver and 0.870 ,) , phosphate of magnesia. These numbers reckoned to 100 parts are :-Phospho~s. . . . . 20*4~2 Chlorine . . . . . . 69.80 evidently indicating oxychloride of phosphorus P C1 0, which requires :* Phosphorus . 32.0 20.71 Chlorine . . 106.5 68.93 Oxygen . . 16.0 10.36 -I___ 155.5 100~00 The liquid in the first receiver-then is merely oxychloride of phos-phorus saturated with hydrochloric acid and holding in solution a variable quantity of chlorophosphuret of nitrogen.The formation of the oxychloride must be regarded as accidental. It arises from the access of air to the pentachloride of phosphorus during its preparation ; from the hygroscopic moisture which it is difficult to remove completely from the chloride of ammonium employed ; and perhaps also from the action of vapour of pentachloride of phos-phorus upon the cork. The amount of chlorophosphuret of nitrogen obtained by any of the processes just described bears but a very small proportion to the yentachloride of phosphorus employed-not more I believe than about; 6 per. cent. The quantity appears very uniform.* The slignt excess of chlorine arises in all probability from a small amount af lirdrochloric acid stjll retaincd by the liquid. 138 DlL GLADSTONE PROPERTIES OF CHLOROPHOSPHURET OF NITROGEN. Chlorophosphuret of nitrogen (at ordinary temperatures) is a solid crystalline body. It melts at about llOo C. (280° F.) into a clear liquid which enters into ebullition at about 240° (464O F.) When immersed however in boiling water it acquires a semi-fluid con- sistence; and I have observed that when liquefied and suffered to cool quietly the temperature will sink below looo C. without congelation taking place. Upon agitating it when in this statc the whole becomes a mass of crystals while the therniometer rises from evolution of latent heat.The form of the crystals as obtained by sublimation is that of a rhomboid of which the obtuse angle measures 131O or 132q the acute 48O or 49O the acute angle of this rhomboid either at one or both ends is often truncated when of course the angle formed is about 114O the hexagonal prism is also found. When crystallized from alcohol or from a mixture of alcohol and ether the same forms appear the hexagonal prism being conimon. By crystallization from ether I haye obtained it in the form of beautifully defined hexagonal pyramids the bases of which are in fact the truncated rhomboid before mentioned the angles being 1320 and 114O These pyramids are found attached base to base. The specific gravity of crystalline chlorophosphuret of nitrogen is somewhat greater than that of water but that of the fused compound is less.At ordinary temperatures the substance under consideration slowly evaporates; but when heated it diffuses a dense vapour having a somewhat agreeable but quite peculiar ociour. The taste of its solution in alcohol is of a bitter character. Chlorophosphuret of nitrogen is not soluble in water; indeed as observed by Liebig it shows great indisposition to be wetted by that liquid behaving in this respect like a fatty body. It is dis-solved by alcohol or chloroform and to a large extent by ether; it is likewise very soluble in bisulphide of carbon and in oil of tur-pentine benzol and other hydrocarbons. Its solubility in oxy-chloride of phosphorus has already been incidentally remarked.A decomposition which its solutions in. ether and alcohol spon-taneously undergo will be reserved for after consideration The original discoverers of this substance remarked that it is totally unaffected by aqueous solutions of either acids or alkalis and that fusion with hydrate of potash does not deconipose it. I find how-ever that if chlorophosphuret of nitrogen be brought in contact ON CHLOROPHOSPHURET OP NITROGEN. with such reagents through the medium of one of its solvents it is by no means so stable. Thus if it be treated with alcoholic solutions of potash soda or ammonia decomposition ensues and chloride with other salts of the alkali remain. Even some metallic salts when added to its solution in alcohol will give rise to a double decomposition ; thus if nitrate of silver be added an instantaneous formation of chloride of silver results.The crystals under consideration may be sublimed without altera- tion in an atmosphere of hydrogen or hydrosulphuric acid gas. When heated with iodine they are equally unaffected. Powerful oxidizing agents attack chlorophosphuret of nitrogen and give rise to the formation of phosphoric acid. Thus when its vapour is passed over chromate of lead or metallic oxides-for instance oxide of copper at a red heat-it is decomposed nitrous fumes being at the same time evolved. Nitric acid itself has no action upon the crystals unless it be fuming and at an elevated temperature yet if a solution in alcohol or oil of turpentine be employed the substance is much more readily attacked by the acid in quest ion.Metals themselves at a high temperature exert a decomposing in- fluence upon the vapour of chlorophosphuret of nitrogen a fact observed by Wohler and Liebig. Thus if it be heated in a tube in contact with metallic silver chloride of silver appears to be formed together with some salt equally insoluble in nitric acid and ammonia a little white sublimate is also formed which is soluble in water and con- tains chlorine. Again if a bright piece of silver be immersed in an ethereal solution of chlorophosphuret of nitrogen in a closed vessel it soon becomes coated with an incrustation of chloride of silver and the insoluble salt before-mentioned after the lapse of some weeks the decomposition will be complete and the ethereal solution will have acquired an acid reaction.Similarly if the substance in question be heated with potassium in an atmosphere of hydrogen gas combination ensues and chloride together with some other salt of potassium is formed And again if the crystals be dissolved in a pure hydrocarbon and pieces of potassium be added and heat applied combination takes place quietly. COMPOSITION OF CHLOROPHOSPHWRET OF NITROGEN. From the decompositions above stated it is evident that the crystalline body contains phosphorus nitrogen and chlorine. As 140 DR GLADSTONE it is produced without the piesence of air or moisture and as the pentachloride of phosphorus and the ammonia or chloride of ammo-nium from which it is formed are both free from oxygen it is sufficiently evident that that element cannot enter into the COM-position of the crystals.In order to satisfy myself as to the presence or absence of hydrogen in this compound I performed the following experiments. 1st. A weighed portion was burnt with chromate of lead and the water was collected as in the ordinary process of organic analysis metallic copper being placed in the anterior portion of the tube and extraordinary precautions being taken that every material employed should be perfect.1 y dry.-2nd. A long combustion-tube was filled with in the first place a weighed portion of the crys- talline body then several inches of copper turnings and reduced copper afterwards some chromate of lead separated €rom the former by a plug of asbestos and then again copper-turnings.To the combustion-tube was attached a srniall tube containing sticks of caustic potash and connected with it was one of Will's nitrogen apparatuses partially fillcd with dilute hydrochloric acid. Com-bustion was performed as usual. So small a trace of water or aiiinionia was obtained in either instance as to preclude the belief that hydrogen forms a constituent of the crystalline body submitted to experiment. The original investigators of this substance attempted an elementary analysis of it. The method adopted by them was that of decomposing the chlorophosphuret in a tube filled with uietallic iron. The gas given off was collected and estiniated as pure nitrogen; whilst the chloride of iron contained in the tube was vashed out and the chlorine precipitated as siher-salt.No attempt was made to estimate thc phosphorus. The results were NitroFen. . . . 11.2 10.1 979.2 per cent Chlorine . . . . 58.3 , > J From these numbers Wohler aud Liebig deduced the forinula P N Cl,; but knowing that the estimations of nitrogen were falla- cious they put it forward with little confidence thinking indeed that it might rather be P N Cl,. I employed various methods of decomposition for the analysis of this substance in order if possible to insure a correct result. I. 0.5225grm. of the crystalline body was dissolved in alcohol and a solution of nitrate of silver was added. Chloride of silver continued to subside for a couple of days.At length 1,246gri. was obtained. ON CHLOROPHOSPHURET OP 3ITROGEN. 11. 0.457 grm. vas decomposed by an alcoholic solution of am-monia. When evaporated to dryness and redissolved in water it yielded 1.0845grm. of chloride of silver. 111. 0*19412grm. was decomposed by an alcoholic solution of pure potash. This was evaporated to dryness and heated to redness in a tube along with fresh potash. The ammonia evolved mas collected in a hydrochloric acid apparatus and yielded 0-327 grm. of ylatinum- salt. The fused mass dissolved in dilute nitric acid yielded 0.4647 grm. of chloride of silver and 0.116 grm. of phosphoric acid estimated by nieans of bayyta. IV. 0.2655grm. was analyseci in the same manner as the preceding except that the fnsion with potash was conducted in a short silver tube inserted in an ordinary glass tube to which the hydrochloric acid apparatus was attached.It yielded 0.393 grni. of platinum-salt and 0.1552 grm.of phosphoric acid. V. 0.4375 grm. was boiled with fuming nitric acid in a vessel so contrived that the yolatilized chlorophosphuret of nitrogen was returned again to the oxidizing liquid. The phosphoric acid esti- mated by ineans of baryta-salt was found to be 0.2615 grni. VI. 0.2357 grm. was dissolved in alcohol and ether and boiled with nitric acid in a vessel similar to that employed in the last experiment. Violent action of course ensued and fresh alcohol and nitric acid were added until it was believed that the oxidation of the chloro- phosphuret was complete.The solution yielded 0.1593 grrn. of phosphoric acid. VII. 0.232 grm. was decomposed by passing it in vapour over red- hot oxide of copper. This method was found unsuitable for the de- termination of the chlorine as a part of it enters into some iiisoluble compound probably the dichloride. The mass remaining after the combustion was dissolved in hydrochloric acid ; and the phosphoric acid was precipitated from a very ammoniacal solution as the ain- monio-phosphate of magnesia. The portioii undissolved by hydro-chloric acid was then digested in strong nitric acid and the phosphoric acid thus fcrmed was precipitated as before. The second quantity of magnesia-salt being impure was again fused with carbonate of potash and the phosphoric acid reprecipitated.The whole amount of pyrophosphate of magnesia obtained was 0.2605 grm. These results reckoned to 100 parts are :-J. 11. 111. IV. v. VI. VII. Phosphorus -7 26.52 25-99 26.55 30.08 31.69 I Nitrogen -10.55 9.19 ---c Chlorine . 58.83 58.53 59-02 -- 1 42 DR GLADSTONE This confirms the formula of the discoverers P N Cl, which would require :-a Phosphorus 96.0 31.84 Xitrogen . . 28.0 9-29 Chlorine . 177.5 58.87 301.5 10OwO0 The majority of my determinations of phosphorus it will be seen indicate an amount considerably below that required by theory ; yet I think this presents no great obstacle. The compounds contain- ing phosphorus and nitrogcn into which the chlorophosphuret of nitrogen is resolved are themselves very difficult of decomposition some unrecorded experiments conducted by other methods yielded estimations of phosphorus which were much smaller and unques- tionably incorrect.Froin the amount of nitrogen and chlorine obtained it is manifest that if the crystals contain no other element than phosphorus beside these such an amount as 26 or 27 per cent requires the addition of 4 or 5 to complete the 100 parts (vide Experiment 111 in which the sum of the three numbers is only 96.09). The 7th experiment does give a result coincident with theory ; yet unfortunately from the difficulties attending it I cannot lay much stress upon this determination. The method adopted in the 6th experiment is I conceive worthy of the greatest reliance and that yields 30.08 per cent of phosphorus.Besides which an indirect method of analysis which will be detailed towards the close of this paper afforded a determination of the amount of phosphorus equal to that required by the formula P N (21,. AZOPHOSPHORIC ACID Ii.on-saZt.-It bas already been remarked that if chlorosulphuret of nitrogen be dissolved in alcohol and potash or ammonia be added decomposition instantly ensues. Now if this solution be evaporated to dryness redissolved in water and rendered perfectly neutral it gives no precipitate on the addition of most inetallic salts thus proving that it contains no phosphoric acid. If however the neutral solution or the solutioii rendered strongly acid be boiled with a salt of sesquioxide of iron a white flocculent precipitate speedily forms.It has the appearance of the ordinary phosphate of the sesquioxide of iron but it is at once distinguishcd from that salt by the two remarliable properties of being insoluble in dilute acids but completely solitble in ammonia. When treated with a solution of ON CHLOROPHOSPHURET OF NITROGEX. potash this salt is immediately decomposed ; sesquioxide of iron remains; and in solution is a potash-salt of the new acid from which the iron-salt may again be formed by neutralization with acid and the addition of any solution of that metal. Alkaline carbonates decompose it upon the application of heat. If it be fused with potash ammonia is evolved; and the fused mass redissolved in acid and treated with ammonia gives ordinary phosphate of iron.Strong sulphuric acid clissolves it and decomposes it when warmed. The action of heat upon this salt is remarkable. When dried at ordi- aary temperatures or at loooC. it has a white or rather a light buff colour ;but when heated to aboat 330° C. (572OF.) it suddenly gives off vapour of water and ammoniacal gas assuming a dark brown colour while a small quantity of a white crystalline body also sublimes. This sublimate is soluble in water; when it is treated with a solution of nitrate of silver a white precipitate is produced which changes immediately to a clear orange-red; and shortly afterwards there is formed a quantity of black substance insoluble in ammonia ap- parently reduced silver. The iron-salt gives off water preparatory to decomposition even when previously dried at 220° C.(428OF.) Although this salt does not present itself in crystals the fact of its being formed in decidedly acid solutions is a tolerable guarantee of its purity. I have prepared it at as low a temperature as 46O C. (114*8*F.),but a higher degree of heat is desirable so as to ensure a complete transformation Analyses were effected by the following methods. I. 0.2735 gym. of salt dried at 1000 C. was fused with pure hydrate of potash in the short silver tube mentioned above inserted within a glass tube. The evolved gas was collected in Will’s hydro- chloric acid apparatus and yielded 0.248 grm. of ammonio-chloride of platinum. The fused mass was then dissolved in water filtered and the phosphoric acid in the solution was precipitated as magnesia- salt.The undissolved oxide was fused with a mixture of the carbon- ates of potash and soda to separate aiiy phosphoric acid which niight still be combined with it following the directions given by Rose in his paper 011 the estimation of phosphoric acid in Pogg. Ann. Part 11. for last year. The amount of sesquioxide of iron obtained was 0.0943 grm. The additional pyrophosphate of magnesia obtained was 0.005 grm. to be added to the previous amount 0.2373 grm. 11. 0,215 grm of salt dried at 70° C. (158O F.) weighed only 0.205 grin. when dried at 120°C. (248O F.) This was decomposed per se by heat in a glass tube to which was attached a tube contain- ing sticks of caustic potash.The loss of weight during thc process of heating was 0.0405 grm. ; the amount of water collected was 0.0145 grm. The mass remaining in the tube was fused with caustic potash; and the ammonia evolved collected in a hydrochloric acid apparatus yielded 0.0215 grm. of platinum-salt. As the substance had been fused with potash in a glass tube it was very probable that some other oxides beside sesquioxide of iron existed in the alkaline mass for this reason the method suggested by Rose foi* the separation of mixed oxides from phosphoric acid by means of nitric acid and mercury was adopted. The amount of sesquioxide of iron was found to be 0.0695 grm; that of pyrophosphate of magnesia obtained was 0.179 grm. 111. A portion of iron-salt which had been allowed to remain seven days in vacuo over sulphuric acid weighed O%A grm ; when dried at between I 20° and 130°C.(248°-2660 F.) it parted with moisture and weighed only 0.2422 grill. The salt heated as in the preceding experiment lost 0*0475grm. The amount of water col- lected in the tube filled v-ith sticks of potash was 0.0.29 grm; the arnnioniacal gas given off and collected in a hydrochloric acid apparatus annexed to the tube for absorbing the moist ure yielded 0.110 grm. of platinum-salt. The remaining mass was fused in the silver tube and evolved gas which afforded 0.022 grm. of pure chloride of ammonium. The amoxiiit of sesquioxide of iron in the alkaline mass was 0.0835 grm IV. 0.2112 gmi. of iron-salt dried at a temperature of 1600 C (320°F.) heated as in preceding experiments showed a loss of 0,0393 grni.The amount of water collected was 0.025 grm. ; that of platinum-salt was 0.0755 grm. The salt was fused with potash as before but the amount of ammonia evolved was not correctly as- certained. The resulting mass was dissolved in acid; arid since I had learnt by experience that the entire amount of phosphoric acid pro-dixced by the decomposition of such substaiices as these phosphorus compounds is seldom if ever precipitated by magnesia-salt the sepa- ration of the sesquioxide of iron from the phosphoric acid was effected as in the preceding cases but the acid itself was estimated by means of baryta. The amount of sesquioxide of iron was 0.071 grni.; that of phosphoric acid 0.133 grm.It will be evident froin consideration of Experiments 111. and IV. that some other gas besides ammonia and vapour of water is evolved when this iron-salt is heated Thus Rater. Ammonia. Actual loss. Exp. 111. 0.0229+ 0*0084= 0.0374 not 0.0475 asp. ITr 0.025 + 0.0057 = 0.0307 , 0.0393 O’J CHLOROPHOSPHUEET OF NITROGEX. If we suppose that the animouia did not exist a3 such in the iron-salt which is of itself improbable but that it was formed under the influence of heat by the combination of nitrogen with hydrogen which was itself obtained from the decomposition of a portion of the water; and that the oxygen thus set free was evolved along with the other gases ve have a theoretical loss coinciding very nearly with that actually found.Decomposed Theoretical Actual Rater. Nitrogen. water. loss. loss. Exp. 111. 0.029 +0.0069 -j-0.0015 x 9 =0.0494 0*0475 Exp. IV. @026 +0.0047+0*0010x 9 =0 0387 0.0393 If we calculate the ammonia evolved in the secoiid experiment on the same principles as this we have assuming x as the amount of hydrogen in the water that wasdecomposed 14X 0.0145f-+9 x =0*0406, 3 from which it appears that the quantity of hydrogen combined to form ammonia was 0.0019 grm. ;and the nitrogen with which it united itself must have been O*OO9 grms. The percentage amount of the elements reckoned from the numbers obtained in the four experiments recorded above is subjoined. The weight of iron-salt as dried at a temperature not lower than looo C.is assumed as the basis of the calculation; and I have also added in brackets the amount of hydrogen and nitrogen in the second experiment as estimated on theoretical grounds from the loss. I. 11. nr. iv. Sescpioxide of iron 34.48 33.90 34-47 33.62 Phosphorus . 25.05 25.07 -27.93 Nitrogeii ... 5.67 C5.071 5-24 -Hydrogen ... -[1-70] 194 1.81 These numbers accord sufiicientl ywith those deduced from the formula Fe,O,. P,NO,. 4FiO. Sesquioxide of irou ....80 34-19 Phosphorus . . .64 27.35 Nitrogen ....... It 593 Hydrogen ....... 4 1.71 Oxygen ........72 30.77 -234 1oo*oo VOL. 111.-NO. x. L I4!6 DR. GLADSTONE If we assume as the basis of our calculation the weight of iron-sal as dried at 70°C. or at ordinary temperatures in vacuo and add the amount of water driven off at a higher degree of heat we have for the second and third experiments I.11. Sesquioxide of iron . . 32.33 32.87 Phosphorus . . . . . 23.92 __. Nitrogen . . [4.83] 5.00 Hydrogen . . . . t2.131 2-36 corresponding with the numbers deduced from the formula Fe 0,. P IS0,.5 HO Sesquioxide of iron . . . . 80 32.92 Phosphorus . . . . 64 26.34 14 5.76 Xitrogen . * . . 5 2.06 Hydrogen . . . . . . . . . . . 80 32.92 Oxygen. -243 loonoo In what light these 5 atoms of water are to be viewed I know not I have in vain sought the aid of powerful microscopes for any crystalline appearance in the precipitate. It seems also that one of the atoms must be regarded in a different manner from the four others since it is driven off at the boiling-point of tvitei; while the rest remain COMPOUND OF THE IRON-SALT VITH A;C.fNONIA~ It has already been stated that the iron-salt is entirely soluble in ammonia.It gives a red solution from which the iron-salt may be again precipitated by the addition of an acid. An attempt was made to obtain this compound salt in the dry state. An ammoniacal solution was carefully evaporated in a water-bath it came out as a dark red mass very soluble in water but manifesting no disposition to crystallize. After being perfectly dried it was treated with water when it separated into two portions; the one soluble containing ammonia and giving a characteristic precipitate when treated with acid; the other like micaceous plates of the colour of red prussiate of potash which appeared to be mainly sesquioxide of iron.Similar salts of other oxides may be produced from the chlorophos- phurct of nitrogen in the same manner as the iron-salt just described ; bnt that is the only one as far as I have observed which tvill preci- ON CHLOROPWOSPHURET OF NITROGEN. pitate from very acid solutions. Hence it is the salt upon the purity of which the greatest reliance can be placed and I accordingly chose it for the most particular examination. Alumina-salt.-This is prepared when a solution of alum is added to an aqueous solution of chlorophosphuret of nitrogen decomposed by ammonia and alcohol which should be slightly acid to test-paper.No precipitate falls in the cold but upon boiling the mixture a white flocculent precipitate is formed. This is an alumina-salt similar to the iron-salt already investigated when dry it is pulverulent upon being heated in a test tube it becomes black then again white giving off ammonia water and a small quantity of the white sub- limate mentioned as being also formed during the destruction of the iron-salt. C~pper-saZt.-When sulphate of copper is added to the same slightly acid solution of chlorophosphuret of nitrogen and the mixture boiled a pale blue flocculent copper-salt precipitates. When heated per se this salt fuses smells up becomes black and afterwards lighter in colour and evolves ammonia vapour of water and the same white sublimate.It is wholly decomposed by a cold solution of potash. An analysis was made. 0,2923 grm of copper-salt dried at lOO*C. was heated in the same manner as the iron-salt. The loss in weight was 0-0468 grm.; the amount of water collected was 003.0 grm. ; that of platinum-salt obtained was 0-0172 grm. The remaining mass was then fused with potash. The amount of pure chloride of ammonium obtained from the evolved gas was 0.011 grm. The oxide of copper was separated from the phosphoric acid by fusion with alkaline carbonates with the pre- cautions recommended by Rose in the memoir already more than once referred to. It weighed 0.124grin. These iiumbers reckoned to 100 parts accord sufficiently with the formula 3 CuO. P NO,.5 HO. Calculated. Found. Oxide of copper . 119 42.20 42-42 Phosphorus . . . 64 22.70 -Nitrogen . . . 14 4.96 4.72 Hydrogen . . . 5 1-77 1.94 80 28.37 -Oxygen * 282 100.00 From the amount of water and ammonia evolved during the heating of this copper-salt compared with the actual loss of weight it 22 mould appear that uiilike the iron-salt a portion of the oxygen set free by the deconiposition of water was not given off along with the other gases. Decomposed Theoretical Actual Water. Nitrogen. water. loss. loss. 0.030 + 0.0108 -i-0*0024x 9 = 0-06.24 instead of 0.0468 Since the heated ixiass after becoming black became again white it seems probable that the phosphuret of the metal or some such compound-to which without doubt the black colour in these de- compositions is owing-was oxidized by the free oxygen ; and this will account for the decrease of weight being less than that expected.SiZz;er-salt.-If to a neutral solution in water of the salts obtained by the decomposition of chlorophosphuret of nitrogen by means of alcohol and ammonia excess of nitrate of silver be added a dense precipitate falls consisting principally of chloride of silver. If this be shaken and removed by filtration and the solution be boiled a bulky white precipitate forms. This salt wlien collected and dried has the appearance of a granular grey powder little affected by light. When heated per se it fuses swells up greatly and evolves the usual gases becoming at the same time black which is aftern-arch exchanged for a greenish colour.A quantity was prepared for analysis by a different process. Some of the iron-salt \+-asdecomposed by a solutiorr of potash in the coId; the resulting solution was neutralized by nitric acid and nitrate of silver was added. Thc salt thus obtained wts analysed in a similar manner to the preceding. It was dried at 160° C. (328O I?,} but it appeared to lose nothing between 8Uo C. (1'76O F.) and that point when it began to soften. I. 0,1385 grni heated pw se showed a loss in weight of 0.005 grm. The amount of water collectccl was 0.0018 grill.; that of platinum-salt obtained was 0.0225grm. After fusion n ith ptash the amount of platinurn-salt obtainect was 0.025 grm. The alkaline mass dissolved in dilute nitric acid and treated with hydrochloric acid gave 0*1075grm.of chloride of silver ; and the phosphoric acid estimated by means of baryta-salt was 0.0499 grm. 11. 0.394 grm. of a separate preparation decomposed by dilute hydrochloric acid yielded 0.333 grin. of chloride of silver. These numbers reckoned to 100 parts yield I. 11. Oxide of silver . G7-15 68.39 Phosphorus . . 13-79 -Nitrogen . . . 2.17 -IIydrogell . . . 0.36 7 ON CHLOROPHOSPHURET OF NITROGEXe Prom the amount of base it would appear that the silver-salt is strictly analogous in composition to the copper-salt just described ; and yet the amount of hydrogen obtaiiied would rather indicate 2 atoms of water than 5. It must however be borne in mind when estimating the value of these analytical results that the varying quantity of white sublimate may always introduce an error more or less great in the determination of hydrogen.Calculation from the formula 3 Ago. P NO,. 5 HO Oxide of silver . . . 348.9 68.16 Phosphorus . . . 64 12.50 Xitrogen . . . . . Hydrogen. . . . . 11 5 2.73 0.98 Oxygen . . . . . 80 15.63 5119 100*00 The comparison between the actual loss of weight in the first expe- riment and that calculated from the amount of water and ammonia found reckoning the whole oxygen to be evolved is as follows :-Decomposed Theoretical Actual Rater. Nitrogen. nater. loss. loss. 0*0018+ 0.0014 + 0.0003 x 9 = 0.0059 0.005 Lead-salt.-The lead-salt may be prepared by siniilar methods.It is white and granular when dry. If decomposed by heat it coin-ports itself in the same manner as the salts previously described. It is decomposed not dissolved by ammonia. Mercury-salt.-Flocculent mercurial salts may be prepared from the potash-salt by double decomposition with either the subnitrate or protonitrate of mercury. That containing the suboxide is white with a slight tinge of yellow. When heated per se after being dried in vacuo it becomes black water and ammonia and the white subli- mate are given off; the mass fuses and swells greatly and metallic mercury eventually sublimes. Raryta-salt.-This salt cannot be obtained in the pure state by adding a solution of n haryta-salt to a neutral or slightly acid solu- tion of decomposed chlorophosphnret of nitrogen.It may however be easily prepare$ when the iron-salt is decomposed by a cold solution of potash the resulting liquid neutralized by acid and nitrate of baryta or chloride of barium added. The salt thus obtained is white and flocculent when dried and heated per se it gives off the same bodies as all the other salts of this acid which 1 have examined becoming in the meantime of a dark brown colour. 150 D11. GLADSTOSE The analysis was effected in the usual way. I. 0.2195 grni. of baryta-salt precipitated from a slightly acid solution and dried at 150° C. (302OF.) showed a loss of weight upon heating of 0.0135 grm. The water collected was 0 0045 grm. ; the platinum-salt obtained 0.069 grm. After fusion with potash the platinum-salt obtained was 0.020grm.The sulphate of baryta pre- cipitated was 0.224grrn. and the pyrophosphate of magnesia pro- duced was 0.137 grm 11. 0.1487 grm. of baryta-salt precipitated from a solution ren-dered slightly ammoniacal and dried at 150° C. showed a loss of weight upon heating of 0 0092 grm. The water collected mas 0.005 grm.; the platinum-salt obtained 0.029 grm. After fusion with potash the platinum-salt obtained was 0.033 grm. The sulphate of baryta precipitated was 0.1415 grm. and the pyrophosphate of magnesia produced was 0.0815 grm. These numbers reckoned to 100 parts accord best with the per- centage deduced from the formula 3 BaO. P NO,. 2 "0. Calculated. Found. I. I1 t Baryta . . . 230 62*84 66.92 62.45 Phosphorus 64 17.49 17.63 15.47 Nitrogeiz .. 14 3.82 2-55 2.62 Hydrogen . 2 0.55 0.64 0.63 Oxygen .. 56 15.30 -366 100*00 The salt analysed in the first experiment appears to have been impure. The actual loss of weight upon heating the salt in each of these experiments is a little less than that calculated from the amount of water and ammonia collected supposing the whole of the oxygen set free to be given off as such. This must be ascribed to the same reason as in the case of the copper-salt. Decomposed Theoretical Actual Water. Xtrogen. water. loss. loss. Oflo45 + 0.0043 + 0*0009 x 9 = 0,0169 instead of 0.0135 0*0040+ 0.0018 + 0.00089 x 9 = 0.0103 , ,)0.0092 In glancing over these analyses it will be remarked that the amount of nitrogen obtained is in every instance below that required by theory and in some cases the deficiency is very considerable.I believe this is solely due to the nitrogen not being entirely converted ON CNLOROPHOSPHURET OP NITROGEN. into ammonia during the fusion with potash and to the difficulty of collecting the whole quantity of gas then evolved. This opinion is supported by the fact that in the copper-salt where the large amount of water permitted the nitrogen to be mostly given off as ammonia when the salt was heated per se the amount of nitrogen found very nearly equals that calculated from the formula ; while in the baryta-salt where the very small amount of water precluded mucn of the nitrogen being thus given off the deficiency was far more considerable.I have also prepared by similar methods compounds of this acid with the oxides of chromium manganese nickel cobalt zinc cad- mium and tin besides strontia lime and magnesia. A11 these present themselves as flocculent precipitates; and all are of a white colour except the cobalt-salt which is pink. No precipitate is ob- tained iipon mixing a solution of the potash-salt with either a solu-tion of bitartrate of antimony and potash or a solution of terchloride of gold. If the iron-salt be decomposed by soda and the alkaline salt thus obtained be rendered slightly acid and a solution of bichloride of platinum be added no precipitatc results. I obtained however a compound containing this metal when a mixture of the bichloride and potash-salt was evaporated to dryness.It wasof a brown colour insoluble in water and soluble with difficulty in hydrochloric acid when heated in a tube it assumed a swimming appearance from the escape of gas; water was given off together with a little white sublimate and-not ammonia-but hydrochloric acid in considerable quantity. The substance in the tube became quite black and after- wards brown like spongy platinum. It is possible that this COM-pound may contain potash. Potash-salt.-The compounds of this acid with the alkalis being soluble in watcr cannot of course be obtained in a fit state for analysis in the same manner as the metallic salts. In order to obtain a pure potash-salt some of the iron-compound was decomposed by means of a quantity of the purest potash not equivalent to thp whole of the iron.The solution was neutral to test-paper whilst a portion of the white salt unconverted into the red oxide of iron was a further guarantee that the whole of the caustic alkali had entered into a new compound The filtered solution was evaporated in vacuo over sulphuric acid. It was hoped that a crystalline salt would thus be obtained but it dried to a greenish gum-like mass deliquescent in moist air but insoluble in alcohol. It was analysed by the addition 152 DR. GLADSTONE of bichloride of platinum and free hydrochloric acid; but owing to the formation of the peculiar platinum-salt noticed above it is doubtful whether the whole of the alkali was converted into the double chloride of platinum and potassium.Yet from 0,1243grni. of the salt dried in vacua thcre was obtained 0.272 grm. of double chloride which is equivalent to Potash-42.35 per cent. Now the conipositioii 3 KO. PzNO,. 5 HO would requirc Potash-46-49 per cent a quantity not much larger. Ammonia-salt.-When the lead-salt is decomposed by dilute am.. monia and the solution thus obtained is evaporated in uacuo over sulphuric acid the ammonia-salt presents itself as a viscid mass without showing the slightest tendency to crystallize. It is very soluble both in water and in alcohol. Free acid.-My first attempts to obtain this acid in the free state were made by deconiposing the copper-salt diffused through water by nieans of a stream of hydrosulphuric acid ;but a breaking- up of the liberated acid into siiupler forms seemed always to ensue at least after the lapse of a short time it was resolved under the influence of water into compounds of ammonia with phosphoric or phosphorous acid.But on treating the silver-salt with dilute hydro- chloric acid a solution was obtained from which the characteristic iron-salt could be readily produced. This mas evaporated down at first by heat afterwards under the air-pump. Some crystals ap- peared which however swelled and broke up before the mass became perfectly dry. A semi-solid non-crystalline substance remained which proved to be the acid in question. The acid thus obtained is deliquescent in moist air readily soluble in water or alcohol and slightly so in ether its solution reddens blue litmus-paper and has an agreeable acid flavour.It may be subjected to a high degree of heat without alteration; but if heated on platinum-foil iu the flame of a spirit-lzmp it fuses blackens and eventually rises in vapour. The salts already described may be prepared from it :thcs if it be treated with ammonia in excess and a minute quantity of a solution of sulphate of sesquioxide of iron be added not the slightest trace of sesquioxide appears but the liquid assumes a clear red colour. This I esteem the most characteristic single test of the acid in question. It appears then that me have here a peculiar acid resembling phos- ON CHLOROPHOSPHURET OF NITROGEN phoric acid both in its terbasic character and in the general physical and chemical character of its salts but differing from phosphoric acid in constitution since it contains one atom of phosphorus and one atom of nitrogen in addition to PO,.Without reference to any particular theory I shall simply denominate it Azophosphoric acid. A list of the salts analysed is annexed in the subjoined table for the purpose of comparison. Salt. Dried at Composition. Azophosphate of iron . below 100° C. Fe 0,. P,NO,. 5 HO 9 >> 100°-1600 C. Fe 0,.P NO,. 4 HO , of copper . 1000 c. 3CuO. Y NO,. 6 HO , of silver . 1000-16O0 C. 3AgO. P NO;. 5 HO , of baryta . 150°C. 3 BaO. P,NO,. 2 130 , of potash Ord.teni. invac 3 KO. P,N05.5 HO? It occurred to me that the readiness with which the azophosphate of iron is produced from the chlorophosphuret of nitrogen might be taken advantage of in the analysis of that substance particularly in reference to the amount of phosphorus.A weighed portion of the crystals was therefore dissolved in alcohol decomposed by ammonia evaporated to dryness and the resulting mass re-dissolved in water. An acid solution of sulphate of sesquioxide of iron was then added and boiling was continued for an hour. The salt thus precipitated was collected on a weighed filter and dried at 100°C The filtered solution was evaporated to dryness treated with a. little hydrate of potash re-dissolved in acid and precipitated by ammonia. The mixture of phosphate and oxide of iron thus obtained was analysed by fusion. 0.2803 grni.of chlorophosphuret of nitrogen yielded 0*180 , , azophosphate of iron and 0.1435 , , pyrophosphate of magnesia. Assuming that phosphorus constitutes 27.35 per cent. of azophos-phate of iron these results indicate Phosphorus-32-00 per cent an estimation equalling or rather just exceeding that required by the formula P N C1; viz. Phosphorus-31*84 per cent. In the present paper I have confined myself to a mere description and analysis of this crystalline body the so-called ‘I Chlorophos- 154 MI%. WILSON phuret of Nitrogen,’’ P N C16;and of a peculiar acid with its salts 4‘ Azophosphoric Acid,” P NO,. Upon the manner of formation of the first cotnpound and upon the reactions by which the second is derived from it I hope to cnter at some future opportunity when I anticipate laying before the Society some further products of the decomposition of chlorophosphuret of nitrogen and among them some which will probably facilitate our understanding of the ratioual com-position of the bodies here described.

ISSN:1743-6893    

DOI:10.1039/QJ8510300135

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

154 NR. WILSON XVIII.-On theAction of Chloride of Cyanogen upon Tohidine. By W. WILSON The perfect homoloy existing between toluidine and ariiline left but little doubt respecting the deportment which the former alka- loid would exhibit when exposed to the influence of chloride of cyanogen ; still the discrepancies which we frequently observe between the various members of one series especially if we rise on the scale of compoimds made it desirable to establish the behaviour of toluidine by experiment. PREPARATION OF TOLTJIDINE. The preparation of toluidine is a process of considerable difficulty inasmuch as the collateral hydrocarbon can be obtained only in comparatively small quantities. The formation of toluol has hitherto been observed in different processes namely in the distillation of tolu-balsam by Deville its discoverer; iii the distillation of dragon's blood (dracyl) by Boudault and Glenard; in the decomposition of toluylic acid by Noad; and lastly it has been met with aniong the hydrocarbons of coal-tar naphtha by Mansfield.I have tried all these methods in order to procure toluol in larger quantities and I find that the source last-mentioned is that which yields this compound most easiIy and in greatest quantity ;-only comparatively minute quantities being obtained by the other processes. The best plan is to select the fraction distilling between looo and 120° C. and to treat this portion with half its bulk of eon-centrated sulphuric acid. I am not prepared to say what substances are removed by this process; the fact is however that a constant boiling-point is more easily reached with than without the use of ON I\IETOLUIDINE sulphuric acid.In all cases a series of tedious distillations is required in order to accomplish this object. The boiling-point of toluol was found to be llOo C. The conversion of toluol into nitro-toluol succeeds without dia- culty in the usual manner. Nitro-toluol was found to boil between 220°and 2,25O,withotit decomposition. Those chemists who have used Zinins' process for the amidation of nitro-compounds are aware how difficult it is to effect the complete conversion of these substances when treated with sulphide of ammo-nium especially if there is but 1equivalent of hyponitric acid present.I have used in my experiments a solution of hydrosulphate of sulphide of potassium with which the nitro-toluol was repeatedly distilled. The advantages which the potassium-compound presents are very remarkable not half the time being required as with sulphide of ammonium; moreover the base once formed has no longer to be separated from the ammonia which in the latter case distils over with it. The toluidine obtained in this manner after having been several times crystallized in the form of oxalate and lastly distilled with caustic lime presents all the properties which its discoverers assigned to it PREPARATION AND ANALYSIS OF METOLUIDINE In subjecting toluidine to the action of chloride of cyanogen. I adopted in the first place the same arrangement that Dr.Hofmann had used in preparing melaniline namely a series of tubes filled with the dry alkaloid through which the chloride of cyanogen was drawn by means of an aspirator. I soon found however that the deportment of toluidine is by no means so simple as that of aniline under similar circumstances. The alkaloid being solid at ordinary temperatures it was necessary to support the action from the very conimencemcnt by the application of heat under the influence of which unless it be very carefully applied the newly formed hydrochlorate appears to undergo some farther metamorphoses. On this account I found it more convenient to introduce toluidine into a slightly bent tube to diffuse it by a gentle heat into a thin laycr over the sides and then to expose this increased surface to the action of the gas.In this manner the heat evolved during the reaction was sufficient to keep the substance in a state of fusion. As soon as the action had ceased the resinous mass consisting almost entirely of hydrochlorate of the new base was dissolved in water to which a small quantity 156 MR. WJLSOY of hydrochloric acid had been added. On mixing the filtered so-lution witb potassa a white precipitate took place which was boiled for some time with the potassa in order to distil off with the aqueous vapours small quantities of toluidine which niight hare escaped the action. The residue was thrown upon a filter sepa-rated by washing froin the chloride of potassium and recrystallized from alcohol.From this solution the new base which I propose to call Metoluidiize a name corresponding to melaniline is deposited iu small crystalline plates. It crystallizes better from a mixture of alcohol and water but by no means with the same facility as melaniline; this substance is but slightly soluble in water but somewhat more so at the boiling-temperature. I have established the composition of metoluidine by analyses of the base itself and by that of the platinum-salt 0.2201 grm. of base gave 0.6048 , of carbon and 0.1454 , of water. These numbers together with those obtained with the platinum-salt lead to the forniula 'SO H17 N3J which requires the follow-ing values Theory. Experiment. r-7 30 equivs. of Carbon .. . 180 75-31 74.54 17 , , Hydrogen . 17 7-11 7-34 3 , , Bitrogen . . 42 17.58 -239 100*00 METOLUIDINE AND BICHLORIDE OF PLATINUM Bletoluidine is readily soluble in hydrochloric acid. The solution yields with bichloride of platinum a dark-yellow precipitate which is insoluble in water and alcohol and may be dried at loo*. On analysis the folloving numbers were obtained I. 0.2685 grm. of platinum-salt gave 0.8980 , , carbonic acid and 0.1025 , , water. 11. 0.1897 , , platinum-salt gave 0.0418 , , platinum. 111. 0.2985 , , platinum-salt gave 0,0659 , , platinum. IV. 0.1096 , , platinum-salt gave: 0.0244 , , platinum. ON METOLUIDINB. These numbers lead to the following percentab.e-comltosition I. XI. 111. IV. -Carbon .40.40 -7 Hydrogen. . 404 --Platinum . -22.03 22.07 22-25 The formula C, H17N,. HCI. Pt C1 requires the following values Theory. Experiment. -30 equivs of Carbon . . . 180.00 40.43 40.40 18 , , Hydrogen. 18.00 4.04 4.24 3 , , Nitrogen . . 42.00 9.43 -3 , , Chlorine . . 106.50 20.93 -1 equiv. , Ylatinuin . . 98.68 22.17 22.15 _I___-1 , , Platinum-salt . 445.18 100*00 The formation of metoluidine is perfectly analogous to that of melaniline; 2 equivalents of toluidine and 1 equivalent of chloride of cyanogen yield 1 equivalent of hydrochlorote of nietoluidine. 2 C, H N + C N C1 = C, 1117N3 13.U. -+ u c Y ToluiclinP. Chloride €X ydr ochIorate oi of Cyauogen. ?kletoluidinc.* * The bzses produced by the action of chloride of cyanogen upon aniline and toluidine exhibit a remarkable analogy with one of the platinum alkaloids obtaiiied by 3%.Reiset which will at once become perceptible if we compare the formula of the chlorides when considered as ammonia compounds Chloride of Reiset’s base { 2 } N IT4 K C1

ISSN:1743-6893    

DOI:10.1039/QJ8510300154

出版商:RSC    

年代:1851

数据来源: RSC

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MR. DANSON ON BJSULPHAMYLIC By JOSEPHDANSON$ F.C.S. Owing to the interesting results which have been obtained by Dr. Muspratt* and Mr. Medlockf with regard to the acids resulting froni the action of nitric acid on the sulphocyanides of ethyl niethyl and amyl and those of ErdmannJ Ge-rathewoh15 and Koppll upon acids produced by the action of nitric acid on the bisulphides of the above organic radicals I have been induced to enter upon the subject with the view of closing the gap which Dr. Muspratt left open in his last paper,S( i. e. proving by analysis the identity of the acid produced by the action of nitric acid on the bisulphide of aniyl with that obtained by Mr. Medlock from the sulphocyanide of arnyl. Gerathewohl and Erdmann give for the formula of the baryta-salt of their acid Ba.C, HI S 0,. HO=Ba. C, H, S 0 differing from Mr. Medlock’s formula Ba. C, Hll S 0 by 1 equivalent of hydrogen. PREPARATION OF BISULPHIDE OF AMYL The preparation of the bisulphide of arnyl is analogous to that of the 1)isulphides of ethyl and methyl. One part of dry sulphamylate of lime intimately mixed with one part of bisulpbide of potassium was introduced into a retort capable of containing three times the quantity of mixture. On the application of heat some water and a small quantity of a colourless oil distilled ;and as the temperature in- creased a reddish-yellow oil passed over possessing a strong odour of garlic. The impure oil was washed with distilled water and after- wards digested with chloride of calcium in order to remove the last * Chem.SOC. QU. J. I 44. $ Chem. SOC. Qu. J. I 368. 2 J. Pr. Chem. XXXIV 447. 8 Lduig’s Chemie der organischen Verbindungen 11 487. 11 Ann. Chem. Phaim. LV 166. 7 On the identity of bisulphethylic with hyposulphethylie acid and of bisulphime-thylic nith hyposulphamethylic acid. Chem. SOC Qu. J. 111 19. AND HYPOSULPHAMYLJC ACIDS traces of moisture. The anhydrous oil was separated from the chlo- ride of calcium by distilling the mixture in a small retort; the pure bisulphide of amyl passed over as a yellow oil. PREPARATION OF THE ACID FROM BISULPHIDE OP AMYL One part of the bisulphide of amyl was placed in a flask immersed in water; one part of nitric acid was added cautiously to it and agitated occasionally.Under these circumstances the action goes on very slowly ;but if the temperature is slightly increased the action is very violent nitrogen binoxide of nitrogen nitrous acid and peroxide of nitrogen passing off. The following equation represents the decomposition Bisulphide of amyl Hyposulphamylic acid. When the disengagement of gas had ceased the liquid which was of a green colour was carefully evaporated over a water-bath till the last trace of nitric acid was expelled a reildish oily fluid re- maining possessing a most peculiar odour and a strong acid taste. In order to obtain the acid in a state of perfect purity the fluid was treated with water in which it readily dissolved and saturated with carefully prepared carbonate of lead-filtered-and the lead solution decomposed by sulphide of hydrogen ;the sulphide of lead was then separated and the filtrate evaporated on a water-bath to expel all the sulphide of hydrogen.A colourless oily liquid remained which is the pure hyposulphamylic acid; The formula resulting from the analysis of the baryta-salt is The salts of this acid possess great similarity to those of hypo-sulphethylic acid and like thcrn readily crystallize. The potash ammonia and lirne-salts crystdlize in colourless plates easily soluble in water and alcohol. The only sa!t which I thought necessary to analyse was the baryta-salt. HYPOSULPHAMYLATE OF BARYTA. When an aqueous solution of the acid is saturated with carbonate of baryta and then evaporated gently on a water-bath pearly scales are deposited which are very soluble in xater and alcohol.160 MR. DANSON ON BISULPHAMYLIC ANALYSIS OF THE SALT. I. 0*3800grms. of salt dried at loooC. gave 0.3860 , of carbonic acid and 0-1760of water. TI 0.1643 , of salt gave 0.0863 grms. of sulphate of baryta = 0.0566 , of baryta = 3444per cent. CENTESIMALLY REPRESEN TED. Found. Analysis of the baryta- Analysis of the ba-salt of the acid produced ryta-salt of theacid from the sulphocyanide produced from the of amyl by the action bisulphide of amyl of nitric acid. by the action of nitric acid. Theory. M ed 1o ck. 1)a11 s on. 10 eqs. Carbon 60 27.33 27.46 2‘9.36 11 , Hydrogen 11 5.01 5.22 5-14 2 , Sulphur 32 14.58 5 , Oxygen 40 18.23 -1 eq Baryta 76.5 34-85 34.59 34-44 219.5 100*00 agreeing with the formula BaO.Clot IC, 8 0,. On comparing the above results we will find that there are good grounds for regarding the acid produced by the action of nitric acid on bisulphide of amyl as identical with that produced by the action of nitric acid on thc sulphocyanide of amyl. Gerathe-wohl’s formula for the baryta-salt yields theoretically Cia44 per cent of hydrogen while mine gives 5.01 per cent. Analysis gives 5.14 per cent. It is very remarkable that one out of the three analyses made by Gerat hewohl corresponds with mine an additional proof of the identity of the acids. In conclusion I will for the sake of com-parison give the amount of carbon hydrogen and barjta found in the analysis aborc referred to along vith MP.Mecllocli’s and niy own. &NI) HYP08ULPHBMYLIC ACIDS. 161 Carbon. I-Twhogen. Baigta. 27-36 5.14 34.4 Danson. 27-33 5.00 34.95 GerathewohI.

ISSN:1743-6893    

DOI:10.1039/QJ8510300158

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年代:1851

数据来源: RSC

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NOTICES OF PAPERS CONTAINED IN THE FORElCN JOURNALS. BY HENRYWATTS,B.A. F,C,S. on cr mode of Preclpitnting all the Metals contained in n Eiquid by one OPeratioxm (InChemico-legal Investigrlions). By Gaultier de Clrubry.* THIS method consists essentially of two parts viz. 1. The destruction of the organic matters by the action of nitro-hydro-chloric acid ; 2. The precipitation of the metals from the resulting solution by electrolytic action. The organic matter suspected to contain poison is introduced into strong fuming hydrochloric acid contained either in a flask or in a tubulated retort having a receiver adapted to it; a gentle heat is then applied and nitric acid added by small portions at a time. The organic matter is thereby completely destroyed with the excep- tion of the fatty substances contained in it.The liquid which is transparent and colourless is then decanted off from the fatty matters ; the latter are washed several times with distilled water and melted at each washing; and the several washings added to the main bulk of the liquid. ‘l’his process is applicable to all descriptions of matter tbat can become the subject of toxicological investigations the stomach intestines liver vomited and excrementitious matters blood urine wine milk the earth of grave-yards stc. all yield to it with the utmost readiness; it is much more expeditious than the ordinary process of incineration with sulphiiric acid and less likely to occasion loss. If arsenic is suspected in the matter under examina- tion the process must be performed with a retort and a receiver as above described and the liquid which passes over added to the rest; because chloride of arsenic being volatile might otherwise be lost by evaporation ; but if the operator is sure of the absence of arsenic the digestion may be performed in a flask.A clear solution having been thus obtained it is concentrated by slow evaporation-to a certain point easily determined by experience * J. Pharm. [3] XVII 125. NOTICES OF FOREIGN PAPERS. 163 -in order to drive off the excess of acid. It is then introduced into the circuit of a constant battery (Bunsen's for example) the poles being formed of platinum or the negative pole of platinum and the positive of zinc if that metal is not to be sought for in the liquid.After a certain time which even under the most unfavourable cir- cumstances never exceeds eight or nine hours the negative pole becomes covered with a criist of the metal or metals contained in the solution. It must be washed with distilled water by means of the wash-bottle and then digested in nitric acid. The solution thus obtained may be easily tested for all the suspected metals such 85 arsenic antimony lead copper zinc kc. the operator not being embarrassed by the presence of a large quantity of liquid. This process is extremely delicate serving for the discovery Of almost infinitesimal quantities of all the metals except silver which rarely OCCUI'S in cases of poisoning. Even lead which in the state of chloride is difficultly soluble in water nevertheless dissolves with case in the excess of aqua-regia.The process has moreover the advantage of precipitating all the metals at once and save3 the necessity of making special researches for each or any of them-a mode of proceeding which from insufficiency of material is often very difficult or even impracticable. The concentrated acid solution obtained as above may likewise be treated with sulphuretted hydrogen (after expelling the nitric acid bg boiling with excess of hydrochloric acid) or by Marsh's process for the detection of arsenic. It is sometimes advantageous to make a pre1irninai.y trial by digest- ing the suspected matters in water or alcohol in which many of the poisons are soluble.If this method be applied and it is afterwards found necessary to pursue that above-described we have only to add the aqueoss or alcoholic liquor to the said solution and proceed as before. The same process may likewise be advantageously applied in the examination of adulterations of food. Bread for example is some-times adulterated with small portions of sulphate of copper. NOW the treatment with aqua-regia enables the chemist to operate with facility and expedition on large quantities of bread whereas the usual method of incineration would be excessively tedious. The most scrupulous care must of course be taken to ensure the purity of the reagents. 16-54 YOTICE9 On the Oupersatiiratiun uf SaJloe Solutions. BY M. x,t~?~~i.* I.Sulphate of soda is much more soluble in hot than in cold water ;hence when a boiling saturated solution of this salt is left to cool in an open vessel exposed to the air a large quantity of beau-tiful transparent crystals are deposited containing 10 equivalents of water of crystallization. Under certain circumstances however when a solution saturated at the boiling temperature is cooled in a vessel hermetically sealed it does not deposit crystals 011 cooling down to the temperature of the air ;the water then retains a larger quantity of the salt than it would bc capable of dissolving at the same tem- perature it may therefore be said to be mpersaturated. A solution thus supersaturated crystallizes as soon as it is brought in contact with the air; but Gay-Lussac has shown?.that this effect is not due to atmospheric pressure. The experiments of &I.Lowel are directed to the further investigation of this phenonienon. 11. Three hot solutions of sulphate of soda were formed; each containing 30 grm of the sulphate and 15 grm. water and en- closed in glass tubes hermetically sealed. The first tube contained nothing but the solution ;into the second were likewise introduced some sharp-edged fragments of glass; and some pieces of platinum were put into the third. For two months during which the tubes were exposed to temperatures varying from 15O to 25O C. (59O to 87O F.) no crystals were deposited even on agitation; but when the temperature fell to 6O or 7' C. (43O or 45O F.) crystals were formed in considerable quantity in all the three tubes The quantity of these crystals showed that the mother-liquids were still in a state of satura-tion they did not increase by agitation.When the temperature of the air rose agitation caused the crystals to disappear but they sepa- rated out again when the temperature fell to 7* or 8O C. On breaking the tubes and decanting the motlier-liquids into capsules the tR.0 following phenomena were observed :-I. The crys-tals in the tubes when touched with a glass rod became opaque throughout their whole mass the opacity beginning at the part touched by the rod; the same effect was produced after a while by mere contact of air. 2. The mother-liquids decanted into the cap- sules solidified in crystalline masses.The crystals in the tubes were sulphate of soda containing 8 or perhaps only 7 atoms of water. This salt has been noticed by Faraday and Ziz The crystals de- rived from the mother-liquids on exposure to the air were ordinary sulphate of soda containing 10 atoms of water. 111. hf. Lawel has made numerous observations on the prepara- tion of sulphate of soda with 8 atoms of water. This salt crystallizes * Cornpt. Rend. XXX 163; also Ann. Ch. Phys. [3] XXIX 62. Ann. Ch. ~'liys. [23 IJ 2C6. OF FOREIGN PAPERS. in 'long prisms with rhombic bases ;it becomes opaque when touched by certain bodies and this effect is attended with evolution of heat. The mother-liquid of these crystals retains at a given temperature a definite quantity of the eight-atom sulphate.Tt has hitherto been supposed that the state of supersaturation of saline solutions is very instable inasmuch as it appears to be destroyed by causes purely mechanical such as agitation or the contact of a solid body which chemically speaking is quite inert. But the pre- ceding experiments show that neither agitation of the liquid nor the introduction of fragments of glass or platinum wire into the super- saturated solution before cooling has any influence on the formation of crystals. The electric current produces no alteration in a solution of sulphate of soda with 8 atoms of water. A solution of this salt evolves heat in ciystallizing as observed by Gay-Lussac; and the crystallized sulphate as already mentioned likewise becomes heated in passing from the transparent to the opaque condition.IV. A boiling saturated solution of sulphate of soda poured into a capsule exposed to the air becomes covered with a pellicle of anhy-drous salt and between 32O and 29O C. (90°and 84O F.) yields crys- tals containing 10 atoms of water the pellicle gradually disappearing. If the capsule into which the boiling solution is poured be placed under a bell-jar so that the air in contact with it is but slowly re- newed (e. g. a jar of the capacity of 6 or 8 litres for a capsule con- taining 1litre of solution) the liquid will retain its state of super-saturation during cooling and no crystals will be formed till the temperature falls below la0 when crystals containing eight atoms of water will be deposited.The solution may continue supersaturated for a week or a fortnight neither sudden jerks nor vibrations nor agitation giving rise to any formation of crystals; but if the bell-jar be removed the liquid solidifies in a mass consisting of crystals containing 10 atoms of water. If quick-lime be placed under the jar the temperature being 24O C. (75O F.) the solution yields crystals containiug 8 atoms of water. If a flask in which boiling water has been saturated with sulphate of soda be covered with a small capsule of glass or porcelain the liquid will remain iii the state of supersaturation. In open tubes of 6 to 10 millimetres diameter the state of supersaturation continues for a very long time-that is to say for four six or eight weeks or even longer.Crystallization always commences at that part of the liquid which is in contact with the air. Y. Agitation does not bring about the crystallization of the sulphate containing 10 atoms of water ;but the introduction of a crystal of the salt or the mere contact of a rod of glass or metal determines it. M. Lowel haa made some very interesting observations on the 266 NOTICES circumstances of contact which may or may not induce the crystal- lization of the ten-atom salt. A rod of glass or metal which deter- mines the formation of the ten-atom sulphate when plunged into the supersaturated solution loses this property if it has been previously heated to between 40° and 100° C. If this were not the case why should a supersaturated solution placed in a basin under a bell-jar remain unaltered till the temperature falls to 8* C.? A rod of glass or metal previously heated to looo C. preserves its property of not inducing crystallization even for ten days or a fortnight the temperature varying from Oo to 20° C. provided that the rod be fitted into a cork and the cork inserted into the mouth of a bottle filled with air so that the greater part of the rod niay be preserved from free contact with the air ; for if the rod be taken out of the bottle and exposed to the air for a quarter of an hour it will afterwards determine the crystallization of the solution. It appears then that rods of glass OP metal lose their activity when heated but recover it by contact with the open air.The rods also lose their activity by contact for twelve hours with water but recover it when dried by free exposure to the air. Water does not induce the crystallization of the supersaturated solution. Cold alcohol determines it; hot alcohol does not. VI. M. Low el has succeeded in forming supersaturated soliltions by dissolving sulphate of soda at temperatures not exceeding 26O C. (79O F.) He has likewise shown that a supersaturated solution of sulphate of soda concentrated by evaporation in a glass vessel pre- viously deprived of its activity yields crystals of the salt containing 8 atoms of water. It would appear says 'ICI. Lowel that those bodies which deter- mine the crystallization of the ten-atom sulphate attract the crystal- line molecules while passive substances repel them.This seems to indicate that the sides of vessels containing a supersaturated solution exert an action opposed to that of the air. VII. In fact without the action of the air and of those bodies which deternitne the crystallization of the ten-atom sulphate we should not have bcen acquainted with any sulphate containing 0 more than 8 or perhaps 7 atoms of water. The latter proportion M. Low el considers more probable than the former. VIlI. Similar phenomena are exhibited by carbonate of soda common alum chrome-alum &c. OF FOREIGN PAPERS. On the Nitride of Boron. By F. Woehier. Balmain,* as is wcll known discovered about eight pears ago a compound of boron and nitrogen to which on account of its allesed property of combining like cyanogen with metals he gave the ana-logous name Bth(gen.-/-At a later pwiod he found tl at all the bodies which he had described as zthonides were one and the same substance liarnely nitride of boron containing an unessential ariiourit of metal.$ He obtained this cornpound by heating boracic acid either with cyanide of potassium or cyanide of zinc or with sulphur and cyanide of merc:ry.I have subsequently found that it may be advan- tageously prepared by ignitiug an ailhydrous mixture of borax and ferrocyanide of potassium.§ The observation that nitride of tungsten 11 is formed when tungstate of potash is heated with sal-ammoniac led mc to attempt the forma-. tion of nitride of boron in a similar manner.This experiment has fully realized my exFectation. I obtained a body posscssing all the properties of the compound prcpared by 13alrnain by means of the cyanides and consisting as I shall show further on of boron and nitrogen in such proportions as to be converted by the action of water,. into boracic acid and ammonia. For the preparation of nitride of boron according to this method one part of pure and perfectly anhydrous borax is intimately mixed with two parts of’ dried sal-ammoniac; the mixture transferred to a porcelain or better to a platinum crucible; the crucible covered and the whole exposed to a full red heat. An ordinary carthen crucible is less suited for the purpose since the product is likely to become contairiinated with iron in conscquence of the formation of sesquichloride.In the preparation of smaller quantities a glass vessel may be employed. By this method a white infasible porous mass is obtained which is to be finely pulverized and heated to perfect ebullition in a large quantity of water to which some hydrochloric acid has been added.7 The nitride of boron is then deposited as a white powder which is separated by filtration well washed with hot water and finally dried. When prepared with earthen crucibles or with impure borax *Chem. Soc. Mem. Vol. I p. 149 and Vol. 11 p. 15. +J. 1%. Chem. B. XXVII S. 422 und B. XXX S. 14. $ J. Pr. chem. SXXIT 494. 11 Berzelius Lehrbuch 111 113. 5 Nachrichten 1850 N. 111 S. 33. fF If in the first place pure water be employed and the filtered solution slowly eva-porated chloride of sodium separates in acute and transparent octohedrons crystals when heated become milk-white without losing either their form or their lustre.From their solution in water the salt is egai obtained in cubes. l68 NOTICE8 wl-hich has not been recrystallized it must be digcsted with concen- trated hydrochloric acid for the purpose of removing foreign mat- ters; but even by this process it is dimcult to obtain it iu a state of purity. When thus prepared the nitride of boron forms a white light powder which when magnified 500 times appears as an amorphous granular milkcwhite mass. It may be rubbed into the skin like talc and imparts to it a high degree of smoothness. It possesses all the characteristic properties assigned to it by Bal- main; becomes luminous in the edge of a flame giving off a greenish-white light ; evolves ammonia in abundance when fused with hydrate of potash; suffers no change either with concentrated acids or with alkalis; and is not affected by ignition in hydrogen or chlorine.In a current of steam it is completely converted even at a moderate red-heat into ammonia and boracic acid the latter being for the most part volatilized with the aqueous vapours ;a solution of borate of ammonia is obtained on their condensation. 1have moreover niade the following observations upon this sub-stance. Exposed for an hour to a temperature at which nickel fuses in a porcelain crucible which was placed in an earthen crucible and sur-muiided by pulverized charcoal nitride of boron remained entirely unchanged neither fusing nor suffering any loss of nitrogen.In an alcohol-flame into which a jet of oxygen is blown it rapidly bums with a greenish-white flame forming vapours of boracic acid. On the contrary it cannot be made to burn by directing a jet of oxygen upon it whilst heated to full redness in a small pla- tinum crucible; nor does it even become luminous under these cir- cumstances. Its most remarkable property of phosphorescing with a greenish-white light of greater brilliancy than is exhibited by any other body is perceptible only if it be ignited in contact with a flame and is invariably attended with slow oxidation. When heated in chlorine it appeared to possess this property in a higher degree but seemed to lose it altogether by thc presence of foreign matters.Nitride of boron is moreover distinguished by the property of forming binoxide of nitrogen and nitrous acid when heated with easily reducible metallic oxides; in this case a reduction of the oxides takes place but without incandescence. When it is heated in a glass tube with protoxide of lead copper or mercury the tube becomes fillrd with dense red vapours. Heated with water in a sealed glass tube to 200°,nitride of boron reproduces ammonia and boracic acid the conversion however at this temperature is effected but very slowly. When the action is allowed to continue many hours the glass of the tube if the substance has not exploded is found to be attacked to a considerable depth aud converted into a white substance resmbling opal ;the water on examination is then found to contain potash silicic acid and boracic acid together with free ammonia.Although even hot concentrated sulphuric acid is without action upon nitride of boron when allowed to remain in contact with it only for a short time it neverthelcss converts the nitride though very slowly into boracic acid and ammonia when heated with it to a temperature at which the acid evaporates. This change is more readily effected by digesting with fuming hydrochloric acid whereupon boroff uoride of ammonium is formed. Nitride of boron exhibits the most remarkable deportment when heated with anhydrous carbonate of potash; it thus becomes con- verted into boracic acid and cyanate of potash the carbonic acid being reduced to the state of carbon which uniting with the nitrogen gives rise to the formation of cyanogen.This is indeed an unex- pected method of producing this radical although it is in perfect accordance with Berzelius's observation that free boron when heated with carbonate of potash burns at the expense of the car- bonic acid and liberates carbon. One equivalent of nitride of boron and 2equivalents of carbonate of potash [BN 4-2 (KO .CO,)] contain the elements of 1equivalcnt of borate and 1equivalent of cyanate of potash (KO .BO -+ KO .C NO). This double decomposition rnay be very readily effected even at a gentle red-heat in a platinum crucible placed over a large spirit-flame.A mixture of nitride of boron and dry carbonate of potash in the above equivalent proportions (1 :3 by weight) fuses readily and quietly to a pellucid liquid at a temperature at which carbonate of soda alone is not liquefied. On cooling it congeals to a highly crystalline white mass which consists nearly of equal parts by weight of borate and cyanate of potash being per- fectly soluble in water. I have converted it into pure and beautifully crystallized urea from which I have prepared cyanuric acid in the crystalline form. If nitride of boron be employed in excess a portion of cyanide of potassium is simultaneously formed from which I wag enabled to prepare prussian-blue and hydrocyanic acid. Nitride of boron even when strongly heated in a porcelain tube with free carbonic acid occasions no decomposition of this gas.As far as the direct proofs of the coniposition of nitride of boron are concerned the aiiillyses when made with specimens of different preparation exhibited considerable discrepancies. It was evident that this body uuless prepared with every possible care is liable to great variations of composition being obstinately cornbined with a foreign admixture which appears chiefly to consist of boracic acid. will not quote these experiments but mill adduce only some closely concordant analyses performed with substances which had been carefully prepared in different operations. Owing to the facility with which nitride of boron evolves ammonia 170 NOTICES when in contact with hydrates no difficulty was experienced in determining the amount of nitrogen.The determination was made exactly as with an organic substance namely by igniting with soda- lime containing somewhat more hydrate of soda than usual in order to render it more fusible. Four analyses with substances of different preparations all of which were made by Dr. Stadlcr gave 48.13 49.63 59.77 arid 51.36 per cent of nitrogen. The nitride of boron employed in the last analysis which yielded 51.36 per cent of nitrogen had been treated with hydiwfluoisic acid. 0.289grm. gave 2.363 grm. of bichloride of platinum and ammo- nium. For the direct determination of the amount of boron there remained only one method namely oxidation by heatins with an accurately weighed quantity of nitrate of lead.The increase in the weight of the fused residue beyond that of the residual oxide of lead could only be boracic acid. This method which may likewise be employed in many other cases is very readily and quickly exeeutccl and appears to give very accurate results. For this purpose the salt must of course be perfectly pure and very finely pulverized. As it is decomposed even at B moderate heat it is necessaty to dry it with great care. The fusion may be effected in a platinum-crucible provided a large excess of the salt be employed ;but if too stnall a quantity be taken a portion of lead is reduced and becomes alloyed with the platinum. The mixing of the substance to be oxidized with the salt is performed in the crucible by means of a thick polished platinum wire the two bodies being very intimately incorporated.As the mass intumesces somewhat strongly it is necessary to heat it at first very carefully. It is afterwards heated to redness for some seconds till the mass flows quietly. 0.180 grm. of nitride of boron which had been treated with hydrofluwic acid and dried at 1504 gave when fused with 6.068 grms. of nitrate of lead 4 334 grms. of fused residue. By deducting the quantity of protoxide of lead contained in the salt used (which amounted to 4.088 grms.) there remained 0,246,representing the boracic acid which had been formed. The latter contained 0.0763 grin. of boron or 42-66 per ccnt in the nitride of boron A secolid experiment yielded 42.23per cent.Five other experiments with nitride of boron obtained in three dif-ferent preparations gave 41-93 41.61 40.88,40.87,40.38 per cent of boron. If me assume the highest numbers found for boron and nitrogen as the most correct we obtain in 100 parts . 4*2*66 Boron Nitrogen . 51.36 Loss . . 5-98 OF FOREIGN PAPERS 171 This loss can be nothing but oxygen which probably exists in the compound in the form of boracic acid; for the nitride as special experiinents have shown contains neither chlorine nor sodium Cilculated in equivalents the above composition wou!d represent a cornpound of 1equivalent of boracic acid with 14 equivalents of nitride of boron (BO +-14 BN) which would contain Boron . 42.617 Kitrogen 51.124 Oxygen .6.259 A compound of this nature however is highly improbable. It may be assumed with far greater probability that the amount of boracic acid which varies considerably remains mechanically mixed in consequence of the mode of formation and of the entirely unfnsed amorphous condition of the nitride of boron ; in a similar manner for instance as sugar if mixed with boracic acid and carbonized would yield a carbon from which it would probably be difficult to extract the entire quantity of boracic acid by means of solvents. Pure nitride of boron BN free from boracic acid has not yet been prepared,-unless Balm ain’s product which has not hitherto been analyeed should be found to be the pure substance. It would contain Boron .43.76 Nitrogen 56-24 b On tho Amido-nitrides of Tungeten. By P.Woehler.u Gay-Lussac and Th6nard have shown? that potassium and sodinm under the influence of heat absorb ammonia with evolution of hydrogen giving rise to compounds of a dark-green colour ;these compouncls have been distinguished by the names of Ammonio-nitride of Potassium and Ammonio-nitride qf’ Sodium The hydrogen disen- gaged during the reaction corresponds to half the volume of ammonia absorbed. In presence of water these compounds are resolved into an alkaline hydrate and ammonia. When heated they are trans-formed into ammoniacal gas and a nitride which in contact with water gives rise to an alkaline hydrate and ammonia; hence the com-position of the nitride must be K3N or Na N.From these facts it may be concluded-in accordance with the * Ann. Pharm. LXXIII. 190 ; Ann. Ch. Phys. [3] XXIX 187. t Recherches Physico-chimiques I 337. 172 XOTICES opinions of Berzelius* and of L. Gmelint-that the green sub-stances obtained by Gay-Lussac and Th6nard are conipounds re- presented by the forniulix KNH and NaNI.1 These properties of the alkali-metals may serve to throw some light on the nature of certain compounds which are formed by the action of ammoniacal gas on tungstic acid or chloride of tungsten raised to a certain temperature. When bichloride of tungsten is subjected to the action of ammo-niacal gas a substance is obtained composed of nitride and amide of tungsten which may therefore be called Amido-nitride of Tungsten.The chloride of tungsten used in this preparation was obtained by burning metallic tungsten in chlorine gas free from atmospheric air. It was then rapidly introduced into a long and perfectly dry glass tube and a current of arnmoniacal gas passed over it the tube being shaken from time to time. It is not necessary to apply heat at the commencement of the operation as the action of the ammonia on the chloride of tungsten develops sufficient heat to fuse part of the sal-ammoniac formed and volatilize the rest which then condenses on the surface of the chloride. Towards the end of the operation however the application of heat from without is necessary care being taken not to exceed the temperature at which the sal-ammoniac sublimes.As soon as all the chlorine is converted into sal-ammoniac and no more of that compound is formed the tube is allowed to cool the current of amrnoniacal gas being kept up all the while. The product of this operation is a black substance exhibiting traces of fusion here and there-an effect which arises from the chloride of tungsten having been partly melted by thc heat produced during the reaction. In this state it is denser and has a kind of metallic lustre resembling that of the graphite from gas-retorts. When heated in the air it first gives off ammonia then takes fire and is converted into tungstic acid. Heated in a porcelain crucible to a temperature near the melting-point of silver it loses its nitrogen and hydrogen and is reduced to the state of metallic tungsten.It likewise behaves in the same manner when heated to low redness in a current of hydrogen ;in this case a large quantity of ammonia is given off. By fusion with hydrate of potash it is converted into tungstate of potash giving off ammonia and hydrogen. It is not acted upon by alkalis in the state of aqueous solution or by acids; it retains with cnergy a certain quantity of chloride of tungsten or of sal-ammoniac and must therefore be purified by digestion first in * Lehrbuch der Chemie 5 Ausg. 11 71. $-Hand-book of Cliemistry (translation) 111 66 OF FOREIGN PAYERS. 173 potash-ley and then in ammonia and afterwards washed with water before it can be considered sufficiently pure for analysis.The tungsten of this compound was estimated either as tungstic acid or as metallic tungsten. The quantities obtained in different evperiments varied between 86.76 and 90.8 per cent according to which results the sum of the nitrogen and hydrogen varies between 13-24!and 9.2 per cent. The specimen which contained 90.8 per cent of tungsten yielded 8.26 per cent of nitrogen by Will and V ar rentr a pp ’s method. From these results it would appear that there exist two amido-nitrides of tungsten; and in fact the compound prepared by the process above-described gives off ammonia with the greatest facility when heated and is transformed into a compound richer in tungsten ; hence it is probable that a portion of this latter compound is formed during the preparation of the former.The compound formed directly by the preceding process is com-posed of 2WN+ WNH,. It contains Calculated. Found. rA-3W.. 285 -86.61 86976 329 loo 00 100.00 Its formation may be represented by the equation 3WC1,+ 9NH =WsN,H + 6NH,C1+ H. On heating this compound in a current of hydrogen it gives off 1 equivalent of nitrogen which is evolved in the form of ammonia and leaves a residue consisting of the second amido-nitride W2N + WNH, which is distinguished by the grey colour of its powder. This aub-stance contains Cdculated. Found. 3 W . 285 90.48 90.80 2N 2H . . . ... 28 2 8-89 0-63 8.24 - 315 100*00 It is formed on heating the first compound mixtures of the two being however produced which vary with the temperature.Both 174 NOTICES these amido-nitrides when strongly heated are reduced to the metallic state. Oxynmido-nitrideof Tungsten.-3 W N + W8N H +2W O,.-This compound is formed by the action of gaseous ammonia on heated tungstic acid. It is not easily obtained in a state of definite composition ;for it readily gives off nitrogen and hydrogen whep heated either in the air or in a current of hydrogen. The tungstic acid used in the preparation of this compound was obtained bg calcining crystallized tungstate of ammonia. It was finely pulverized then spread in a thin layer over the inner surface of a long glass tube and exposed to a current of ammoniacal gas. Heat was applied till a faint incandescence showed itself the tube being frequently turned.The operation was complete when the evolution of water ceased. In the course of the process the decomposing action which the compound cxerts 011 gaseous ammonia becomes apparent. If the tungstic acid were placed in a porcelain tube and the temperature raised to the melting-point of silver nothing but metallic tungsten or a mixture of the metal and the oxyarnido-nitride woidcl be obtained. This compound is of a pure black colour. When prepared with non-pnlverized tungstic acid-e. g. in the state in which it is obtained by calcining tungstate of ammonia-it forms black scales having a semi-metallic lustre. When heated it gives off ammonia. It resists the action of acids and alkalis; but if the action of the ammonia on the tungstic acid has not been exhausted potash in the state of aqueous solution disengages a small quantity of ammonia from the c~tmpound and abstracts a corresponding quantity of tungstic acid.Hypochlorite of soda decomposes the compound nitrogen being evolved accompanied by an odour of chloride of nitrogen and tung- state of soda formed. Oxyamido-nitride of tungsten burns brilliantly when heated in the air and is converted into tungstic acid. Like metallic tungsten and tungstic oxide it burns when heated with red lead or oxide of copper. It is completely reduced to the metallic state by ignition in a current of hydrogen water and ammonia being evolved. When heated with water in a sealed tube it supports with- out alteration a temperature of 230"C.This compound gave by analysis results nearly corresponding to the forniula 3TNN +W,NH2 +2W0,. Its composition in 100 parts is as follows Calculated Found. Tungsten . . 8804 88.Q3 Nitrogen . . . . 7.44 7.15 Hydrogen 0.27 0.20 Oxygen . . .i 425 464 OF FOREIGN PAPERS. The mutual decomposition of tungstic acid and ammonia appears then to be less simple than might be supposed from considering merely the composition of these substances; for it might have been supposed that 1 equivalent of tungstic acid and 1 equivalent of ammo-nia would produce 3 equivalents of water and I equivalent of nitride of tungsten W N containing 87.11 per cent of the metal a quantity nearly the same as that contained in the oxyamido-nitride.The latter compound or at least a substance analogous to it may be obtained by fusing at a high temperature in a platinum crucible a mixture of tungstate of potash with a large excess of sal-amnioniac the whole being covered with a layer of chloride of potassium. If the fused product be afterwards treated with water and the tungstic acid removed by means of weak potash-ley a black heavy residue is obtained which is the new compound. When examined by a microscope with a magnifying power of 100 it is found to consist of black iiietallic molecules. It is this substance which Wohler six-and-twen ty years ago erroneously described under the nsnie of black oxide of tungsten.* It contains nitrogen and hydrogen and gives off a large quantity of ammonia not only by contact with alkalis but even when simply heated by itself.The presence of the hydrogen in a compound formed at PO high a temperature is difficult to account for unless it be aclmitted that this hydrogen does not enter into the moleciile till water is introduced Another curious fact is that this substance when heated to whiteness in a close vessel yields metallic tungsten. For the rest this body exhibits the same charac- ters as that which is obtained by the direct action of ammoiiiacal gas. It yielded between 88 aiid 89 per cent of tungsten; but when de- composed by a current of' chlorine which caused it to volatilize in the state of chloride and of acid chloride it likewise left a residue f potash amounting to between 1 and 2 per cent.When a mixture of tungstate of soda and sal-ammoniac is fused beneath a layer of chloride of sodium and afterwards treated with' water and dilute solution of potash a dark-brown substance is obtained which when examined by the microscope is seen to con-sist of a black and a dark copper-coloured substance. Wohler is of opinion that the latter is the tungstate of tungstic oxide and soda which he described some time ago. Brown oxide of tungsten slightly calcined in a current of ammo-niacal gas likewise yields a hydrogenized and azotized body mixed however with unaltcred oxide which may be easily recognized by its dark-brown colour. When strongly ignited in a porcelain tube it leaves the pure metal. Berzelius states that tungstic oxide is reduced to the metallic state by strong ignition in a current of hydrogen.According to * Pogg. Ann. 11,347. 176 NOTICES Wohler’s observations on the contrary tungstic acid is reduced to the state of tungstic oxide when heatedin an atmosphere of hydrogen to the melting-point of silver but the oxide undergoes no further change. The observations of Berzelius probably applies to an oxide containing a small quantity of alkali. Tttngstic oxide when very pure has a fine brown colour inclining to violet. Under the micro- scope it has a metallic aspect very much like that of gun-metal; it appears to be slightly fretted or crystalline. Wijhler has not succeeded in obtaining a nitride of tungsten free from hydrogen. On calcining tungstic acid in cyanogen gas a black substance having a metallic aspect was obtained and a con-siderable quantity of carbonic oxide.The black substance when treated with potash yielded a little ammonia ;nitrogen therefore enters into its constitution but it likewise contains carbon. The amount of tungsten contained in it was 64.5 per cent. On the Action of Ammonta on Chloroplntinate of Ammonium. By C. Gerhlrrdt and LI. Laurent.. It is known that chloroplatinate of ammonium when digested with concentrated ammonia dissolves completely without colouring the liquid. This product has been examined by Laurent and Gerhardt. Alcohol throws down from it an abundance of white flakes which on drying are converted into a pale-yellow resinous mass easily soluble in water.The alcoholic liquid contains a large quantity of ammonia ;and even the dried resin must be re-dissolved in boiling alcohol because it always retains a considerable quantity of sal- ammoniac. The resin dried at 160° C. gave by analysis results nearly corre-spoading to the formula Pt C1 N H,. Calculated. Found. r-7 (-A-7 .99.0 59.1 579 57.4 58.2 Pt L CI ...35.5 21.2 22.4 -20.4 N . ,28.0 16.7 15.0 -H,. .. 5.0 3.0 3.1 -167.5 100.0 98.4 The substance analysed was not absolutely pure; for when heated to 1609-210°C. it gave off traces of water and ammonia and when more strongly heated evolved hydrochloric acid and became insoluble. The impossibility of obtaining the substance in regular *Compt. Rend. Trar. Chim. 1849,113 ;Anu.Ch. Phwm. LSXII 223. OF FOREIGN PAPERS 177 form precluded the more accurate investigation of this circumstance. It was however ascertained that the body forms white precipitates with oxalate sulphate and carbonate of ammonia ; these preci-pitates however refused to crystallize and yielded variable results 011 analysis. The precipitate formed by carbonate of ammonia gives off carbonic acid when brought in contact with acids. Nitrate of silver added to the solution of the resin forms a precipitate which appears to be a mixture of chloride of silver and another platinum-salt in- soliible in water. Whatever may be the composition of these precipitates it may be safely concluded that the resin is the chloride of a platinum-base analogous to those discovered by Gros and Reiset.On the Cyanogen-compounds of Titanium. By F. Wwhler. 1. Chloride of Cyanogen and Tii!anium.*-Cy C1 + 2 Ti Cl,.-In the memoir on titanium contained in this Journal vol. 11 p. 352 the author states that chloride of cyanogen and chloride of titanium combine in definite proportions. Had it not been for the existence of this coinpound it is probable that the copper-coloured cubic crystals of titanium would still for a long time have been regarded as the pure metal; for it was this compound which by its volatility and ten- dency to form a crystalline substance betrayed the existence oi cyanogen in the copper-coloured crystals. The investigation of its composition was therefore a matter of some interest. The compound is formed immediately and with great rise of temperature when gaseous chloride of cyanogen is brought in contact with chloride of titanium.? In a short time the latter is converted into a bulky yellow crystalline mass which must be gently heated and repeatedly agitated in order to saturate it com-pletely with chloride of cyanogen.The chloride of cyanogen and. titanium is lemon-yellow and very volatile. At a temperature considerably below looo it begins to * Ann. Ch. Pharm. LXXIII 219. t The chloride of cyanogen is most easily prepared as follows ;-A saturated solution of cyanide of mercury into which an excess of finely pounded cyanide has been sifted is saturated with chlorine gas and the upper part of the containing-vessel above the liquid likewise filled with the gas.The vessel is then closed and left in a dark place, till after repeated agitation the whole of the chlorine is absorbed or the ahole of the cyanide of rnerciiry dissolved. Any free chlorine which remains may be removed by agitating the liquid with metallic mercury. The solution is then poured into a flask the ilask connected with a chloride-of-calcium tube and the latter with a gas-delivery tube and heat applied till the liquid enters into gentle ebullition from the escape of chloride of cyanogen. If it be desired to obtain the chloride of cyanogen in the free state either liquid or crystallized the object may be attained by passing the gas into B tube surrounded with snQwand salt. VOI”. ITT,-NO x’. S 178 NOTICES volatilize and sublimes iu transparent lcnion-yellow crystals which appear to be rhombic octohedrons.In damp air it fumes very strongly and soon becomes milk-white emitting at the same time the pungent odorxr of chloride of cyanogen. Water dissolves it with great rise of temperature and evolution of gaseous chloride of cyanogen forming a perfectly clear solution. It dissolves without ' alteration in heated chloride of titanium and separates a wain in crystals on cooling. It absorbs ammoniacal gas with great evolution of heat ; forming a deep orange-red compound which likewise turns white in damp air and is decomposed by water with partial separation of titanic acid. The composition of chloride of cyanogen and titanium is expressed by the formnla Cy Cl + 2Ti Cl, which gives in 100 parts Chloride of cyanogen .. . . . 24.4141 Chloride of titanium . . . 75*56 1oo*oo To analyse the compound an indefinite quantity of chloride of titanium was introduced into a weighed bulb-apparatus; spread in a thin layer over the inner surface; then completely saturated with chloride of cyanogen; and the product weighed after all excess of chloride .of cyanogen had been removed by a current of dry air. The compound was then carefully dissolved in water and the titanic acid precipitated at a boiling heat by aqueous ammonia. In this manner 3.008 grm. of the compound yielded 0.964 grm. titanic acid corresponding to 2,283 grm. or 75.89 per cent of chloride of titanium. Bichloride of tin does not appear to form any similar compound with chloride of cyanogen.11. Compound of Bichloride qf Titanium with IZydrocyaizic acid.*-H Cy + Ti Cl,.-When anhydrous hydrocyanic acid is poured upon bichloride of titanium combination t'akes place instantly with rise of temperature and ebullition and the two liquids are converted into a pulverulent yellow mass. On account of the violence of the action it is advisable either to cool theliquids to Oo C. before mixing or to conduct the hydrocyanic acid in the gaseous form into the liquid chloride of titanium contained in a tubulatcd retort. When the saturation is complete thc excess of hydrocyanic acid is distilled off at a gentle heat and the compound sublimed iiito the neck of the retort bythe application of a gentle heat in order to purify it from any titanic acid with which it may be mixed.This compound is very volatile and begins to sublime at a tem-* Ann. Ch Pharm. LXXIXI. 226. OF FOREIGN PAPERS perature below 100°. It then condenses in transparent lustrous lemon-yellow crystals very much like those of the chloride of cyanogen and titanium even in their form which is that of a rhombic octohedron sometimes simple sometimes combined with other forms. The compound does not fuse before volatilizing; but yet the crystals when quickly sublimed generally unite into a coherent mass which separates from the glass on cooling. The compound fumes slightly in the air smells strongly of hydrocyanic acid soon turns white and deliquesces to a transparent viscid solution.When passed in the state of vapour through a glass tube heated to low redness it is decomposed and covers the glass with copper- coloured nitride of titanium having a darker colour than usual from separation of carbon. It is not altered by sublimation in chlorine gas the hydrogen not being separated by that treatment. This compound appears by analysis to contain 1 equivalent of hydrocyanic acid and 1 equivalent of bichloride of titanium Cy I1 + Ti Cl, whereas the chloride of cyanogen and titanium contains 2 equiva-lents of bichloride of titanium According to this formula it should contain in 100 parts Hydrocyanic acid. . . . . 22~14 Bichloride of titanium . . . 77.86 3.962 grm. of this compound weighed in the neck of the retort in which it had sublimed-the neck having been melted off for the purpose -then dissolved in water and precipitated with ammonia at a boiling heat yielded 1.316 grm.of ignited titanic acid corre-sponding to 3.117 grm. or 78.67 per cent of bichloride of titanium. A compound with 2 equivalents of the bichloride would contain 87-55 per cent. On the Physiological Action of Analogously Constituted Chemical Compounds. By J. Schlossbergcrr A series of experiments on the action of chemically pure Methyl-alcohol and Amyl-alcohol made by the author partly alone partly in conjunction with Professor Griesinger on dogs cats and rabbits led to the following results I. Both these alcohols exert upon the animal organism an action precisely similar to that of coninion alcohol (ethyl-alcohol) inasmuch as they uniformly when administered in comparatively small doses excite intoxication to a greater or less degree and in large doses * Ann.Ch. Pharm. LXXIII 212. x2 180 NOTICES produce perfectly comatose sleep. With regard to energy of narcotic action amyl-alcohol appears scarcely to surpass absolute ethyl- or mcthyl-alcohol. Large powerfal dogs bore doses of an ounce of wood-spirit or half an ounce of fusel-oil without passing from the state of coma or apparent death to that of actual death. 11. Both these alcohols just like cthyl-alcohol are very quickly decomposed in the blood so that frequently after the lapse of a few hours their odour cannot be detected-or at most but slightly-in that fluid even on distillation.In two cases however when the carotid artery was opened half an hour after the injection of a con- siderable quantity of fusel-oil into the stomach a very distinct odour of fusel-oil was perceived in the blood of that vessel; the same was apparent in severalinstames in the blood of the jugular veins and of the heart. The alcohols are therefore partially at least absorbed from the stomach into the blood without ulteralion. In certain glands such as the spleen and liver which contain large quantities of blood thc odour continued very distinct and for a very long time after the introduction of the alcohol into the stomach. In the brain of animals on the contrary into whose system wood-spirit or fusel-oil had been injected by the stomach or the rectum the odour of these substances was never uninistakeably perceptible.111. On the mucous membranes the above-mentioned anhydrous alcohols act precisely in the same manner as common alcohol altering the structure of the epithelium drying it up making it easily sepa- rable and producing partial reddening and extravasation of blood on the mucous membrane itself. IV. The question whether these alcohols during their decomposi- tion in the circulating system are converted into the corresponding acids (ise. undergo eremacausis) before they are completely burned- the author was unable to bring to a satisfactory solution iiiasrnuch as his experiments gave contradictory results. In two experiments (on dogs) in which wood-spirit was injected into the stomach and the liquid part of the blood after the separation of the coagulable por- tions was distilled with very diIute sulphuric acid a distillate was obtained which gave unmistakeable reactions of formic acid (with oxide of silver oxide of mercury &c.) But in a similar experiment with fusel-oil no valerianic acid could be discovered in the blood by similar means although that acid is so easily recognized by its odour.Bouchardat and Sandras believe that they found traces of acetic acid in the blood of animals whose food had been soaked in brandy. With regard to the first-mentioned result (with wood-spirit) it still remains to be decided whether the blood of dogs in its normal state thct is when the animaIs are fed on a mixed diet does not contain trzces of formic acid.Thc author often observed that the liver and spleen of animals xhich had taken considerable quantities of fusel-oil from one to four OF FOREIGN PAI'ERS. hours before death gave out a pure and distinct odour of valerianic acid after they had lain exposed to the air for several days although during dissection they merely smelt of fusel-oil. The odour of valerianic acid became apparent before the commencement of putre- faction ;moreover from causes which the author was unable to trace it was sometimes emitted and sometimes not even under circumstances which to all appearance were perfectly similar. V. In the urine of animals which had taken single or repeated doses of the alcohols the odour of the alcohol itself was in some cases perceptible in others not; but no distinct indications of formic or valerianic acid were ever found in it.A few experiments with z;aZerianic and butyric acid showed that these volatile acids of the series C H 0 (a fact long known in the case of acetic and formic acid) when introduced into the stomach in the concentrated state produce violent inflammation of the mu-cous membrane with local softening and hemorrhage viz. at the "Fundus." In conclusion the author states his intention of instituting similar experiments with acids analogous to benzoic acid with respect to which an interesting question arises viz. whether these acids pass into the urine in the form of hippuric acid (as is stated to be the case with cinnamic acid) or whether after their administration the urine becomes charged with analogous but not identical coiijugate acids.On the Passage of Ciiminic Acid througk tho Animal S3eteni. ]By A. W. Hofmann. Some observations lately made by J. Schlossberger on the physiological action of organic substances analogously constituted reminded me of a few experiments commenced several years ago but interrupted by other researches. Some investigations of the derivatives of curninic acid (cuniol nitrocumol cumidine and cumonitrile) carried out in my laboratory and exhibiting in an unmistakeable manner the perfect parallelisni of this series with the compounds derived from benzoic acid sug-gested the idea of studying the influence of the animal organism upon that acid.Shortly after Mr. Alex. Ure had made the remarkable observation that benzoic acid introduced into the organism is found again in the urine in the form of hippuric acid the deportment under the same circumstances of cinnamic acid so closely allied to benzoic acid was studied by MM. Erdmann and Marchand. 182 NOTICES These chemists ascertained that cinnaniic acid is likewise converted in its passage through the organism into hippuric acid ari observa- tion which has been lately coniirmed by the experiments of Wohler and Frerichs. This result might have bcen anticipated if we recollect how readily ciniiamic acid is transformed into benzoic acid by the influence of oxidizing agents. The homology of cuniinic acid with benzoic acid appeared to promise a different result.This acid has been converted into benzoic acid only by very indirect processes namely by the removal of car- bon by the action of the alkaline earths and treatmeiit of the resulting carbohydride with nitric acid. It was not improbable that the passage of this acid tlirough the organism would give rise to the secretion in the urine of an acid homologous to hippuric acid of a glycocoll-cuminic acid and it was with the hope of obtaining this acid that the experiment mas made. After having satisfied myself by experiments with rabbits that cuminic acid is perfectly iiinoxious I took in the evening several grammes of this acid without feeling the slightest inconvenience. Several others making a similar experiment I rapidly procured the quantity of urine necessary to operate upon.It was evaporated on the water-bath to the consistence of a syrup when yellow needles were deposited which after re-crystallization with animal charcoal were found to be pure cuminic acid. In order to fix this result by a number the purified acid was subjected to combustion. 0.2478grm. of acid gave 0.6586 , carbonic acid and yy 0.1640 , , water. Theory. Experiment. -20 equivs. of Carbon . . 120 73.19 72.66 12 , st Hydrogen . . 12 7.33 7-37 4 , , Oxygen . . . 32 19.48 -II_-1 equiv. , Cuminic acid . 164 100.00 From the preceding experiment it is evident that the cuminic acid unlike benzoic acid passes through the organism without under- going any change.The experiment was repeated several times with the same result; the amount also of acid deposited from the urine very nearly agreed with the quantity taken considering the loss which is unavoidable under such circumstances. I did not succeed in detecting together with cuminic acid another peculiar acid in the urine. The unfavourable result obtained vith cuminic acid induced me to try the same experiment with an acid still nearer allied to benzoic acid. Cuminic acid differs from benzoic acid by 3 (C H,) whilst toluylic acid discovered by nlr. Noad contains only C H more than benzoic acid. Cuniinic acid . . . . C,oH,204 '18 Toluylic acid . . . . c16H8 '4 Benzoic acid . . . . . C,,*H6 0 Toluylic acid also was found to be perfectly innoxious and could be taken to the amount of several grammes without inconvenience.I was unable to detect any toluylic acid in the urine. On treating however the urine with ether a small quantity of an indifferent substance was dissolved which crystallized after the evaporation of the latter in perfectly regular and highly lustrous crystals. The great difficulty of obtaining larger quantities of toluylic acid free from nitrotoluylic acid has prevented me from entering into a complete investigation of the crystalline compound. Researches on the Volatile Oils obtained in the Distillation of Wood. By A. Cahoars.' When crude commercial wood-spirit is mixed with water a pale-yellow volatilc oil separates from it and rises to the surface of' the liquid.This oil is not a pure definite compound; in fact when sub-mitted to distillation it begins to boil at about 90° C. while the last portions do not pass over below 200°. The ultimate analysis and rapour-density of these products affording no satisfactory information respecting their constitution the crude-oil was agitated with concen- trated sulphuric acid whereby it was separated into a brown-rcd viscid mass and a clear liquid having an aromatic odour the latter floating on the top. The clear liquid when washed with an alkaline ley then diluted dried over fused chloride of calcium and distilled from anhydrous phosphoric acid began to boil at 108O C.; the last portions distilled over between 160"and liOo. A considerable por- tion of this product passed over between 108O and 11%);this was '4 HIO * Compt.Rend. SSS 320. 184 NOTICES collected apart. Other fixed boiling-points were likewise obtained ; one between l28O and 130°; another between 145O and 148O ;the last between 164 and 168O. The product which boils bctween 108 and llOo is ToZuoZ (Deville's benzoene) c, 13,. The mean of several vapour-densities of this compound was found to be equal to 3.27; it represents 4 volumes of vapour and accords very nearly with the theoretical density 3.24. To establish com-pletely the identity of this substance with toluol it was treated with fuming nitric acid the products thereby obtained were mononitro- toluol and binitro-toluof. The former of these treated with an alco- holic solution of hydrosulphate of ammonia yielded toluidine possessing all the properties ascribed to it by its discoverers; the second is transformed into a new alkaloid called Nitro-toluidine the formation of which has been previously mentioned by M.Cahours in a note relating to anisol; its formula is This alkaloid which crystallizes in yellow needles yields with hydro- chloric nitric sulphuric and phosphoric acid definite compounds the forrnule of which as determined by analysis are Hydrochlorate . .C1 H. C, H,N2 0 Nitrate . . . ,NO,. C, H N 0, HO. Sulphate . . SO,. C,,HsN 0 HO. Treated with chloride of benzoyl or chloride of cumyl it yields com- pounds andogous to the amides and anilides. The product which boils between 128 and 1304 exhibits properties closely resembling those of toluol differing from it in fact only by containing a larger quantity C H it is therefore an homologue of toluol.Several analyses and three vapour-densities perfectly agree-ing among themselves lead to the formula C16H, = 4 volumes of vapour. To this compound M. Cahours gives the name of XyZoZ or Xylesze. Treated with fuming nitric acid it yields products analogous to those obtained from toluol. MonoizitroxyZoZ when dissolved in alcohol and treated with hydrosulphate of ammonia yields a base analogous to toluidine; it may be called XyZidine. The liquid which boils at 148O exhibits the coiiiposition and all thc properties of cumol c,,H]p 01" FOREIGN P PERS. The analyses and vapour-densities agree perfectly with this formula.To denionstrate the identity of this substance with cumol it was treated with fuming nitric acid and yielded two compounds present- ing all the properties of mononitro-cumol and binitro-cumol; the latter compounds treated with hydrosulphate of ammonia yielded cumidine and nitro-cumidine. M. Cahours has likewise repeated the investigation of mesitilol and found that it boils between 162' and 164O C.; his experiments confirm the composition assigned to this compourid by Dr. Hof-ma n n namely c18Hlz =4 volumes of vapoui; (Vide p. 17 of this volume). Mesitilol is isomeric but not iden- tical with cumol; for not only does its boiling-point differ con-siderably from that of cumo1 but it likewise gives totally different products by contact with various reagents.Under the influence of fuming nitric acid it yields three distinct products viz,:-1. ~onor~itro-~e~tiZoZ, when the acid is not used in excess and especial care is taken to keep the reacting substances cool. 2. When more nitric acid is used and the temperature is allowed to rise the product is Binitro-mesitilol a compound discovered by Dr. H ofm ann. 8. When instead of nitric acid a tnixture of nitric acid and fuming sulphuric acid is used the product is Trinitro-mesitilol a substance whose formation and properties are described by M. Cahours in a memoir on the action of a mixture of sulphuric aud nitric acid on organic substances.* Hence it appears that mesitilol by contact with nitric acid gives rise to three products derived by substitution of hyponitric acid vapour for hydrogen these products may be thus expressed The first of these bodies viz.mononitro-mesitilol when treated with an alcoholic solution of potash becomes heated and evoIves two products on distillation. -One -of these is a liquid which i,i formed in very small quantities only and possesses the properties of an alkaloid; the other which is solid dissolves very readily in alcohol and separates from it by spontaneous evaporation in tubular crystals of great beauty. Its composition as found by analysis COY-responds to the formula Hl, NO It is therefore isomeric with mononitro-niesitilol. * Ann. Ch. Pharm LXIX 230. 186 NOTICES The last hydrocarbon obtained by treating the volatile oil of wood with sulphuric acid that namely which boils between 164’ and 168”,has exactly the composition of cumol and mesitilol; its con-delisation is moreover the same as that of these bodies and yet it is not identical with either.It appears then that the volatile oil which is produced in the distillation of wood and contaminates the ordinary mood-spirit of commerce contains hydrocarbons identical with those which are obtained in the distillation of coal-tar and which have been lately examined by Rlr. Mansfield. These results establish an intimate relation between coal and the woody matter which may be regarded as its origin.--In certain specimens of wood-spirit the author has found an oil inuch more volatile than the preceding; it begins to boil at about 5S0 C.the last portions distilling over between 90° and 100”. This very volatile oil is almost wholly composed of two substances the one which constitutes about three-fourths of it is the acetate of methyl as shown by its ultimate analysis the density of its vapour and its behaviour with reagents; the other pssesses the properties and composition of Freniy’ s nietacetone C, H, 0,= 4 volumes of vapour. on the Formation of Succinic hid by the Oxidation of Butpic Acid. By RE. Dessnignes.* Gerhardt in his “Pr6cis de Chimie Organique,” has remarked that parallel to the series of monobasic fatty acids whose general formula is C €1 O, there may also be fornied a series of bibasic acids according to the formula C €I,,-% 0,.Almost all the acids of thesc two parallel series are produced simu1taneons;y when fatty bodies of high combining number arc oxidized by nitric acid; and it may be conceived that each terni of the bibasic series is formed by simple oxidation of the corresponding terni in the monobasic series ; but excepting in the case of acetic and oxalic acid the possibility of this trailsforination had yet to be demonstrated by experiment. Succinic acid in the one series is collateral to butyric acid in the other; and Dessaigiies has in fact succeeded in forming the first of these acids by the oxidation of the second In an apparatus * Compt. Rend. XXX 49. OF FOICEIGN PSPERS. 187 consisting of a retort and a long tube serving both for adapter and receiver-the junctions being ground with emeyy ad the connection made without the use of cork-30 gramnzes of very pure butyric acid prepared by the fermentation of flesh and fecula was heated with twice its volume of nitric acid of specific gravity 1.40.The appa- ratus was inclined in such a manner that the condensed vapoura of the butyric acid constantly fell down again into the retort and nitric acid was added from time to time. Although the niixture was continually surmounted by a red atmosphere of nitrous gas the action was very slow and was far from being complete even after continuing for ten days of twenty-four hours each. Finally when the red vapours were no longer visible the liquid was cautiously distilled till a crystalline residue was obtained.This residue was soiled with a substance which attracted moisture froin the air and from which it could not be purified by prolonged heating in the water-bath ; it was alternately purified by pressure between folds of paper. The crystals when thus purified presented all the physical characters and chemical reactions of succinic acid. The quantity obtained was not sufficient to allow of its complete purification for the purpose of ultimate analysis; but a silver-salt was prepared and gave by calcination 64.33 per cent of silver the calculated quantity being 65-05. on the Formation of Aspartic Acid from stmalate of Ammenla. By M. Dossaignss.* We are indebted to Piria for the interesting observation that asparagin and aspartic acid when submitted to the oxidizirig action of nitrous gas disengage nitrogen and leave a residue of malic acid.From this it follows that these two bodies may be regarded as aniides of malic acid corresponding for example to ovamide and oxamic acid. If this be the case we ought to be able to reproduce asparagin and aspartic acid synthetically. The action of ammonia on malic ether ought to produce asparagin. The author did not succeed in his attempts to prepare malic ether but he has obtained aspartic acid by means of the biinalate of ammonia. When bimalate of ammonia is heated in the oil-bath to 160°-* Compt. Rend. XXX,324. 188 NOTICES 200° C. it fuses with intuniescence and disengages water very slightly impregnated with ammonia.The residue is a reddish transparent and somewhat resinous mass which is but very slightly soluble in water even at a boiling heat. By repeated washings ~k ith warm water an amorphous pulverulent substance is obtained having a pale brick-red colour and an earthy taste. This sub-stance is a new azotized acid which differs in all its reactions from aspartic acid; it is very stable It dissolves in concen-trated acids on the application of heat and is precipitated un-changed from the solution by water even after boiling for a few moments. But when heated for five or six hours with nitric or hydrochloric acid it undergoes a remarkable transformation. The action is complete when no further precipitate is formed on the addition of water.The solution when evaporated to dryness in the water-bath leaves a brown crystalline strongly acid residue which is a compound of hydrochloric acid and an organic substance. This compound is easily purified by means of charcoal and is then obtained in beautiful colourless crystals. On dissolving these crystals in a tolerably large quantity of warm water dividing the solution into two equal parts neutralizing one of them exactly with ammonia and adding it to the other the liquid yielded on cooling a quantity of small brilliant prisms consisting of aspartic acid. The acid thus obtained does not agree in crystalline form with aspartic acid obtaincd from asparagin; but the salts which it forms with lime soda and the oxides of copper and silver crystallize in the same forms as the corresponding aspai-tates and yield by analysis the same quantity of base.The crystallized acid itself likevise yields by ultimate analysis the same numbers as those obtained by the combustion of aspartic acid. On the Fibrin of Mascnlar Flesh. By Justus Liebig.* When very finely chopped meat is freed by digestion in cold water and pressure from all its soluble ingredients there remains a white tasteless residue consisting of true muscular fibre together with nervous and cellular tissue Muscular fibre is generally considered to be identical with the fibrin of blood; this however is an error arising perhaps from the close resemblance between the physical properties of the two substances. 4 Ann Ch. Pharm.LXXIIT 125. OF FOREIGN PAPERS. When blood-fibrin is imintrsed in water containing -?u per cent of hydi-ochloric acid it quickly swells up to a gelatinous mass; if stronger acid be added the jelly shrinks up again nearly to its fornicr bulk biit if subsequently imniersed in pure water smells up like a sponge. This experiment may be repeated several times without occasioning the solution of any perceptible quantity of blood-fibrin in tlie liquid. The fibrin of muscular flesh behaves in a totally different nianner. Wheii it is immersed in water containing the above-mentioned pro- portion of acid the greater part dissolves immediately and coin-pletely forming a solution rendered slightly turbid by fatty particles which however may be completely though with difficulty separated by filtration; the filtered liquid is perfectly clcar.The solution of the fibrin takes place at ordinary temperatures. The liquid when neutralized coagulates to it thick whitc gelatinous mass easily soluble in excess of alkali. Common salt and other saline solutions added to the alkaline solution produce a coaguluni which dissolves on the addition of a large quantity of warm water. The precipitate obtained on neutralizing the hydrochloric acid solution of the flesh-fibrin is soluble in lime-water and the solution when boiled yields a coagulum like a dilute solution of white of egg. If the precipitate be previously boiled in water it is rendered insoluble in lime-water. It is especially remarkable that this con-stituent of muscular flesh which is so easily soluble in water acidu- lated with hydrochloric acid is contaiued in very unequal quantities in the flesh of different animals.Thus the flesh of poultry or of oxen dissolves almost wholly ; whereas mutton leaves a considerable residne ; and in veal the insoluble portion considerably exceeds the half. The insoluble residuc is elastic and white but softer and more gelatinous than the original flesh like blood-fibrin swollen up in slightly acidulated water. Thc coniposition of flesh-fibrin differs from that of blood-fibrin approaching more nearly to that of albumen. Dr. Strecker found in it carbon 54*6and 53-67; hydrogen 7.28 and 7-27; nitrogen 15.84 and 16.26; sulphur 1-21,1.02 and 1.11; ash 1.4. Blood-fibrin constitutes only a fraction per cent of blood.Accord-ing to the most careful analyses it contains more nitrogen than muscle-fibrin ;hence the supposition that it serves for the formation of the latter is very doubtful. An important constituent of blood- fibrin is iron which is invariably found in it Liebig has never succeeded in obtaining blood-fibrin free from iron. The absence of iron in this substance has often been asserted on the ground of its leaving a white ash; but even this colourless ash contains a con- siderable quantity of iron. TT'hen well Tashed blood-fibrin is coiiipletel y immersed in water 190 NOTICES contained in a vessel which can be closed and placed in a warm situation putrefaction rapidly sets in. The fibrin gradually becomes coloured loses its coherence and in about three weeks dissolves completely forming a very slightly coloured liquid in which a few black flakes are seen to float about their colour arising from sulphide of iron ;these flakes may be easily separated by filtration.The solu- tion thus obtained is undistinguishable from a solution of albumen ; when heated it coagulates in a gelatinous iriass possessing all the characters of albumen and liken& the same composition as appears from an analysis made by Dr. Strecker which gave carbon 53.9; hydrogen 6.99 ; nitrogeri 1558; sulphur 1.59 -1.45 ; ash 0.28. This albumen is probably one of the most remarkable products of putrefaction. During the process of conversion a very fetid volatile product is formed together with a small quantity of free hydrogen.The liquid filtered from the coagulated albumen contained a small quantity of an azotized body not yet further examined. Method of obtaining Metacetic Acid in large quantltiee. By Fr. ICellcr.+ A convenient qiiantity (2 or 3 lbs.) of bran is mixed to a semi-fluid consistence with ten times its weight of water at 50°-GOo C. (122°-1400 F.) and with a fourth-part of coarsely-divided leather (scrapings of tanned ox-hide are the best adapted to the pur- pose); pounded chalk is then added and the whole left to ferment in a warm place. The process is complete in the course of three or four weeks in winter and in a few days in summer ;its termination is indicated by the sinking together of the mass which was previously spongy and intumescent.The mass is then strained and washed with hot water; the lime-salt converted into soda-salt ;and the acid sepa- rated by sulphuric acid. To separate any acetic or butyric acid that might be present a portion of the liquid was saturated with carbonate of soda the rest added to it and the free acid separated from the saline residue by distillation. This residue was found to consist of a mixture of acetate and metacetate of soda. In all subsequent experiments n.hich the author made with the view of discovering the presence of any other acid besides metncetic the silver-salt prepared from he residue was found to have the same composition viz. * Ann. Ch. Pharm. LXXIII 205. OF FOREIGN PAPERS.-Calculated. Fouad. C . . . . 36 19.89 19.73 H,. . . . 5 2.76 2-72 Ag . . . . 108 59.55 59.32 32 0 . . . . -17.80 -18.23 181 100.00 100~00 The silver-salt when newly prepared may be recrystallized from hot water without perceptible blackening ; but after drying over sul-phuric acid it is for the most part decomposed by boiling with water. The lead-salt prepared by saturating the pure acid with hydrated oxide of lead formed a radiated crystalline mass which when heated by the hand deliquesced to a viscid liquid. The baryta-salt dried up to a gumtny mass but after a while swelled up in cauliflower-like tufts which effloresced and fell to pieces on expo- sure to the air. This salt contains 36.38 per cent (9 at.) of water of crystallization which it loses when heated to 140°C.1.43 grm. treated with sulphuric acid yielded 1,186Ba 0. SO = 54.42per cent baryta. The soda-salt was only once obtained in the crystalline state after being heated to fusion and then dissolved in the smallest possi- ble quantity of water. It was generally obtained in the form of a greasy mass. All these salts when thrown upon water in small frag- ments exhibit a rotatory movement similar to that of the butyrates. On the Action of certain Reagents iipon Qninino. By Dr. Vogel Jian.* Brandes has shown that when a solution of snlphate of quinine is mixed with chlorine-water and caustic ammonia added the liquid acquires an emerald-green colour. Starting from this experiment the author has succeeded by the use of a few other reagents in producing very characteristic changes of eolour in the solution of sulphate of quinine.If to a solution of sulphate of quinine mixed with chlorine water there be added instead of ammonia an excess of concentrated solution of ferrocyanide of potassium a dark-red colour is immediately produced and remains unaltered for some hours but afterwards especially 011 exposure to light passes into green. This reaction of quinine is * Ann. Ch. Pharni LXXIII 221. 192 NOTICES OF FOREIGN PAPERS. highly characteristic and well-adapted for a lect ure experiment. If caustic-potash be used in place of ammonia the solution acquires a sulphur-yellow colour. Instead of chlorine a solution of chloride of lime mixed with hydrochloric acid may be advantageously used in which case on addition of ammonia a green powder is precipitated.The preceding reactions are not produced with cinchonine and may therefore be regarded as marks of distinction between the two alkaloids. According to the most recent reports of chemists there ap- pears to be a prospect of preparing the vegetable alkaloids directly from their elements; hence it is much to be desired that character- istic reactions should be discovered- especially such as depend 011 change of colour-which may serve as standard tests by which the nature of the artificial products may be determined.

ISSN:1743-6893    

DOI:10.1039/QJ8510300162

出版商:RSC    

年代:1851

数据来源: RSC